CN102967970B

CN102967970B - The manufacture method of array base palte, liquid crystal display cells and array base palte

Info

Publication number: CN102967970B
Application number: CN201210315144.7A
Authority: CN
Inventors: 一户大吾
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2011-09-01
Filing date: 2012-08-30
Publication date: 2016-05-25
Anticipated expiration: 2032-08-30
Also published as: TWI531828B; CN102967970A; KR101919481B1; JP2013054125A; KR20130025338A; TW201312204A; JP5741331B2

Abstract

The invention provides the manufacture method of a kind of array base palte, liquid crystal display cells and array base palte. Form dielectric film and array base palte is provided by the radiation-sensitive resin composition that there is high radioactive ray speed and can harden at low temperatures, use this array base palte and liquid crystal display cells is provided. Use radiation-sensitive resin composition, and form dielectric film (12) by the heat hardening of low temperature, and form alignment film (10) and manufacturing array substrate (1) by hardening at subcritical temerature, described radiation-sensitive resin composition contains [A] and in same or different polymer molecules, has the construction unit of the base that comprises following formula (1) and polymer and [B] photoacid generator of the construction unit that contains epoxy radicals. Liquid crystal display cells comprises array base palte (1).

Description

The manufacture method of array base palte, liquid crystal display cells and array base palte

Technical field

The present invention relates to the manufacture method of a kind of array base palte, liquid crystal display cells and array base palte.

Background technology

Liquid crystal display cells is holding liquid crystal and forming in a pair of substrates such as glass substrate for example. On the surface of a pair of substrateThe alignment film of controlling LCD alignment can be set. Liquid crystal display cells to from backlight or outside the light performance of radiating of the light source such as light doFor the function of fine optical gate (shutter), make that light is partial to be seen through or carry out shading and show. Liquid crystal display cells toolThere are the excellent features such as slim, light weight.

Liquid crystal display cells is as the calculator centered by character demonstration etc. or the demonstration of clock exploitation originallyElement. Thereafter,, due to the exploitation of simple matrix mode, dot matrix shows that transfiguration easily makes purposes be extended to the demonstration of notebook computerIn element etc. In addition, due to the exploitation of active matric-type, become the good image quality that can realize contrast ratio or response performance excellence,Also overcome the problems such as high-precision refinement, colorize and visual angle expansion, thereby purposes has been extended to the display applications of desktop computerDeng in. Recently, realize the high-speed response of wider visual angle or liquid crystal or the raising of display quality etc., thereby as large-scaleSlim TV display element.

And liquid crystal display cells requires the raising of higher image quality further or brightness.

In the liquid crystal display cells of active matric-type, in one of them in a pair of substrate of holding liquid crystal, grid are joinedLine and signal wiring arrange as clathrate, at the cross part of grid distribution and signal wiring, thin film transistor (TFT) (ThinFilm are setTransister, TFT) etc. switch active element, forming array substrate. On array base palte, pixel electrode is configured in by grid joinsOn the region that line and signal wiring surround, form the pixel as display unit by this pixel electrode.

In liquid crystal display cells, in the situation that wish realizes brightness raising, effectively make pixel electrode become large. Can lead toCross the area of pixel electrode is become greatly as much as possible, numerical aperture is improved, thereby brightness is increased. In this case, exampleHaving as described in Patent Document 1 as known, make pixel electrode and grid distribution or signal wiring overlapping, numerical aperture is improvedTechnology. In patent documentation 1, disclosed following liquid crystal display cells: in array base palte, distribution and pixel electrode itBetween the thick dielectric film that comprises organic material is set, suppress thus coupling capacitance between pixel electrode and distribution and increase, andNumerical aperture is improved. And, in patent documentation 2, disclose the resin combination that is suitable for forming dielectric film.

Prior art document

Patent documentation

Patent documentation 1 Japanese Patent Laid-Open 2001-264798 communique

Patent documentation 2 Japanese Patent Laid-Open 2004-264623 communiques

Liquid crystal display cells is as described in Patent Document 1 such, in array base palte distribution and pixel electrode itBetween when the thick dielectric film that comprises organic material is set, the electric connection of the switch elements such as TFT and pixel electrode can be used absolutelyContact hole set on velum is realized.

Form contact hole on the dielectric film that comprises organic material time, effectively utilize photoetching technique. In this situationUnder, as the formation material of dielectric film, as recorded in patent documentation 2, preferably use the resin combination of radioactivity-sensitive(hereinafter referred to as radiation-sensitive resin composition). And particularly radiation-sensitive resin composition is widely used so-calledEurymeric.

Using in the dielectric film of Positively radiation-sensitive resin combination, if sense, radioactive ray are in developer solutionDissolubility increases, thereby sensing part is removed. Therefore,, in the time using Positively radiation-sensitive resin combination, can pass throughThe forming section of the contact hole to dielectric film is irradiated radioactive ray and is formed with comparalive ease desired contact hole. In addition, at thisIn invention, so-called " radioactive ray " are the concepts that comprises luminous ray, ultraviolet ray, far ultraviolet, X ray, charged particle beam etc. RightIn this kind of Positively radiation-sensitive resin combination, for desired position that can be in the dielectric film of manufacturing is with institute's phaseThe shape of hoping forms contact hole, requires to have high radioactive ray speed, and can realize excellent patterning performance.

And, when there is the situation of dielectric film of contact hole with radiation-sensitive resin composition manufacture, manufactureThe flexible problem that becomes of dielectric film in step.

That is, using the radiation-sensitive resin composition manufacture of prior art to there is the situation of the dielectric film of contact holeUnder, irradiating after radioactive ray (hereinafter referred to as " exposure ") and development, must carry out high temperature by 230 DEG C～260 DEG C of left and rightHeating and carry out the sclerosis of dielectric film. Therefore,, in the dielectric film of the prior art by photoetching technique, exist at manufacturing stepThe worry of middle generation thermal expansion or the variation of contraction equidimension. Contact hole in dielectric film is strict with the pipe of allocation position and sizeReason, exceedes tolerance band in the dimensional variations of dielectric film, sometimes in the formation of contact hole, produces bad phenomenon.

According to more than, expect to carry out the dielectric film on manufacturing array substrate with radiation-sensitive resin composition, and suppressThermal expansion or contraction, form desired contact hole. The radioactivity-sensitive that therefore, can harden at the temperature lower than prior artIt is effective that resin combination becomes. For example, the sense that can harden under the heating-up temperature below 220 of the temperature lower than prior art DEG CRadiate linear resin combination, the radioactivity-sensitive resin composition hardening under particularly preferably can the heating-up temperature below 200 DEG CThing. The radiation-sensitive resin composition with this kind of hardening characteristics can provide following dielectric film, and described dielectric film is logicalThe dielectric film that carries out heat hardening after the patterning of overexposure and development and manufacture, and there is desired performance.

And, recently, consider from energy-conservation viewpoint, become and require to make to manufacture to have in the liquid crystal display cells of array base palteHeating steps low temperature. That is, array base palte with use in the manufacture of liquid crystal display cells of this array base palte, require to makeThe step low temperature that the cure step of each constitutive requirements etc. must heat and realize energy-conservation.

According to more than, strong expect to realize there is high radioactive ray speed, and can pass through the temperature lower than prior artSclerosis under degree and form the radiation-sensitive resin composition of the dielectric film with contact hole.

And strong expectation is used this kind of radiation-sensitive resin composition, realizes and having by lower than prior artManufacturing step at temperature and the array base palte of the dielectric film manufactured. In addition, strong expectation realizes and uses this kind of array base palte instituteThe liquid crystal display cells forming.

Summary of the invention

The present invention forms in view of above problem. That is, the object of the invention is to use there is high radioactive ray senseLuminosity, and the radiation-sensitive resin composition that can harden at the temperature lower than prior art and dielectric film is provided, and carryFor the array base palte and the manufacture method thereof that comprise this dielectric film.

And other objects of the present invention are to use has high radioactive ray speed, and can be lower than prior artTemperature under the radiation-sensitive resin composition that hardens and dielectric film is provided, and provide and use the array that comprises this dielectric filmThe liquid crystal display cells that substrate forms.

The 1st aspect of the present invention relates to a kind of array base palte, and it is used in liquid crystal display cells, comprising:

Switch active element,

The dielectric film that configures on this switch active element,

The contact hole that forms on this dielectric film,

Via this contact hole with switch active element be electrically connected pixel electrode,

The alignment film forming on described pixel electrode,

Described array base palte is characterised in that: dielectric film is by the radiation-sensitive resin composition institute of containing following compositionThe dielectric film forming:

[A] has the construction unit that comprises the represented base of following formula (1) and contains in same or different polymer moleculesHave epoxy radicals construction unit polymer and

[B] photoacid generator;

Alignment film is use the crystal aligning agent that comprises the radioactivity-sensitive polymer with light regiospecific base and comprise notAny number of in the crystal aligning agent of the polyimides of tool light regiospecific base and the alignment film of gained;

[changing 1]

In formula (1), R¹And R²Independent is respectively hydrogen atom, alkyl, cycloalkyl or aryl, these alkyl, cycloalkyl or virtuePart or all of the hydrogen atom of base also can be substituted base and replace, and wherein, do not have R¹And R²Be the feelings of hydrogen atomCondition; R³Be alkyl, cycloalkyl, aralkyl, aryl or-M (R⁴)₃Represented base, part or all of the hydrogen atom of these basesAlso can be substituted base and replace, wherein M is Si, Ge or Sn, R⁴For alkyl; R¹With R³Also can link and form cyclic ether.

In the 1st aspect of the present invention, preferably [B] photoacid generator comprises the represented oxime sulfonates base of following formula (2);

[changing 2]

In formula (2), R^B1Be alkyl, cycloalkyl or aryl, part or all of the hydrogen atom of these bases also can be bySubstituting group replaces.

In the 1st aspect of the present invention, preferably radiation-sensitive resin composition contains freely following formula (C-1) of [C] choosingAt least a kind of chemical combination of the group that represented compound, phosphonium salt, mercaptan compound and block isocyanate compound formsThing;

[changing 3]

In formula (C-1), R⁷～R¹⁶Independent is respectively hydrogen atom, electron-withdrawing group or amino; Wherein, R⁷～R¹⁶In at least 1Individual is amino; And the alkylene that all or part of of the hydrogen atom of above-mentioned amino can be also 2～6 by carbon number replaces; A isThe alkylene that singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number are 2～6; Wherein, onAll or part of of hydrogen atom of stating methylene and alkylene also can be replaced by cyano group, halogen atom or fluoroalkyl.

In the 1st aspect of the present invention, preferably alignment film is to use to comprise that to have the radioactivity-sensitive of light regiospecific base poly-The crystal aligning agent of compound and the alignment film that obtains.

The 2nd aspect of the present invention relates to a kind of liquid crystal display cells, it is characterized in that the battle array that comprises the 1st aspect of the present inventionRow substrate.

The 3rd aspect of the present invention relates to a kind of manufacture method of array base palte, it is characterized in that comprising the steps:

[1] on the substrate that is formed with switch active element, form the radioactivity-sensitive resin composition that contains following compoundThe step of the film of thing:

[B] photoacid generator;

[2] at least a portion of the film to described radiation-sensitive resin composition is irradiated the step of radioactive ray;

[3] film that has irradiated radioactive ray in step [2] is developed, obtain the step of the film that is formed with contact holeSuddenly; And

[4] film of gained in step [3] hardened and form the step of dielectric film;

[changing 4]

In the 3rd aspect of the present invention, preferably [B] photoacid generator comprises the represented oxime sulfonates base of following formula (2),

[changing 5]

In formula (2), R^B1Be alkyl, cycloalkyl or aryl, part or all of the hydrogen atom of these bases also can be gotReplace for base.

In the 3rd aspect of the present invention, preferably radiation-sensitive resin composition contains freely following formula (C-1) of [C] choosingAt least a kind of chemical combination of the group that represented compound, phosphonium salt, mercaptan compound and block isocyanate compound formsThing;

[changing 6]

In formula (C-1), R⁷～R¹⁶Independent is respectively hydrogen atom, electron-withdrawing group or amino; Wherein, R⁷～R¹⁶In at least1 is amino; And the alkylene that all or part of of the hydrogen atom of above-mentioned amino can be also 2～6 by carbon number replaces; A isThe alkylene that singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number are 2～6; Wherein, onAll or part of of hydrogen atom of stating methylene and alkylene also can be replaced by cyano group, halogen atom or fluoroalkyl.

In the 3rd aspect of the present invention, be preferably further included in 200 DEG C of following steps that form alignment film.

In the 3rd aspect of the present invention, be preferably to use to comprise to there is light and join 200 DEG C of following steps that form alignment filmsThe crystal aligning agent of the radioactivity-sensitive polymer of tropism's base and comprising is not had a LCD alignment of polyimides of light regiospecific baseAny number of in agent and form alignment film.

The effect of invention

According to the present invention, provide a kind of by thering is high radioactive ray speed and the radioactivity-sensitive that can harden at low temperaturesThe dielectric film that resin combination forms, and the array base palte and the manufacture method thereof that comprise this dielectric film are provided.

And, according to the present invention, provide a kind of sense that can harden at low temperatures by thering is high radioactive ray speed to putThe dielectric film that ray resin combination forms, and the liquid crystal display that comprises the array base palte with this dielectric film unit is providedPart.

Brief description of the drawings

Fig. 1 is the mode sectional drawing that represents the major part structure of the array base palte of this example.

Fig. 2 is the model utility electrode wiring figure of the array base palte of this example.

Fig. 3 is the mode sectional drawing of the liquid crystal display cells of this example.

The explanation of symbol:

1: array base palte

4,11: substrate

5: source electrode

6: drain electrode

7: grid

8: switch active element

9: transparency electrode

10: alignment film

12: dielectric film

13: black matrix"

14: public electrode

15: colored pattern

17: contact hole

18: source distribution

19: grid distribution

21: liquid crystal display cells

22: colored filter substrate

23: liquid crystal layer

27: backlight light

28: Polarizer

Detailed description of the invention

Array base palte and liquid crystal display cells to example of the present invention are illustrated.

< liquid crystal display cells >

The liquid crystal display cells of this example is to use the array base palte of this example and the color liquid crystal that forms is aobviousShow element. Below, use the structure of the graphic array base palte to this example and the liquid crystal display cells of this exampleStructure is illustrated.

The liquid crystal display cells of this example for example can be made as the color liquid crystal display device of active matric-type. This enforcementThe liquid crystal display cells of form can be made as the array base of this example that is formed with switch active element, electrode and dielectric filmPlate is situated between every liquid crystal layer and the structure of subtend with the colored filter substrate that is formed with transparency electrode.

Array base palte 1 shown in Fig. 1 is an example of the array base palte of this example. At wherein one of transparency carrier 4Individual face disposes switch active element 8. And, dispose the source electrode 5, drain electrode 6, the grid 7 that are connected with switch active element 8. ?Switch active element 8 is provided with dielectric film 12, disposes the transparency electrode 9 as pixel electrode on dielectric film 12.

Transparency electrode 9 is by the nesa coating institute that comprises indium oxide (IndiumTinOxide, ITO) doped with tin etc.Form. The alignment film 10 of controlling LCD alignment can be set as shown in figure in transparency electrode 9. To connect the mode of dielectric film 12And the recess structure arranging is contact hole 17, make transparency electrode 9 and drain electrode 6 be electrically connected via this part. Its result becomesCan carry out as the transparency electrode 9 of pixel electrode and the electric connection of switch active element 8.

And, as shown in Figure 2, on array base palte 1, source distribution 18 and grid distribution 19 are arranged as rectangular. In sourceNear the cross part of distribution 18 and grid distribution 19, the switch active element 8 that comprises source electrode 5, drain electrode 6, grid 7 is set, source electrode 5 withSource distribution 18 connects, and grid 7 is connected with grid distribution 19. On array base palte 1, form as mentioned above the each pixel being divided.

As described later, in the array base palte 1 of this example, dielectric film 12 be be formed with source electrode 5 electrodes such as grade withThe radiation-sensitive resin composition that is coated with this example on the substrate 4 of switch active element 8, has carried out formation contact hole 17After essential patterning, make its sclerosis and form. The radiation of this example using in the formation of dielectric film 12Property resin combination for example can be made as eurymeric.

The radiation-sensitive resin composition of this example has following feature: there is high radioactive ray speed,After patterning, can form dielectric film 12 by the sclerosis at the temperature lower than prior art. For example can pass through at 220 DEG CHeat hardening at following temperature and form dielectric film 12. And the composition by making radiation-sensitive resin compositionGoodization, also can form dielectric film 12 by the heat hardening at the temperature below 200 DEG C of low temperature more. Therefore, dielectric film12 can suppress the dimensional variations in cure step, and can form the contact hole 17 of desired allocation position and size. And,The array base palte 1 of this example for example can be below 220 DEG C sclerosis, furthermore as 200 DEG C of low temperature more withUnder sclerosis and form dielectric film 12, becoming can be by than the more heating of low temperature and manufactured of prior art.

In addition, in the array base palte 1 of this example, form after transparency electrode 9, LCD alignment control can be set with joiningTo film 10. Alignment film 10 can use the LCD alignment that comprises the radioactivity-sensitive polymer with light regiospecific base as described laterAgent or comprise do not have light regiospecific base polyimides crystal aligning agent and form. In the case, become and can pass through low temperatureHeating-up temperature and form alignment film 10, for example become and can form alignment film 10 by 200 DEG C of following heating-up temperatures. CauseThis, in the array base palte 1 of this example, for example, can form dielectric film 12 with inferior low-temperature heat by 200 DEG C, anotherFor example can form alignment film 10 by 200 DEG C of following low-temperature heats outward. Therefore, the array base palte 1 of this example hasAlignment film 10, becoming can be by manufacturing than the heating at the lower temperature of prior art.

Secondly, the liquid crystal display cells of this example of the array base palte that uses this example is illustrated.

Liquid crystal display cells 21 shown in Fig. 3 is the color liquid crystals that comprise array base palte 1 and colored filter substrate 22Display element is an example of the liquid crystal display cells of this example. Liquid crystal display cells 21 is for example film transistor typeTwisted nematic (TwistedNematic, TN) mode liquid crystal display element, has the array of this example shown in Fig. 1Substrate 1 is situated between every the liquid crystal layer 23 that comprises TN liquid crystal and the structure of subtend with colored filter substrate 22.

Array base palte 1 has following structure as shown in Figure 3: in the face configuration of liquid crystal layer 23 sides of transparency carrier 4There are source electrode 5, drain electrode 6, grid 7, switch active element 8, dielectric film 12. And, on dielectric film 12, be provided with as pixel electrodeTransparency electrode 9. On dielectric film 12, be provided with and connect the contact hole 17 of dielectric film 12, via this part by transparency electrode 9 withDrain electrode 6 is electrically connected. Its result becomes can carry out as the transparency electrode 9 of pixel electrode and electrically connecting of switch active element 8Connect. In transparency electrode 9, be provided with alignment film 10 for LCD alignment control.

Colored filter substrate 22 disposes redness, green and blue micro-at the face of liquid crystal layer 23 sides of transparency carrier 11Little colored pattern 15 and black matrix" 13. Red, green and blue colored pattern 15 is arranged as the shape of the rules such as clathrateShape. In addition, about the color of colored pattern 15, be not merely defined in above-mentioned redness, green and blue this 3 look, can also selectSelect other colors or further add yellow and make the colored pattern of 4 looks. And, can arrange colored pattern of all kinds and structureBecome colored filter substrate.

On colored pattern 15 and black matrix" 13, be provided with transparent public electrode 14. Colored filter substrate 22 withThe face that liquid crystal layer 23 joins is provided with the alignment film same with array base palte 1 10. Array base palte 1 is joined with colored filter substrate 22If be necessary to implement orientation processing to film 10, thereby realize clamping between array base palte 1 and colored filter substrate 22The homogeneous orientation of liquid crystal layer 23.

And the distance being situated between every liquid crystal layer 23 and between array base palte 1 and the colored filter substrate 22 of subtend can be by notIllustrated distance piece and maintaining, is generally 2 μ m～10 μ m. Array base palte 1 is set by periphery with colored filter substrate 22Encapsulant (not shown) and interfixing.

In array base palte 1 and colored filter substrate 22, configure respectively in the opposition side of the side of joining with liquid crystal layer 23There is Polarizer 28.

In Fig. 3, symbol 27 is to liquid crystal layer from the back light unit (not shown) of light source that becomes liquid crystal display cells 21The 23 backlight light that irradiate. Back light unit for example can use combination to have cold cathode fluorescent tube (ColdCathodeFluorescentLamp, CCFL) etc. the back light unit of the structure that forms of fluorescent tube and scatter plate. And, can also use withWhite LED is the back light unit of light source. White LED for example can be enumerated and use red LED, green LED, the indigo plant with independent spectrumLook LED and obtain the White LED of white light, is combined red LED, green LED, blue led and obtained in vain by colour mixtureThe White LED of coloured light, is combined blue led, red LED, green-emitting phosphor and is obtained the white of white light by colour mixtureLED, is combined blue led, red light-emitting phosphor, green emitting fluorophor and is obtained the white of white light by colour mixtureLED, obtains the White LED of white light by the colour mixture of blue led, YAG class fluorophor, by blue led, orange luminescence fluorescenceBody, green emitting fluorophor are combined and are obtained the White LED of white light by colour mixture, by glimmering to ultraviolet LED, emitting red lightLight body, green emitting fluorophor, blue-light-emitting fluorescent material are combined and are obtained White LED of white light etc. by colour mixture.

About the liquid crystal mode of the liquid crystal display cells 21 of this example, except above-mentioned TN pattern, can also establishFor STN Super TN (SuperTwistedNematic, STN), coplanar conversion (In-PlanesSwitching, IPS), verticalStraight orientation (VerticalAlignment, VA) or optical compensation birefringence (OpticallyCompensatedBirefringence, OCB) etc. liquid crystal mode. In this case, particularly about alignment film 10, select to realize the most applicable eachThe alignment film of the orientation of the liquid crystal layer 23 of liquid crystal mode. For example, be VA pattern at the liquid crystal display cells 21 of this exampleWhen liquid crystal display cells, alignment film 10 uses the alignment film of vertical orientation type.

As mentioned above, the liquid crystal display cells 21 of this example has the array base palte 1 of this example. At array baseIn plate 1, realize the electric connection of transparency electrode 9 and drain electrode 6 via contact hole set on dielectric film 12 17. Array base palte 1Dielectric film 12 can use the radiation-sensitive resin composition of this example, and by under 200 DEG C of following low temperature for exampleHeat hardening and form. Therefore,, in the liquid crystal display cells 21 of this example, in array base palte 1, can pass through institute's phaseThe contact hole 17 of allocation position and the size of hoping and realize transparency electrode 9 and drain 6 electric connection.

Secondly, the main composition element of the array base palte of the liquid crystal display cells to this example, can be by than existingThe formation of the dielectric film that has the heating at the temperature that technology is low and harden is described in detail. The particularly array of this exampleThe dielectric film of substrate can use the radiation-sensitive resin composition of this example and form, below to this exampleRadiation-sensitive resin composition is described in detail.

< radiation-sensitive resin composition >

The radiation-sensitive resin composition using in the manufacture of the dielectric film of the array base palte of this example contains:[A] specific polymer (below also referred to as " [A] polymer ") and [B] photoacid generator. And, can further contain hereinafter institute[C] compound describing in detail. And, except [A] composition ([A] polymer) and [B] composition ([B] photoacid generator), can further contain[C] composition ([C] compound) having in addition, only otherwise undermine effect of the present invention, also can contain other any compositions. HaveMore than the radiation-sensitive resin composition of this example of composition can be used as the radiation-sensitive resin composition of eurymeric. WithUnder, each composition contained in the radiation-sensitive resin composition of this example is illustrated.

< [A] polymer >

[A] polymer has the structure list that comprises the represented base of following formula (1) in same or different polymer moleculesUnit (below also referred to as " construction unit (1) ") and the construction unit that contains epoxy radicals, also can optionally have other structure listsUnit. The aspect of [A] polymer is not particularly limited, and can enumerate:

(i) these two kinds of structures of the construction unit that there is construction unit (1) in same polymer molecule and contain epoxy radicalsUnit, and in [A] polymer, there is the situation of a kind of polymer molecule;

(ii) in a polymer molecule, there is construction unit (1), in the polymer molecule different from it, have and containThe construction unit of epoxy radicals, and in [A] polymer, there is the situation of 2 kinds of polymer molecules;

(iii) these two kinds of structures of the construction unit that there is construction unit (1) in a polymer molecule and contain epoxy radicalsUnit has construction unit (1) in the polymer molecule different from it, from further different polymer of these moleculesIn molecule, there is the construction unit that contains epoxy radicals, in [A] polymer, have the situation of 3 kinds of polymer molecules;

Except (i)～(iii) in the polymer molecule of defined, in [A] polymer, further comprise anotherThe situation of outer one kind or two or more polymer molecule etc.

[changing 7]

In above-mentioned formula (1), R¹And R²Independent is respectively hydrogen atom, alkyl, cycloalkyl or aryl, these alkyl, cycloalkylOr part or all of the hydrogen atom of aryl also can be substituted base and replace and (wherein, do not have R¹And R²Be hydrogen atomSituation). R³Be alkyl, cycloalkyl, aralkyl, aryl or-M (R⁴)₃(M is Si, Ge or Sn to represented base, R⁴Alkyl),Part or all of these hydrogen atoms also can be substituted base and replace. R¹With R³Also can link and form cyclic ether.

< construction unit (1) >

Construction unit (1) comprises the represented base of above-mentioned formula (1). The represented base of above-mentioned formula (1) have ethylidene ether structure orKetal structure, becomes for alkali more stablely, dissociates on the other hand and to generate the base of polar group (following under sour existenceAlso referred to as " acid dissociation base "). Therefore, in construction unit (1), due to by irradiating radioactive ray and by [B] described later lightThe acid that acid agent generates, acid dissociation base dissociates. Its result, has construction unit (1) and for alkali insoluble [A] polymerBecome alkali solubility. Below, the represented base of above-mentioned formula (1) contained in construction unit (1) is described in more detail.

In above-mentioned formula (1), R¹And R²It is 1～30 straight chain shape and branch-like alkyl that represented alkyl is preferably carbon number,In this alkyl chain, also can there is oxygen atom, sulphur atom, nitrogen-atoms. The concrete example of abovementioned alkyl for example can be enumerated methyl, ethyl, justThe straight chain shape alkane such as propyl group, normal-butyl, n-pentyl, n-hexyl, n-octyl, dodecyl, n-tetradecane base, n-octadecane baseBase, the branch-like alkyl such as isopropyl, isobutyl group, the tert-butyl group, neopentyl, 2-hexyl, 3-hexyl.

In above-mentioned formula (1), R¹And R²It is 3～20 cycloalkyl that represented cycloalkyl is preferably carbon number, also can be manyRing also can have oxygen atom in ring. The concrete example of above-mentioned cycloalkyl for example can be enumerated cyclopropyl, cyclopenta, cyclohexyl, ring heptanBase, ring octyl group, bornyl, norborny, adamantyl etc.

In above-mentioned formula (1), R¹And R²It is 6～14 aryl that represented aryl is preferably carbon number, can be monocycle, also canFor the structure that monocycle links, also can be condensed ring. The concrete example of above-mentioned aryl for example can be enumerated phenyl, naphthyl etc.

In above-mentioned formula (1), R¹And R²Part or all of hydrogen atom also can be substituted base and replace. This kind gotDai Ji for example can enumerate halogen atom, hydroxyl, nitro, cyano group, carboxyl, carbonyl, cycloalkyl (can apply aptly by this cycloalkylState the explanation of cycloalkyl), aryl (this aryl can be applied the explanation of above-mentioned aryl aptly), alkoxyl (be preferably carbon number and be 1～20 alkoxyl, for example, can enumerate methoxyl group, ethyoxyl, propoxyl group, n-butoxy, amoxy, own oxygen base, heptan oxygen base, pungent oxygenBase etc.), acyl group (is preferably carbon number and is 2～20 acyl group, for example, can enumerate acetyl group, propiono, bytyry, isobutyrylDeng), acyloxy (is preferably carbon number and is 2～10 acyloxy, for example, can enumerate acetoxyl group, acetoxyl group, butyryl acyloxy, uncleButyryl acyloxy, uncle's penta acyloxy etc.), alkoxy carbonyl (is preferably carbon number and is 2～20 alkoxy carbonyl, for example, can enumerate firstOxygen base carbonyl, ethoxy carbonyl, propoxycarbonyl etc.), alkylhalide group (part for the hydrogen atom of abovementioned alkyl or cycloalkyl orAll replaced by halogen atom the base forming, for example, can enumerate perfluoro-methyl, perfluor ethyl, perfluoro propyl, fluorine cyclopropyl, fluorine ringButyl etc.) etc. About the circulus in aryl, cycloalkyl etc., can enumerate abovementioned alkyl as substituting group further.

In above-mentioned formula (1), R³Represented alkyl, cycloalkyl and aryl can be applied R¹And R²In explanation. In above-mentioned formula(1) in, R³It is 7～20 aralkyl that represented aralkyl is preferably enumerated carbon number, for example, can enumerate benzyl, phenethyl, naphthylMethyl, naphthyl ethyl etc. In above-mentioned formula (1), R³-M (R⁴)₃Represented base for example can be enumerated TMS, front threeBase germane base etc. As also can be to this R³Represented aralkyl or-M (R⁴)₃A part for the hydrogen atom of represented base orThe substituting group all replacing can adopt aptly also can be to above-mentioned R¹And R²Part or all of hydrogen atom getThe substituting group in generation.

In above-mentioned formula (1), R¹With R³Also can link and form cyclic ether. This kind of cyclic ether for example can be enumerated 2-epoxy thirdAlkyl, 2-tetrahydrofuran base, 2-THP trtrahydropyranyl, 2-dioxane hexyl etc. A part for the hydrogen atom of this cyclic ether orAll also can be replaced by above-mentioned substituting group.

Construction unit (1) becomes the official with ethylidene ether structure or ketal structure owing to having on carbon atom by bondEnergy base, therefore can have this ethylidene ether structure or ketal structure.

On above-mentioned other carbon atoms, become the functional group with ethylidene ether structure by bond and for example can enumerate 1-Methoxy ethoxy, 1-ethoxy ethoxy, 1-positive propoxy ethyoxyl, 1-isopropoxy ethyoxyl, 1-n-butoxy ethoxyBase, 1-isobutoxy ethyoxyl, 1-sec-butoxy ethyoxyl, 1-tert-butoxy ethyoxyl, 1-cyclopentyloxy ethyoxyl, 1-hexamethyleneOxygen base oxethyl, 1-norborny oxygen base oxethyl, 1-bornyl oxygen base oxethyl, 1-phenoxy group ethyoxyl, 1-(1-naphthalene oxygenBase) ethyoxyl, 1-benzyloxy ethyoxyl, 1-benzene ethoxy ethoxy, (cyclohexyl) (methoxyl group) methoxyl group, (cyclohexyl) (secondOxygen base) methoxyl group, (cyclohexyl) (positive propoxy) methoxyl group, (cyclohexyl) (isopropoxy) methoxyl group, (cyclohexyl) (hexamethylene oxygenBase) methoxyl group, (cyclohexyl) (phenoxy group) methoxyl group, (cyclohexyl) (benzyloxy) methoxyl group, (phenyl) (methoxyl group) methoxyl group,(phenyl) (ethyoxyl) methoxyl group, (phenyl) (positive propoxy) methoxyl group, (phenyl) (isopropoxy) methoxyl group, (phenyl) (ringOwn oxygen base) methoxyl group, (phenyl) (phenoxy group) methoxyl group, (phenyl) (benzyloxy) methoxyl group, (benzyl) (methoxyl group) methoxyl group,(benzyl) (ethyoxyl) methoxyl group, (benzyl) (positive propoxy) methoxyl group, (benzyl) (isopropoxy) methoxyl group, (benzyl) (ringOwn oxygen base) methoxyl group, (benzyl) (phenoxy group) methoxyl group, (benzyl) (benzyloxy) methoxyl group, 2-tetrahydrofuran base oxygen base, 2-tetra-Hydrogen pyranose oxygen base, 1-TMS oxygen base oxethyl, 1-trimethyl germane base oxygen base oxethyl etc.

In these bases, can enumerate 1-ethoxy ethoxy, 1-cyclohexyloxy ethyoxyl, 2-THP trtrahydropyranyl oxygen base, 1-positive thirdOxygen base oxethyl is as preferred base.

By with above-mentioned other carbon atom bonds become the functional group with ketal structure for example can enumerate 1-methyl isophthalic acid-Methoxy ethoxy, 1-methyl isophthalic acid-ethoxy ethoxy, 1-methyl isophthalic acid-positive propoxy ethyoxyl, 1-methyl isophthalic acid-isopropoxyEthyoxyl, 1-methyl isophthalic acid-n-butoxy ethyoxyl, 1-methyl isophthalic acid-isobutoxy ethyoxyl, 1-methyl isophthalic acid-sec-butoxy ethoxyBase, 1-methyl isophthalic acid-tert-butoxy ethyoxyl, 1-methyl isophthalic acid-cyclopentyloxy ethyoxyl, 1-methyl isophthalic acid-cyclohexyloxy ethyoxyl, 1-Methyl isophthalic acid-norborny oxygen base oxethyl, 1-methyl isophthalic acid-bornyl oxygen base oxethyl, 1-methyl isophthalic acid-phenoxy group ethyoxyl, 1-Methyl isophthalic acid-(1-naphthoxy) ethyoxyl, 1-methyl isophthalic acid-benzyloxy ethyoxyl, 1-methyl isophthalic acid-benzene ethoxy ethoxy, 1-hexamethyleneBase-1-methoxy ethoxy, 1-cyclohexyl-1-ethoxy ethoxy, 1-cyclohexyl-1-positive propoxy ethyoxyl, 1-cyclohexyl-1-isopropoxy ethyoxyl, 1-cyclohexyl-1-cyclohexyloxy ethyoxyl, 1-cyclohexyl-1-phenoxy group ethyoxyl, 1-cyclohexyl-1-benzyloxy ethyoxyl, 1-phenyl-1-methoxy ethoxy, 1-phenyl-1-ethoxy ethoxy, 1-phenyl-1-positive propoxyEthyoxyl, 1-phenyl-1-isopropoxy ethyoxyl, 1-phenyl-1-cyclohexyloxy ethyoxyl, 1-phenyl-1-phenoxy group ethyoxyl,1-phenyl-1-benzyloxy ethyoxyl, 1-benzyl-1-methoxy ethoxy, 1-benzyl-1-ethoxy ethoxy, 1-benzyl-1-are justPropoxyl group ethyoxyl, 1-benzyl-1-isopropoxy ethyoxyl, 1-benzyl-1-cyclohexyloxy ethyoxyl, 1-benzyl-1-phenoxy groupEthyoxyl, 1-benzyl-1-benzyloxy ethyoxyl, 2-(2-methyl-tetrahydrofuran base) oxygen base, 2-(2-methyl-THP trtrahydropyranyl)Oxygen base, 1-methoxyl group-cyclopentyloxy, 1-methoxyl group-cyclohexyloxy etc.

In these bases, can enumerate 1-methyl isophthalic acid-methoxy ethoxy, 1-methyl isophthalic acid-cyclohexyloxy ethyoxyl as preferably thisA little bases.

The concrete example of the above-mentioned construction unit (1) with ethylidene ether structure or ketal structure for example can be enumerated following formula (1-1)The represented construction unit of～formula (1-3).

[changing 8]

In above-mentioned formula (1-1) and formula (1-3), R ' is hydrogen atom or methyl. R¹、R²And R³Same with the explanation of above-mentioned formula (1)Justice.

The free-radical polymerised monomer that has of the represented construction unit (1) of above-mentioned formula (1-1)～formula (1-3) is provided(below also referred to as " monomer that contains ethylidene ether structure ") for example can be enumerated: (methyl) acrylic acid-1-alkoxy alkyl, (firstBase) acrylic acid-1-(cycloalkyloxy) Arrcostab, (methyl) acrylic acid-1-(halogenated alkoxy) Arrcostab, (methyl) acrylic acid-The list that (methyl) esters of acrylic acids such as 1-(aralkoxy) Arrcostab, (methyl) acrylic acid THP trtrahydropyranyl ester contain ethylidene ether structureBody; 2,3-bis-(1-(trialkylsilanyl oxygen base) alkoxyl) carbonyl)-5-ENB, 2,3-bis-(1-(trialkyl germane baseOxygen base) alkoxyl) carbonyl)-5-ENB, 2,3-bis-(1-alkoxyl alkoxy carbonyl)-5-ENB, 2,3-bis-(1-(cycloalkyloxy) alkoxy carbonyl)-5-ENB, 2,3-bis-(1-(aralkoxy) alkoxy carbonyl)-5-ENB etc.The monomer that ENB class contains ethylidene ether structure; 1-alkoxyl alkoxystyrene, 1-(halogenated alkoxy) alkoxystyrene,The monomer that the phenylethylenes such as 1-(aralkoxy) alkoxystyrene, THP trtrahydropyranyl oxygen base styrene contain ethylidene ether structure.

In these compounds preferably (methyl) acrylic acid-1-alkoxy alkyl, (methyl) acrylic acid THP trtrahydropyranyl ester,1-alkoxyl alkoxystyrene, THP trtrahydropyranyl oxygen base styrene, more preferably (methyl) acrylic acid-1-alkoxy alkyl.

Provide the concrete example of the monomer that contains ethylidene ether structure of said structure unit (1) for example can enumerate: methacrylic acid-1-ethoxy ethyl ester, methacrylic acid-1-methoxyl group ethyl ester, methacrylic acid-1-n-butoxy ethyl ester, methacrylic acid-1-Isobutoxy ethyl ester, methacrylic acid-1-tert-butoxy ethyl ester, methacrylic acid-1-(2-chloroethoxy) ethyl ester, metering systemAcid-1-(2-ethyl hexyl oxy) ethyl ester, methacrylic acid-1-positive propoxy ethyl ester, methacrylic acid-1-cyclohexyloxy ethyl ester,Methacrylic acid-1-(2-cyclohexyl ethyoxyl) ethyl ester, methacrylic acid-1-benzyloxy ethyl ester, methacrylic acid-2-tetrahydrochysene pyrroleMutter base ester,

Acrylic acid-1-ethoxy ethyl ester, acrylic acid-1-methoxyl group ethyl ester, acrylic acid-1-n-butoxy ethyl ester, acrylic acid-1-isobutoxy ethyl ester, acrylic acid-1-tert-butoxy ethyl ester, acrylic acid-1-(2-chloroethoxy) ethyl ester, acrylic acid-1-(2-secondThe own oxygen base of base) ethyl ester, acrylic acid-1-positive propoxy ethyl ester, acrylic acid-1-cyclohexyloxy ethyl ester, acrylic acid-1-(2-cyclohexylEthyoxyl) ethyl ester, acrylic acid-1-benzyloxy ethyl ester, acrylic acid-2-THP trtrahydropyranyl ester,

2,3-bis-(1-(TMS oxygen base) ethyoxyl) carbonyl)-5-ENB, 2,3-bis-(1-(trimethyl germaniumAlkyl oxy) ethyoxyl) carbonyl)-5-ENB, 2,3-bis-(1-methoxy ethoxy carbonyl)-5-ENB, 2,3-bis-(1-(cyclohexyloxy) ethoxy carbonyl)-5-ENB, 2,3-bis-(1-(benzyloxy) ethoxy carbonyl)-5-ENB,

To or m-1-ethoxy ethoxy styrene, to or m-1-methoxy ethoxy styrene, to or the positive fourth of m-1-Oxygen base oxethyl styrene, to or m-1-isobutoxy ethoxybenzene ethene, to or m-1-(1,1-dimethyl ethyoxyl) secondOxygen base styrene, to or m-1-(2-chloroethoxy) ethoxybenzene ethene, to or m-1-(2-ethyl hexyl oxy) ethoxybenzeneEthene, to or m-1-positive propoxy ethoxybenzene ethene, to or m-1-cyclohexyloxy ethoxybenzene ethene, to or m-1-(2-Cyclohexyl ethyoxyl) ethoxybenzene ethene, to or m-1-benzyloxy ethoxybenzene ethene etc.

Said structure unit (1) can use a kind or two or more is used in combination.

Provide preferable methyl acrylic acid-1-ethoxy ethyl ester in the monomer that contains ethylidene ether structure of said structure unit (1),Methacrylic acid-1-n-butoxy ethyl ester, methacrylic acid-2-THP trtrahydropyranyl ester, methacrylic acid-1-benzyloxy ethyl ester.

Provide the monomer that contains ethylidene ether structure of construction unit (1) can use commercially available compound, also can use with public affairsThe method of knowing and synthetic compound. The ethylidene ether structure that contains of the represented construction unit (1) of above-mentioned formula (1-1) for example, is providedMonomer can be by making as described as follows (methyl) acrylic acid react and synthesize with vinethene under the existence of acid catalyst.

[changing 9]

In formula, R ', R¹And R³Respectively with above-mentioned formula (1-1) in R ', R¹And R³Correspondence, R⁵And R⁶As-CH (R⁵)(R⁶)And with above-mentioned formula (1-1) in R²Corresponding.

As the content of the construction unit (1) in [A] polymer, if [A] polymer due to acid show alkali solubility, fromAnd performance cured film desired heat resistance, be not particularly limited, in a polymer molecule, comprise construction unit (1) withIn the situation of the construction unit that contains epoxy radicals, for all construction units contained in [A] polymer, throw with monomerEnter than meter and be preferably 5 quality %～70 quality %, more preferably 10 quality %～60 quality %, be particularly preferably 20 quality %～50 quality %.

In addition, in a polymer molecule, there is construction unit (1), and there is the epoxy of containing in another polymer moleculeIn the situation of the construction unit of base, as the content with the construction unit (1) in a polymer molecule of construction unit (1),For all construction units contained in this polymer molecule, in monomer input ratio, be preferably 40 quality %～99 quality %, more preferably, below 50 quality %～98 quality %, are particularly preferably 55 quality %～95 quality %.

The construction unit > that < contains epoxy radicals

The construction unit that [A] polymer has said structure unit (1) and contains epoxy radicals. The structure that contains epoxy radicalsUnit is to be derived from the construction unit with the free-radical polymerised monomer that contains epoxy radicals, and contains epoxy radicals. This epoxy radicalsCan enumerate Oxyranyle (1,2-epoxy construction), expoxy propane base (1,3-epoxy construction). By making [A] polymer at moleculeIn there is the construction unit that comprises Oxyranyle or expoxy propane base etc., can improve by the radioactivity-sensitive of this example and setThe hardness of the dielectric film of fat composition and gained and further improve heat resistance.

Provide the concrete example of the monomer that contains epoxy radicals of the above-mentioned construction unit that contains epoxy radicals for example can enumerate propyleneAcid glycidyl ester, GMA, acrylic acid-3,4-epoxy butyl ester, methacrylic acid-3,4-epoxy fourthBase ester, acrylic acid-3-methyl-3,4-epoxy butyl ester, methacrylic acid-3-ethyl-3,4-epoxy butyl ester, acrylic acid-5,6-epoxy hexyl ester, methacrylic acid-5,6-epoxy hexyl ester, methacrylic acid-5-methyl-5,6-epoxy hexyl ester, methylAcrylic acid-5-ethyl-5,6-epoxy hexyl ester, acrylic acid-6,7-epoxy heptyl ester, methacrylic acid-6,7-epoxy heptyl ester;

Methacrylic acid-3,4-epoxycyclohexyl ester, methacrylic acid-3,4-epoxycyclohexyl methyl esters, methacrylic acid-3,4-epoxycyclohexyl ethyl ester, methacrylic acid-3,4-epoxycyclohexyl propyl ester, methacrylic acid-3,4-epoxycyclohexyl fourthEster, methacrylic acid-3, the own ester of 4-epoxycyclohexyl, acrylic acid-3,4-epoxycyclohexyl ester, acrylic acid-3,4-epoxy hexamethyleneBase methyl esters, acrylic acid-3,4-epoxycyclohexyl ethyl ester, acrylic acid-3,4-epoxycyclohexyl propyl ester, acrylic acid-3,4-epoxide ringHexyl butyl ester, acrylic acid-3, (methyl) acrylic compounds that the own ester of 4-epoxycyclohexyl etc. contains Oxyranyle;

Adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether,Alpha-Methyl-adjacent vinyl benzyl glycidol ether, an Alpha-Methyl-vinyl benzyl glycidol ether, Alpha-Methyl-to vinyl benzylThe vinyl benzyl glycidol ethers such as base glycidol ether;

Adjacent ethenylphenyl glycidol ether, an ethenylphenyl glycidol ether, to ethenylphenyl glycidol etherDeng ethenylphenyl glycidol ethers;

3-(acryloyl-oxy ylmethyl) expoxy propane, 3-(acryloyl-oxy ylmethyl)-3-methyl expoxy propane, 3-(propyleneAcyloxy methyl)-3-ethyl expoxy propane, 3-(acryloyl-oxy ylmethyl)-3-benzyl ring Ethylene Oxide, 3-(2-acryloxyEthyl) expoxy propane, 3-(2-acryloxy ethyl)-3-ethyl expoxy propane, 3-(2-acryloxy ethyl)-3-ethylExpoxy propane, 3-(2-acryloxy ethyl)-3-benzyl ring Ethylene Oxide;

3-(methacryloxy methyl) expoxy propane, 3-(methacryloxy methyl)-3-methyl expoxy propane,3-(methacryloxy methyl)-3-ethyl expoxy propane, 3-(methacryloxy methyl)-3-benzyl ring Ethylene Oxide,3-(2-methacryloxyethyl) expoxy propane, 3-(2-methacryloxyethyl)-3-ethyl expoxy propane, 3-(2-methacryloxyethyl)-3-ethyl expoxy propane, 3-(2-methacryloxyethyl)-3-phenyl epoxy thirdAlkane;

2-(acryloyl-oxy ylmethyl) expoxy propane, 2-(acryloyl-oxy ylmethyl)-2-methyl expoxy propane, 2-(propyleneAcyloxy methyl)-2-ethyl expoxy propane, 2-(acryloyl-oxy ylmethyl)-2-benzyl ring Ethylene Oxide, 2-(2-acryloxyEthyl) expoxy propane, 2-(2-acryloxy ethyl)-2-ethyl expoxy propane, 2-(2-acryloxy ethyl)-2-phenylExpoxy propane;

2-(methacryloxy methyl) expoxy propane, 2-(methacryloxy methyl)-2-methyl expoxy propane,2-(methacryloxy methyl)-2-ethyl expoxy propane, 2-(methacryloxy methyl)-2-benzyl ring Ethylene Oxide,2-(2-methacryloxyethyl) expoxy propane, 2-(2-methacryloxyethyl)-2-ethyl expoxy propane, 2-(2-methacryloxyethyl)-2-ethyl expoxy propane, 2-(2-methacryloxyethyl)-2-benzyl ring Ethylene OxideDeng (methyl) acrylic compounds that contains expoxy propane base etc. The above-mentioned construction unit that contains epoxy radicals can be used alone orPerson is used in combination two or more.

From making and the copolyreaction of other free radical polymerization monomers and the developability of radiation-sensitive resin compositionGood viewpoint is considered, preferable methyl glycidyl acrylate, methacrylic acid-2-first in the above-mentioned monomer that contains epoxy radicalsBase ethylene oxidic ester, methacrylic acid-3,4-epoxy radicals cyclohexyl ester, methacrylic acid-3,4-epoxycyclohexyl methyl esters, 3-(methacryloxy methyl)-3-methyl expoxy propane, 3-(methacryloxy methyl)-3-ethyl expoxy propane.

As the content of the construction unit that contains epoxy radicals in [A] polymer, as long as can bring into play the desired of dielectric filmHeat resistance be not particularly limited, in a polymer molecule, comprise construction unit (1) and the construction unit that contains epoxy radicalsSituation under, for all construction units contained in [A] polymer, be preferably 10 matter in monomer input ratioBelow the above 60 quality % of amount %, more preferably, below the above 55 quality % of 15 quality %, be particularly preferably above 50 matter of 20 quality %Below amount %.

On the other hand, in a polymer molecule, there is construction unit (1), and have and contain in another polymer moleculeIn the situation of the construction unit of epoxy radicals, as contained in a polymer molecule with the construction unit that contains epoxy radicalsThe construction unit that contains epoxy radicals, with respect to the content of all construction units, is preferably 10 quality % in monomer input ratioBelow above 80 quality %, more preferably below the above 70 quality % of 20 quality %, be particularly preferably the above 60 quality % of 25 quality % withUnder.

Other construction units of < >

Provide the free radical polymerization monomer of other construction units can enumerate the freedom with carboxyl or derivatives thereof, hydroxylBase polymerizable monomer etc.

The above-mentioned free radical polymerization monomer with carboxyl or derivatives thereof can be enumerated acrylic acid, methacrylic acid, butyleneAcid, 2-acryloxy ethyl butanedioic acid, 2-methacryloxyethyl butanedioic acid, the adjacent benzene of 2-acryloxy ethyl six hydrogenThe monocarboxylic acids such as dioctyl phthalate, 2-methacryloxyethyl hexahydrophthalic acid; Maleic acid, fumaric acid, citraconic acid, Zhong KangThe dicarboxylic acids such as acid, itaconic acid; The acid anhydrides of above-mentioned dicarboxylic acids etc.

The example of the above-mentioned free radical polymerization monomer with hydroxyl can be enumerated 2-Hydroxy ethyl acrylate, acrylic acid-3-The acrylic acid hydroxyalkyl acrylates such as hydroxy propyl ester, acrylic acid-4-hydroxyl butyl ester, acrylic acid-4-hydroxymethyl cyclohexyl methyl esters;

Methacrylic acid-2-hydroxy methacrylate, methacrylic acid-3-hydroxy propyl ester, methacrylic acid-4-hydroxyl base butyl ester,Methacrylic acid-5-hydroxyl pentyl ester, the own ester of methacrylic acid-6-hydroxyl, methacrylic acid-4-hydroxymethyl-cyclohexyl methyl estersDeng methacrylic acid hydroxyl Arrcostab etc.

From with the stable on heating sight of the copolyreaction of other free radical polymerization monomers and the interlayer dielectric of gained etc.Point considers, these have in the free radical polymerization monomer of hydroxyl preferably 2-Hydroxy ethyl acrylate, acrylic acid-3-hydroxyl thirdEster, acrylic acid-4-hydroxyl butyl ester, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-4-hydroxyl butyl ester, acrylic acid-4-hydroxylYlmethyl-cyclohexyl methyl esters, methacrylic acid-4-hydroxymethyl-cyclohexyl methyl esters.

The example of other free radical polymerization monomers can be enumerated the acrylic acid alkyl such as methyl acrylate, isopropyl acrylateEster;

Methyl methacrylate, EMA, n-BMA, the secondary butyl ester of methacrylic acid, methylThe alkyl methacrylates such as tert-butyl acrylate; Cyclohexyl acrylate, acrylic acid-2-methyl cyclohexyl, acrylic acid three encircle[5.2.1.0^2，6] decane-8-base ester, acrylic acid-2-(three ring [5.2.1.0^2,6] decane-8-base oxygen base) ethyl ester, the different ice of acrylic acidThe acrylic acid alicyclic ring family Arrcostabs such as sheet ester;

Cyclohexyl methacrylate, methacrylic acid-2-methyl cyclohexyl, methacrylic acid three encircle [5.2.1.0^2,6] last of the ten Heavenly stemsAlkane-8-base ester, methacrylic acid-2-(three ring [5.2.1.0^2,6] decane-8-base oxygen base) ethyl ester, isobornyl methacrylateDeng methacrylic acid alicyclic ring family Arrcostab;

Acrylic acid aryl ester and acrylic acid aralkyl esters such as phenyl acrylate, acrylic acid benzyl ester;

The aryl ester of methacrylic acid and the aralkyls of methacrylic acid such as phenyl methacrylate, methacrylic acid benzyl esterBase ester;

The dicarboxylic acid dialkyl esters such as diethyl maleate, DEF, diethyl itaconate;

Methacrylic acid tetrahydro furfuryl ester, methacrylic acid tetrahydrofuran base ester, methacrylic acid oxinane-2-methylThe unsaturated five-ring heterocycles methacrylate that ester etc. comprise 1 oxygen atom and unsaturated hexa-member heterocycle methacrylate;

4-methacryloxy methyl-2-methyl-2-ethyl-DOX, 4-methacryloxy methyl-2-methyl-2-isobutyl group-DOX, 4-methacryloxy methyl-2-cyclohexyl-DOX, 4-firstBase acryloyl-oxy ylmethyl-2-methyl-2-ethyl-DOX, 4-methacryloxy methyl-2-methyl-2-are differentThe unsaturated five-ring heterocycles methacrylate that butyl-DOX etc. comprise 2 oxygen atoms;

4-acryloyl-oxy ylmethyl-2,2-dimethyl-DOX, 4-acryloyl-oxy ylmethyl-2-methyl-2-secondBase-DOX, 4-acryloyl-oxy ylmethyl-2,2-diethyl-DOX, 4-acryloyl-oxy ylmethyl-2-Methyl-2-isobutyl group-DOX, 4-acryloyl-oxy ylmethyl-2-cyclopenta-DOX, 4-acryloyl-oxyYlmethyl-2-cyclohexyl-DOX, 4-acryloxy Ethyl-2-Methyl-2-ethyl-DOX, 4-thirdAlkene acyloxy propyl group-2-methyl-2-ethyl-DOX, 4-acryloxy butyl-2-methyl-2-ethyl-1,3-bis-The unsaturated five-ring heterocycles acrylate that butyl oxide link etc. comprise 2 oxygen atoms;

Styrene, AMS, a methyl styrene, p-methylstyrene, to methoxy styrene, 4-isopropyl alkeneThe vinyl aromatic compounds such as base phenol;

N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleimide butyrate, N-succinimido-6-MalaysiaGet the N positions such as acid imide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridinyl) maleimideFor maleimide;

1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene equiconjugate dienes compound;

Acrylonitrile, methacrylonitrile, acrylamide, Methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetateDeng other unsaturated compounds.

Set from making copolyreaction and radioactivity-sensitive with the above-mentioned free radical polymerization monomer with reactive functional group baseThe good aspect of developability of fat composition is considered, optimization styrene, 4-isopropyl alkene in these other free radical polymerization monomersBase phenol, methacrylic acid three encircle [5.2.1.0^2，6] decane-8-base ester, methacrylic acid tetrahydro furfuryl ester, 1,3-butadiene,4-acryloyl-oxy ylmethyl-2-methyl-2-ethyl-DOX, N-N-cyclohexylmaleimide, N-benzyl maleimideAmine, methacrylic acid benzyl ester etc.

The GPC(gel permeation chromatography of [A] polymer) polystyrene conversion quality mean molecule quantity (hereinafter referred to as" Mw ") be preferably 2.0 × 10³～1.0×10⁵, more preferably 5.0 × 10³～5.0×10⁴. By the Mw that makes [A] polymer beAbove-mentioned scope, can make radioactive ray speed and the alkali-developable of the radiation-sensitive resin composition of this example improve.

And, the GPC(gel permeation chromatography of [A] polymer) polystyrene conversion number average molecular weight (hereinafter referred to asFor " Mn ") be preferably 2.0 × 10³～1.0×10⁵, more preferably 5.0 × 10³～5.0×10⁴. By the Mn that makes copolymer beAbove-mentioned scope, can make the sclerous reaction in the time of the sclerosis of film of the radiation-sensitive resin composition of this example carryHigh.

In addition, the molecular weight distribution " Mw/Mn " of [A] polymer is preferably below 3.0, more preferably below 2.6. By makingThe Mw/Mn of [A] polymer is below 3.0, can improve the developability of dielectric film of gained etc. The sense radiation that comprises [A] polymerLinear resin constituent can not produce to develop and easily forms desired pattern form residually in the time developing.

The manufacture method > of < [A] polymer

[A] polymer can be by containing ethylidene ether structure monomer, the monomer that contains epoxy radicals, other construction units are providedMonomer free-radical polymerized and manufacturing. In same polymer molecule, comprise construction unit (1) and contain epoxy radicals being manufactured onWhen the two the situation of [A] polymer of construction unit, use and at least comprise the monomer that contains ethylidene ether structure and contain epoxy radicalsThe mixture of monomer carry out copolymerization. On the other hand, be manufactured in a polymer molecule, have construction unit (1) andIn the polymer molecule different from it, have [A] polymer of the construction unit that contains epoxy radicals, make in advance toThe polymerism solution that comprises less the monomer that contains ethylidene ether structure carries out radical polymerization and obtains the have construction unit polymerization of (1)Thing molecule, makes the polymerism solution that at least comprises the monomer that contains epoxy radicals carry out radical polymerization and obtain to have containing in additionThe polymer molecule of the construction unit of epoxy radicals, is finally mixed both and is made [A] polymer.

In order to manufacture the solvent using in the polymerisation of [A] polymer for example can enumerate alcohols, ethers, glycol ethers,Ethylene glycol alkyl ether acetic acid esters, diethylene glycol alkyl ether, propylene-glycol monoalky lether, propylene-glycol monoalky lether acetic acid esters, propane diolsMonoalky lether propionic ester, aromatic hydrocarbon based, ketone, other ester classes etc.

The polymerization initiator using in polymerisation in order to manufacture [A] polymer can use and be known as radical polymerizationThe compound of initator. Radical polymerization initiator for example can be enumerated two (the 2-methyl of 2,2 '-azobis isobutyronitrile, 2,2 '-azoMethyl propionate), 2,2 '-azo is two-(2,4-methyl pentane nitrile), 2,2 '-azo is two-(4-methoxyl group-2,4-methyl pentane nitrile)Deng azo-compound; Benzoyl peroxide, lauroyl peroxide, the peroxidating pivalic acid tert-butyl ester, 1,1 '-bis--(t-butyl peroxyBase) organic peroxide such as cyclohexane; And hydrogen peroxide.

< [B] photoacid generator >

[B] photoacid generator is can pass through to irradiate radioactive ray and acidic compound. Radioactive ray for example can be as described aboveUse luminous ray, ultraviolet ray, far ultraviolet, electron beam, X ray etc. The radiation-sensitive resin composition of this exampleCan bring into play by comprising [B] photoacid generator the radiation characteristic of eurymeric, as the radiation-sensitive resin composition of eurymericAnd use. [B] photoacid generator is such as, as long as producing by irradiating radioactive ray the compound of acid (carboxylic acid, sulfonic acid etc.),Be not particularly limited. As [B] photoacid generator in radiation-sensitive resin composition, containing form, can be described laterizationThe form of the photoacid generator (being also called below " [B] photoacid generator ") of compound can be also as [A] polymer or other polymerizationsA part for thing and the light that imports produces the form of acidic group can be also these both forms.

[B] photoacid generator can be enumerated oxime sulfonates compound or sulfimine compound etc., wherein preferred oxime sulfonatesCompound.

< oxime sulfonates compound >

Above-mentioned oxime sulfonates compound is preferably the compound that contains the represented oxime sulfonates base of following formula (2).

[changing 10]

In above-mentioned formula (2), R^B1Be alkyl, cycloalkyl or aryl, part or all of the hydrogen atom of these bases alsoCan be substituted base replaces.

In above-mentioned formula (2), R^B1Alkyl to be preferably carbon number be 1～10 straight chain shape or branch-like alkyl. R^B1AlkylThe alkoxyl that can be also 1～10 by carbon number or alicyclic group (comprise the bridge connected alicyclic rings such as 7,7-dimethyl-2-oxo norbornyFamily's base, is preferably bicyclic alkyl etc.) replace. R^B1Aryl to be preferably carbon number be 6～11 aryl, more preferably phenyl or naphthyl.R^B1Aryl can be also 1～5 by carbon number alkyl, alkoxy or halogen atom replace.

The above-claimed cpd that contains the represented oxime sulfonates base of above-mentioned formula (2) more preferably following formula (3) is representedOxime sulfonates compound.

[changing 11]

In formula (3), R^B1With the R in formula (2)^B1Explanation synonym. X is alkyl, alkoxy or halogen atom. M is 0～3Integer. Be 2 or 3 o'clock at m, multiple X can be identical also can be different. As the alkyl of X be preferably carbon number be 1～4 straight chain shape orBranch-like alkyl.

In formula (3), being preferably carbon number as the alkoxyl of X is 1～4 straight chain shape or branch-like alkoxyl. As X'sHalogen atom is preferably chlorine atom or fluorine atom. M is preferably 0 or 1. In formula (3), m is 1, X is getting of methyl, XSubrogate the compound that is set to ortho position.

The concrete example of the represented oxime sulfonates compound of above-mentioned formula (3) for example can be enumerated following formula (3-i)～formula (3-v)The compound (3-i), compound (3-ii), compound (3-iii), compound (3-iv) and the compound (3-v) that represent respectivelyDeng.

[changing 12]

These compounds can be used alone or two or more is used in combination, also can with other light as [B] compositionAcid agent is used in combination. Above-claimed cpd (3-i) [(5-sulfonyl propyl base oxygen base imino group-5H-thiophene-2-subunit)-(2-firstBase phenyl) acetonitrile], compound (3-ii) [(5H-octyl group sulfonyl oxygen base imino group-5H-thiophene-2-subunit)-(2-methylbenzeneBase) acetonitrile], compound (3-iii) [(camphor sulfonyl oxygen base imino group-5H-thiophene-2-subunit)-(2-aminomethyl phenyl) secondNitrile], compound (3-iv) [(5-p-toluenesulfonyl oxygen base imino group-5H-thiophene-2-subunit)-(2-aminomethyl phenyl) acetonitrile]And compound (3-v) [(5-octyl group sulfonyl oxygen base imino group)-(4-methoxyphenyl) acetonitrile] can commercially available product form obtain.

< sulfimine compound >

As [B] photoacid generator and preferred sulfimine compound for example can be enumerated N-(trimethyl fluoride sulfonyl oxygen base) amberAmber acid imide, N-(camphor sulfonyloxy) succinimide, N-(4-aminomethyl phenyl sulfonyloxy) succinimide, N-(2-tri-Methyl fluoride phenyl sulfonyloxy) succinimide, N-(4-fluorophenyl sulfonyloxy) succinimide, N-(trimethyl fluoride sulfonylOxygen base) phthalimide, N-(camphor sulfonyloxy) phthalimide, N-(2-trifluoromethyl sulfonyloxy)Phthalimide, N-(2-fluorophenyl sulfonyloxy) phthalimide, N-(trimethyl fluoride sulfonyl oxygen base) diphenylMaleimide, N-(camphor sulfonyloxy) diphenyl maleimide, 4-(aminomethyl phenyl sulfonyloxy) diphenyl Malaysia acylImines, N-(2-trifluoromethyl sulfonyloxy) diphenyl maleimide, N-(4-fluorophenyl sulfonyloxy) diphenyl horseCome acid imide, N-(phenyl sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-aminomethyl phenyl sulphurAcyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(trifluoro-methanesulfonyl oxy) dicyclo [2.2.1] heptan-5-Alkene-2,3-dicarboxyl acid imide, N-(nine fluorine butyl sulfonyloxies) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide,N-(camphor sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(camphor sulfonyloxy)-7-oxa-pairRing [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(trimethyl fluoride sulfonyl oxygen base)-7-oxabicyclo [2.2.1] heptan-5-Alkene-2,3-dicarboxyl acid imide, N-(4-aminomethyl phenyl sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acyl AsiaAmine, N-(4-aminomethyl phenyl sulfonyloxy)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-trifluoroAminomethyl phenyl sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-trifluoromethyl sulphonyl oxygenBase)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-fluorophenyl sulfonyloxy) dicyclo [2.2.1]Heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-fluorophenyl sulfonyloxy)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-bis-Carboxyl acid imide, N-(trimethyl fluoride sulfonyl oxygen base) dicyclo [2.2.1] heptane-5,6-oxygen base-2,3-dicarboxyl acid imide, N-(camphor sulfonyloxy) dicyclo [2.2.1] heptane-5,6-oxygen base-2,3-dicarboxyl acid imide, N-(4-aminomethyl phenyl sulphonyl oxygenBase) dicyclo [2.2.1] heptane-5,6-oxygen base-2,3-dicarboxyl acid imide, N-(2-trifluoromethyl sulfonyloxy) dicyclo[2.2.1] heptane-5,6-oxygen base-2,3-dicarboxyl acid imide, N-(4-fluorophenyl sulfonyloxy) dicyclo [2.2.1] heptane-5,6-oxygen base-2,3-dicarboxyl acid imide, N-(trimethyl fluoride sulfonyl oxygen base) naphthyl dicarboxyl acid imide, N-(camphor sulfonyloxy)Naphthyl dicarboxyl acid imide, N-(4-aminomethyl phenyl sulfonyloxy) naphthyl dicarboxyl acid imide, N-(phenyl sulfonyloxy) naphthylDicarboxyl acid imide, N-(2-trifluoromethyl sulfonyloxy) naphthyl dicarboxyl acid imide, N-(4-fluorophenyl sulfonyloxy)Naphthyl dicarboxyl acid imide, N-(pentafluoroethyl group sulfonyl oxygen base) naphthyl dicarboxyl acid imide, N-(seven fluoropropyl sulfonyloxies)Naphthyl dicarboxyl acid imide, N-(nine fluorine butyl sulfonyloxies) naphthyl dicarboxyl acid imide, N-(ethylsulfonyl oxygen base) naphthylDicarboxyl acid imide, N-(sulfonyl propyl oxygen base) naphthyl dicarboxyl acid imide, N-(butyl sulfonyloxy) naphthyl dicarboxyl acyl AsiaAmine, N-(amyl group sulfonyloxy) naphthyl dicarboxyl acid imide, N-(hexyl sulfonyloxy) naphthyl dicarboxyl acid imide, N-(heptylSulfonyloxy) naphthyl dicarboxyl acid imide, N-(octyl group sulfonyloxy) naphthyl dicarboxyl acid imide, N-(nonyl sulfonyloxy) naphthaleneBase dicarboxyl acid imide etc.

In [B] discussed above photoacid generator, certainly make radioactive ray speed improve and the consideration of deliquescent viewpoint, asThe above is preferably oxime sulfonates compound like that, more preferably contains the compound of the represented oxime sulfonates base of formula (2), entersOne step is the represented oxime sulfonates compound of formula (3) more preferably. Wherein particularly preferably can be used as commercially available product and obtain [(5-Sulfonyl propyl base oxygen base imino group-5H-thiophene-2-subunit)-(2-aminomethyl phenyl) acetonitrile], [(5H-octyl group sulfonyl oxygen base AsiaAmino-5H-thiophene-2-subunit)-(2-aminomethyl phenyl) acetonitrile], [(5-p-toluenesulfonyl oxygen base imino group-5H-thiophene-2-Subunit)-(2-aminomethyl phenyl) acetonitrile], [(camphor sulfonyl oxygen base imino group-5H-thiophene-2-subunit)-(2-aminomethyl phenyl) secondNitrile], [(5-octyl group sulfonyl oxygen base imino group)-(4-methoxyphenyl) acetonitrile].

[B] photoacid generator can be used alone a kind, also two or more can be mixed and uses. As the sense radiation of this exampleThe content of [B] photoacid generator in linear resin constituent is preferably 0.1 quality for [A] polymer 100 mass partsPart～10 mass parts, more preferably 1 mass parts～5 mass parts. If the content of [B] photoacid generator is above-mentioned scope, can make senseRadiate the radioactive ray speed optimization of linear resin combination, can maintain the transparency and formation dielectric film.

< [C] compound >

The radioactivity-sensitive of this example using in the manufacture of the dielectric film of the array base palte of this exampleResin combination can contain [C] compound. [C] compound is the compound of bringing into play function as curing agent, that is promote byThe sclerosis of the film that radiation-sensitive resin composition forms. Therefore, for simplicity, be also referred to as [C] compound (firmlyAgent) or [C] curing agent etc. [C] compound is freely represented compound, phosphonium salt, the mercaptan compound of following formula (C-1) of choosingAnd at least a kind of compound of the group that forms of block isocyanate compound. Radiation-sensitive resin composition contains and is selected from[C] compound of this specific compound group, therefore can make the hardening temperature of dielectric film more effectively reduce. By making this enforcementThe radiation-sensitive resin composition of form contains [C] compound, and becoming can be by 180 DEG C～200 DEG C grades for example below 200 DEG CHardening temperature and manufacture dielectric film. Below, to being described in detail as each compound of [C] compound.

[the represented compound of formula (C-1)]

[C] compound is preferably at least a kind of change of the choosing group that freely the represented compound of following formula (C-1) formsCompound. As [C] compound, there is above-mentioned specific compound amino and short of electricity subbase by selection, can more effectively make absolutelyThe hardening temperature of velum reduces.

[changing 13]

In above-mentioned formula (C-1), R⁷～R¹⁶Independent is respectively hydrogen atom, electron-withdrawing group or amino. Wherein, R⁷～R¹⁶InAt least 1 is amino. And the alkylene that all or part of of this amino hydrogen atom can be also 2～6 by carbon number replaces. AFor singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or the carbon number alkylene that is 2～6. Wherein,All or part of of the hydrogen atom of above-mentioned methylene and alkylene also can be replaced by cyano group, halogen atom or fluoroalkyl.

The R of above-mentioned formula (C-1)⁷～R¹⁶Represented electron-withdrawing group for example can be enumerated halogen atom, cyano group, nitro, trifluoroMethyl, carboxyl, acyl group, alkyl sulphonyl, alkoxyl sulfonyl, dicyano vinyl, tricyano vinyl, sulfonyl etc. ThisPreferred nitro, alkoxyl sulfonyl, trifluoromethyl in a little bases. The represented base of A is preferably sulfonyl, also can be replaced by fluoroalkylMethylene.

As the represented compound of above-mentioned formula (C-1),

Preferably 2, two (4-aminophenyl) HFC-236fas, 2 of 2-, two (4-aminophenyl) succinonitrile, 4, the 4 '-diaminourea two of 3-Benzophenone, benzoic acid-4,4 '-diaminourea phenyl ester, 4,4 '-diamino diphenyl sulfone, more preferably 4,4 '-diamino diphenyl sulfone,Two (4-aminophenyl) HFC-236fas of 2,2-.

The represented compound of above-mentioned formula (C-1) can be used alone or two or more is mixed and is used. As above-mentioned formula(C-1) represented compound containing proportional, for [A] polymer 100 mass parts, be preferably 0.1 mass parts～20Mass parts, more preferably 0.2 mass parts～10 mass parts. By making containing of the represented compound of above-mentioned formula (C-1) proportionalFor above-mentioned scope, can effectively promote the sclerosis of the dielectric film being formed by radiation-sensitive resin composition.

[phosphonium salt]

Phosphonium salt can use at least a kind of the choosing group that freely the represented compound of following formula (4) forms.

[changing 14]

In above-mentioned formula (4), A¹For phosphorus atoms. R²¹～R²⁴Independent alkyl, the carbon that is hydrogen atom, carbon number and is 1～20 respectivelyNumber is the aralkyl that 6～18 aryl or carbon number are 7～30. Wherein, part or all of the hydrogen atom of these bases also can quiltReplace. Q^-It is 1 valency anion.

R in above-mentioned formula (4)²¹～R²⁴Represented carbon number is that 1～20 alkyl for example can be enumerated straight chain shape or branch-likeMethyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tridecyl, the tetradecaneBase, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc.

R in above-mentioned formula (4)²¹～R²⁴Represented carbon number is that 6～18 aryl for example can be enumerated phenyl, naphthyl etc.

R in above-mentioned formula (4)²¹～R²⁴Represented carbon number is that 7～30 aralkyl for example can be enumerated benzyl, phenethylDeng.

Q in above-mentioned formula (4)^-1 represented valency anion for example can be enumerated chloride ion, bromide ion, iodateThing ion, cyanide ion, nitrate ion, nitrite ion, hypochlorite ion, chlorition, chlorate anions fromSon, mistake chloranion, high manganese ion, bicarbonate ion, dihydrogen phosphate ions, hydrogen sulfide radical ion, thiocyanic acidRadical ion, Carboxylic Acid Ions, azochlorosulfonate acid ion, phenoxy group ion, tetrafluoro boric acid salt ion, four aryl boric acid salt ions, hexafluoro-antimonic acidSalt ion etc.

Phosphonium salt for example can be enumerated tetraphenylphosphoniphenolate tetraphenyl borate salts, tetraphenylphosphoniphenolate four (p-methylphenyl) borate, fourBen Ji Phosphonium four (to ethylphenyl) borate, tetraphenylphosphoniphenolate four (p-methoxyphenyl) borate, tetraphenylphosphoniphenolate four are (rightEthoxyl phenenyl) borate, tetraphenylphosphoniphenolate four (to tert-butoxy phenyl) borate, tetraphenylphosphoniphenolate four (tolyl) boronHydrochlorate, tetraphenylphosphoniphenolate four (m-methoxyphenyl) borate, three (p-methylphenyl) Ben Ji Phosphonium four (p-methylphenyl) borate,Four (p-methylphenyl) Phosphonium four (p-methylphenyl) borate, three (p-methoxyphenyl) Ben Ji Phosphonium four (p-methylphenyl) boric acidSalt, tetraphenylphosphoniphenolate rhodanate, Ding base triphenyl phosphonium rhodanate, Jia base triphenyl phosphonium rhodanate, p-methylphenyl triphenylPhosphonium rhodanate etc.

Preferred Ding base triphenyl phosphonium rhodanate in Zhe Xie phosphonium salt. Phosphonium salt can be used alone or two or more mixing is madeWith.

As the phosphonium salt in radiation-sensitive resin composition containing proportional, with respect to [A] polymer 100 mass parts andSpeech is preferably 0.05 mass parts～10 mass parts, more preferably 0.1 mass parts～5 mass parts. Led to and make containing of phosphonium salt proportionalFor above-mentioned particular range, the sclerosis that can realize radiation-sensitive resin composition promotes.

[mercaptan compound]

Mercaptan compound is the compound in 1 molecule with more than 2 sulfydryl.

Mercaptan compound, as long as having more than 2 sulfydryl in 1 molecule is not particularly limited, can use choosing freely followingAt least a kind of the group that the represented compound of formula (5) forms.

[changing 15]

In above-mentioned formula (5), R³¹For methylene, the carbon number alkylene that is 2～10. Wherein, one of the hydrogen atom of these basesDivide or all also can be replaced by alkyl. Y¹For singly-bound ,-CO-or-O-CO-^*. Wherein, have^*Key and R³¹Bond. N is 2～10 integer. A²For also thering is the n valency alkyl that the carbon number of one or more ehter bonds is 2～70, or when the situation that is 3 at n beThe represented base of following formula (6).

[changing 16]

In above-mentioned formula (6), R³²～R³⁴The independent alkylene that is methylene or carbon number and is 2～6 respectively. "^*" represent respectively key.

As the represented compound of above-mentioned formula (5), be typically carboxylate that can use mercaptan carboxylic acid and polyalcohol etc.The mercaptan carboxylic acid who forms carboxylate for example can enumerate thioacetic acid, 3-mercaptopropionic acid, 3-sulfydryl butyric acid, 3-mercaptopentanoic acid etc. AndAnd the polyalcohol that forms carboxylate for example can be enumerated ethylene glycol, propane diols, trimethylolpropane, TEG, two seasons penta 4Alcohol, BDO, pentaerythrite etc.

The represented compound of above-mentioned formula (5) is preferably trimethylolpropane tris (3-mercaptopropionic acid) ester, pentaerythrite four(3-mercaptopropionic acid) ester, two (3-mercaptopropionic acid) esters of TEG, dipentaerythritol six (3-mercaptopropionic acid) ester, pentaerythrite four(TGA) ester, Isosorbide-5-Nitrae-bis-(3-sulfydryl butyryl acyloxy) butane, pentaerythrite four (3-sulfydryl butyric acid) ester, pentaerythrite four(3-mercaptopentanoic acid) ester, 1,3,5-tri-(3-sulfydryl butoxyethyl group)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones.

The compound in 1 molecule with more than 2 sulfydryl of mercaptan compound also can use following formula (7)～following formula(9) represented compound.

[changing 17]

[changing 18]

In above-mentioned formula (7), R⁴¹For methylene or the carbon number alkylene that is 2～20. R⁴²For methylene or carbon number are 2～6Straight chain or branch's alkylene. K is 1～20 integer.

In above-mentioned formula (8), R⁴³～R⁴⁶Independent is respectively hydrogen atom, hydroxyl or the represented base of following formula (9). Wherein,R⁴³～R⁴⁶At least 1 be the represented base of following formula (9).

[changing 19]

In above-mentioned formula (9), R⁴⁷For methylene or carbon number be 2～6 straight chain or branch's alkylene.

Mercaptan compound can be used alone or two or more is mixed and is used. In radiation-sensitive resin compositionMercaptan compound containing proportional, for [A] polymer 100 mass parts, be preferably 1 mass parts～20 mass parts, moreBe preferably 5 mass parts～15 mass parts. Be above-mentioned particular range by making containing of mercaptan compound proportional, can realize sense radiationThe sclerosis of linear resin constituent promotes.

[block isocyanate compound]

Block polyisocyanate compound is that NCO is reacted with the compound that contains reactive hydrogen base (blocking agent)And become the compound of inertia at normal temperature, and there is following character: if it is heated, blocking agent dissociates and bearsNCO. By making radiation-sensitive resin composition contain block polyisocyanate, can be used as effective crosslinking agent andCarry out isocyanates-hydroxyl cross-linking reaction, thereby realize the sclerosis promotion of radiation-sensitive resin composition.

Block polyisocyanate compound can be by by aliphatic or alicyclic diisocyanate and derivative polyisocyanateEster with have reactive hydrogen compound (blocking agent) known reaction and obtain.

Vulcabond for example can be enumerated tetramethylene diisocyanate, pentane vulcabond, hexa-methylene two isocyanidesAcid esters (HDI), 2,2,4-trimethyl-1,6-bis-isocyanate group hexanes, 2,4,4-trimethyl-1,6-bis-isocyanate group hexanes, badPropylhomoserin vulcabond, IPDI (IPDI), 1, two (isocyanates ylmethyl) cyclohexanes, 4 of 3-, 4-bis-encirclesHexyl methane diisocyanate, ENB vulcabond, methylene phenylene diisocyanate, 4,4 '-diphenyl methane two isocyanidesAcid esters, 1,5-naphthalene diisocyanate, tolidine vulcabond, dimethylaniline isocyanates, Isosorbide-5-Nitrae-tetramethylene two isocyanidesAcid esters, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 3-isocyanates methyl-3,5,5-front threeBasic ring hexyl diisocyanate etc.

As commercially available product, for example, can enumerate Duranate(registrar with the compound of the oxime blocked isocyanate prepolymer base of butanoneMark) TPA-B80E, DuranateTPA-B80X, DuranateE402-B80T, DuranateMF-B60XN, DuranateMF-B60X, DuranateMF-B80M(are above to be manufactured by industrial group of Asahi Chemical Industry); With active methylene group blocked isocyanate prepolymer baseCompound can enumerate Duranate(registration mark) industrial group of MF-K60X(Asahi Chemical Industry); There is (methyl) acryloyl groupThe block body of isocyanate compound can be enumerated Karenz(registration mark) MOI-BP, Karenz(registration mark) MOI-BM(withAbove manufactured by clear and electrician company).

In these commercially available products, using Duranate(registration mark) situation of E402-B80T, DuranateMF-B60XTime show high pliability, use by making with the class of mixing of other compounds, can freely control its hardness, thereforePreferably use.

For example can enumerate fulminuric acid ester type PIC, contracting two by the derivative PIC of vulcabondUrea type PIC, carbamate type PIC, allophanate type PIC etc. The viewpoint of self-hardeningConsider, preferably fulminuric acid ester type PIC.

Blocking agent for example can be enumerated alcohol compound, phenolic compound, active methylene group compounds, thio-alcohol chemical combinationThing, amides compound, imide analog compounds, glyoxaline compound, pyrazole compound, carbamide compounds, oximes chemical combinationThing, aminated compounds, imine compound, pyridine compounds and their etc.

It is molten that alcohol compound for example can be enumerated methyl alcohol, ethanol, propyl alcohol, butanols, 2-Ethylhexyl Alcohol, methyl cellosolve, butylFine agent, methyl carbitol, phenmethylol, cyclohexanol etc.;

Phenolic compound for example can enumerate phenol, cresols, ethyl-phenol, butylphenol, nonyl phenol, dinonyl phenol,Styrenated phenol, hydroxybenzoate etc.;

Active methylene group compounds for example can be enumerated dimethyl malenate, diethyl malonate, methyl acetoacetate, secondEthyl acetoacetic acid ethyl ester, acetylacetone,2,4-pentanedione etc.;

Sulfur alcohol compound for example can be enumerated butanethiol, lauryl mercaptan etc.;

Amides compound for example can be enumerated antifebrin, acetamide, epsilon-caprolactams, δ-valerolactam, γ-Ding Nei acylAmine etc.;

Imide analog compounds for example can be enumerated succinimide, maleimide etc.;

Glyoxaline compound for example can be enumerated imidazoles, glyoxal ethyline etc.; Pyrazole compound for example can be enumerated 3-methylPyrazoles, 3,5-dimethyl pyrazole, 3,5-ethyl pyrazoles etc.;

Carbamide compounds for example can be enumerated urea, thiocarbamide, ethylene-urea etc.;

Oxime compound for example can be enumerated formaldoxime, acetaldoxime, acetoxime, diacetylmonoxime, cyclohexanone oxime etc.; Aminated compoundsFor example can enumerate diphenylamine, aniline, carbazole etc.;

Imine compound for example can be enumerated Ethylenimine, polymine etc.;

Pyridine compounds and their for example can be enumerated 2 hydroxy pyrimidine, 2-oxyquinoline etc.

Block polyisocyanate compound can be used alone or two or more is mixed and is used. Set as radioactivity-sensitiveContaining of block polyisocyanate compound in fat composition is proportional, for [A] polymer 100 mass parts, is preferably0.1 mass parts～10 mass parts, more preferably 0.5 mass parts～5 mass parts. By making containing of block polyisocyanate compoundProportional is above-mentioned scope, and the sclerosis that can realize radiation-sensitive resin composition promotes.

Other any composition > of <

The radioactivity-sensitive tree of this example using in the formation of the dielectric film of the array base palte of this exampleFat composition, except above-mentioned [A] polymer and [B] photoacid generator, also can contain [C] compound (curing agent), in additionAlso can in the scope that does not undermine effect of the present invention, optionally contain antioxidant, surfactant, connect airtight auxiliary agent, alkalizationOther any compositions such as compound, quinone di-azido compound, plasticizer. This kind of any composition can be used alone a kind or by 2 kinds withOn be used in combination.

The modulation > of < radiation-sensitive resin composition

The radioactivity-sensitive tree of this example using in the formation of the dielectric film of the array base palte of this exampleFat composition can, by except above-mentioned [A] polymer and [B] photoacid generator, further mix [C] compound (curing agent)And optionally and add any composition and modulate. And the radiation-sensitive resin composition of this example just can be used asThe radiation-sensitive resin composition of type and using. The radiation-sensitive resin composition of this example is preferably modulated to dissolvingOr be dispersed in the state in suitable solvent and use. For example, in solvent by [A] composition ([A] polymer), [B] composition([B] photoacid generator), [C] composition ([C] compound) and conduct arbitrarily [D] composition of composition are mixed with the ratio of regulation,Can modulate thus radiation-sensitive resin composition.

The solid concentration of the radiation-sensitive resin composition of this example (refers to contained gathering in polymer solutionThe quality of compound shared ratio in the gross mass of polymer solution) can appoint according to application target or desired thickness etc.Meaning set, be preferably 5 quality %～50 quality %, more preferably 10 quality %～40 quality %, further more preferably 15 quality %～35 quality %.

< solvent >

As the solvent that can use in the modulation of the radiation-sensitive resin composition of this example, as mentioned aboveSuch suitable use is dissolved equably or is disperseed each composition, and the solvent not reacting with each composition. This kind of solvent for example can be listed asLift alcohols, ethers, diethylene glycol alkyl ether, ethylene glycol alkyl ether acetate esters, propylene-glycol monoalky lether class, propane diols list alkaneBase ether acetic acid ester class, propylene-glycol monoalky lether propionic acid ester, aromatic hydrocarbon based, ketone, ester class etc.

As this kind of solvent, alcohols for example can be enumerated phenmethylol, DAA etc.; Ethers for example can enumerate oxolane orThe dialkyl ethers such as Di Iso Propyl Ether, di-n-butyl ether, two n-pentyl ethers, diisoamyl ether, di-n-hexyl ether etc.;

Diethylene glycol alkyl ether for example can be enumerated diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diformazanEther, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether etc.; Ethylene glycol alkyl ether acetate esters for example can be enumerated methyl cellosolve secondAcid esters, ethyl cellosolve acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate etc.;

Propylene-glycol monoalky lether class for example can be enumerated propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, the third twoAlcohol monobutyl ether etc.;

Propylene-glycol monoalky lether acetate esters for example can be enumerated propylene glycol methyl ether acetate, dihydroxypropane single-ether acetic acidEster, propylene glycol monopropyl ether acetic acid esters, propylene glycol monobutyl ether acetic acid esters etc.;

Propylene-glycol monoalky lether propionic acid ester for example can be enumerated propylene glycol monomethyl ether propionate, dihydroxypropane single-ether propionic acidEster, propylene glycol monopropyl ether propionic ester, propylene glycol monobutyl ether propionic ester etc.;

Aromatic hydrocarbon based toluene, the dimethylbenzene etc. for example can enumerated;

Ketone for example can be enumerated butanone, methyl iso-butyl ketone (MIBK), cyclohexanone, 2-HEPTANONE, 4-hydroxy-4-methyl-2-pentanone etc.;

Ester class for example can be enumerated methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 2-hydroxyl thirdAcetoacetic ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate,Butyl Glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy methyl propionate, 3-hydracrylic acid secondEster, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, methoxyl groupEthyl acetate, methoxyacetic acid propyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethyoxyl secondPropyl propionate, ethoxyacetic acid butyl ester, propoxyl group methyl acetate, propoxyl group ethyl acetate, propoxyl group propyl acetate, propoxyl group acetic acidButyl ester, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 2-methoxypropionic acidMethyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, 2-secondOxygen base ethyl propionate etc.

From dissolubility or excellent dispersion, with the non-reacted of each composition and easily form the viewpoints such as film and consider, thisPreferred ethers, diethylene glycol alkyl ether, ethylene glycol alkyl ether acetate esters, the propanediol monoalkyl such as dialkyl ether in a little solventsEthers, propylene-glycol monoalky lether acetate esters, ketone and ester class, particularly preferably diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether,Methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monomethyl ether acetic acidEster, propylene glycol monoethyl ether acetate, cyclohexanone, propyl acetate, isopropyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxylBase-2 Methylpropionic acid methyl esters, 2-hydroxy-2-methyl ethyl propionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate,2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester. These solvents can be used alone or two or more is mixed and is used.

And preferably Di Iso Propyl Ether, di-n-butyl ether, two n-pentyl ethers, diisoamyl ether, two are just own in these solventsThe ethers such as dialkyl ether such as base ether, most preferably isoamyl ether. By using this kind of solvent, can this implemented by slot coated methodWhen the radiation-sensitive resin composition of form is for example coated on large-size glass substrate, make drying steps time shorten, andMake coating further improve (inhibition crawling).

Except above-mentioned solvent, also can be further optionally also by benzylisoeugenol, hexyl ether, diethylene glycol list firstEther, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol,Phenmethylol, acetic acid benzyl ester, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, carbonThe high boiling solvents such as acid propylene diester, acetic acid ethylene glycol monophenyl ether, carbitol acetic acid esters.

The radiation-sensitive resin composition being obtained by above composition and modulator approach can form by hardening at subcritical temeratureThere is the dielectric film of contact hole. For example, can obtain and have by 180 DEG C～200 DEG C low hardening temperatures of geometric ratio prior artThe dielectric film of the good reliabilitys such as solvent resistance. And, the array base palte of this example can be provided by hardening at subcritical temerature.

Secondly, the array base palte of this example can comprise the alignment film of controlling LCD alignment. As this exampleThe alignment film forming on array base palte, can use the crystal aligning agent of this example and form. Therefore, below to this realityThe orientation inorganic agent of executing form, particularly its main component is illustrated.

< crystal aligning agent >

The crystal aligning agent that forms this example of alignment film on the array base palte of this example is to contain to have[L] radioactivity-sensitive polymer of light regiospecific base or do not have [M] polyimides of light regiospecific base as the liquid of main componentBrilliant orientation agent. These compositions all can for example form alignment film under 200 DEG C of heating-up temperatures with inferior low temperature. Particularly contain toolThe crystal aligning agent that has [L] radioactivity-sensitive polymer of light regiospecific base, can more form alignment film under low temperature, is more preferablyCrystal aligning agent. As mentioned above, the crystal aligning agent of this example can form alignment film by the heating steps of low temperature,Therefore can not make the dielectric film that is located at lower floor be exposed to the state of high-temperature heating and form alignment film.

In addition, on the array base palte of this example, form alignment film this example crystal aligning agent only otherwiseUndermine effect of the present invention and can contain [N] other compositions. Below these compositions are illustrated.

[[L] radioactivity-sensitive polymer]

[L] radioactivity-sensitive polymer contained in the crystal aligning agent of this example has light regiospecific basePolymer. The light regiospecific base should [L] radioactivity-sensitive polymer having is that to give film by irradiation anisotropicFunctional group, in this example, particularly composes by the person at least arbitrarily who produces photoisomerization reaction and light dimerization reactionGive the anisotropic base of film.

As light regiospecific base, particularly select free azobenzene, stilbene, alpha-imino-'beta '-ketoester, spiral shell pyrrole for having to be derived fromMutter, Luo oxazine, cinnamic acid, chalcone, stilbene azoles, benzylidene phthalimide, cumarin, dibenzenyl and anthracene institute structureThe base of the structure of at least a kind of compound of the group becoming. As above-mentioned smooth regiospecific base, in these, particularly preferably there is the meat of being derived fromThe base of the structure of cinnamic acid.

As [L] radioactivity-sensitive polymer with light regiospecific base, be preferably above-mentioned smooth regiospecific base directly or warpThe polymer being formed by concatenating group bond. This kind of polymer for example can be enumerated: at least any at polyamic acid and polyimidesOn polymer, bond has the compound that above-mentioned smooth regiospecific base forms; On the polymer different from polyamic acid and polyimidesThe compound that bond has above-mentioned smooth regiospecific base to form. In the time of the latter's situation, there is polymer basic of light regiospecific baseSkeleton for example can be enumerated poly-(methyl) acrylate, poly-(methyl) acrylamide, polyvinylether, polyolefin, polysiloxaneDeng.

As radioactivity-sensitive polymer, preferably taking polyamic acid, polyimides or polysiloxane as basic frameworkRadioactivity-sensitive polymer. For example, and polysiloxane particularly preferably in these, can pass through International Publication (WO)The method of recording in No. 2009/025386 description and obtaining.

[[M] polyimides]

In the crystal aligning agent of this example, contained [M] polyimides is not have a polyamides Asia of light regiospecific baseAmine.

This kind do not had [M] polyimides of light regiospecific base and can be closed by the polyamic acid dehydration that makes not have light regiospecific baseRing and carry out imidizate and obtain. This kind do not had the polyamic acid of light regiospecific base for example can be by making tetracarboxylic dianhydride and twoAmine reacts and obtains, and can obtain according to the method for recording in Japanese Patent Laid-Open 2010-97188 communique.

[M] polyimides can be the amic acid structure fully dehydrating closed loop having as the polyamic acid of its predecessorThe complete acid imide compound forming, also can be only a part of dehydration closed-loop, amic acid structure and the acid imide of amic acid structureRing structure the part acid imide compound of depositing. [M] polyimides preferably its acid imide rate is more than 30%, more preferably 50%～99%, further more preferably 65%～99%. This acid imide rate is to represent that with percentage imide ring structure number is with respect to polyamidesThe shared ratio of total of the amic acid structure number of imines and imide ring structure number. Herein, a part for imide ring also canFor different imide ring, for example can be as recorded in Japanese Patent Laid-Open 2010-97188 communique and obtain.

[[N] other compositions]

The crystal aligning agent of this example can contain and has the radioactivity-sensitive polymer of light regiospecific base and the light of not having[N] other compositions beyond the polyimides of regiospecific base. [N] other compositions for example can be enumerated [L] with light regiospecific baseRadioactivity-sensitive polymer and do not have polymer beyond [M] polyimides of light regiospecific base, curing agent, hardening catalyst,Hardening accelerator, epoxide, functional silanes compound, surfactant, sensitising agent etc.

Above, the main composition element of the array base palte to this example is illustrated, secondly to this exampleThe manufacture method of array base palte be illustrated.

The manufacture method > of < dielectric film, alignment film and array base palte

In the manufacture of the array base palte of this example, comprise the radioactivity-sensitive resin group by above-mentioned exampleThe step that becomes thing and manufacture dielectric film is as key step. Can form and be formed with contact hole by the manufacturing step of this dielectric filmDielectric film. And, in order to form alignment film on the array base palte of this example, comprise the liquid crystal by above-mentioned exampleOrientation agent and the step that forms alignment film are as manufacturing step. Below, to thering is this example of dielectric film and alignment filmThe manufacture method of array base palte is illustrated.

In the manufacture method of the array base palte of this example, preferably on substrate, form dielectric film, and with following suitableOrder and at least comprise following step [1]～step [4]. And, in order to form alignment film on array base palte, preferably in step[4] after, comprise step [5].

[1] be formed with (expression source electrode, drain electrode, grid, source distribution and the grid distribution etc. such as switch active element and electrode.Below be sometimes generically and collectively referred to as electrode etc.) substrate on form radiation-sensitive resin composition film step (be sometimes referred to as below" step [1] ").

[2] at least a portion of the radiation-sensitive resin composition film forming in step [1] is irradiated to radioactive rayStep (being sometimes referred to as below " step [2] ").

[3] (be sometimes referred to as below " step to irradiated the step that the film of radioactive ray develops in step [2][3]”）。

[4] film that has carried out developing in step [3] is carried out to heat hardening and the step that forms dielectric film (has belowTime be called " step [4] ").

[5] on the substrate with the dielectric film that has carried out sclerosis in step [4], form crystal aligning agent film,200 DEG C following heats and forms the step (being sometimes referred to as below " step [5] ") of alignment film this film.

And, between above-mentioned steps [4] and step [5], preferably be contained on the dielectric film forming in step [4] and establishPut the step of transparency electrode.

The manufacture method of the array base palte of this example that can be by comprising above each step, is used this exampleRadiation-sensitive resin composition forms the insulation that comprises contact hole on the substrate that is formed with switch active element or electrode etc.Film. And, can use the crystal aligning agent of this example and on substrate, form alignment film. Its result, can pass through this enforcementThe manufacture method of the array base palte of form and form the array base palte of this example, it is included in desired position and is formed withThe dielectric film of the contact hole of desired size, and be included in the dielectric film forming than at the low temperature of prior art.

As array base palte described above and that manufacture, consider from energy-conservation viewpoint, in the low temperature of expecting heating stepsSituation under also become suitable array base palte.

Below, each step is described in detail.

[step [1]]

In this step, on substrate, form the film of the radiation-sensitive resin composition of this example. At this baseOn plate, be formed with switch active element, source electrode, drain electrode, grid, source distribution and grid distribution etc. These switch active elements etc. areOn substrate, repeatedly carry out passing through by common semiconductor film film forming, the formation of known insulating barrier, photolithographic etching etc.The element that known method forms.

After the forming surface coating radiation-sensitive resin composition of the switch active element of this substrate etc., preferably addHeat (being also called preliminary drying) and except desolventizing, thus film formed.

The material of substrate for example can be enumerated the glass such as soda-lime glass or alkali-free glass, quartz, silicon, resin etc. The tool of resinStyle can enumerate PET, polybutylene terephthalate, polyether sulfone, Merlon, aromatic polyamide,Ring-opening polymerization polymer and the hydride etc. thereof of polyamidoimide, polyimides, cyclic olefin. And, also can be optionally to theseSubstrate is implemented in advance by the chemicals treatment of silane coupler etc., Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, trueThe suitable pretreatment such as empty evaporation.

The coating process of radiation-sensitive resin composition for example can adopt spray-on process, rolling method, spin-coating method (sometimes also to claimFor method of spin coating or circulator method), slot coated method (slit die rubbing method), bar type rubbing method, ink-jet application method etc. are suitableSuitable method. Preferred spin-coating method or slot coated method in these methods.

Above-mentioned preliminary drying condition is different because of kind, the allotment ratio etc. of each composition, is preferably 70 DEG C～120 DEG C, can be made as 1 pointAbout clock～10 minute.

[step [2]]

Secondly,, in step [2], at least a portion of the film forming in step [1] is irradiated to radioactive ray. Now,In the time that only the part to film is irradiated, for example can be by being situated between every the mask pattern corresponding with forming desired contact holePhotomask and the method for irradiating.

What the radioactive ray that use in irradiation were suitable is the radioactive ray that photoacid generator is used. In these radioactive ray, excellentSelect wavelength to be in the radioactive ray of the scope of 190nm～450nm, particularly preferably comprise the ultraviolet radioactive ray of 365nm.

Radiation exposure amount (light exposure) is by illumination photometer (OAImodel356, OpticalAssociatesInc. manufacture) and measure the value of the intensity under the wavelength 365nm of the radioactive ray that irradiate, be preferably 100J/m²～3,000J/m²，More preferably 500J/m²～2,000J/m²。

[step [3]]

Secondly,, in step [3], by the film after radiation exposure is developed, will not need part (radioactive rayIlluminated portion) remove, thereby obtain there is regulation shape, be formed with the film of desired contact hole.

The developer solution using in development is the aqueous solution of alkalescence preferably. The example of contained alkali can enumerate NaOH,The inorganic bases such as potassium hydroxide, sodium carbonate, sodium metasilicate, sodium metasilicate, ammonia; The season such as TMAH, tetraethyl ammonium hydroxideAmmonium salt etc.

And, the water-miscible organic solvent such as methyl alcohol, ethanol or the surface that in this kind of alkaline aqueous solution, also can add appropriate amountActivating agent and using. Consider from the viewpoint that obtains suitable developability, the concentration of the alkali in alkaline aqueous solution can preferably be made as 0.1Quality %～5 quality %. Developing method for example can be by covering the suitable methods such as liquid method, infusion process, vibration infusion process, spray process.Developing time is different because of the composition of radiation-sensitive resin composition, be preferably 10 seconds～and about 180 seconds. This kind of development treatment continuesAfter, the flowing water for example carrying out 30 seconds～90 seconds cleans, and then for example makes it air-dry with compressed air or compressed nitrogen, thus can shapeBecome desired pattern.

[step [4]]

Secondly, in step [4], can use the heater such as hot plate, baking oven, the film of patterning (is also heatedBe called rear baking), promote thus the sclerous reaction of [A] polymer contained in radiation-sensitive resin composition, make and haveThe cured film of desired characteristic and obtain dielectric film. Heating-up temperature in this step is for example preferably 120 DEG C～220 DEG C. AndAnd, the radiation-sensitive resin composition of this example forming in the case of use contains above-mentioned [C] composition, preferablyHeating-up temperature in this step is made as to for example 120 DEG C～200 DEG C, is more preferably made as and becomes 120 DEG C～180 DEG C of low temperature more.

Heat time is different because of the kind of heating machine, for example, the in the situation that of carrying out heating steps on hot plate, can be made as 5Minute～30 minutes; The in the situation that of carrying out heating steps in baking oven, can be made as 30 minutes～90 minutes. Also can use and carry out 2The substep baking of inferior above heating steps etc. Carry out as described above, can on substrate, form the contact that has that is made as targetThe dielectric film in hole. The thickness of the dielectric film forming is preferably 0.1 μ m～8 μ m, and more preferably 0.1 μ m～6 μ m, further more excellentElect 0.1 μ m～4 μ m as.

By the step according to above, the radiation-sensitive resin composition of this example can be used as has contact holeThe formation material of dielectric film and suitable use, and can form the dielectric film of the array base palte of this example.

And, preferably in step [4], form after dielectric film, be included in the step that transparency electrode is set on this dielectric film.For example, can utilize sputtering method etc. and on dielectric film, form the transparency conducting layer that comprises ITO. Secondly, can utilize photoetching process and rightThis transparency conducting layer carries out etching, forms transparency electrode on dielectric film. Transparency electrode forms pixel electrode, by via insulationThe contact hole of film and can with substrate on switch active element be electrically connected. In addition, transparency electrode, except ITO, can be usedThere is the transparent material of transmissivity high for visible ray and electric conductivity and form. For example can use indium zinc oxide(IndiumZincOxide, IZO) or ZnO(zinc oxide) or tin oxide etc. and forming.

[step [5]]

The substrate with dielectric film that uses gained in step [4] forms transparency electrode as described above on dielectric filmAfter, in transparency electrode, be coated with the crystal aligning agent of this example. Coating process for example can use rolling method, spin-coating method, sealThe suitable coating processes such as brush method, ink-jet method. Secondly, the substrate that is coated with crystal aligning agent is carried out to preliminary drying, after carrying out thereafterDry and formation film, therefrom manufacturing array substrate. Preliminary drying condition is for example at 40 DEG C～120 DEG C, to be 0.1 minute～5 pointsClock. Rear baking condition be 120 DEG C～230 DEG C, be preferably and at 150 DEG C～200 DEG C, more preferably 150 DEG C～180 DEG C, carry out preferablyIt is 5 minutes～200 minutes, more preferably 10 minutes～100 minutes. The thickness of the film after rear baking is preferably 0.001 μ m～1 μM, more preferably 0.005 μ m～0.5 μ m.

The solid concentration of the crystal aligning agent using in the time of coating of liquid crystalline orientation agent is (beyond the solvent of crystal aligning agentThe total weight of composition shared ratio in the gross weight of crystal aligning agent) can consider viscosity, volatility etc. and suitable choosingSelect, be preferably the scope of 1 % by weight～10 % by weight.

Use the crystal aligning agent that comprises [L] radioactivity-sensitive polymer with light regiospecific base at crystal aligning agentWhen situation, give control by irradiating linear polarization or the radioactive ray of part polarisation or the radioactive ray of non-polarisation at above-mentioned filmThe LCD alignment ability of LCD alignment processed. So polarisation radiation exposure is processed corresponding with the orientation of alignment film. Herein, radiationLine for example can use ultraviolet ray and the luminous ray of the wavelength light that comprises 150nm～800nm. Particularly preferably use and comprise 300nmThe ultraviolet ray of the wavelength light of～400nm is as radioactive ray. When used radioactive ray are the situation of linear polarization or part polarisationTime, irradiation can, from carrying out perpendicular to the direction of real estate, also can carry out giving tilt angle to liquid crystal from tilted direction, Er QieyiThese Combination of Methods can be carried out. In the time irradiating the situation of radioactive ray of non-polarisation, direction of illumination must be tilted direction.

The exposure of radioactive ray is preferably 1J/m²Above and less than 10,000J/m², more preferably 10J/m²～3,000J/m²。

Use and comprise while not having the situation of crystal aligning agent of [M] polyimides of light regiospecific base at crystal aligning agent,Also can be by the film after rear baking directly as alignment film. And, also can optionally reel as used to the film embodiment after rear bakingThe processing (friction treatment) that has the roller of the cloth of fibers such as comprising nylon, artificial silk, cotton to rub on fixed-direction, thus composeGive LCD alignment ability.

The in the situation that of as mentioned above forming alignment film on array base palte, can use above-mentioned crystal aligning agent and at 200 DEG CFollowing heating-up temperature, be further to form alignment film under 180 DEG C of following heating-up temperatures. Therefore, can avoid in above-mentioned steps[1] dielectric film forming in～step [4] is exposed under the state of high temperature in the formation step of alignment film. And, this realityThe array base palte of executing form can comprise dielectric film and the alignment film of the contact hole with desired configuration and size, can pass throughManufacture than the heating at the low temperature of prior art.

[embodiment]

Below, based on example, example of the present invention is described in detail, but with this example, the present invention is not carried outLimited explanation.

In the following, the quality mean molecule quantity (Mw) of polymer and number average molecular weight (Mn) can be passed through according to followingThe gel permeation chromatography (GPC) of condition and measuring.

Device: GPC-101(Showa Denko K. K manufactures)

Tubing string: by GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combination in addition

Mobile phase: oxolane

Tubing string temperature: 40 DEG C

Flow velocity: 1.0mL/min

Sample solution concentration: 1.0 quality %

Sample injection rate: 100 μ L

Detector: differential refractometer

Standard substance: monodisperse polystyrene

The synthetic > of < [A] polymer

[synthesis example 1]

In the flask with condenser pipe and mixer, pack two (2,4-methyl pentane nitrile) 7 mass parts, two of 2,2 '-azo intoEthylene glycol methyl ether 200 mass parts. Secondly drop into methacrylic acid 5 mass parts, methacrylic acid-2-THP trtrahydropyranyl ester 40 matterAmount part, styrene 5 mass parts, GMA 40 mass parts, methacrylic acid-2-hydroxy methacrylate 10 mass partsAnd α-methylstyrenedimer 3 mass parts carrying out after nitrogen replacement, slowly start to stir. Make the temperature rise to 70 of solutionDEG C, this temperature maintenance 5 hours is obtained to the polymer solution that comprises copolymer (A-1). The polystyrene of copolymer (A-1) changesCalculating quality mean molecule quantity (Mw) is 9,000. And the solid concentration of the polymer solution of gained is 31.3 quality % herein.

[synthesis example 2]

In the flask with condenser pipe and mixer, pack two (2 Methylpropionic acid methyl esters) 7 mass parts, third of 2,2 '-azo intoGlycol monomethyl ether acetic acid esters 200 mass parts. Secondly drop into methacrylic acid-2-THP trtrahydropyranyl ester 85 mass parts, metering systemAcid-2-hydroxy methacrylate 7 mass parts, methacrylic acid 8 mass parts are also carried out after nitrogen replacement, slowly start to stir. Make solutionTemperature rise to 80 DEG C, obtains by this temperature maintenance 6 hours the polymer solution that comprises copolymer (a-1). Copolymer (a-1)Polystyrene conversion quality mean molecule quantity (Mw) be 10,000. And the solid content of the polymer solution of gained is dense hereinDegree is 29.2 quality %.

[synthesis example 3]

In the flask with condenser pipe and mixer, pack two (2,4-methyl pentane nitrile) 7 mass parts, two of 2,2 '-azo intoEthylene glycol methyl ether 200 mass parts. Secondly drop into GMA 52 mass parts, methacrylic acid benzyl ester 48Mass parts is also carried out after nitrogen replacement, slowly starts to stir. Make the temperature rise to 80 DEG C of solution, this temperature is kept 6 hoursAnd the polymer solution that acquisition comprises copolymer (aa-1). The polystyrene conversion quality mean molecule quantity of copolymer (aa-1)(Mw) be 10,000. And the solid concentration of the polymer solution of gained is 32.3 quality % herein.

The modulation > of < radiation-sensitive resin composition

[embodiment 1]

The solution of the copolymer that comprises gained in synthesis example 1 (A-1) (be equivalent to copolymer (A-1) 100 mass parts (GuShape thing) amount) in mix as [(camphor sulfonyl oxygen base imino group-5H-thiophene-2-subunit)-(2-methylbenzene of [B] compositionBase) acetonitrile] (BASF AG manufacture " CGI1380 ") 4 mass parts, conduct [D] composition become three of antioxidant-(3,5-Two-tertiary butyl-4-hydroxy benzyl)-fulminuric acid ester (" AdekastabAO-20 " that ADEKA company manufactures) 1 mass parts,As silicone surfactant (" SH8400FLUID " that Dong Li DOW CORNING Co., Ltd. manufactures) 0.20 quality of [D] compositionγ-glycidoxypropyltrimewasxysilane 3.0 mass parts of part, conduct [D] composition, using aperture is the thin of 0.2 μ mFilm filter filters, and modulates thus radiation-sensitive resin composition (S-1).

[embodiment 2]

(be equivalent to comprising the copolymer (a-1) of gained and the solution of copolymer (aa-1) in synthesis example 2 and synthesis example 3Total 100 matter that copolymer (a-1) and each 50 mass parts of copolymer (aa-1) (solid content) are mixed with 1 to 1 ratioThe amount of amount part) middle [(5-sulfonyl propyl base oxygen base imino group-5H-thiophene-2-subunit)-(2-methyl mixing as [B] compositionPhenyl) acetonitrile] 4,4 '-diaminourea two of (BASF AG manufacture " IRGACUREPAG103 ") 4 mass parts, conduct [C] compositionPhenylsulfone 0.5 mass parts, conduct [D] composition become three of antioxidant-(3,5-, bis--tertiary butyl-4-hydroxy benzyl)-different threeThe silicone surface-active of paracyanogen acid esters (" AdekastabAO-20 " that ADEKA company manufactures) 1 mass parts, conduct [D] compositionThe γ of agent (" SH8400FLUID " that eastern beautiful DOW CORNING Zhu Shihui company manufactures) 0.20 mass parts, conduct [D] composition-shrink sweetOil oxygen base propyl trimethoxy silicane 3.0 mass parts, use aperture is that the membrane filter of 0.2 μ m filters, modulation thusRadiation-sensitive resin composition (S-2).

< evaluating characteristics >

[embodiment 3]

Use the radiation-sensitive resin composition (S-1, S-2) of modulating by example 1 and example 2, as described belowEvaluate characteristic, and the insulation obtaining to the film being formed by these radiation-sensitive resin compositions or as its cured filmFilm is evaluated various characteristics.

(1) evaluation of radioactive ray speed

On the chromium film forming glass of 550mm × 650mm, be coated with HMDS (HMDS), at 60 DEG C, carry out 1 pointThe heating (being also called below " HMDS processing ") of clock. On this HMDS chromium film forming glass after treatment, use slit die coatingMachine " TR632105-CL " and radiation-sensitive resin composition S-1 that coating is modulated in example 1, will arrive pressure setting and be100Pa and under vacuum, solvent being removed. , further 90 DEG C at carry out the preliminary drying of 2 minute, form thus thickness and be thereafterThe film of 3.0 μ m. Secondly, the MPA-600FA exposure machine that uses Canon Co., Ltd to manufacture, is situated between every line and the gap with 60 μ mThe mask of the mask pattern of (10 to 1), is made as variable by light exposure and film is irradiated after radioactive ray, with covering liquid method in 0.40 matterIn the tetramethylammonium hydroxide aqueous solution of concentration of amount %, at 25 DEG C, develop. Developing time is made as to 80 seconds herein. ItsInferior, the flowing water carrying out 1 minute with ultra-pure water cleans, and is dried thereafter, therefrom at HMDS chromium film forming glass after treatment baseOn plate, form pattern. Now, investigation is used so that the intermittent pattern of 6 μ m dissolves necessary light exposure completely and evaluates. ?This value is 500J/m²In following situation, can judge into speed good. Using radiation-sensitive resin composition S-1In the pattern forming, its value becomes 500J/m²Below, the radioactive ray speed of known radiation-sensitive resin composition S-1 is goodGood.

Secondly, the radiation-sensitive resin composition S-2 modulating in use-case 2, according to method similar to the aboveCarry out the evaluation of radioactive ray speed. In the pattern forming using radiation-sensitive resin composition S-2, above-mentioned value becomes500J/m²Below, the radioactive ray speed of known radiation-sensitive resin composition S-2 is good.

(2) sunproof evaluation

Use circulator that the radiation-sensitive resin composition S-1 modulating in example 1 is coated on glass substrate, soAfter at 90 DEG C, on hot plate, carry out the preliminary drying of 2 minutes and form the film that thickness is 3.0 μ m. This glass substrate is dried in cleaningIn case, at 220 DEG C, carry out the rear baking of 1 hour, make cured film and obtain dielectric film. By UV irradiation unit (excellent will prosperous (Ushio)" UVX-02516S1JS01 " that company manufactures) with the illumination of 130mW, this dielectric film is irradiated to 800,000J/m²。

Compare with the thickness of pre-irradiation, if the film reduction of postradiation thickness is below 2%, can judge film formingLight resistance good. Using radiation-sensitive resin composition S-1 in the dielectric film that forms, film reduction become 2% withUnder, known have a good light resistance.

Secondly, the radiation-sensitive resin composition S-2 modulating in use-case 2 will carry out in cleaning ovenThe temperature of rear baking be made as 180 DEG C, form dielectric film according to method similar to the above in addition. Secondly, according to upperState same method and carry out the sunproof evaluation of the dielectric film of gained. Use radiation-sensitive resin composition S-2 and formThe film reduction of dielectric film become below 2%, known have a good light resistance.

In addition, in above sunproof evaluation, do not need formed film patterning, therefore omitted the step of developingSuddenly, only carrying out film forms step, light fastness test and heating steps and evaluates.

(3) stable on heating evaluation

The radiation-sensitive resin composition S-1 similarly modulating in use-case 1 with above-mentioned sunproof evaluation,On silicon substrate, form film. By this silicon substrate in cleaning oven, carry out the heating of 1 hour at 220 DEG C, make cured film andObtain dielectric film. Secondly, measure the thickness (T1) of the dielectric film of gained. Secondly, by the silicon substrate that is formed with this dielectric film cleanIn clean baking oven, at 240 DEG C, carry out 1 hour append after baking, measure the thickness (t1) that appends the dielectric film after baking, calculate byThe Thickness Variation rate that causes in appending baking | t1-T1|/T1} × 100[%]. When Thickness Variation rate is below 3% time, can sentenceBe broken into heat resistance good. In the dielectric film forming using radiation-sensitive resin composition S-1, Thickness Variation rate becomes 3%Below, known have a good heat resistance.

Secondly, the radiation-sensitive resin composition S-2 modulating in use-case 2 will carry out in cleaning ovenHeating-up temperature be made as 180 DEG C, form dielectric film according to method similar to the above in addition. And, measuring gainedThe thickness of dielectric film after, in cleaning oven, at 240 DEG C, carry out 1 hour append baking etc., according to side similar to the aboveMethod, carries out the stable on heating evaluation of the dielectric film of gained. The dielectric film that uses radiation-sensitive resin composition S-2 and formAbove-mentioned Thickness Variation rate becomes below 3%, and known have a good heat resistance.

(4) evaluation of transmissivity

The radiation-sensitive resin composition S-1 similarly modulating in use-case 1 with above-mentioned sunproof evaluation,On silicon substrate, form film. This silicon substrate in cleaning oven, carry out the heating of 1 hour at 220 DEG C, is made to cured film and obtainedObtain dielectric film. Use spectrophotometer (" 150-20 type dual-beam " that company of Hitachi manufactures) to measure under wavelength 400nmTransmissivity and evaluate. Now, the transmissivity less than 90% under wavelength 400nm, can judge into the transparency notGood. Using radiation-sensitive resin composition S-1 in the dielectric film that forms, the transmissivity under wavelength 400nm become 90% withUpper, the known transparency is excellent, has good transmission characteristics.

Secondly, use the radiation-sensitive resin composition S-2 modulating in example 2, will in cleaning oven, enterThe heating-up temperature of row is made as 180 DEG C, forms dielectric film in addition according to method similar to the above. And, according to upperState same method, carry out the stable on heating evaluation of the dielectric film of gained. Use radiation-sensitive resin composition S-2 and formThe transmissivity under wavelength 400nm of dielectric film become more than 90%, the known transparency is excellent, has good transmissivity spyProperty.

(5) evaluation of voltage retention

The radiation-sensitive resin composition S-1 modulating in use-case 1, is spin-coated on surface and is formed with and prevents sodiumThe SiO of ion stripping₂Film is further on the soda-lime glass substrate of regulation shape by ITO electrode evaporation. Secondly, clean at 90 DEG CIn clean baking oven, carry out the preliminary drying of 10 minutes, forming thickness is the film of 2.0 μ m.

Secondly, be not situated between every photomask and with 500J/m²Light exposure film is exposed. Thereafter, at 220 DEG C, cleanIn clean baking oven, carry out the rear baking of 30 minutes, make film sclerosis make permanent cured film and form dielectric film.

Secondly, be mixed with 0.8mm bead sealant by this be formed with the substrate of pixel with only by ITO electrodeAfter evaporation is the baseplate-laminating of regulation shape, inject the liquid crystal MLC6608(trade name that Merck & Co., Inc. manufactures), make liquid crystal listUnit.

Secondly, liquid crystal cells is put into the thermostat layer of 60 DEG C, by liquid crystal voltage conservation rate mensuration system (Dongyang technology" the VHR-1A type " that company manufactures) and the voltage retention of mensuration liquid crystal cells. Now apply the rectangular wave that voltage is 5.5V,Mensuration frequency is 60Hz. Herein so-called voltage retention be (the liquid crystal cells potential differences after 16.7 milliseconds)/(0 millisecond time instituteThe voltage applying) } value. If the voltage retention of liquid crystal cells is below 90%, represent that liquid crystal cells cannot be at 16.7 millisecondsTime in by applying voltage and remain the level of regulation, cannot make fully LCD alignment, and produce liquid crystal display cellsThe possibility of the bad image retention of demonstration etc. " burning trace " high.

The voltage retention with the liquid crystal cells of the dielectric film that uses radiation-sensitive resin composition S-1 and form surpassesCross 90%, known have a good voltage retention characteristic.

Secondly, the radiation-sensitive resin composition S-2 modulating in use-case 2 will carry out in cleaning ovenThe temperature of rear baking be made as 180 DEG C, form dielectric film according to method similar to the above in addition, make and be formed with that this is exhaustedThe liquid crystal cells of velum and carry out the evaluation of voltage retention. Having the radiation-sensitive resin composition of use S-2 formsThe voltage retention of the liquid crystal cells of dielectric film exceedes 90%, and known have a good voltage retention characteristic.

Known according to above evaluation result: the radiation-sensitive resin composition S-1 of example 1 and the sense of example 2 radiationLinear resin constituent S-2 all has excellent radioactive ray speed. And known: the radioactivity-sensitive resin of use-case 1The radiation-sensitive resin composition S-2 of constituent S-1 and example 2 and the equal light resistance of dielectric film, the heat resistance and transparent that formProperty excellence, and can form the good liquid crystal cells of voltage retention characteristic.

The manufacture > of < array base palte

[embodiment 4]

Use by example 1 the radiation-sensitive resin composition S-1 of gained, use circulator to be coated on and be formed withOn the substrate of switch active element or electrode etc. On this substrate, being formed with switch active element, source electrode, drain electrode, grid, source joinsLine and grid distribution etc. These switch active elements etc. are the film forming of repeatedly carrying out common semiconductor film on substrate, knownThe element that insulating barrier forms, forms by known method by photolithographic etching etc.

Secondly, in the cleaning oven of 90 DEG C, carry out the preliminary drying of 10 minutes and form film. Secondly, use exposure machine (heightMedium pressure mercury lamp), be situated between every the photomask with the desired pattern such as contact hole pattern, light exposure is made as to 500J/m²And to instituteThe film obtaining carries out radiation exposure. Thereafter, use 0.40 quality % tetramethylammonium hydroxide aqueous solution and at 25 DEG C with coveringAfter liquid method is developed, the pure water carrying out 1 minute cleans. Remove unwanted part by developing, formation is formed withThe film of the regulation shape of contact hole. Further in baking oven, the rear baking carried out at 220 DEG C 1 hour processes and makes its sclerosis, shapeBecoming thickness is the dielectric film of 3.0 μ m.

Secondly,, for the substrate that is formed with dielectric film, use sputtering method and on dielectric film, form and comprise the transparent of ITO and leadElectricity layer. Secondly, by photoetching process, transparency conducting layer is carried out to etching, on dielectric film, form transparency electrode.

Carry out as described above and manufacture the array base palte of this example. In the array base palte of this example of gained, absolutelyThe desired position of velum forms the contact hole of desired size, realizes the electric connection of transparency electrode and drain electrode.

[embodiment 5]

The radiation-sensitive resin composition S-2 modulating in use-case 2, by the rear baking processing of carrying out in baking ovenTemperature is made as 180 DEG C, forms dielectric film in addition according to the method same with example 4 on substrate, forms transparency electrodeAnd carry out the manufacture of array base palte. In the array base palte of this example of gained, be formed with in the desired position of dielectric filmThe contact hole of desired size, realizes as the electric connection between transparency electrode and the drain electrode of pixel electrode.

[embodiment 6]

(thering is the manufacture of the array base palte of light alignment film)

In this example, the array base palte of gained in use-case 4, uses and comprises the radiation with light regiospecific baseThe crystal aligning agent of property polymer and form light alignment film.

First,, in the transparency electrode of the array base palte of example 4, be coated with as comprising and there is light orientation by circulatorIn the example 6 of No. 2009/025386 description of International Publication (WO) of the crystal aligning agent of the radioactivity-sensitive polymer of property baseThe crystal aligning agent A-1 recording. Secondly, on the hot plate of 80 DEG C, carry out, after the preliminary drying of 1 minute, nitrogen being carried out in insideIn the baking oven of displacement, at 180 DEG C, carry out the heating of 1 hour and form the film that thickness is 80nm. Secondly, use Hg-Xe lamp andGlan-Taylor prism, from the direction of 40 ° of inclinations for the direction perpendicular to substrate surface, irradiates this film coated surface200J/m²The polarisation ultraviolet ray of the open-wire line that comprises 313nm, manufacture the array base palte with light alignment film.

[embodiment 7]

(thering is the manufacture of the array base palte of light alignment film)

In this example, the array base palte of gained in use-case 5, similarly uses to comprise with example 6 to have light orientationProperty base radioactivity-sensitive polymer crystal aligning agent and form light alignment film, manufacture and there is the array base palte of light alignment film.

[embodiment 8]

(thering is the manufacture of the array base palte of vertical orientation film)

In this example, the array base palte of gained in use-case 4, uses to comprise and does not have a polyimides of light regiospecific baseCrystal aligning agent and form vertical orientation film.

First,, in the transparency electrode of the array base palte of example 4, be coated with as comprising and do not have a light orientation by circulatorProperty base the vertical orientation film of crystal aligning agent of polyimides form manufacture with AL60101(JSRCorporation). ItsInferior, on the hot plate of 80 DEG C, carry out after the prebake of 1 minute, in the baking oven that inside has been carried out to nitrogen replacement, at 180 DEG C, carry outThe heating of 1 hour and form the film that thickness is 80nm, manufactures the array base palte with vertical orientation film.

[embodiment 9]

In this example, the array base palte of gained in use-case 5, similarly uses to comprise with example 8 and does not have a light orientationProperty base polyimides crystal aligning agent and form vertical orientation film, manufacture and there is the array base palte of vertical orientation film.

The manufacture > of < liquid crystal display cells

[embodiment 10]

The array base palte of gained in use-case 7. And, prepare the colored filter base of manufacturing by known methodPlate. This colored filter substrate on transparency carrier by small colored pattern and black square red, green and blue this 3 lookBattle array is configured to clathrate, disposes transparent public electrode on colored pattern. And, in the common electrical of colored filter substrateExtremely go up the light alignment film that on array base palte, person is identical that is formed on forming with in example 6, make the subtend that is formed with alignment filmSubstrate. Use these a pair of substrates, after being fitted with sealant, inject TN liquid crystal and between substrate clamping liquid crystal layer, manufactureColor liquid crystal display device. The liquid crystal display cells of this example has the knot same with the liquid crystal display cells shown in above-mentioned Fig. 3Structure. The liquid crystal display cells of this example demonstrates excellent operation characteristic and display characteristic and reliability.

In addition, the present invention is not limited to above-mentioned each example, can be not departing from the scope of purport of the present inventionCarry out various distortion and implement.

Utilizability in industry

Array base palte of the present invention can by compared with prior art more the heating steps of low temperature manufacture, and haveHigh reliability. Therefore, array base palte of the present invention can use aptly and require the large of excellent display quality and reliabilityIn type LCD TV purposes etc.

Claims

1. an array base palte, is used in liquid crystal display cells, comprising:

Switch active element,

The dielectric film that configures on described switch active element,

The contact hole that forms on described dielectric film,

The pixel electrode that is electrically connected with described switch active element via described contact hole,

The alignment film forming on described pixel electrode,

Described array base palte is characterised in that: described dielectric film is by the radiation-sensitive resin composition institute of containing following compositionThe dielectric film forming:

[A] has the construction unit that comprises the represented base of following formula (1) and contains ring in same or different polymer moleculesThe polymer of the construction unit of oxygen base,

[B] photoacid generator and

Freely represented compound, phosphonium salt, mercaptan compound and the block isocyanate compound institute of following formula (C-1) of [C] choosingAt least a kind of compound of the group forming,

In formula (C-1), R⁷～R¹⁶Independent is respectively hydrogen atom, electron-withdrawing group or amino; Wherein, R⁷～R¹⁶In at least 1 beAmino; And the alkylene that all or part of of the hydrogen atom of above-mentioned amino can be also 2～6 by carbon number replaces; A be singly-bound,The alkylene that carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number are 2～6; Wherein, above-mentioned methyleneAll or part of of the hydrogen atom of base and alkylene also can be replaced by cyano group, halogen atom or fluoroalkyl;

Described alignment film is use the crystal aligning agent that comprises the radioactivity-sensitive polymer with light regiospecific base and comprise notAny number of in the crystal aligning agent of the polyimides of tool light regiospecific base and the alignment film of gained;

In formula (1), R¹And R²Independent is respectively hydrogen atom, alkyl, cycloalkyl or aryl, these alkyl, cycloalkyl or arylPart or all of hydrogen atom also can be substituted base and replace, and wherein, do not have R¹And R²Be the situation of hydrogen atom; R³Be alkyl, cycloalkyl, aralkyl, aryl or-M (R⁴)₃Represented base, part or all of the hydrogen atom of these bases also canReplace to be substituted base, wherein M is Si, Ge or Sn, R⁴For alkyl; R¹With R³Also can link and form cyclic ether.

2. array base palte according to claim 1, is characterized in that:

[B] photoacid generator comprises the represented oxime sulfonates base of following formula (2);

In formula (2), R^B1Be alkyl, cycloalkyl or aryl, part or all of the hydrogen atom of these bases also can be substitutedBase replaces.

3. array base palte according to claim 1 and 2, is characterized in that:

Described alignment film uses the crystal aligning agent that comprises the radioactivity-sensitive polymer with light regiospecific base to obtainAlignment film.

4. a liquid crystal display cells, is characterized in that comprising the array base palte according to described in any one in claims 1 to 3.

5. a manufacture method for array base palte, is characterized in that comprising:

The painting of the radiation-sensitive resin composition that [1] formation contains following composition on the substrate that is formed with switch active elementThe step of film:

[B] photoacid generator and

In formula (C-1), R⁷～R¹⁶Independent is respectively hydrogen atom, electron-withdrawing group or amino; Wherein, R⁷～R¹⁶In at least 1For amino; And the alkylene that all or part of of the hydrogen atom of above-mentioned amino can be also 2～6 by carbon number replaces; A is singleThe alkylene that key, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number are 2～6; Wherein, above-mentionedAll or part of of the hydrogen atom of methylene and alkylene also can be replaced by cyano group, halogen atom or fluoroalkyl;

[3] the described film that has irradiated radioactive ray in step [2] is developed, obtain the step of the film that is formed with contact holeSuddenly; And

[4] film of gained in step [3] hardened and form the step of dielectric film;

6. the manufacture method of array base palte according to claim 5, is characterized in that:

[B] photoacid generator comprises the represented oxime sulfonates base of following formula (2),

In formula (2), R^B1Be alkyl, cycloalkyl or aryl, part or all of the hydrogen atom of these bases also can be substituted baseReplace.

7. according to the manufacture method of the array base palte described in claim 5 or 6, it is characterized in that further comprising: 200 DEG C withThe step of lower formation alignment film.

8. the manufacture method of array base palte according to claim 7, is characterized in that:

Described is to use to comprise the radioactivity-sensitive polymer with light regiospecific base 200 DEG C of following steps that form alignment filmCrystal aligning agent and comprising do not have any number of in the crystal aligning agent of polyimides of light regiospecific base and join described in formingTo film.