CN106662694A

CN106662694A - Method for manufacturing optical element, optical element obtained using said method, and image display device provided with said optical element

Info

Publication number: CN106662694A
Application number: CN201580041457.XA
Authority: CN
Inventors: 利光惠理子; 内田直幸
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Rayon Co Ltd
Priority date: 2014-08-01
Filing date: 2015-07-30
Publication date: 2017-05-10
Also published as: KR20170040207A

Abstract

The purpose of the present invention is to provide a method for manufacturing an optical element that is easy to pattern and exceptional in terms of dimensional accuracy, the optical element having a uniform optical film and protective film free of coating defects, and being unaffected by water or solvents. The present invention pertains to the method for manufacturing an optical element, the method having: (I) a step for forming an anisotropic optical film on a substrate and then performing an insolubilization process; (II) a step for then forming a protective layer over the optical film; and (III) a step for providing a mask over and exposing the protective layer, and developing the protective layer using an alkali solution, thereby patterning the protective layer and the optical film.

Description

The manufacture method of optical element, obtain optical element and with the light using the method Learn the image display device of element

Technical field

The present invention relates to a kind of manufacture method of the optical element for liquid crystal indicator etc., specially comprising being formed at The manufacture method with anisotropic blooming and its optical element of protective layer on substrate.Further use to possess Above-mentioned manufacture method obtains the image display device of optical element and above-mentioned optical element.

Background technology

In order to control optical activity and birefringence in showing in LCD (liquid crystal display), using linear polarization mating plate and Circularly polarizing plate.In order to prevent the reflection of extraneous light in OLED (organic EL element), also circularly polarizing plate is being used.It is so far Only, in these polarized light pieces (optical element), widely use always make iodine or with dichroic organic pigment dissolving or It is adsorbed in by polyvinyl alcohol Polymer material, and the film is stretched as into one direction film-form, makes iodine or have The polarized light piece that dichroic organic pigment occurs orientation and obtains.However, what is so manufactured is existing with anisotropy Blooming, it is different with macromolecular material according to the pigment that uses, and there is heat resistance or light resistance is insufficient, manufacture liquid crystal is filled The problems such as yield rate difference of polarized light piece laminating when putting.

To solve these problems, people have studied by the base material such as glass or transparent membrane, applying shearing force The solution containing dichroism pigment is coated with simultaneously, dichroism pigment is orientated, and manufacture has anisotropic optics The method (patent document 1～8) of film.

On the other hand, people carry out from 1 plate base mother metal cutting out the operation of multiple substrates for liquid crystal cells.This Kind in the case of, formed on substrate multiple shapes (patterning) be specify pattern after with anisotropic blooming, It is split as substrate respectively and is used.Patent Document 3 discloses following method：By containing that the coating on substrate is arranged Have on the film of dichroism pigment, give insoluble liquid and cleaned using the part such as ink-jet method, so as to the shape on substrate The film containing dichroism pigment after the pattern of regulation is turned into multiple shapes.

The aqueous solution using dichroism pigment be Patent Document 9 discloses as ink, to the film of gained directly or Ground connection is printed in unit inside, forms the method with anisotropic blooming.Disclose having after insoluble On anisotropic blooming, carry out pattern by flexible printing with alignment films to the liquid crystal of polyimides and formed to burn till, it To dissolve and remove with anisotropic blooming by etch cleaning afterwards.Disclose due to anisotropic optics Film is located at the inner side of glass substrate and is protected by glass substrate, therefore need not carry out to be difficult to anisotropic optics Film causes antistatic process for the hard conating process and electrostatic for damaging etc..

Prior art literature

Patent document

Patent document 1:The flat 8-511109 publications of Japanese Patent Laid

Patent document 2:Japanese Patent Laid-Open 2008-69300 publication

Patent document 3:Japanese Patent Laid-Open 2004-348043 publication

Patent document 4:Japanese Patent Laid-Open 2002-277636 publication

Patent document 5:Japanese Patent Laid-Open 2007-272211 publication

Patent document 6:Japanese Patent Laid-Open 2007-186428 publication

Patent document 7:Japanese Patent Laid 2001-504238 publication

Patent document 8:Japanese Patent Laid-Open 2006-48078 publication

Patent document 9:Japanese Patent Laid 2004-534283 publication

Patent document 10:Japanese Patent Laid-Open 2008-233819 publication

The content of the invention

The solved problem of invention

It is multiple using cutting out from 1 plate base mother metal when manufacture is comprising the optical element with anisotropic blooming For the method for the substrate of liquid crystal cells.In this case, more situation is：Multiple figures for forming regulation are formed on substrate After the shape of case with anisotropic blooming, it is split respectively, used as substrate.

Additionally, as the In-Cell types liquid crystal display dress possessed in the inner surface side of substrate with anisotropic blooming It is that electrode and colour filter etc. be arranged at into each in liquid crystal cells in advance with anisotropic blooming when putting and using Layer is formed as to the convex part of substrate (hierarchic structure part) in substrate upper strata poststack.

However, being coated with containing dichroism pigment on whole substrate mother metal using the method described in the grade of patent document 1～8 During solution, due to by the solution coating to the part outside above-mentioned hierarchic structure, the part that need not be coated with, because This, must carry out removing the operation of unwanted part after coating.

Method as multiple substrates for liquid crystal cells are cut out from 1 plate base mother metal, such as it is contemplated that between use Coating process of having a rest only selects the pattern for specifying, is coated with for forming the composition with anisotropic blooming.If however, The interval of interval coating is shortened in order to expeditiously cut out liquid crystal cells substrate from 1 plate base mother metal, is then existed following Problem：The discharge for forming the composition with anisotropic blooming is difficult to control to, coating defects is produced, it is impossible to obtain Optically uniformly there is anisotropic blooming, optical uniform optical element can not be obtained then.

When using the method described in patent document 1 and 2 etc. whole substrate mother metal be coated with containing dichroism pigment During solution, till the part that the part outside the pattern form of regulation can be applied to, need not be coated with.Therefore, it is necessary to Carry out eliminating the operation of unwanted part after coating, but for this eliminates operation, the not yet precision from pattern form and production The angle of rate is sufficiently carried out research.

Although it is open just like described in patent document 3 by insoluble liquid being given with the part such as ink-jet method and being carried out clear Wash, so as to form the method that multiple shapes turn to predetermined pattern on substrate, but processing speed is slow, be unsuitable for using large-scale base Plate shape is into multiple patterns.Additionally, because insoluble processing speed is slow, the cleaning after insoluble liquid is given has each The time is needed till heterotropic blooming, tends to being susceptible to by with the insoluble liquid drying on anisotropic blooming The crackle with anisotropic blooming for causing and rupture etc..Additionally, to anisotropy after insoluble liquid is given Blooming when protective layer etc. is set, need the operation for being configured protective layer and the operation of pattern formation carried out to protective layer Deng there is a problem of that manufacturing process complicates.

In patent document 9, after insoluble with anisotropic blooming, the liquid crystal of polyimides is orientated Film carries out flexible printing, thus carries out pattern formation and burns till.The inventors discovered that：Even if existing with anisotropic blooming After insoluble, in being also easily dissolved in polyimide solution (METHYLPYRROLIDONE (NMP) etc.), produce have it is each to different Dissolving, stripping of blooming of property etc. and the reduction of polarised light function.

Additionally, the inventors discovered that：When using method described in patent document 9, after pattern is formed, in order to polyamides is sub- Amine carries out sub- amidatioon, needs to be burnt till at high temperature, on bringing impact with anisotropic blooming, substrate etc..It is right In this point, even if when ultraviolet hardening polyimides is used as polyimide resin, it is also desirable to 300 DEG C or so of Asia Amidatioon operation (patent document 10), therefore there is a problem of same.

The present invention is completed to solve technical problem as above, its object is to provide one kind on substrate comprising tool There is the manufacture method of the optical element of anisotropic blooming and protective layer, the manufacture method makes the patterning of above-mentioned blooming Become easy, additionally, make above-mentioned blooming and diaphragm be that dimensional accuracy is excellent, the uniform film without coating defects, and then not Affected by the water or solvent used in manufacturing process.

It is further an object that a kind of simple and easy method to being patterned with anisotropic blooming is provided, Becoming that dimensional accuracy is excellent, lack without coating with anisotropic blooming and protective layer for gained is provided in a kind of said method The method of sunken uniform film, further, also provides a kind of by manufacturing after being formed with anisotropic blooming The manufacture method of the optical element of the impact of water or solvent used in operation.

Method for solving problem

The present inventor has found the manufacturer in optical element to reach the result that above-mentioned purpose is repeated further investigation In method, by with specific method will be insoluble after patterned with anisotropic blooming and protective layer, can be with Above-mentioned problem is solved, so as to complete the present invention.

That is, purport of the invention is as described below.

[1] a kind of manufacture method of optical element, it is characterised in that the optical element is included：Substrate, with anisotropic Blooming and protective layer, the manufacture method of the optical element has following (I) operations～(III) operation,

(I) continuously it is coated with substrate for forming the composition with anisotropic blooming, is formed and there is anisotropy Blooming, then by salt exchange to the operation that insoluble process is carried out with anisotropic blooming；

(II) after the insoluble process with photosensitive resin coating composition on anisotropic blooming, formed and protected The operation of sheath；

(III) by mask being arranged on the protective layer for being formed and being exposed, developed using alkaline solution, to institute State protective layer and the operation patterned with anisotropic blooming after the insoluble process.

[2] manufacture method of the optical element according to above-mentioned [1], it is characterised in that the alkali used in (III) operation Property solution contain in potassium hydroxide and TMAH at least any one.

[3] manufacture method of the optical element according to above-mentioned [1] or [2], it is characterised in that (III) operation it Afterwards, with following (IV) operations,

(IV) by heating, the operation of the protective layer melt flows after patterning is made.

[4] a kind of optical element, it is characterised in that carried out using the manufacture method described in any one in above-mentioned [1]～[3] Manufacture.

[5] a kind of image display device, it is characterised in that with the optical element described in above-mentioned [4].

Invention effect

According to the manufacture method of the optical element of the present invention, simply can carry out on substrate multiple with anisotropy Blooming patterning.Further, obtain in said method to become dimensional accuracy with anisotropic blooming excellent Different, the uniform film without coating defects, therefore the excellent optical element such as polarised light performance can be obtained.Therefore, cutting out from 1 Substrate mother metal is particularly useful when marking off multiple optical elements and the substrate that is split to form, and wherein optical element possesses The solvent (NMP etc.) or the water as cleaning solvent of alignment films formation are used after being formed with anisotropic blooming Operation.

Description of the drawings

[Fig. 1] Fig. 1 is the photo of the optical element 1 of gained in embodiment 1.

[Fig. 2] Fig. 2 is the microphotograph of the end of the optical element 1 of gained in embodiment 1.

[Fig. 3] Fig. 3 is in the pattern with anisotropic blooming, to represent what is be etched with anisotropic blooming The skeleton diagram of state.

[Fig. 4] Fig. 4 is the skeleton diagram for representing the state for making protective layer be melt flows.

[Fig. 5] Fig. 5 expose for the developed removing of protective layer for representing (VIII) operation with anisotropic blooming Partial skeleton diagram.

[Fig. 6] Fig. 6 (a) and Fig. 6 (b) is to represent to be made with anisotropic blooming quilt in (III) operation or (VIII) operation The skeleton diagram of the state of etch, Fig. 6 (a) represents feelings of the profile portion with anisotropic blooming and protective layer in same position Condition, Fig. 6 (b) represents there is anisotropic blooming in the inner side of the profile portion of protective layer.

[Fig. 7] Fig. 7 is the skeleton diagram for representing (V) operation～(IX) operation.

[Fig. 8] Fig. 8 (a)～Fig. 8 (c) be represent reference example 5 in obtain optical element polarised light performance photo, Fig. 8 (a) It is the photo for side by side placing 2 optical elements, Fig. 8 (b) is the photo of parallel overlap, the photograph that Fig. 8 (c) square crossings ground is overlapped Piece.

Symbol description

A protective layers it is developed removing and expose with anisotropic blooming part

1 substrate

2 have anisotropic blooming

3 protective layers

4 optical elements

Specific embodiment

Below to being specifically described for implementing representational mode of the invention, but the present invention leads without departing from it Purport, is not just limited by the following manner.

In the present invention, " (methyl) acrylic acid " refers to both comprising acrylic acid and methacrylic acid, " (methyl) acrylate ", " (methyl) acryloyl " etc. also illustrates that same implication.Additionally, the material of " (poly-) " was added before monomer name means the list Body and the polymer.

" weight % " is respectively identical meanings with " quality % ", " weight portion " and " mass parts " in this specification.

The present invention is comprising substrate, the manufacture method with anisotropic blooming and the optical element of protective layer.This (hereinafter, operation (I) has the first method of the described manufacture method of the invention at least operation with following (I)～(III) When be expressed as " (I) operation ".Additionally, in the same manner as (I) operation, operation, the operation of (III) (II) etc. are expressed as sometimes " (II) operation ", " (III) operation " etc..).

If the manufacture method of the present invention has (I) operation～(III) operation, according to (I) operation → (II) operation → (III) The order of operation is carried out, and is not particularly limited, and between each operation, can also have other operations.For example, in (I) work Also there can be other operations between sequence and (II) operation.

The second method of the manufacture method of optical element of the present invention, at least with following (V) operation～ (VIII) operation.

(V) continuously it is coated with substrate for forming the composition with anisotropic blooming, is formed and there is anisotropy Blooming, then by salt exchange to the operation that insoluble process is carried out with anisotropic blooming.

(VI) after the insoluble process with photosensitive resin coating composition on anisotropic blooming, formed and protected The operation of sheath.

(VII) development that is exposed and being carried out by developer solution, the operation that above-mentioned protective layer is patterned.

(VIII) by the developed removing of protective layer the part exposed with anisotropic blooming, with acidic aqueous solution or After alkaline aqueous solution contact, the operation washed.

If the present invention manufacture method have (V) operation～(VIII) operation, according to (V) operation → (VI) operation → (VII) order of operation → (VIII) operation is implemented, and is not particularly limited, and between each operation, can also have it His operation.For example, can also have other operations between (V) operation and (VI) operation.

(optical element)

The optical element of the present invention is comprising the acquisition by continuous coating on the surface of the substrate with anisotropic blooming Be arranged on the protective layer on anisotropic blooming.Additionally, optical element is not limited in anisotropic Blooming and protective layer, can be having other layers for improving polarised light performance, improving the purpose such as mechanical strength.

Additionally, pattern (pattern) in the present invention represent be typeset on substrate (pay け in face) with anisotropic light The character pattern of film is learned, patterning (patterning) is represented and forms pattern.Additionally, profile portion is referred to anisotropic light Learn the peripheral part of the pattern of film.In addition, the patterning in the present invention mean from 1 plate base mother metal to cut out it is multiple for liquid crystal list During the substrate of the unit, division with anisotropic blooming, but it is not limited to this.

(substrate)

As the substrate of the present invention, it is not particularly limited, but preferably there is good surface texture, contact angle characteristic and water suction The substrate of characteristic.As the base material for forming such a substrate, for example, can enumerate the inorganic material such as glass and macromolecular material.

As macromolecular material, triacetate system resin, acrylic resin, polyester based resin, polycarbonate-based tree can be enumerated Fat, PET series resin, triacetyl cellulose prime system resin, norbornene resin, cyclic polyolefin hydrocarbon system Resin, polyimides system resins, polyurethane series resin etc..These materials can be used alone a kind, also and can use two or more.Especially Ground, preferably includes the base material containing macromolecular material.

The water absorption rate of substrate, usually less than 5%, preferably less than 3%, more preferably less than 1%.Due to by making suction Water rate is not excessive, it is suppressed that the moisture absorption of substrate when forming the film of anisotropic material with wet type membrane formation, thus tends to being difficult to There are the coating defects caused by the warpage of substrate.Further, since also can suppress to be formed with rubbing method that there is anisotropic light The substrate swelling after film is learned, thus tends to being difficult to optical defect.In addition, " water absorption rate " in present embodiment refers to employing The determination of test method of ASTM D570 impregnate 4 hours in 23 DEG C of water when weight rate value.

From making with anisotropic materials such as pigments contained in anisotropic blooming, more well edge is certain square To from the viewpoint of orientation, can have on the face with anisotropic blooming in the formation of substrate, pre-set alignment films Deng.With regard to the forming method of alignment films, can be according to " liquid crystal brief guide " (Wan Shan Co., Ltd., the distribution of on October 30th, 2000) 226 Page～page 239 etc. described in known method.Additionally, the shape of substrate can be the film-form (sheet) of fixed dimension, also may be used For continuous film shape (banding).Additionally, the thickness of substrate is usually 0.01mm～3mm, preferably 0.02mm～2mm.

The total light transmittance of substrate is usually more than 80%, preferably more than 85%, more preferably more than 90%.In addition, this " total light transmittance " in specification refers to the value determined using integrating sphere colour assessment apparatus, is diffused transmission light and parallel rays The aggregate value of transmitted light.

[have (I) operation, (II) operation and (III) operation, comprising substrate, with anisotropic blooming and guarantor The manufacture method of the optical element of sheath]

＜ is with regard to (I) operation ＞

The present invention manufacture method as (I) operation have continuously be coated with substrate for formed have anisotropic optics The composition of film, forms and has anisotropic blooming, is then exchanged to described with anisotropic blooming by salt Carry out the operation of insoluble process.

(there is anisotropic blooming)

The vertical of in the thickness direction from the film and face both direction of any square crossing is referred to anisotropic blooming On electromagnetic property in any two direction amounted to selected in three directions of body coordinate system, with anisotropic light Learn film.As electromagnetic property, the electrical properties such as the optical property such as absorption, refraction, resistance, electric capacity can be enumerated.

As with optically anisotropic films such as absorption, refractions, for example, can enumerate linear polarization photosphere, circular polarization photosphere, phase Potential difference film, electric anisotropy film etc..Also suitably conduct photosphere, phase can be polarized in the present invention with anisotropic blooming Potential difference film, electric anisotropy film are used, useful especially as polarization photosphere.

Thickness with anisotropic blooming is not particularly limited, but dry film thickness is preferably more than 10nm, more excellent Elect more than 50nm as.On the other hand, preferably less than 3 μm, more preferably less than 1 μm.By making with anisotropic optics (III) operation described later, (VIII) operation are being carried out figure in above range by the thickness of film with anisotropic blooming During case, it can be ensured that the scope with the dissolving of anisotropic blooming, tend to easily controllable dissolving.Further, tend to obtaining In film pigment be uniformly directed and uniform thickness.

(anisotropic material and the composition that there is anisotropic blooming for formation)

For the anisotropic material with anisotropic blooming of the present invention, if can be presented above-mentioned anisotropic Material, is not particularly limited.Further, since make using wet that on substrate there is anisotropic blooming, because It is (hereinafter sometimes called " for being formed with anisotropic that this is preferably the composition containing anisotropic material and solvent The composition of blooming ".).

As for forming the pattern of the composition with anisotropic blooming, being solution shape, alternatively gel, It can be the state being scattered in anisotropic material in solvent.Additionally, outside these compositions, can also as needed containing bonding Agent resin, monomer, curing agent, additive etc..

Herein, go out from the viewpoint with anisotropic blooming that formation after solvent evaporation is formed with high-orientation Send out, be preferably used to form the composition that the composition with anisotropic blooming is the state of liquid crystalline phase.In addition, this explanation It is that the state of liquid crystalline phase is referred in book《The basis of liquid crystal and application》(the good work in Song Ben Zheng Yijiaotian cities, 1991) page 1～16 Described state in page.Nematic phase described in particularly preferred page 3.

Herein, as long as anisotropic material can form the material with anisotropic blooming, pigment can be enumerated Deng.As using pigment as anisotropic material with anisotropic blooming, anisotropy pigmented film can be enumerated.It is logical Cross and use pigment, tend to obtaining electromagnetic property it is excellent with anisotropic blooming, especially can make as polarization photosphere With.

(pigment)

As the pigment of the present invention, using dichroism pigment.Additionally, being orientated for control, pigment preferably has liquid crystalline phase Pigment.Herein, the pigment with liquid crystalline phase means the pigment for showing lyotropic liquid crystalline in a solvent.It is by being coated with formation With anisotropic blooming, the pigment for showing lyotropic liquid crystalline used in the present invention is preferably soluble in water or organic molten It is particularly preferably water-soluble in agent.Further preferably《Organic conceptional diagram-basis and application》(first Tian Shansheng writes, and three go out altogether Version, 1984) defined in inorganic value less than organic value compound.In addition, water solubility refers to that pigment is in water under room temperature In generally more than 0.1 weight % of dissolving, it is more than 1 weight % of preferred dissolving.

Under the free state for being not salt form, its molecular weight is preferably more than 200 to the pigment of the present invention, particularly preferably More than 300.Furthermore it is preferred that being less than 1500, particularly preferably less than 1200.

Additionally, the pigment for showing lyotropic liquid crystalline of the present invention individually can only use a kind, also two or more can be applied in combination.

As pigment, specifically can enumerate azo system pigmen, stilbene system pigment, cyanine system pigment, phthalocyanine system pigment, condense it is many Ring system pigment (perylenes system, oxazines system) etc..Among these pigments, preferably can obtain highly in anisotropic blooming The azo system pigmen of molecules align.Azo system pigmen refers to the pigment of the azo group at least with more than 1.From tone and system From the viewpoint of making aspect, the quantity of the azo group in one molecule be preferably more than 2, preferably less than 6, more preferably 4 with Under.Pigment used in the present invention is not particularly limited, and can use known pigment.

As pigment, for example, can enumerate Japanese Patent Laid-Open 2006-079030 publication, Japanese Patent Laid-Open 2010- No. 168570 publications, Japanese Patent Laid-Open 2007-302807 publication, Japanese Patent Laid-Open 2008-081700 publication, Japan The flat 09-230142 publications of open patent, Japanese Patent Laid-Open 2007-272211 publication, Japanese Patent Laid-Open 2007- No. 186428 publications, Japanese Patent Laid-Open 2008-69300 publication, Japanese Patent Laid-Open 2009-169341 publication, Japan Open patent 2009-161722 publications, Japanese Patent Laid-Open 2009-173849 publication, Japanese Patent Laid-Open 2010- No. 039154 publication, Japanese Patent Laid-Open 2010-180314 publication, Japanese Patent Laid-Open 2010-266769 publication, Japan Open patent 2010-031268 publications, Japanese Patent Laid-Open 2011-012152 publication, Japanese Patent Laid-Open 2011- No. 016922 publication, Japanese Patent Laid-Open 2010-100059 publication, Japanese Patent Laid-Open 2011-141331 publication, Japan The flat 08-511109 publications of open patent 2011-190313 publications, Japanese Patent Laid, Japanese Patent Laid 2001- No. 504238 publications, Japanese Patent Laid-Open 2006-48078 publication, Japanese Patent Laid-Open 2006-98927 publication, Japan are specially Sharp JP 2006-193722 publication, Japanese Patent Laid-Open 2006-206878 publication, Japanese Patent Laid-Open 2005-255846 Number publication, Japanese Patent Laid-Open 2007-145995 publication, Japanese Patent Laid-Open 2007-126628 publication, Japan Patent are special Open 2008-102417 publications, Japanese Patent Laid-Open 2012-194357 publication, Japanese Patent Laid-Open 2012-194297 public affairs Report, Japanese Patent Laid-Open 2011-034061 publication, Japanese Patent Laid-Open 2009-110902 publication, Japanese Patent Laid-Open 2011-100059 publications, Japanese Patent Laid-Open 2012-194365 publication, Japanese Patent Laid-Open 2011-016920 publication Deng described pigment.

Pigment used in the present invention can be used directly with the form of free acid, and the part that can be acidic group is salt The pigment of form.Additionally, also can simultaneously there is the pigment of salt form and the pigment of free acid form.

In the case of obtaining pigment with salt form during manufacture, can directly be used, it is also possible to be transformed into desired salt shape State (salt exchange).The method that salt is exchanged can arbitrarily use known method, for example, can enumerate following method.

1) add the strong acid such as hydrochloric acid in the aqueous solution of the pigment obtained with salt form, make pigment and entered with the form of free acid After row acid out, with the neutralization pigment acidic groups of the alkaline solution (such as lithium hydroxide aqueous solution) with desired ion balance Group, the method for carrying out salt exchange.

2) in the aqueous solution of the pigment obtained with salt form, the excessive neutrality with desired ion balance is added Salt (such as lithium chloride), in the method that the form of cake of saltouing carries out salt exchange.

3) for the aqueous solution of the pigment obtained with salt form, processed using storng-acid cation exchange resin, made pigment Carried out after acid out with the form of free acid, with the alkaline solution (such as lithium hydroxide aqueous solution) with desired ion balance Neutralization pigment acidic-group, the method for carrying out salt exchange.

4) aqueous solution for making the pigment obtained with salt form is acted in advance with the alkaline solution with desired ion balance The storng-acid cation exchange resin that (such as lithium hydroxide aqueous solution) is processed, the method for carrying out salt exchange.

Additionally, the acidic-group that the pigment used in the present invention has becomes free acid form or becomes salt shape State, the pH of pKa and pigment aqueous solution depending on pigment.As the example of above-mentioned salt form, the alkali such as Na, Li, K gold can be enumerated The salt of category, ammonium salt, the salt of organic amine that can be replaced by alkyl or hydroxyalkyl etc..

As the example of organic amine, the low-grade alkylamine that carbon number 1～6 can be enumerated, the carbon number 1～6 being optionally substituted by a hydroxyl group Low-grade alkylamine, low-grade alkylamine of carbon number 1～6 etc. for being replaced by carboxyl.

In the case of these salt forms, its species is not limited to a kind, but can exist simultaneously various.Additionally, in the present invention, Pigment can be used individually, it is also possible to by and with these two or more compounds, in addition it is also possible to not make what orientation was reduced Degree mixes the pigment beyond foregoing illustrative pigment and is used.It is possible thereby to make with various form and aspect with each to different The blooming of property.

The example of the pigment for mixing during pigment other as mixing, directly Huang 12, C.I. is straight can to enumerate C.I. Connect yellow 34, C.I. directly yellow 86, C.I. directly yellow 142, C.I. directly yellow 132, C.I. Indian yellows 25, C.I. direct oranges 39, C.I. direct orange 72, C.I. direct oranges 79, C.I. acid oranges 28, C.I. directly red 39, C.I. directly red 79, C.I. it is directly red 81st, C.I. directly red 83, C.I. directly red 89, C.I. acid reds 37, C.I. directly purple 9, C.I. directly purple 35, C.I. it is directly purple 48th, the direct indigo plant 90, C.I. direct greens of the direct indigo plant 83, C.I. of the direct indigo plant 67, C.I. of the direct indigo plant 1, C.I. of the direct purples 57, C.I. of C.I. 42nd, C.I. direct greens 51, C.I. direct greens 59 etc..

(for forming the solvent of the composition with anisotropic blooming)

As solvent it is suitable have water, the organic solvent with water miscibility or their mixture.As organic solvent Concrete example, can enumerate the di-alcohols such as the alcohols such as methyl alcohol, ethanol, isopropanol, alcohol, glycerine, ethylene glycol, diethylene glycol, and methyl is molten Dioxanes such as fine agent, ethyl cellosolve etc..These can be used alone, it is also possible to mixes two or more and is used.

(concentration of the anisotropic material in for forming the composition with anisotropic blooming)

The concentration of the anisotropic material in for forming the composition with anisotropic blooming is each to different according to having The membrance casting condition of the blooming of property and it is different, but more than preferably 0.01 weight %, more than more preferably 0.1 weight %, preferably Below 50 weight %, below more preferably 30 weight %.By making anisotropic material concentration in above range, acquisition can Carry out the viscosity for forming the composition with anisotropic blooming of uniform film coated, and anisotropy material Material tends to separating out.Additionally, tending to obtaining the anisotropy such as sufficient dichroic ratio in anisotropic blooming.

(for forming the additive of the composition with anisotropic blooming)

For formed with anisotropic blooming composition in, can further as needed mixed surfactant, The additives such as levelling agent, coupling agent, pH adjusting agent.There is the situation that wetability, coating etc. are improved by additive.

As surfactant, it is possible to use any number of in anionic property, cationic and nonionic.Its addition concentration does not have Be particularly limited to, but for formed with anisotropic blooming composition in concentration be usually 0.05 weight % with On, below preferably 0.5 weight %.By making it in the scope, the additive effect of surfactant can be obtained, and be tended to not Hinder the orientation of pigment molecular.

For the anisotropic material in suppressing for forming the composition with anisotropic blooming into salt or aggegation Etc. purposes such as unstability, it is also possible to be mixed for being formed the composition with anisotropic blooming constituent it Before, under the either case afterwards or in mixing, the pH adjusting agent such as known acid/base of addition.In addition, outside above-mentioned, as adding Plus agent can be used " being coated with additive (Additive for Coating) ", J.Bieleman is compiled, Willey-VCH (2000) Described known additive.

(there is the coating process of anisotropic blooming)

If the coating process with anisotropic blooming of the present invention is continuously coated with, it is not particularly limited.The present invention In so-called continuous coating do not refer to the interval coating of each pattern, and refer to and continuously correspond to the area for constituting multiple patterns (division) Domain is coated.Even if in the case of multiple patterns are arranged on substrate, also once can be continuously coated with, it is not necessary that press Multiple patterns each be separately coated.

Formed with anisotropy as will be continuously coated with for composition of the formation with anisotropic blooming Blooming method, be not particularly limited, can for example enumerate and be write with former rugged brave time《Coating engineering (コーティ Application グ engineerings)》 Method, the grand chief editor of state of village of city described in page 253～page 277 of (Co., Ltd. towards storehouse bookstore, the distribution of on March 20th, 1971) 《The initiative of molecule coordinating material and using (Fen Association Tone material Chong System と ying use)》(Co., Ltd. C MC is published, 1998 3 Months 3 days issue) method described in page 118～page 149, with slit die rubbing method, spin-coating method, spraying process, stick coating method, roller coat The method that method, scraper for coating method, curtain coating processes, spray (fountain) method, infusion process etc. are coated.Wherein, slit die Tool rubbing method due to tend to obtain high uniformity with anisotropic blooming, thus it is preferred that.

Be coated with for formed with anisotropic blooming composition when, for formed have anisotropic light Learn the supply method of the composition of film, supply interval to be not particularly limited.Due to there is coating fluid supply operation become it is numerous and diverse or Situations such as coating film thickness produces variation with the end of during the beginning of coating fluid, therefore in the thickness with anisotropic blooming When relatively thin, particularly preferably while continuously feeding for forming the composition with anisotropic blooming, while being applied Cloth.

It is coated with the speed for forming the composition with anisotropic blooming and is usually 1mm/ more than the second, preferably 5mm/ is more than the second.Additionally, usually below the 1000mm/ seconds, preferably below the 800mm/ seconds.It is above-mentioned model by making coating speed Enclose, tend to while the anisotropy with anisotropic blooming is obtained, being uniformly coated with.

In addition, for formed with anisotropic blooming composition coating temperature be usually more than 0 DEG C, 80 DEG C with Under, preferably less than 40 DEG C.Additionally, for the humidity during coating for forming the composition with anisotropic blooming, it is excellent Elect more than 10%RH, more preferably more than 30%RH as, on the other hand, preferably below 80RH%.

(insoluble process)

In the present invention, will be formed on the substrate and be had after anisotropic blooming, will be made with each to different by salt exchange The process that the blooming of property will not be dissolved in the water is used as insoluble process.By the insoluble process of the present invention, tool is reduced There is the dissolubility of the pigment in anisotropic blooming, suppress pigment that there is the dissolution in anisotropic blooming from this, The stability with anisotropic blooming can be improved.Specifically, it is valence mumber that for example can enumerate the few ion exchange of valence mumber Be larger than ion (for example, by the ion exchange of 1 valency for multivalence ion) process.

It is preferred that after insoluble process, solubility of the pigment with anisotropic blooming in water is below 1 mass %, Below the angle of the stability with anisotropic blooming, more preferably 0.8 mass %.

(insoluble liquid)

The present invention it is insoluble used in insoluble liquid be not particularly limited.Japanese Patent Laid-Open 2007- can for example be used No. 241267 publications, Japanese Patent Laid-Open 2009-199075 publication, Japanese Patent Laid-Open 2010-44130 publication, Japan Open patent 2010-197760 publications, Japanese Patent Laid-Open 2011-257489 publication, Japanese Patent Laid-Open 2012- Insoluble liquid described in No. 058427 publication etc. etc..

The pH of the insoluble liquid used in the present invention is not particularly limited, but the principle based on cation exchange, contributes to The cation concn of ion exchange is necessary for more than a certain fixed concentration.Therefore, sometimes must than depend on material certain is special Determine pH and more lean on acidic side.Additionally, the tone of insoluble liquid is also not particularly limited, but preferably polarization photosensitiveness is not interfered with substantially Colourless, the light color of energy.

Insoluble liquid used in the present invention is not particularly limited, and preferably comprises insoluble compound and solvent.It is insoluble Compound and solvent can be a kind, it is also possible to using various.

As insoluble compound, preferably with the multivalent ion with sulfo group, carboxyl, phospho and hypophosphorous acid base forming salt Compound.Specifically can enumerate the inorganic salts of Mg, Ca etc., polyamine based compound, the polymer with cationic groups and As the mixture of compound etc. of metal ion in insoluble liquid.Among these compounds, polyamine based compound is due to subtracting It is few it is insoluble after the crackle with anisotropic blooming and it is preferred that.

Polyamine based compound refers to the compound of the amino for having more than 2 in its intramolecular.Additionally, polyamine based compound The quantity of amino that has of a molecule be usually more than 2, additionally, its upper limit is usually less than 20, preferably less than 10.It is logical Crossing makes the quantity of amino in appropriate scope, and polyamine based compound can spread with anisotropic blooming, become It is insoluble with anisotropic blooming in making.

As polyamine based compound, aliphatic poly amine compound and aromatic polyamine based compound can be enumerated.Wherein, preferred fat Fat adoption amine compound.

As the specific example of aliphatic poly amine compound, the diaminourea such as diamino hexane, diamino decane can be enumerated Alkane compound；The DACHs such as 1,4- cyclohexanediamine；The diamino cycloalkane chemical combination such as 4,4' methylene bis cyclo-hexylamine Thing；Polyethylene polyamine compounds such as diethylenetriamines, penten, double (hexa-methylene) triamines etc..Wherein, preferably Polyethylene polyamine compound, particularly preferably double (hexa-methylene) triamines.

As the specific example of aromatic polyamine based compound, phenylenediamine, xylylene diamine etc. can be enumerated.Wherein, preferred benzene Diamines.

Polymer with cationic groups is the polymer with cationic groups on main chain or side chain.As Cationic groups, for example, can enumerate amino；The alkyl monosubstituted aminos such as methylamino, ethylamino；The dioxanes such as dimethylamino, lignocaine Base amino；Guanidine radicals；Imino group；Ammonium salt base；There is group of nitrogen-atoms etc. in a part for ring.Additionally, cation property copolymer Can be used alone or two or more kinds may be used.

Contained metal ion can be 1 valence metal ion in insoluble liquid, but preferably polyvalent metal ion.Polyvalent metal from Son can enumerate alkaline-earth metal ions or transition metal ions.These metal ions can pass through the chemical combination for making to have the metal ion Thing dissolves in appropriate solvent and produces in the solution.As the compound with above-mentioned metal ion, can enumerate barium chloride, Multivalent metal salts such as lead chloride, iron chloride, magnesium chloride, calcium carbonate, calcium phosphate etc..

As the above-mentioned polymer with cationic groups and metal ion, Japanese Patent Laid-Open 2010- can be specifically used Material cited by No. 44130 publications etc..

The solvent of insoluble liquid preferably can dissolve the polar solvent of ion.Water, ionic liquid etc. can specifically be enumerated.At this Among, from from the viewpoint of economy and security, preferred water.

The amount of the insoluble compound in insoluble liquid, as long as having ion-exchange capacity, is just not particularly limited, can basis The species of insoluble compound and solvent, viscosity of insoluble liquid in 25 DEG C etc. and suitably adjust.Preferably saturated concentration More than 10%, more preferably more than the 20% of saturated concentration.Furthermore it is preferred that for saturated concentration (100%) below, more preferably Less than the 90% of saturated concentration.By making it within this range, the precipitation of the unnecessary insoluble compound of suppression can be tended to, and And can rapidly carry out insoluble reaction.

(additive of insoluble liquid)

The insoluble liquid of the present invention can be containing additives such as thickener, NMF, surfactants.Additionally, in insoluble liquid The amount of additive, can suitably adjust according to additive, insoluble compound, species of solvent etc..

The preparation method of the insoluble liquid of the present invention is not particularly limited.For example can by above-mentioned insoluble compound with it is molten Solution mixes to above-mentioned concentration range is become, and is stirred as needed so as to dissolve in a solvent.Additionally, can basis Need to mix used additive in a solvent so as to respectively become above-mentioned concentration range.In addition, time, the order of mixing Etc. being also arbitrary.

(insoluble method)

Thawless method will be carried out with anisotropic blooming to be not particularly limited, can enumerate infusion process；From having The method that the top of anisotropic blooming supplies insoluble liquid；By spraying, curtain coating, roller coat, dip-coating, painting of floating Cloth, the method for blowing the insoluble liquid of the coating such as painting (blow I and go out コート)；Deng.The present invention's is non-with anisotropic blooming It is often thin, with the tendency for being susceptible to peel off due to the contact with object.It is therefore preferable that using can suppress with each to different Property blooming polarised light performance decline, suppress film the defect such as stripping method.

(cleaning after insoluble)

Being cleaned with anisotropic blooming after preferred pair is insoluble.The method of cleaning is not particularly limited, and can make With dipping, from anisotropic blooming top supply cleaning fluid flowing water clean, ultrasonic wave clean etc..Additionally, In cleaning can additional employing CF carry out shaking etc. the effect for promoting cleaning.Or, it is also possible to by multiple these method groups Conjunction is cleaned.

In said method, not needing for the reason for becoming the stripping with anisotropic blooming and defect can not applied Power this point, preferred dipping.

Cleaning fluid is not particularly limited, and can specifically use pure water, it is possible to use methyl alcohol, ethanol, isopropanol are with the addition of in pure water Liquid Deng alcohol etc..To improve cleaning, these materials can control cleaning containing cleaning additive and surfactant etc. Additive.

The drying means with anisotropic blooming after cleaning is not particularly limited, and can enumerate air-dried, air blast and do Dry, vacuum drying, heat drying etc..It is excellent from suppressing from the viewpoint of the crackle with anisotropic blooming among these Choosing uses air-dried or forced air drying.Additionally, also these dryings can be combined.

＜ (II) operation) ＞

As (II) operation in the present invention, with (I) operation after insoluble process with anisotropic blooming Photosensitive resin coating composition and form the operation of protective layer.

(protective layer)

The protective layer of the present invention is in order at after protecting operation and element with anisotropic blooming from after to make The purpose that stimulates and impact etc. and the layer that formed, while also functioning to as removing being not required to anisotropic blooming The part wanted and the effect of the resist for being patterned.

If the protective layer of the present invention is formed by the photosensitive resin coating composition on anisotropic blooming Layer, be not particularly limited, but have optically anisotropic material due to hindering with anisotropic optics The performance of film, thus it is preferred that.Optical anisotropy in the present invention refers to, the thickness direction and any square crossing from protective layer Face in 2 directions three-dimensional coordinate system amount to 3 directions selected in any 2 directions electromagnetic property on have Anisotropy.

Based on not damaging the optical characteristics with anisotropic blooming, the preferred protective layer thickness of protective layer of the present invention is The light transmittance of 550nm during 500nm is more than 80%, more preferably more than 85%, particularly preferably more than 90%.The upper limit does not have Especially limit, it is preferably higher.

(photosensitive polymer combination)

Photosensitive polymer combination for forming the protective layer of the present invention contains photoresist.If photosensitive polymer combination It is the composition for causing the dissolubility in developer solution to change via the irradiation of light, is not particularly limited, preferably via light Irradiation and crosslink reaction or polymerisation and the negative photosensitive type photosensitive polymer combination that solidifies.

Additionally, the photosensitive polymer combination of the present invention can be containing polymerization initiator, the sensitization sensitizer such as pigment, accelerator, each Plant curing agent, heat-curing resin, surfactant, cohesive improver, levelling agent, organic solvent etc..

(photoresist)

Photoresist used in the photosensitive polymer combination of the present invention is not particularly limited, for example, can enumerate containing freely Compound, the compound containing cationic polymerizable group of base polymerism unsaturated group etc..

(compound containing free-radical polymerised unsaturated group)

The compound containing free-radical polymerised unsaturated group of the present invention is have at least one ethene insatiable hunger in intramolecular With the compound of group.From from the viewpoint of reactivity, ethene unsaturated group is preferably pi-allyl or (methyl) acryloyl Base.

As the compound containing free-radical polymerised unsaturated group, for example, can enumerate unsaturated carboxylic acid and polyhydroxylated Polyurethane (methyl) acrylate of the esters, hydroxyl (methyl) acrylate compounds and polyisocyanate compounds of compound Epoxy (methyl) esters of acrylic acid of class, (methyl) acrylic acid or hydroxyl (methyl) acrylate compounds and polyepoxides Deng.

Aronix series, the NK series of chemical company of Xin Zhong villages, Nof Corp. of East Asia Synesis Company can specifically be enumerated Blemmer series, Light acrylate series, the Viscoat series of the organic company in Osaka of chemical company of common prosperity society etc..

(compound containing cationic polymerizable group)

As the compound containing cationic polymerizable group of the present invention, the compound containing epoxy radicals, oxygen heterocycle can be enumerated The compound of butyl, the compound containing vinyl etc..

Among this, the compound of epoxy radicals is preferably comprised.JER series, the Daicel that Mitsubishi Chemical Ind can for example be enumerated is public The Celloxide series of department, the Epokukdo series of Zhu Jin chemical companies of Nippon Steel, the NC- of Japanese chemical drug company, XD-, The series such as EPPN-, EOCN-, EPICLON of DIC companies etc..Additionally, in addition, also can suitably use and methacrylic acid contracting The compound containing ethene unsaturated group such as water glyceride carries out resin of copolymerization etc..

As the compound of oxygen heterocycle butyl, the OXT series, the OXE-10 of the organic company in Osaka of East Asia Synesis Company can be enumerated Or 30, using the copolymer resins etc. of these compounds.

As the photoresist of the present invention, including at least the compound containing cationic polymerizable group, freedom is compared Base polymerism unsaturated group, more they tending to can be in low temperature or heat cure in the short time, it is easy to suppress to anisotropic The fire damage of blooming.

Additionally, it is also preferred that by the compound containing cationic polymerizable group with containing free-radical polymerised unsaturated group change Compound is applied in combination.By being applied in combination, it is easy to take into account high exposure sensitivity and Thermocurable, tend to being readily available by using The development of exposed and developed liquid and the excellent diaphragm of the easy degree of patterning and protection feature that carry out.As specific excellent The combination of compound is selected, following combination etc. can be enumerated：The change containing ethene unsaturated group with epoxy radicals on side chain Compound and the copolymer and unsaturated carboxylic acid of the compound with (methyl) acryloyl group and the group of the esters of polyol Close.

(thermoplastic resin)

In the manufacture method of the optical element of the present invention, when with (IV) operation described later, photosensitive polymer combination is preferred Containing thermoplastic resin.As thermoplastic resin, can enumerate acrylic resin, phenolic resin, polyurethane resin, polyester, nylon, Polyimides, Merlon, derivative of these materials etc..In addition, can also give on these resins polymerizable group and Crosslinkable groups.

If the present invention thermoplastic resin in (IV) operation implement heating when at a temperature of occur soften resin, Then it is not particularly limited, from the deliquescent angle with the compatibility of other compositions and in coating solvent, as preferred Example can enumerate acrylic resin, polyurethane resin, phenolic resin etc..In addition, in these resins, also into there is radical polymerization Conjunction property unsaturated group, cationic polymerizable group, other crosslinked groups etc., in this case, can have concurrently it is above-mentioned containing from The effect of the compound by the compound of base polymerism unsaturated group and/or containing cationic polymerizable group.

As the resin for having the compound containing free-radical polymerised unsaturated group and thermoplastic resin concurrently, example can be enumerated (methyl) acrylic acid is such as adopted to the Epocryls such as ZAR, ZCR, CCR of Japanese chemical drug company, (methyl) third Resin after olefin(e) acid ethylene oxidic ester etc. is polymerized as copolymer composition carries out resin of open loop etc..

As the resin for having the compound containing free-radical polymerised unsaturated group and thermoplastic resin concurrently, for example will can enumerate The novolac epoxy resins such as NC, EOCN, XD, EPPN of Japanese chemical drug company, (methyl) glycidyl acrylate and (3- ethyl oxygen Azetidine -3- bases) resin being polymerized as copolymer composition such as methyl (methyl) acrylate etc..

(polymerization initiator)

The photosensitive polymer combination of the present invention can also contain polymerization initiator.Radical polymerization can be enumerated as polymerization initiator Light trigger, Cationic photoinitiator, radical polymerization thermal initiator, cationic polymerization thermal initiator etc..These polymerizations Among initiator, from the angle for being easy to curability of protective layer, preferably use radical polymerization light trigger and/or sun from Sub- polymerization photoinitiator.

(radical polymerization light trigger)

The radical polymerization light trigger suitably used in the photosensitive polymer combination of the present invention is not particularly limited.For example Can enumerate and be remembered containing Japanese Patent Laid-Open No. Sho 59-152396 publication, No. 61-151197 each publication of Japanese Patent Laid-Open No. Sho etc. The metallocene compound of the titanocenes compound of load；Six aryl connection described in Japanese Patent Laid-Open 2000-56118 publication etc. Imdazole derivatives；Halomethylation oxadiazole derivatives described in Japanese Patent Laid-Open 10-39503 publication etc.；Halomethyl- S- pyrrolotriazine derivatives；The N- such as N-phenylglycine aryl-alpha-amido acids；N- aryl-a-amino acid salt；N- aryl-α-ammonia The free radical activity agent such as base esters of gallic acid；Alpha-aminoalkyl benzophenone derivatives；Japanese Patent Laid-Open 2000-80068 publication, Japan Oxime ester derivative described in open patent 2006-36750 publications etc.；Deng.

Among these materials, oxime ester derivative class and/or alpha-aminoalkyl benzophenone derivatives class are also easy in than relatively thin film Guarantee sensitivity, thus it is preferred that.

As oxime ester derivative class, such as Japanese Patent Laid-Open 2000-80068 publication, Japanese Patent Laid-Open can be enumerated Oxime and ketoxime ester based compound described in 2006-36750 publications etc..

As alpha-aminoalkyl benzophenone derivatives class, for example, can enumerate 2- methyl isophthalic acids (4- (methyl mercapto) phenyl) -2- morpholino -1- Acetone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyls)-butanone -1,2- benzyl -2- dimethylamino -1- (4- Quinoline is for phenyl) -1- butanone, 4- dimethyl aminoethyl benzoic ethers, 4- dimethylamino isoamyl benzene formic acid esters, 4- diethyl Double (the 4- diethyls of aminoacetophenone, 4- dimethylamino propiophenones, 2- ethylhexyls-Isosorbide-5-Nitrae-dimethyl aminobenzoate, 2,5- Base amino benzal) cyclohexanone, 7- diethylamino -3- (4- diethylamino benzoyls) cumarin, 4- (diethylamino) Chalcone etc..

(Cationic photoinitiator)

The suitable Cationic photoinitiator used in the photosensitive polymer combination of the present invention is by luminous ray, purple The irradiation of outside line etc. and produce cationic species or lewis acid, cause cation-curable composition polymerisation material.

As Cationic photoinitiator, for example, can enumerate the salt such as aromatic iodonium salts, aromatic series sulfonium salt, aromatic diazo Salt, iron-arene complex etc..Among these materials, from the angle of curability, optimization aromatic salt compounded of iodine or aromatic matte Salt.Additionally, in order to ensure the electrical reliability of adjacent with photo-sensitive resin liquid crystal layer in image display device, it is especially excellent Select aromatic series Dian salt.

Aromatic series Dian salt is the compound with diaryl iodonium cation, and aromatic series sulfonium salt is with triaryl matte sun The compound of ion.These cations in pairs, constitute Cationic photoinitiator with anion (anion).

Hexafluorophosphoric acid salt anionic PF can be enumerated as the anion for constituting Cationic photoinitiator₆ ^-, hexafluoro antimonate it is cloudy Ion SbF₆ ^-, five fluorine hydroxyl metaantimmonic acid salt anionic SbF₅(OH)^-, hexafluoroarsenate salt anionic AsF₆ ^-, tetrafluoro boric acid salt anionic BF₄ ^-, four (pentafluorophenyl group) borate anion B (C₆F₅)₄ ^-Deng.Wherein, in order to ensure in image display device with photonasty The electrical reliability of the adjacent liquid crystal layer of resin bed, preferred hexafluorophosphoric acid salt anionic PF₆ ^-。

As aromatic series sulfonium salt, as specific example can enumerate such as CPI-100P of San Apro companies, CPI-101A, CPI-200K, CPI-210S, Adeka Optomer SP-150, SP-170, SP-171 of ADEKA companies etc..

As aromatic series Dian salt, the PHOTOINITIATOR that Sol ties up Japanese firm can be enumerated as specific example 2074th, the IRGACURE250 of BASF Japanese firms, the WPI-113 of the CI-5102 and Guang Chun medicines company of Cao Da companies of Japan, WPI-116 etc..

(combination of photoresist and polymerization initiator)

The combination of the photoresist and polymerization initiator of the present invention is not particularly limited, and goes out from the angle for guaranteeing photo-curable Send out, the combination of preferred free radical polymerization photoinitiator and the compound containing free-radical polymerised unsaturated group, containing sun from The compound of sub- polymerizable group and the combination of Cationic photoinitiator, it is further and with what these were combined.

(solvent of photosensitive polymer combination)

Solvent used in the photosensitive polymer combination of the present invention, if to not having bad shadow with anisotropic blooming Ring, be not particularly limited, because being dried after being necessary to be coated, preferably select boiling point (pressure 1013.25 [hPa] condition Under.Hereafter about the such of boiling point.) be 100～300 DEG C scope flux.More preferably there is 120～280 DEG C of boiling point Organic solvent.

As organic solvent, can enumerate glycol monoalkyl ethers, glycol dialkyl ether class, glycol alkyl ether acetate esters, Alkyl acetate class, ethers, ketone, unitary or polyalcohols, aliphatic hydrocarbon, aliphatic hydrocarbon, ester ring type hydro carbons, aromatic series Hydro carbons, chain or ring-type esters, alkoxyl carboxylic acids, halogenated hydrocarbons, ether ketone, nitrile etc..

Among these materials, from the good equilibrium of coating, surface tension etc., to the constituent of photosensitive polymer combination The of a relatively high angle of solubility is set out, preferred diol alkylether acetates class.Additionally, organic solvent can be used alone, also can 2 It is used in combination more than kind.

Following material is for example enumerated as organic solvent.

(glycol monoalkyl ethers)

As glycol monoalkyl ethers, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol list can be enumerated Butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propane diols mono-n-butyl ether, glycol tertiary butyl ether, diethylene glycol monomethyl ether, two Ethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxy amylalcohol, DPE, dipropylene glycol monomethyl ether, 3- Methyl -3- methoxybutanols, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, tripropylene glycol methyl ether etc..

(glycol dialkyl ether class)

Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol can be enumerated as glycol dialkyl ether class Diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, dimethyl ether etc..

(glycol alkyl ether acetate esters)

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol can be enumerated as glycol alkyl ether acetate esters Mono-n-butyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, the third two Alcohol monobutyl ether-acetate, methoxybutyl acetic acid esters, 3- methoxybutyl acetic acid esters, methoxypentyl acetic acid esters, diethylene glycol Methyl ether acetate, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol mono-n-butyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid Ester, triethylene glycol monomethyl ether acetic acid esters, Triethylene glycol ethyl ether acetic acid esters, 3- methyl -3- methoxybutyl acetic acid esters etc..

(glycol diacetate class)

As glycol diacetate class, ethylene acetate, 1,3-BDO diacetate esters, 1,6- hexylene glycol diethyls can be enumerated Acid esters etc..

(acetate alkyl esters)

As acetate alkyl esters, adnoral acetate etc. can be enumerated.

(ethers)

Amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl oxide, diamyl ether, ethyl isobutyl ether, two hexyl ethers can be enumerated as ethers Deng.

(ketone)

As ketone, acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl Ketone, methyl isoamyl ketone, two different can be enumerated Propyl group ketone, DIBK, methyl iso-butyl ketone (MIBK), cyclohexanone, ethyl pentyl group ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl Base ketone, methoxy pentanone etc..

(unitary or polyalcohols)

As unitary or polyalcohols, can enumerate ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propane diols, butanediol, Diethylene glycol, DPG, triethylene glycol, methoxyl methyl amylalcohol, glycerine, benzyl alcohol etc..

(aliphatic hydrocarbon)

As aliphatic hydrocarbon, can enumerate pentane, normal octane, diisobutylene, n-hexane, hexene, isoprene, cinene, Dodecane etc..

(ester ring type hydro carbons)

As ester ring type hydro carbons, hexamethylene, hexahydrotoluene, methylcyclohexene, connection hexamethylene etc. can be enumerated.

(aromatic hydrocarbon)

As aromatic hydrocarbon, benzene,toluene,xylene, cumene etc. can be enumerated.

(chain or ring-type esters)

As chain or ring-type esters, amyl formate, Ethyl formate, ethyl acetate, butyl acetate, propyl acetate, second can be enumerated Sour pentyl ester, methyl isobutyrate, Ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl isobutyrate (IBIB), isobutyric acid first Ester, ethyl caprilate, butyl stearate, ethyl benzoate, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, 3- methoxyl groups Methyl propionate, 3- methoxypropionates, 3- methoxy propyl propyl propionates, 3- methoxy propyl acid butyl esters, gamma-butyrolacton etc..

(alkoxyl carboxylic acids)

3- methoxypropionic acids, 3- ethoxy-propionic acids etc. can be enumerated as alkoxyl carboxylic acids.

(halogenated hydrocarbons)

As halogenated hydrocarbons, chlorobutane, chloropentane etc. can be enumerated.

(ether ketone)

As ether ketone, methoxy pentanone etc. can be enumerated.

(nitrile)

As nitrile, acetonitrile, benzonitrile etc. can be enumerated.

As above-mentioned commercial solvents are met, can enumerate Mineral spirit, Barsolq#2, Apco#18Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso#150, Shell TS 28Solvent, carbitol (Carbitol), ethyl carbitol (Ethyl Carbitol), butyl carbitol (Buthyl Carbitol), methyl cellosolve (Methyl Cellosolve), ethyl cellosolve (Ethyl Cellosolve), ethyl cellosolve acetate (Ethyl Cellosolve Acetate), methylcellosolve acetate, diethylene glycol dimethyl ether (Diglyme) etc. (being trade name).

In solvent used in the photosensitive polymer combination of the present invention, the containing ratio for preferably making total solid content is 3 weights Amount more than %, more than more preferably 5 weight %.On the other hand, preferably it is below 30 weight %, more preferably 20 weight % Below.By being more than above-mentioned lower limit, tend to easily controlling the thickness of protective layer, by being the above-mentioned upper limit Value is following, tends to the working life for being easy to maintain photosensitive polymer combination.

(preparation of photosensitive polymer combination)

The preparation method of photosensitive polymer combination of the present invention is not particularly limited, for example, can by above-mentioned each composition with it is molten Agent mixes jointly, by stirring or applying ultrasonic wave so as to which dissolving disperses, and is prepared.In addition, preparing photoresist group During compound, the compound in the compound containing free-radical polymerised unsaturated group or containing cationic polymerizable group is liquid During body shape, it is also possible to replace solvent with them.

The present invention photosensitive polymer combination preferably after above-mentioned each composition is mixed jointly with solvent, by using Filter is filtered, gel component, waste, trace meter that thus may produce insoluble matter, resin etc. in synthesis etc. Remove.As filter, for example can be using Entegris Optimizer, CUNO NanoSHIELD, Zeta Plus EC ( For trade name) etc..The size of the sieve mesh of filter is preferably little as much as possible, at least the preferably smaller than thickness of protective layer.By making The size of the sieve mesh of filter is less, tends to that insoluble matter, gel component, waste, trace meter etc. can be reduced, and suppresses to protective layer The shrinkage cavity of photosensitive polymer combination when carrying out film forming.Furthermore it is possible to suppress the defects such as foreign matter and the shrinkage cavity of insertion protective layer, Thus tend to suppressing developer solution described later invade lower floor with anisotropic blooming.

(coating process of protective layer)

The protective layer of the present invention can use method shown in the coating process with anisotropic blooming etc., pass through The photosensitive resin coating composition on anisotropic blooming and obtain.Uniformity and the letter of operation from diaphragm The angle slightly changed is set out, and coating is preferably continuous coating.After this, when photosensitive polymer combination contains solvent, can be with Protective layer is dried.Drying can be added by using cleaning oven, hot plate, infrared ray, halogen heater, microwave irradiation etc. Hot equipment is heated and carried out.It is preferably clean from the angle for being easy to equably heat the entirety of film among this Net baking oven and hot plate.

As long as the heat resistance of drying condition according to the species of solvent and with anisotropic blooming etc. carries out appropriate selection i.e. Can.Angle for readily available stable curability after being fully dried is set out, and long-time is preferably carried out at high temperature and is dried. Additionally, the time from required for being dried is short, the excellent viewpoint of productivity ratio and heating are difficult to affect have anisotropic blooming From the viewpoint of substrate, preferably at low temperature the short time is dried.Herein, baking temperature is usually more than 40 DEG C, preferably For more than 50 DEG C, on the other hand, usually less than 120 DEG C, preferably less than 100 DEG C.

Drying time is preferably more than 15 seconds, more preferably more than 30 seconds, furthermore it is preferred that being less than 5 minutes, more preferably 3 points Below clock.Drying can be carried out by hypobaric drying method, also can simultaneously using heating and hypobaric drying method.

The thickness of protective layer is not particularly limited, and dry film thickness is preferably more than 100nm, more preferably 200nm with On.On the other hand, preferably less than 5 μm, more preferably less than 4 μm.By making the thickness of protective layer in above range, then Tend to being easy to while completing：The protectiveness with anisotropic blooming to lower floor, in order to will be with anisotropic light Learn film to be patterned and guaranteed the film-strength of protective layer, maintain the optical characteristics with anisotropic blooming.

It is not particularly limited with the relation of the thickness of protective layer with anisotropic blooming, can is wherein any one party It is larger.When with (IV) operation described later, thickness the greater of protective layer becomes can the sealing that carried out by melt flows It is more easy to obtain, thus it is preferred that.

Preferred film thickness difference with anisotropic blooming Yu protective layer, is calculated as more than 100nm, more preferably with dry film thickness For more than 500nm.Furthermore it is preferred that being less than 4 μm, more preferably less than 3 μm.Additionally, thickness can also be identical.By making thickness Difference in specific scope, the alkaline solution for being intended to fully clean used in removing (III) operation becomes easy.Additionally, During with (IV) operation, tend to easily taking into account the easiness of above-mentioned cleaning removing and to exposing with anisotropic blooming Portion is sealed.

＜ (III) operation ＞

The manufacture method of the present invention has following operation as (III) operation：By arranging mask on the protective layer for being formed And be exposed, developed using alkaline solution, to the protective layer and insoluble process after with anisotropic light Learn film to be patterned.

This operation is mask to be arranged on the protective layer formed in (II) operation and is exposed, and a part of protective layer occurs poly- Reaction is closed, the non-exposed portion (non-polymeric portion) of protective layer is dissolved by carrying out via the development of alkaline solution.Its feature exists In carrying out with anisotropic blooming for the lower floor for while protective layer dissolves, making to be present in the protective layer after dissolving Dissolving is peeled off, and is patterned.This operation can adopt single developer solution, by the non-exposed portion of protective layer in an operation Patterned with thawless both with anisotropic blooming, simplification and the manufacturing cost of operation can be completed Cut down.

(exposure)

If the light source used in exposure can make protective layer be polymerized, it is not particularly limited.Specifically, xenon can for example be enumerated Lamp, halogen lamp, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc lamp, fluorescence The light sources such as lamp, LED, argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, royal purple The LASER Light Sources such as color semiconductor laser, near infrared ray semiconductor laser.Herein in the light using specific wavelength, also may be used Using optical filter.

Light exposure is usually 0.01mJ/cm²More than, preferably 0.1mJ/cm²More than, more preferably 1mJ/cm²More than, additionally, logical It is often 1000mJ/cm²Hereinafter, preferably 800mJ/cm²Hereinafter, more preferably 500mJ/cm²Below.

(mask of protective layer)

If the material of the mask with light-proofness of the present invention, then be not particularly limited, can be using in semiconductor patterning operation The hard mask for using and emulsion mask, or it is processed as shades such as the metal of desired pattern, metallic film etc..

Hard mask can be by as described below and obtain：Chromium film is set thinly to be attached on glass or synthetic quartz, then to sense Photosensitiveness resist is coated, after exposure imaging, by etching except the film that dechromises, then, by removing the against corrosion of upper strata again Agent film, forms exposure pattern and obtains.

Emulsion mask is to add main by gelatin materials and the silver halide structure as photosensitive thing on float glass and resin film Into film mask, can obtain likewise by being exposed, developing, be fixed with the negative film of photo.

(developer solution)

Alkaline solution used in the development of the present invention is not particularly limited, preferably more than pH7.5, more preferably more than pH8. Furthermore it is preferred that being below pH14, more preferably below pH12.By making it within the range, tend to being easy to make protective layer and tool There is anisotropic blooming dissolving to occur or peels off.

NaOH, potassium hydroxide, calcium hydroxide, ammonium hydroxide, TMAH, sodium carbonate, carbonic acid can specifically be enumerated Hydrogen sodium etc..Among these materials, from material accessibility and the angle of the easiness of the pH of control developer solution, preferably use Potassium hydroxide and/or TMAH.

Additionally, the alkaline solution used in the development of the present invention also can live containing water system, nonionic system, other soluble surfaces Property agent.

(developing method)

With regard to developing method and its condition, it is not particularly limited.As developing method, immersion development, paddle development, spray can be enumerated Mist development, brush development, supersonic wave development etc..Among this, immersion development and spray development adhere to spot due to being difficult to, it is easy to Equably developed thus it is preferred that.Additionally, for the viewpoint of the usage amount for reducing developer solution, preferred paddle development.

With regard to development temperature, generally more than 10 DEG C, preferably more than 15 DEG C, additionally, on the other hand, generally below 50 DEG C, excellent Carry out in being selected in less than 45 DEG C.It is preferred that passing through directly or after being cleaned using other solvents or water to shake off after development Or compressed air is dried.Herein so-called other solvents are preferably selected will not dissolve the protective layer after exposure and with each to different Property blooming and developer solution for mixed style solvent.

＜ other operations ＞

To obtain the optical element of the present invention, also there can be operation outside above-mentioned (I) operation～(III) operation.For example may be used Enumerate the operation that alignment films are set on substrate, the operation that wetability is given to plate, protective layer melt flows are made by heating Operation etc..

(operation of alignment films is set on substrate)

To improve the orientation with anisotropic blooming, orientation can be set on substrate before above-mentioned (I) operation Film.Page 226～page 239 etc. institutes of " liquid crystal brief guide " (Wan Shan Co., Ltd., the distribution of on October 30th, 2000) can specifically be used The known method recorded.

(giving the operation of substrate wetability)

It is to suppress that there is anisotropic blooming for being formed when being formed with anisotropic blooming by coating The shrinkage cavity of composition, can give wetability to substrate.The process of lyophobic parts is formed as wetability is given, without especially limit It is fixed, can enumerate as physical or chemically modifying process means sided corona treatments, corona treatment, ultraviolet irradiation (UV Ozone) process etc. surface treatment.Now, also lyophily state can be adjusted by adjusting gas composition and process time.

(operation ((IV) operation) of protective layer melt flows is made by heating)

Used as (IV) operation, can have makes the protective layer in (III) operation after patterning to the manufacture method of the present invention by heating The operation of melt flows (Melt Flow).

As shown in figure 4, carrying out melt flows by making protective layer, will can expose after development with anisotropic blooming The side of profile portion is sealed.

If the method for melt flows can soften the protective layer after development, by the profile portion with anisotropic blooming Side seals, then be not particularly limited condition.From the angle of the heat resistance with anisotropic blooming, heating-up temperature is excellent Elect less than 200 DEG C, particularly preferably less than 180 DEG C as.Additionally, for the solidification for further promoting protective layer by heating Purpose, preferably more than 100 DEG C, particularly preferably more than 120 DEG C.

From the angle for avoiding the deterioration with anisotropic blooming, the heat time is preferably short as much as possible, but for Further promote the purpose of the solidification of protective layer, it is preferably longer, usually more than 1 minute, preferably more than 10 minutes, generally For less than 120 minutes, preferably less than 60 minutes.

Heating means can freely select known method, can enumerate such as hot plate, IR baking ovens, convection oven etc..

(III) profile portion with anisotropic blooming at the end of operation can be with the profile portion of protective layer Same position, or also can be in any one of both insides of profile portion of protective layer.With anisotropic optics The profile portion of film (symbol 2) and protective layer (symbol 3) is shown for example such as Fig. 6 (a) of the situation of same position, with each to different Property blooming (symbol 2) protective layer (symbol 3) profile portion inside situation example such as Fig. 6 (b) shown in.

As manufacture method of the invention when with (IV) operation, as illustrated in fig. 3 will be with each preferably in (III) operation The profile portion of heterotropic blooming (symbol 2) is removed to the inside of the profile portion of protective layer (symbol 3).By make into After row removing, the protection layer segment in the profile more lateral with anisotropic blooming becomes the melt in (IV) operation What is flowed sufficiently reserves portion's (Japanese：Paste generation), the thus salable side with anisotropic blooming profile portion of protective layer Face.

As the profile portion with anisotropic blooming than protective layer profile portion more to the distance that inner side is deep, preferably It is more than the thickness with anisotropic blooming, preferably below 5mm.By more than the lower limit that is above-mentioned, tending to Even if also can fully protect the profile portion side with anisotropic blooming in the operation after, on the other hand, lead to Cross and be below above-mentioned higher limit, tend to that the time required for the patterning with anisotropic blooming can be suppressed.

Make the inside of the profile portion that the profile portion with anisotropic blooming is protective layer or the wheel with protective layer Wide portion is the method for same position, is not particularly limited.Can be adjusted by the pH of the adjustment of developing time, developer solution, addition Surfactant etc. and be suitably adjusted.Specifically, with anisotropic blooming, compared to protective layer, tend to easy Because being correspondingly etched with its time of contact with developer solution.Therefore, if extending developing time, can make with each to different The profile portion of the blooming of property be correspondingly than protective layer profile portion more in the inner part.Additionally, the pH or addition by developer solution The adjustment of agent, adjustable etch has the speed of anisotropic blooming.

[there is the manufacture method of the optical element of (V) operation～(VIII) operation]

As the 2nd aspect of the present invention comprising substrate, the system with anisotropic blooming and the optical element of protective layer Method is made, the manufacture method with following (V) operations～(VIII) operation can be enumerated.

(V) continuously it is coated with substrate for forming the composition with anisotropic blooming, is formed and there is anisotropy Blooming, then by salt exchange to the operation that insoluble process is carried out with anisotropic blooming；

(VI) after the insoluble process with photosensitive resin coating composition on anisotropic blooming, formed and protected The operation of sheath；

(VII) development carried out via exposure and by developer solution, the operation that above-mentioned protective layer is patterned.

In above-mentioned manufacture method, above-mentioned developer solution preferably comprises organic solvents more than 80 capacity %.Additionally, above-mentioned photosensitive Property resin combination preferably comprises thermoplastic resin.Additionally, the above-mentioned thickness with anisotropic blooming is preferably protected Below the thickness of layer.

The developer solution that developer solution in above-mentioned (VII) is preferably the organic solvent containing more than 80 capacity % and constitutes.Additionally, on In stating (VIII) operation, it is above-mentioned with anisotropic blooming be preferably etched profile portion same position with protective layer or Till the inside of profile portion.

Further, it is preferable to have following (IX) operations.

(IX) by heating, the operation of the protective layer melt flows after patterning is made.

Moreover, it relates to using above-mentioned optical element manufacture method manufacture optical element and possess the optical element Image display device.

The present invention the manufacture method including (V) operation～(VIII) operation, if according to (V) operation → (VI) operation → (VII) order of operation → (VIII) operation is implemented, and is not particularly limited, and can also have other between each operation Operation.For example, can also have other operations before (V) operation and (VI) operation.

According to the manufacture method of the above-mentioned optical element with (V) operation～(VIII) operation, can be without coating defects ground, appearance Change places and will uniformly there is anisotropic blooming and protective layer to be patterned.Additionally, can not be anisotropic by having Blooming formed after manufacturing process used in water and solvent impact, suppress have anisotropic blooming dissolving, stripping From generation, the polarised light function loss for waiting.

Therefore, cut out mark off the substrate that multiple optical elements are split to form from 1 plate base mother metal when be particularly useful, Wherein optical element possesses after being formed with anisotropic blooming using the solvent (NMP etc.) or work of alignment films formation For the operation of the water of cleaning solvent.

((V) operation)

The present invention has following operation as (V) operation：Continuously it is coated with substrate and there is anisotropic optics for being formed The composition of film, forms and has anisotropic blooming, is then exchanged to described with anisotropic blooming by salt Carry out the operation of insoluble process.(V) operation is identical with above-mentioned (I) operation, and preferred scope etc. is also identical.

((VI) operation)

The present invention as (VI) operation have carry out in (V) operation it is insoluble after with anisotropic blooming coating Photosensitive polymer combination, forms the operation of protective layer.(VI) operation is identical with above-mentioned (II) operation, the also phase such as preferred scope Together.

((VII) operation)

The manufacture method of the present invention has following operation as (VII) operation：By what is carried out via exposure and by developer solution Development, the operation that the protective layer is patterned.

It is by the exposed and developed method for being patterned：Arrange exposure on the protective layer formed in above-mentioned (VI) operation to cover Mould is exposed, and makes a part of protective layer that polymerisation to occur.Further, remove by by exposing the light irradiation that carries out The protective layer of the part of polymerisation is not carried out, development treatment is carried out, pattern layers will be protected.

(exposure)

The protective layer if light source used in exposure can be polymerized, is not particularly limited.Specifically, with above-mentioned (III) operation in Cited light source is identical, and preferred scope of light exposure etc. is also identical.

(developer solution)

If the developer solution of the present invention is while the non-exposed portion of protective layer is dissolved to the protective layer of exposure portion and under it Portion does not produce dysgenic developer solution with anisotropic blooming, is not particularly limited, but preferably with organic molten Agent is the developer solution of principal component.The content of the organic solvent of the developer solution with organic solvent as principal component, preferably comprises 80 appearances The organic solvent of amount more than %, further preferably more than 90 capacity %.Can be 100 capacity % additionally, there is no higher limit.It is logical Crossing makes it within the range, can not dissolve with anisotropic blooming, and only protective layer is developed, and further becomes In the electrical reliability for not damaging protective layer.Additionally, in addition to organic solvent, developer solution can also contain water, nonionic system table Face activating agent etc..

The concrete example of the organic solvent used in developer solution as the present invention, for example, can enumerate above-mentioned photosensitive polymer combination Solvent one described in solvent etc..Among these solvents, due to dissolving protective layer well, protection will not be made when being dried Layer generation albefaction, thus preferred diol alkylether acetates class and glycol alkyl ether acetate esters, particularly preferred propane diols list first Ether acetic acid ester and propylene glycol monomethyl ether.The present invention developer solution used in organic solvent can make a kind, it is also possible to mix 2 kinds with Enterprising enforcement is used.

(developing method)

With regard to developing method and its condition, it is not particularly limited.As the side enumerated in developing method, with above-mentioned (III) operation Method is identical, and preferred developing method is also identical.Additionally, development temperature is also identical with above-mentioned (III) operation, preferred scope also phase Together.

((VIII) operation)

The manufacture method of the present invention has following operation as (VIII) operation：The portion that the developed removing of protective layer is exposed Point with anisotropic blooming, with acidic aqueous solution (hereinafter referred to " method (1) ") or alkaline aqueous solution is (hereinafter After referred to as " method (2) ") contacting, washed.By the operation, the pattern with anisotropic blooming can be carried out Change.

Herein, the developed removing of protective layer and the part exposed refer to by the patterning of (VII) operation except deprotection Layer, and be exposed to outside with anisotropic blooming.Refer specifically to the part represented by the symbol a of Fig. 5.

(method (1))

Method (1) for by protective layer it is developed remove the part exposed with anisotropic blooming by acid water-soluble Liquid is carried out after water dissolvable process, washes the method with anisotropic blooming removed after water dissolvable with water.

The water dissolvable of method (1) is processed from the surface with anisotropic blooming contacted with acidic aqueous solution and carried out. On the other hand, speed with anisotropic blooming surface intrusion of the acidic aqueous solution from after insoluble process is slow.This The slow of intrusion speed of the acidic aqueous solution in anisotropic blooming is planted, acidic aqueous solution is being easily controlled to tool (acidic aqueous solution under the part of the pattern that there is protective layer to having the horizontal etch of anisotropic blooming The intrusion of anisotropic blooming) while, can also suppress sour composition to being mixed into anisotropic blooming (contamination).Therefore, in the electrical reliability for paying attention to the dimensional accuracy with anisotropic blooming and height When, it is preferred to use method (1).

In method (1), because acidic aqueous solution invading with anisotropic blooming surface from after insoluble process Speed it is slow, process to the bottom with anisotropic blooming compared to water solubility is carried out in single treatment, it is many It is secondary that following circulation is repeated：By surface water soluble → remove the washing of the surface of water soluble part → by new surface water It is solubilized, can shorten water dissolvable process time, thus it is preferred that.

If the aqueous solution of the acidic aqueous solution acidity used in the present invention, is not particularly limited, for example, by sulfuric acid, The organic acid such as the inorganic acids such as hydrochloric acid, nitric acid and acetic acid, oxalic acid is suitably dissolved in the solution in water.Among these materials, from electricity Gas reliability, smell, corrosivity, operability are angularly set out, and organic acid are preferably used, particularly preferably using oxalic acid.Additionally, this A little acid are alternatively the mixture of many kinds of substance.

Above-mentioned acidic aqueous solution also can be containing additives such as thickener, NMF, surfactants.

(method (1) water dissolvable processing method)

Using above-mentioned acidic aqueous solution to the method for water dissolvable process is carried out with anisotropic blooming without special Limit, the method that dipping possesses the substrate with anisotropic blooming in acidic aqueous solution can be enumerated；From with it is each to The method that the top of the blooming of the opposite sex supplies acidic aqueous solution；Carry out on possessing the substrate with anisotropic blooming The method of acidic aqueous solution spraying；Pass through curtain coating, roller coat, leaching on possessing the substrate with anisotropic blooming Apply, floating is coated with (Off ローティ Application グ U ート), blows the method that painting etc. is coated with acidic aqueous solution；Deng.The present invention with each Heterotropic blooming is very thin, with the tendency for being susceptible to peel off due to the contact with object.It is therefore preferable that using can To suppress the reduction of the polarised light performance with anisotropic blooming, the method for suppressing the defects such as the stripping of film.

(washing of the method (1) with anisotropic blooming is removed)

By washing remove water dissolvable process after with anisotropic blooming.The method of washing is without especially limit It is fixed, impregnated, paddle, atomizing etc. can be enumerated.

If the water used in washing is removed is acidity, become to be difficult to dissolution with anisotropic blooming, therefore, in order to Efficiently remove and there is anisotropic blooming, preferably avoid the acidic aqueous solution used in water dissolvable process from being mixed into In rinse water.From this starting point, atomizing of new water etc. is preferably supplied all the time, preferred planning during impregnated prepares multiple water Groove etc..

In addition, it is possible to use alkali compounds etc. adjusts pH so that rinse water will not become acid, if but rinse water becomes alkalescence, The part for then not carrying out water dissolvable process is also easy to dissolution with anisotropic blooming, it is difficult to which patterning is controlled System, thus it is not preferred.

In any case, it is preferably to be rinsed with the clean water being mixed into without unwanted solution final.

(method (2))

Method (2) for by make protective layer it is developed remove expose part with anisotropic blooming and acid water The method that solution is contacted and dissolves removing.After insoluble process with anisotropic blooming in alkaline aqueous solution for can It is molten, thus by contacting with alkaline aqueous solution, be directly dissolved and remove.

Method (2) can be removed in single treatment with the short time has anisotropic blooming, thus is paying attention in operation Alkaline aqueous solution is preferably used during reasonability.

Alkaline aqueous solution used in the present invention is the solution for being suitably dissolved in water alkali compounds.Alkaline chemical combination Thing is not particularly limited, and can be inorganic alkaline compound, or organic basic compound.Additionally, these alkaline chemical combination Thing is also being a kind, or various mixtures.Further, also can be containing thickener, NMF, surfactant etc. Additive.

As inorganic alkaline compound, for example, can enumerate NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, carbonic acid Potassium, sodium acid carbonate, saleratus, sodium metasilicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, Sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide etc..

As organic basic compound, the monoethanolamine of MEA, diethanol amine, triethanolamine etc. can be enumerated；Monomethyl The methyl amine of amine, dimethyl amine, Trimethylamine etc.；The ethylamine of MEA, diethylamide, triethylamine etc.；Single isopropyl The isopropylamine of amine, diisopropylamine etc.；N-butylamine；The isopropanol of monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine etc. Amine；Aziridine；Ethene diimine；TMAH (TMAH)；Choline etc..

Among these materials, from the angle of electrical characteristic, preferred organic basic compound, particularly preferably using TMAH.

(removing method of the method (2) with anisotropic blooming)

In method (2), by contacting with alkaline aqueous solution, dissolving removes the method with anisotropic blooming without special Limit.The method that dipping possesses the substrate with anisotropic blooming in alkaline aqueous solution can be enumerated；From with it is each to The method that the top of the blooming of the opposite sex supplies alkaline aqueous solution；Carry out on possessing the substrate with anisotropic blooming The method of alkaline aqueous solution spraying；Pass through curtain coating, roller coat, leaching on possessing the substrate with anisotropic blooming Painting, coating of floating, the method for blowing the alkaline aqueous solution such as painting；Deng.The present invention's is very thin with anisotropic blooming, With the tendency for being susceptible to peel off due to the contact with object.It is therefore preferable that using can suppress with anisotropic The reduction of the polarised light performance of blooming, the method for suppressing the defects such as the stripping of film.

(method (2) method for washing)

By contacting with alkaline aqueous solution, dissolving is removed to be had after anisotropic blooming, by washing, can be removed With the alkali compounds remained in anisotropic blooming.By removing what is remained in anisotropic blooming Alkali compounds, can suppress to the excessive etch with anisotropic blooming part, tend to obtaining the electric of optical element Reliability.

The method of washing is not particularly limited, and can enumerate impregnated, paddle, atomizing etc..Among these methods, from alkaline chemical combination The angle of the removal efficiency of thing is set out, and atomizing of new water etc. is preferably supplied all the time.Preferably prepare in the situation of impregnated Tank of multiple washings etc., fully removes alkali compounds.

The drying means with anisotropic blooming carried out after method (1) and method (2) is without especially limit It is fixed, air-dried, forced air drying, vacuum drying, heat drying etc. can be enumerated.Among these, there is anisotropic optics from suppression From the viewpoint of the crackle of film, preferably use and air-dry or forced air drying.Additionally, can be combined these dryings using.

The degree that etch has anisotropic blooming in said method is not particularly limited, can be with the profile of protective layer Portion is the inside of the profile portion of same position, or protective layer.With anisotropic blooming (symbol 2) and protection The profile portion of layer (symbol 3) is shown for example such as Fig. 6 (a) of the situation of same position, with anisotropic blooming (symbol 2) for protective layer (symbol 3) profile portion inside situation example such as Fig. 6 (b) shown in.

Be not particularly limited with the relation of the thickness of protective layer with anisotropic blooming, can for wherein any one party compared with Greatly.When with (IX) operation described later, thickness the greater of protective layer becomes can the sealing that carried out by melt flows It is more easy, thus it is preferred that.

Preferred film thickness difference with anisotropic blooming Yu protective layer, is calculated as more than 100nm, more with dry film thickness Preferably more than 500nm.Furthermore it is preferred that being less than 4 μm, more preferably less than 3 μm.Additionally, thickness can also be identical.By making The difference of thickness in a specific range, tends to easily acid or alkaline water-soluble used in fully cleaning removing (VIII) operation Liquid.Additionally, when there is (IX) operation, tending to easily taking into account the easiness of above-mentioned cleaning removing and to anisotropic optics The sealing of the exposed division of film.

The etch with anisotropic blooming is made in the inner side of the profile portion of protective layer and the profile with protective layer Portion is the method for same position, is not particularly limited, but in the wheel for making the etch with anisotropic blooming be protective layer During the inner side in wide portion, can enumerate in (VIII) operation completely remove unprotected part with anisotropic optics Jing goes through the methods such as of short duration time after film.Additionally, making the etch with anisotropic blooming identical with the profile portion of protective layer The method of position, can enumerate in (VIII) operation be fully able to remove unprotected part with anisotropic light The moment for learning film enters the methods such as washing step.

In the manufacture method of the present invention, when with (IX) operation described later, such as Fig. 6 (b) preferably in (VIII) operation It is shown to make with (symbol 2) etch of anisotropic blooming to the inside of the profile portion of protective layer (symbol 3).It is logical Crossing makes to carry out protection layer segment after etch, on the outside of the profile with anisotropic blooming to become in (IX) operation Melt flows sufficiently reserve portion's (paste generation), the salable side with anisotropic blooming profile portion of protective layer.

As the profile portion with anisotropic blooming than protective layer profile portion more to the distance that inner side is deep, preferably It is more than the thickness with anisotropic blooming, it is then preferred that be below 5mm, more preferably less than 500 μm, particularly preferably Less than 50 μm.By more than the lower limit that is above-mentioned, tending to that the profile portion side with anisotropic blooming can be made On the other hand fully protected in operation after, by being below above-mentioned higher limit, tend to suppressing having Time required for the patterning of anisotropic blooming, it is also easy to remove acid or the alkali used in (VIII) operation.

(other operations)

To obtain the optical element of the present invention, also there can be operation outside above-mentioned (V) operation～(VIII) operation.For example may be used Enumerate the operation that alignment films are set on aforesaid substrate, the operation that wetability is given to substrate, protective layer melt is made by heating Operation of flowing etc..

(operation of alignment films is set on substrate)

To improve the orientation with anisotropic blooming, orientation can be set on substrate before above-mentioned (V) operation Film.Page 226～page 239 etc. institutes of " liquid crystal brief guide " (Wan Shan Co., Ltd., the distribution of on October 30th, 2000) can specifically be used The known method recorded.

(giving the operation of substrate wetability)

It is to suppress that there is anisotropic blooming for being formed when being formed by coating with anisotropic blooming Composition shrinkage cavity, can to substrate give wetability.The process of lyophobic parts is formed as wetability is given, without special Limit, can implement as physical or chemically modifying process means sided corona treatments, corona treatment, ultraviolet irradiation The surface treatments such as (UV ozone) process.Now, also lyophily state can be adjusted by adjusting gas composition and process time.

((IX) operation makes the operation of protective layer melt flows by heating)

Used as (IX) operation, after above-mentioned (VIII) operation, also can have makes the operation of protective layer melt flows by heating. As shown in the lowermost such as Fig. 7, by making protective layer (symbol 3) melt flows, can be to exposing after development with each to different The side of the blooming profile portion of property is sealed.By the sealing, image that can further after optical element is formed Improve in the operation of display device to the protection with anisotropic blooming.Cut out from 1 plate base mother metal mark off it is many It is particularly useful when individual In-Cell types optical element and the substrate that is split to form, wherein optical element possesses with each Heterotropic blooming formed after using alignment films formation solvent (NMP etc.) operation.

(IX) in operation, the heating means such as method, temperature, time of the melt flows of protective layer, with above-mentioned (IV) operation Identical, preferred scope etc. is also identical.

＜ optical element ＞

The optical element of the present invention is not limited in anisotropic blooming and protective layer, and for improving photosensitiveness is polarized Can, improve the purposes such as mechanical strength, it is possible to have other layers.

Additionally, optical element can also be using adhesion layer or anti-reflection layer；Alignment films；With the function as phase retardation film, make For the function of brightness enhancement film, the function as reflectance coating, the function as Transflective film, as the function etc. of scattering film The layer of optics function；Deng as substrate, it is also possible to stacking is formed by the layer with various functions that is coated with or fits, as stacking Body is used.

These layers can suitably be arranged according to manufacturing process, characteristic and function, and position, order of its stacking etc. are without special Limit.For example, the position for forming above layers can be to be formed on protective layer, additionally, also can be provided with anisotropy Blooming substrate back on face formed.On the other hand, the order of above layers is formed, can be with anisotropic light Before learning the formation of film, also can be upon formation.

Layer with these optics functions can be formed by method as described below.

Layer with the function as phase retardation film can be by the way that the phase retardation film obtained using method as described below be fitted in Constitute other layers of optical element etc. and formed.

Phase retardation film can be for example, by enforcement Japanese Patent Laid-Open 2-59703 publication, Japanese Patent Laid-Open 4-230704 Extension described in number publication etc. is processed, or implement process of record such as Japanese Patent Laid-Open 7-230007 publication etc. and Formed.

Layer with the function as brightness enhancement film, can be strengthened by the brightness that will be obtained using method as described below Film fits in other layer of grade of composition optical element and is formed.

Brightness enhancement film can be for example, by using such as Japanese Patent Laid-Open 2002-169025 publication and Japanese Patent Laid-Open Method described in 2003-29030 publications forms minute aperture or will select different more than 2 layers of centre wavelength of reflection Cholesteric liquid crystal layers are overlapped and formed.

With the layer as reflectance coating or the function of Transflective film can for example, by will by evaporation or sputtering obtain Metallic film carry out fitting etc. with other layers for constituting optical element and formed.

Layer with the function as scattering film, can be for example, by the coating on other layers for constituting optical element containing fine-grained Resin solution and formed.

Additionally, with the layer as phase retardation film and the function of optical compensation films can by by discotic liquid crystal compounds, The liquid crystal compounds such as nematic crystal compound are coated on other layers for constituting optical element and are allowed to be orientated and formed.

＜ image display device ＞

When optical element in the present invention is used for into the various image display devices such as LCD and OLED, the composition of image display device Etc. being not particularly limited, position of optical element etc. is also not particularly limited.For example, can be in the electricity for constituting image display device Optical element is directly formed on the surface of electrode substrate etc. or colour filter, or the substrate of optical element will be formed with as these figures As the component parts of display device is used.Additionally, may also set up alignment films of liquid crystal etc. on the optical element of the present invention.

This point, the light of the present invention can be formed by coating with anisotropic blooming and protective layer in view of the present invention Learning element can also be suitably used for the purposes such as Flexible Displays.

Embodiment

Hereinafter more specific detail, but the present invention are carried out to the present invention without departing from its purport by embodiment, Just do not limited by below example.In addition, in following record, " part " expression " mass parts ".

The assay method ＞ of ＜ transmissivities, polarization luminosity and contrast

Transmissivity, polarization luminosity and contrast use the spectrophotometric for possessing glan-thompson (Glan Thompson) polarizer Meter (great mound electronics (strain) system, ProductName " RETS-100 ") and try to achieve.To with anisotropic blooming incident straight polarization The measure light of light, based on transmissivity wavelength dependency (Ty (λ), Tz (λ), Tm by determining the 400nm～800nm for obtaining (λ)), via calculating as follows, calculate and determine the monomer transmissivity (Tm) [%] of element, polarization luminosity (PE) [%], right Than degree (CR).

Tm [%]=Σ V (λ) D₆₅(λ)Tm(λ)/ΣV(λ)D₆₅(λ)x100

Ty [%]=Σ V (λ) D₆₅(λ)Ty(λ)/ΣV(λ)D₆₅(λ)x100

Tz [%]=Σ V (λ) D₆₅(λ)Tz(λ)/ΣV(λ)D₆₅(λ)x100

CR=Ty/Tz

PE={ (Ty-Tz)/(Ty+Tz) }^1/2x100

The meaning of each symbol is as follows.

Tm(λ)：The monomer transmissivity with anisotropic blooming in each wavelength

Tz(λ)：The transmissivity with anisotropic blooming to the axial polarised light of absorption in each wavelength

Ty(λ)：The transmissivity with anisotropic blooming to the axial polarised light of polarised light in each wavelength

D₆₅(λ)：The measure of the object color under each wavelength is with the intensity of light source (etalon optical power of CIE, ISO)

V(λ)：The luminosity coefficient wavelength dependency defined by International Commission on Illumination, International Bureau of Weights and Measures

[embodiment 1]

(for forming the making of the composition 1 with anisotropic blooming)

It is represented by the lithium salts and 1 part of following formula (2) of the pigment represented by 20 parts of following formula (1) of stirring and dissolving in 79 parts of water Pigment, make for formed with anisotropic blooming composition 1.

[changing 1]

(making of insoluble liquid 1)

75.6 parts of the sulfuric acid of 6N is added in 24.4 parts of double (hexa-methylene) triamines (Tokyo chemical conversion company system), is stirred molten Solution, makes insoluble liquid 1.The viscosity of insoluble liquid 1 is 50cP.

(making of photosensitive polymer combination 1)

Each composition shown in mixture table 1, being adjusted to solid component concentration using methyl proxitol acetate becomes 15 weight %, Make photosensitive polymer combination 1.

In addition, each composition in table is as described below.

Photopolymerization monomer (compound containing free-radical polymerised unsaturated group) a-1：The acrylic acid of dipentaerythritol six Ester (Xin Zhong villages chemistry (strain) system)

Resin (compound containing free-radical polymerised unsaturated group) b-1：Japanese chemical drug (strain) ZAR1035 processed (belongs to Epoxy radicals (methyl) acrylate.In bisphenol A type epoxy resin addition acrylic acid, further addition succinyl oxide is formed Resin.Molecular weight 13,000, acid number is about 100)

Radical polymerization light trigger (alpha-aminoalkyl benzophenone derivatives class) c-1：BASF (strain) IRGACURE907 processed

Surfactant：DIC (strain) RS-72-K processed (have the fluorine system surfactant of polymerizable group)

[table 1]

The composition of photosensitive polymer combination 1	(weight portion)
		Photopolymerization monomer a-1	47.4
Resin b-1	47.4
		Radical polymerization light trigger c-1	5
Surfactant	0.2

((I) operation)

Used as substrate, preparation forms alignment films in glass substrate of electrode (10 × 10cm, thickness 0.7mm), and (polyimides thickness is about 60nm), the substrate after the friction treatment in end face carrying out horizontal direction.In the alignment films, using die coater (wet coating thickness 2 μm, handpiece speed 15mm/s) continuously it is coated with for forming the composition 1 with anisotropic blooming so as to do naturally It is dry, so as to formed thickness be about 0.4 μm with anisotropic blooming.In addition, coating when environmental condition be 23 DEG C, 50RH%.

Make to be formed with the substrate with anisotropic blooming and be impregnated in 3 seconds in insoluble liquid 1.Take out substrate it Afterwards, using softened water, sufficiently cleaning is implemented in order to unnecessary insoluble liquid is rinsed, then carries out the wind of substrate It is dry.

((II) operation)

After carrying out insoluble process in (I) operation with anisotropic blooming, the photonasty tree of about 1.0mL is added dropwise Oil/fat composition 1, adjusting the rotating speed of spin coater makes thickness become 500nm, carries out the rotary coating of 40 seconds.Then carry out on hot plate 90 DEG C, the heat drying of 90 seconds, form protective layer.

((III) operation)

Using 3kW high-pressure sodium lamps, via the mask with negative pattern (round shape of 1 inch of Φ), with 500mJ/cm²Light exposure Substrate to forming matcoveredn in (II) operation is exposed.

Then, the substrate after exposure is carried out the shake dipping of 90 seconds in 0.06% potassium hydroxide aqueous solution (developer solution), Developed.After development, fully shaken after impregnation cleaning using 25 DEG C of softened waters, blowing out pressurised air is dried to it, Obtain optical element 1.The defects such as the peeling of film are not found on optical element 1.

The photo from thereon shooting of optical element 1 is as shown in Figure 1.The part of the dark circles in central authorities is the (symbol of optical element 1 Number 4).Understand the unwanted part (after insoluble with anisotropic blooming and protective layer) beyond optical element 1 The exposure imaging of (III) operation in by embodiment 1 is disposably removed.Additionally, the end of the optical element 1 of Fig. 1 is put Big photo is as shown in Figure 2.The end shape of optical element 1 (symbol 4) is good, it is known that obtain the excellent optics unit of dimensional characteristic Part.Additionally, when determining the properties of polarized light of the element using the RETS-100 of great mound electronics, showing monomer transmissivity 41.0%th, the good value of polarization luminosity 99.4%, it is known that with the abundant characteristic as optical element.

((IV) operation)

Then, the optical element 1 is carried out the heating of 30 minutes with 180 DEG C of baking oven.The phase of the optical element 1 after observation heating As the SEM in the section of the part of the profile portion with anisotropic blooming, with micro- sem observation protective layer is confirmed The melt flows as shown in the figure of the lowermost of Fig. 4, seal the profile portion side with anisotropic blooming.

[embodiment 2]

(making of polymer A)

In possessing and having a flask of reflux condenser, mixer and nitrogen access tube, methacrylic acid bicyclopentyl ester (day is added Vertical chemical conversion (strain) system " FA-513M ") 11 mass parts, the mass parts of GMA 61, methacrylic acid -4- hydroxyls The mass parts of phenylester 14, the mass parts of propylene glycol methyl ether acetate 400, dimethyl -2,2 '-azo two (2 Methylpropionic acid ester) 8.0 mass parts, after carrying out nitrogen displacement, stir while make liquid temperature rise to 80 DEG C, and 6 hours anti-is carried out at 80 DEG C Should.Further, carry out dimethyl -2 of 1 hour at 100 DEG C, the resolution process of 2 '-azo two (2 Methylpropionic acid ester) it Afterwards, under 80 DEG C of reduced pressures, propylene glycol methyl ether acetate is distilled, being concentrated into solid component concentration becomes a 50 mass % left side The right side, obtains polymer A.The weight average molecular weight (Mw) of the polymer A is about 9,000.

In addition, weight average molecular weight is made with " the gel permeation chromatography system LS Solution " of Shimadzu Seisakusho Ltd. using Shimadzu Made " Column GPC-804 " is measured.

The repetition from the vinyl compound containing epoxy radicals (GMA) in polymer A The content ratio of cellular construction is 67 moles of %, from the vinyl compound (metering system containing cyclic aliphatic group Sour bicyclopentyl ester) repeat unit structure content ratio be 13 moles of %, from the ethene containing aromatic series hydroxyl The content ratio of the repeat unit structure of based compound (methacrylic acid -4- hydroxy benzenes base esters) is 20 moles of %.In polymer A The structure of the repetitive for containing is as follows.

[changing 2]

(making of photosensitive polymer combination 2)

Each composition of table 2 is weighed respectively, is stirred using magnetic stirring apparatus and is completely dissolved it, further continue to stir 10 minutes.Then, filtered using 0.02 μm of FD5A XFR of Optimizer V47 of Entegris companies, obtained photosensitive Property resin combination 2.

[table 2]

The content of (* 1) solid constituent

(* 2) are also comprising from polymer A, the solvent of B

In addition, the structure of each composition shown in table 2 is as follows.In structural formula, Et represents ethyl.

(the compound OXT-121 containing cationic polymerizable group (East Asia Synesis Company system))

[changing 3]

(Cationic photoinitiator IRGACURE250 (BASF AG's system))

[changing 4]

(sensitizer UVS-1331 (Kawasaki chemical conversion company system))

[changing 5]

(accelerator ET-2201 (Kawasaki chemical conversion company system))

[changing 6]

(levelling agent BYK-330 (Bi Ke chemical companies system))

Polyether-modified poly- methyl alkyl siloxane

((I) operation)

Used as substrate, preparation forms alignment films in glass substrate of electrode (10 × 10cm, thickness 0.7mm), and (thickness about 60nm's is poly- Acid imide film) and the substrate after the friction treatment in end face carrying out horizontal direction.

In the alignment films, continuously it is coated with using die coater (2 μm of wet coating thickness, handpiece speed 15mm/s) and is had for formation The composition 1 of anisotropic blooming, is spontaneously dried by making it, formed thickness be about 0.4 μm with anisotropic Blooming.In addition, environmental condition during coating is 23 DEG C, 50RH%.

The substrate with anisotropic blooming will be formed with to be impregnated with 5 seconds in insoluble liquid 1.Take out substrate it Afterwards, cleaned using softened water, then carried out air-drying for substrate.

((II) operation)

After carrying out insoluble process in (I) operation with anisotropic blooming, the photonasty tree of about 0.5mL is added dropwise Oil/fat composition 1, adjusts the rotating speed of spin coater, carries out the rotary coating of 50 seconds, makes the thickness after the development of (III) operation described later Become 1.5 μm.Then 90 DEG C, the heat drying of 90 seconds are carried out on hot plate, protective layer is formed.

((III) operation)

Using 3kW high-pressure sodium lamps, via the mask with negative pattern, with 50mJ/cm²Light exposure to the shape in (II) operation Substrate into matcoveredn is exposed.

Then, the substrate after exposure is carried out one side shake one of 3 minutes in 0.04% potassium hydroxide aqueous solution (developer solution) Side is developed, and carries out the washing of 30 seconds using flowing water afterwards, and blowing out pressurised air is dried to it, obtains optical element 2.Light Learn element 2 to be patterned, do not find the defects such as the peeling of film.

((IV) operation)

Then, the optical element 2 is carried out the heating of 30 minutes with 180 DEG C of baking oven.Under protective layer with anisotropy Blooming be the uniform and good film for coming off etc. that there is no crackle, film.

(evaluation of properties of polarized light)

The evaluation of properties of polarized light is carried out to the optical element 2 of gained.Optical element 2 is divided into two halves, observation is overlapped During pattern during to become crossed Nicol or parallel-nicol, light is confirmed by equably shading or transmission.

[embodiment 3]

(making of polymer B)

In possessing and having a flask of reflux condenser, mixer and nitrogen access tube, the single first with tricyclodecane skeleton is added Base acrylate (Hitachi's chemical conversion (strain) system " FA-513M ") 16 mass parts, the mass parts of GMA 61, methyl The mass parts of acrylic acid 12, the mass parts of diethylene glycol methyl ethyl ether 300, dimethyl -2,2 '-azo two (2 Methylpropionic acid ester) 9 Mass parts, after carrying out nitrogen displacement, stir while make liquid temperature rise to 80 DEG C, carry out 6 hours reacting at 80 DEG C, obtain Polymer B.The weight average molecular weight (Mw) of the polymer B is about 8,000.In addition, weight average molecular weight is with the " solidifying of Shimadzu Seisakusho Ltd. Glue penetration chromatographic system LS Solution " are measured using " the Column GPC-804 " of Shimadzu Seisakusho Ltd..

The structure of the repetitive contained in polymer B is as described below.

The repetitive from the vinyl compound containing epoxy radicals (GMA) in polymer B The content ratio of structure is 67 moles of %, from (the methacrylic acid two of the vinyl compound containing cyclic aliphatic group Cyclopentyl ester) the content ratio of repeat unit structure be 11 moles of %, from the repeat unit structure of methacrylic acid Content ratio is 22 moles of %.

[changing 7]

(making of photosensitive polymer combination 3)

Each composition of table 2 is weighed, is implemented in the same manner as the photosensitive polymer combination 2 of embodiment 2, obtain photosensitive resin composition Thing 3.

Except the shake time in the potassium hydroxide aqueous solution (developer solution) for making 0.04% in (III) operation is 1 minute Outward, (I) operation～(III) operation is carried out similarly to Example 2, obtains optical element 3.Optical element 3 is patterned, and does not send out The defects such as the peeling of existing film.

((IV) operation)

Then, the optical element 3 is heated similarly to Example 2.

Under protective layer is the uniform and good film for coming off etc. that there is no crackle, film with anisotropic blooming.

(evaluation of properties of polarized light)

Optical element 3 to gained, carries out similarly to Example 2 the evaluation of properties of polarized light.Confirming optical element 3 can Equably shading or transmission are carried out to light.

[reference example]

＜ contains manufacture method ＞ of the compound 1 of cationic polymerizable group

In possessing and having a flask of reflux condenser, mixer and nitrogen access tube, the single first with tricyclodecane skeleton is added Base acrylate (Hitachi chemical conversion (strain) system " FA-513M ") 47 mass parts, the mass parts of GMA 61, the third two The mass parts of alcohol methyl ether acetate 400, dimethyl -2,2 '-azo two (2 Methylpropionic acid ester) 8.0 mass parts, carry out nitrogen and put After changing, stir while make liquid temperature rise to 80 DEG C of To, carry out 6 hours reacting at 80 DEG C.Further, at 100 DEG C Dimethyl -2 of 1 hour are carried out, after the resolution process of 2 '-azo two (2 Methylpropionic acid ester), under 80 DEG C of reduced pressures, is steamed Propylene glycol methyl ether acetate is evaporated, being concentrated into solid component concentration becomes 50 mass % or so, and acquisition contains cationically polymerizable The compound 1 of group.The weight average molecular weight (Mw) of the resin is about 11,000.

[changing 8]

The preparation ＞ of ＜ photosensitive polymer combinations 4

Among the composition of photosensitive polymer combination 4 as shown in table 3, Cationic photoinitiator is weighed respectively first (Irg250), sensitizer (UVS-1331), accelerator (ET-2201), radical polymerization light trigger (Irg369) and free radical Polymerization thermal initiator (VAm-110), adds wherein the propylene glycol methyl ether acetate (PGMEA) as organic solvent, uses Magnetic stirring apparatus is stirred and is completely dissolved it.

Then, the composition of photosensitive polymer combination 4 other than the above is added, further continues to stir 10 minutes.Then, make Filtered with 0.02 μm of FD5A XFR of Optimizer V47 of Entegris companies, obtained photosensitive polymer combination 4.

The preparation ＞ of ＜ photosensitive polymer combinations 5

Among the composition of photosensitive polymer combination 5 as shown in table 3, Cationic photoinitiator is weighed respectively first (Irg250), sensitizer (UVS-1331), accelerator (ET-2201), add wherein the propane diols list first as organic solvent Ether acetic acid ester (PGMEA), is stirred using magnetic stirring apparatus and is completely dissolved it.

Then, the composition of photosensitive polymer combination 5 other than the above is added, further continues to stir 10 minutes.Then, make Filtered with 0.02 μm of FD5A XFR of Optimizer V47 of Entegris companies, obtained photosensitive polymer combination 5.

[table 3]

The content of (* 1) solid constituent

(* 2) are also comprising the solvent from the compound 1 containing cationic polymerizable group

[reference example 4]

((V) operation)

Used as substrate, preparation forms alignment films in glass substrate of electrode (10 × 10cm, thickness 0.7mm), and (polyimides thickness is about The substrate of friction treatment 60nm) and in end face carrying out horizontal direction.In the alignment films, using die coater (wet film It is thick 2 μm, handpiece speed 15mm/s) continuously it is coated with for forming the composition 1 with anisotropic blooming, by making it certainly So be dried, formed thickness be about 0.4 μm with anisotropic blooming.In addition, coating when environmental condition be 23 DEG C, 50RH%.

Make to be formed with the substrate with anisotropic blooming and be impregnated with 5 seconds in insoluble liquid 1.Take out substrate it Afterwards, cleaned using softened water, then carried out air-drying for substrate.

((VI) operation)

After carrying out insoluble process in (V) operation with anisotropic blooming, the photonasty tree of about 0.5mL is added dropwise Oil/fat composition 4, adjusts the rotating speed of spin coater so that the thickness after the development of next operation (VII) operation becomes 1 μm, carries out 50 The rotary coating of second.Then, 90 DEG C, the heat drying of 90 seconds are carried out on hot plate, protective layer is formed.

((VII) operation)

Using 3kW high-pressure sodium lamps, via the mask with negative pattern, with 500mJ/cm²Light exposure in (VI) operation The substrate for forming matcoveredn is exposed.

Then, by the substrate after exposure, using propylene glycol methyl ether acetate as developer solution, carry out 30 seconds shake while Dipping, is developed.After development, after being cleaned using softened water, it is dried, on anisotropic blooming Form the protective layer after patterning.

((VIII) operation)

Substrate after (VII) operation after 30 seconds shake dippings, is imposed softened water and carry out circulating water in 1N oxalic acid aqueous solutions Wash.By carrying out 3 operations, completely remove the developed removing of protective layer and the part exposed with anisotropic optics Film, is dried, and obtains optical element 4.When being confirmed to optical element 4 with microscope, can be observed with anisotropy Blooming be etched to 1.5 μm or so of the inside of the profile portion for comparing protective layer.Additionally, under protective layer with it is each to The blooming of the opposite sex is the uniform and good film for coming off etc. that there is no crackle, film.

((IX) operation)

Then, the optical element 4 of gained in (VIII) operation is carried out the heating of 30 minutes with 180 DEG C of baking oven.Observation heating During the SEM in the section of the part equivalent to the profile portion with anisotropic blooming of optical element 4 afterwards, guarantor is confirmed Sheath carries out melt flows, seals the profile portion side with anisotropic blooming.Additionally, having under protective layer Anisotropic blooming is the uniform and good film for coming off etc. that there is no crackle, film.

Additionally, reference example 5 as be described hereinafter, by 2 optical elements 4 it is orthogonal or parallel overlap, it is thus identified that it is used as optical element Play function.

[reference example 5]

The photosensitive polymer combination 4 of reference example 4 is changed into photosensitive polymer combination 5, further by (VII) operation Light exposure is changed to 200mJ/cm², other are similarly carried out, and obtain optical element 5.Microscope is adopted in the same manner as reference example 4 When confirming optical element, it is etched with anisotropic blooming to 1.5 μm of an inside left side for the profile portion for comparing protective layer It is right.Additionally, under protective layer with anisotropic blooming be do not exist crackle, film come off etc. it is uniform and good Film.Further, when observing section SEM, confirming protective layer carries out melt flows, seals with anisotropic blooming Profile portion side.Additionally, under protective layer with anisotropic blooming be do not exist crackle, film come off etc. it is equal Even and good film.

As shown in Fig. 8 (a)～(c), 2 optical elements 5 are carried out into orthogonal or parallel overlap, it is thus identified that it is used as optical element Play function.

[reference example 6]

In addition to (VIII) operation is by following carrying out, other are carried out in the same manner as reference example 5, obtain optical element 6.

((VIII) operation)

Substrate after (VII) operation is carried out into the shake dipping of 20 seconds in the 0.4%TMAH aqueous solution, protective layer quilt is completely removed Development remove and the part exposed with anisotropic blooming, impose softened water and carry out flowing and wash and done It is dry.

The section of the part equivalent to the profile portion with anisotropic blooming of the optical element 6 obtained by observation During SEM, confirming protective layer carries out melt flows, seals the profile portion side with anisotropic blooming.Additionally, protecting Under sheath is the uniform and good film for coming off etc. that there is no crackle, film with anisotropic blooming.

Further, in the same manner as reference example 5,2 optical elements 6 are carried out into orthogonal or parallel overlap, it is thus identified that its conduct Optical element plays function.

Illustrate in detail and with reference to specific implementation, but those skilled in the art know, can be without departing from Make various changes and modifications to the spirit and scope of the present invention.The application is based on Japan Patent Shen filed in August in 2014 1 day Please (Patent 2014-157886), Japanese patent application (Patent 2014-157887), in March, 2015 filed in August in 2014 1 day Japanese patent application (Patent 2015-059748) filed in 23 days and Japanese patent application (Patent filed in 22 days July in 2015 2015-144891), it is introduced to this paper as with reference to by its content.

Claims

1. a kind of manufacture method of optical element, it is characterised in that the optical element is included：Substrate, with anisotropic Blooming and protective layer, the manufacture method of the optical element has following (I) operations～(III) operation,

2. the manufacture method of optical element according to claim 1, it is characterised in that used in (III) operation Alkaline solution contain in potassium hydroxide and TMAH at least any one.

3. the manufacture method of optical element according to claim 1 and 2, it is characterised in that (III) operation it Afterwards, with following (IV) operations,

4. a kind of optical element, it is characterised in that be that usage right requires that the manufacture method in 1～3 described in any one is carried out Manufacture.

5. a kind of image display device, it is characterised in that with the optical element described in claim 4.