CN101075089A - Method for forming pattern, color filter, structure material and liquid crystal display device - Google Patents
Method for forming pattern, color filter, structure material and liquid crystal display device Download PDFInfo
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- CN101075089A CN101075089A CN 200710104913 CN200710104913A CN101075089A CN 101075089 A CN101075089 A CN 101075089A CN 200710104913 CN200710104913 CN 200710104913 CN 200710104913 A CN200710104913 A CN 200710104913A CN 101075089 A CN101075089 A CN 101075089A
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Abstract
The invention provides a Method for forming pattern, color filter, characterized in that it has the following steps to form the colordisc part; it forms the phototonus resin bed consisting of the phototonus resin compounds on the substrate; it scans for exposure while modulates the plain edge based on pattern data so as to form the two dimensional image; it develops the phototonus resin bed which is exposure. The Gamma of the phototonus resin bed is 1-15, exposure energy profile of the exposure device in the pattern exposure step is 10-50.
Description
Technical field
The present invention relates to a kind of liquid crystal indicators such as small type mobile devices, giant display, the color filter that in this liquid crystal indicator, uses, structured material and pattern formation method of in the manufacturing of this color filter, using of being used for.
Background technology
Liquid crystal indicator is very compact and have in the past equal above performance as the CRT monitor of main flow, so replacing CRT monitor in recent years.
The coloured image that shows with liquid crystal indicator is to form by process as described below, that is: see through the light of the substrate that the color filter that is made of plurality of color etc. constitutes, directly make each chromatic colorant that constitutes this color filter, the photosynthetic image sample that becomes of painted plurality of color.Common so, at present 3 color pixels with the redness (R) that constitutes color filter, green (G), blue (B) form coloured image.And then, form the structured materials such as rib that the liquid crystal cells spacing remained certain clearance material or control liquid crystal aligning.
These pixels can utilize repetition to form method manufacturings such as resin bed, exposure and then development on substrate.Wherein, multiplicity is the number of look.As above-mentioned exposure method, except using exposed mask, method with exposures such as mercury vapor lamps, in recent years, above-mentioned exposed mask that need not high price and carry out maskless (maskless) exposure.As this maskless exposure, for example, there is the method for use polygon prism (polygon mirror) (for example to open the 2002-523905 communique with reference to the spy as the method for using laser such as semiconductor laser or limit modulation plain edge relative scanning.), use the method for DMD (Digital Micromirror Device (digitalmicromirrordevice)) (for example to open the 2004-56080 communique with reference to the spy.) etc.
But, in these maskless exposures, be difficult to make the fixed in shape of the pattern that will form, need further perfect.Particularly black matrix or gap material etc. need rectangular profile (profile) in nature at it.
Summary of the invention
The present invention proposes in view of above-mentioned shortcoming in the past just, promptly the object of the present invention is to provide a kind of liquid crystal indicator that can form the pattern formation method of the pattern of good shape, the color filter with pattern of good shape, structured material and use this color filter and structured material.
Above-mentioned problem in the past is to utilize following the present invention to realize.That is, pattern formation method of the present invention,
＜1〉a kind of pattern formation method is characterized in that, it is the pattern formation method that forms the pattern of color filter parts at least through the following stated operation, that is:
The photo-sensitive resin that forms the photo-sensitive resin that is made of photosensitive polymer combination on substrate forms operation;
With respect to described photo-sensitive resin, the limit is carried out relative scanning based on view data modulation plain edge and is exposed, and forms the pattern exposure operation of two dimensional image; With
The developing procedure that the described photo-sensitive resin that has exposed is developed,
The γ of described photo-sensitive resin is 1～15, and
The exposure energy profile (energyprofile) of the exposure device that uses in described pattern exposure operation is 10～50.
Wherein, described γ is: the survival rate of the thickness the when exposure energy in the time will carrying out pattern exposure to the photo-sensitive resin of certain thickness is made as E, exposure back development treatment is made as under the situation of Y, with the relation curveization between the survival rate of exposure energy E and thickness, in this curve, the survival rate Y of thickness becomes 50% point, and (survival rate at this point is made as Y
50, exposure energy is made as E
50) in E
50Slope (the Y of the straight line of ± Δ E
50+ Δ-Y
50-Δ)/(logE
50+ Δ-logE
50-Δ) value, described exposure energy profile is: the exposure energy E in the time of will carrying out pattern exposure to the photo-sensitive resin of certain thickness is made as 100%, with the related curveization between the location coordinate of exposure area and this E, in this curve, exposure energy becomes 50% point, and (coordinate at this point is made as P
50, exposure energy is made as E
50) in the slope (E of straight line
50+ Δ-E
50-Δ)/(P
50+ Δ-P
50-Δ) value.
＜2〉according to above-mentioned＜1〉described pattern formation method, it is characterized in that,
Described pattern exposure utilizes laser explosure device to carry out, and described exposure device possesses: light irradiating means; Optical modulator body, it has a plurality of acceptance from the light of described light irradiating means and the drawing section that penetrates; Microlens array, it is arranged with lenticule (microlens), and this lenticule has the aspheric surface of the aberration that the distortion (ひ ず body) that can revise the outgoing plane in the described drawing section causes.
＜3〉according to above-mentioned＜1〉described pattern formation method, it is characterized in that,
Described photosensitive polymer combination contains resin, monomer or oligomer, Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system and polymerization inhibitor.
＜4〉according to above-mentioned＜3〉described pattern formation method, it is characterized in that,
(Off エ ノ チ ア ジ Application) is Ji at least a in the phenoxazine (Off エ ノ キ サ ジ Application) for described polymerization inhibitor has the phenol hydroxyl for the being selected from compound, phenothiazine of (Off エ ノ one Le water acidic group).
＜5〉according to above-mentioned＜3〉or＜4〉described pattern formation method, it is characterized in that,
The content of described relatively monomer and oligomer, the content of described polymerization inhibitor is in the scope of 0.005～0.5 quality %.
＜6〉a kind of color filter is characterized in that,
Use above-mentioned＜1 〉～＜5 in any described pattern formation method make.
＜7〉a kind of structured material is characterized in that,
Use above-mentioned＜1 〉～＜5 in any described pattern formation method make.
＜8〉a kind of liquid crystal indicator is characterized in that,
Possess above-mentioned＜6〉described color filter.
＜9〉a kind of liquid crystal indicator is characterized in that,
Possess above-mentioned＜7〉described structured material.
Utilize the present invention, a kind of liquid crystal indicator that can form the pattern formation method of the pattern of good shape, the color filter with pattern of good shape, structured material and use this color filter and structured material can be provided.
Description of drawings
Fig. 1 is expression with the figure of the relation between the survival rate Y after the development of the log value of curve representation exposure energy E and photo-sensitive resin.
Fig. 2 is that expression is made as 100% with exposure energy E, the related figure between the location coordinate P of exposure area and its E.
Fig. 3 is the stereographic map of the outward appearance of the image exposing apparatus that uses among the present invention of expression.
Fig. 4 is the stereographic map of structure of the scanner (scanner) of the image exposing apparatus of presentation graphs 3.
Fig. 5 (A) is the vertical view that is illustrated in the exposure area that forms in the photosensitive material, (B) is the figure of arrangement of the exposure range (area) of each photohead of expression.
Fig. 6 is the stereographic map of brief configuration of photohead of the image exposing apparatus of presentation graphs 3.
Fig. 7 is the sectional view of the above-mentioned photohead of expression.
Fig. 8 is the partial enlarged drawing of the structure of expression digital micromirror device (DMD).
Fig. 9 (A) and (B) be the key diagram that expression is used to illustrate the work of DMD.
Figure 10 (A) and (B) be to be illustrated in DMD not under the situation of the situation of tilted configuration and tilted configuration, the configuration of post and the vertical view of sweep trace relatively expose.
Figure 11 (A) is the stereographic map of the structure of expression fiber array (fiber array) light source, (B) is the front view of the arrangement of the luminous point in the laser injection part of expression fiber array light source.
Figure 12 is the structural drawing of expression multimode (multimode) optical fiber.
Figure 13 is the vertical view that the structure of ripple LASER Light Source is closed in expression.
Figure 14 is the vertical view of the structure of expression laser module (module).
Figure 15 is the outboard profile of the structure of expression laser module shown in Figure 14.
Figure 16 is the partial front elevation view of the structure of expression laser module shown in Figure 14.
Figure 17 is the calcspar of the electric structure of the above-mentioned image exposing apparatus of expression.
Figure 18 (A) and (B) be the figure of example in the use zone of expression DMD.
Figure 19 is the figure of distortion of the reflecting surface of the expression micro mirror of representing to constitute DMD with level line.
Figure 20 is with curve representation figure about the distortion of the reflecting surface of this mirror on 2 diagonals of above-mentioned micro mirror.
Figure 21 is the front view (A) and the outboard profile (B) of the microlens array that uses in the above-mentioned image exposing apparatus of expression.
Figure 22 is lenticular front view (A) and the outboard profile (B) that expression constitutes above-mentioned microlens array.
Figure 23 is illustrated in 1 cross section the synoptic diagram based on above-mentioned lenticular spot condition on (B) in (A) and other cross sections.
Figure 24 a is illustrated in the image exposing apparatus of the present invention, simulates near the result's of the beam diameter of lenticular spot position figure.
Figure 24 b is illustrated in the figure that the analog result identical with Figure 24 a represented in other positions.
Figure 24 c is illustrated in the figure that the analog result identical with Figure 24 a represented in other positions.
Figure 24 d is illustrated in the figure that the analog result identical with Figure 24 a represented in other positions.
Figure 25 a is in the image exposing apparatus that is illustrated in the past, simulates near the result's of the beam diameter of lenticular spot position figure.
Figure 25 b is the figure that represents the analog result identical with Figure 25 a in other positions.
Figure 25 c is the figure that represents the analog result identical with Figure 25 a in other positions.
Figure 25 d is the figure that represents the analog result identical with Figure 25 a in other positions.
Figure 26 is the lenticular front view (A) and the outboard profile (B) of the formation microlens array that uses in other image exposing apparatus of the present invention of expression.
Figure 27 is the synoptic diagram based on the lenticular spot condition of Figure 26 of expression for (B) in (A) and other cross sections in 1 cross section.
Figure 28 is the front view (A) and the outboard profile (B) of lenticular another example of expression.
Figure 29 is the front view (A) and the outboard profile (B) of lenticular another example again of expression.
Figure 30 is the figure with the example of curve representation spherical lens shape.
Figure 31 is the figure with the example of the lenticular other lenses face shape of using among curve representation the present invention.
Figure 32 is the stereographic map of other examples of expression microlens array.
Figure 33 is the vertical view of another example of expression microlens array.
Figure 34 is the vertical view of another example again of expression microlens array.
Figure 35 is the figure of another example again of expression microlens array.
Figure 36 (A) is the example of expression along the sectional view of the optical axis of the structure of other different photoheads that show combination optical system, (B) being an example that is illustrated under the situation of not using microlens array etc. to the vertical view of the light image that is exposed the face projection, (C) is an example that is illustrated under the situation of using microlens array etc. to the vertical view of the light image that is exposed the face projection.
Embodiment
Pattern formation method of the present invention, it is characterized in that, it is the pattern formation method that forms the pattern of color filter parts at least through the following stated operation, that is: the photo-sensitive resin that forms the photo-sensitive resin that is made of photosensitive polymer combination on substrate forms operation; With respect to described photo-sensitive resin, the limit is carried out relative scanning based on view data modulation plain edge and is exposed, and forms the pattern exposure operation of two dimensional image; With the developing procedure that the described photo-sensitive resin that will expose develops, the γ of described photo-sensitive resin is 1～15, and the exposure energy profile of the exposure device that uses in described pattern exposure operation is 10～50.
Wherein, described γ is: the survival rate of the thickness the when exposure energy in the time will carrying out pattern exposure to the photo-sensitive resin of certain thickness is made as E, exposure back development treatment is made as under the situation of Y, relation curve between the survival rate of exposure energy E and thickness (graph) is changed, in this curve, the survival rate Y of thickness becomes 50% point, and (survival rate at this point is made as Y
50, exposure energy is made as E
50) in E
50Slope (the Y of the straight line of ± Δ E
50+ Δ-Y
50-Δ)/(logE
50+ Δ-logE
50-Δ) value, described exposure energy profile is: the exposure energy E in the time of will carrying out pattern exposure to the photo-sensitive resin of certain thickness is made as 100%, the location coordinate of exposure area is changed with the related curve (graph) between this E, in this curve, exposure energy becomes 50% point, and (coordinate at this point is made as P
50, exposure energy is made as E
50) in the slope (E of straight line
50+ Δ-E
50-Δ)/(P
50+ Δ-P
50-Δ) value.
By utilizing the exposure device of exposure energy profile in above-mentioned scope, the photo-sensitive resin of γ value in above-mentioned scope of photo-sensitive resin exposed, can form the good pattern of shape.
Below, at first above-mentioned γ value and above-mentioned exposure energy profile as important content of the present invention are narrated, then structure of the present invention is elaborated.
The γ of＜photo-sensitive resin 〉
Below the γ value of photo-sensitive resin is defined.
The survival rate of the thickness the when exposure energy in the time will carrying out pattern exposure to the photo-sensitive resin of certain thickness is made as E, exposure back development treatment is made as under the situation of Y, and logE and Y become curved line relation shown in Figure 1.In this curve, the survival rate Y of thickness become 50% point (below, be made as Y at the survival rate of this point
50, exposure energy is made as E
50) in E
50Slope (the Y of the straight line of ± Δ E
50+ Δ-Y
50-Δ)/(logE
50+ Δ-logE
50-Δ) value is γ.
Development treatment when in addition, utilizing following method to measure the γ value of above-mentioned photo-sensitive resin.
At first, under the situation that has thermoplastic resin or middle layer (comprising oxygen-proof membrane) etc. on the above-mentioned photo-sensitive resin, with 30 ℃ 50 seconds, flat burner pressure 0.04MPa, using triethanolamine is that developer solution (contains triethanolamine 30 quality % with the pure water dilution, polypropylene glycol, the glycerine monostearate, Tween-60, stearoyl ether amounts to and contains 0.1 quality %, the liquid of trade name: T-PD2 (Fujiphoto (strain) system) to 12 times (mixing with the ratio of 11 mass parts pure water)) spray development with 1 mass parts T-PD2, blow to substrate surface, get rid of liquid, remove this thermoplastic resin or middle layer etc.
Be positioned at photo-sensitive resin under the state of substrate surface, undertaken by following operation, that is: utilize spray to spray pure water 10 seconds to this substrate surface, carry out the pure water spray Cleaning for High Capacity, blow, the liquid that reduces on the substrate accumulates.Then, using sodium carbonate is the developer solution (sodium bicarbonate that contains 0.38 mol with the pure water dilution, 0.47 the sodium carbonate of mol, the nekal of 5 quality %, anionic surfactant, defoamer, stabilizing agent, trade name: T-CD1 (Fujiphoto (strain) system) is to 5 times liquid), with 29 ℃ 30 seconds, pyramid type nozzle pressure 0.15MPa, spray development, then, with pure water washing agent (is contained phosphate silicate non-ionic surfactant defoamer stabilizing agent, trade name: T-SD1 Fujiphoto (strain) system) is diluted to 10 times and use, with 33 ℃ 20 seconds, pyramid type nozzle pressure 0.02MPa, with the spray ejection, and then utilization has the rotating brush of nylon hair, the image that wiping forms is removed residue.
In the present invention, above-mentioned γ is 1～15th, necessary condition, and then be preferably 2～13, be preferably 3～10 especially.γ can not form the pattern of definite shape less than under 1 the situation, on the contrary, under 15 situation, the photo-sensitive resin muting sensitivityization, becoming needs exposure for a long time, produces rate variance.
In addition, be controlled at method in the above-mentioned scope, can enumerate the method for using polymerization inhibitor or monomer oligomer as γ with photo-sensitive resin.The back is described in detail polymerization inhibitor or monomer oligomer.
＜exposure energy profile 〉
In pattern formation method of the present invention, below the value of the exposure energy profile of exposure device is defined.
Exposure energy E in the time of will carrying out pattern exposure to the photo-sensitive resin of certain thickness is made as 100%, the location coordinate P of exposure area is changed with the related curve (graph) between its E, as shown in Figure 2.Fig. 2 is the energy profile that is illustrated in line width 10 μ m.In this curve, energy becomes=50% point (below, be made as P at the coordinate of this point
50, exposure energy is made as E
50) in the slope (E of straight line
50+ Δ-E
50-Δ)/(P
50+ Δ-P
50-Δ) value is exposure energy profile value.
As the main cause that enable line figure changes, can enumerate laser spots system (more little, the energy profile value is big more), lenticule focal length (focal length is more little, and exposure energy profile value is more little) etc.
In the present invention, the exposure energy profile is necessary for 10～50, but this exposure energy profile is preferably 10～40, and more preferably 10～35.If the exposure energy profile is less than 10, then becoming is difficult to form good pattern, if surpass 50, though can form good pattern, exposure device need become high performance, and cost increases.
＜pattern formation method 〉
Pattern in the present invention is to use photosensitive polymer combination (following be called simply sometimes " resin combination ".) pattern that forms, it is characterized in that, be included in the operation that forms resin bed on the substrate, carry out the operation of pattern exposure, the operation of development.
-photo-sensitive resin formation operation-
In above-mentioned formation method, as the method that on substrate, forms resin bed, can enumerate (a) and utilize application of resin method for compositions such as known applying device and (b) use resin transfer material, utilize method that laminating machine (laminator) attaches etc.In addition, at this coating method and laminating method are described, the back is described in detail resin combination and resin transfer material.
(a) utilize the coating of applying device
In the pattern formation method of the present invention, the coating of resin combination can utilize known coating method, and for example spin-coating method, curtain formula showering (curtain coat) method, slit coating process, dip coating, air knife blade coating (air knife coat) method, rolling method, wire bar rod are coated with (wire bar coat) method, intaglio coating process or utilize the coatings such as extrusion coating (extrusi connects coat) method of the use funnel of putting down in writing in No. 2681294 instructions of United States Patent (USP) (hopper).Wherein, preferred especially the use utilized the slit coating process that has slot-shaped nozzle (slit coating machine) coating in slot-shaped hole in liquid ejection part.In addition, as the preferred concrete example of above-mentioned slot-shaped nozzle, can enumerate the spy and open 2004-89851 communique, spy and open 2004-17043 communique, spy and open 2003-170098 communique, spy and open 2003-164787 communique, spy and open 2003-10767 communique, spy and open slot-shaped nozzle and the slit coating machine that 2002-79163 communique, spy are opened record in the 2001-310147 communique etc.
Utilizing coating to form under the situation of resin bed, as its thickness, be preferably 1.0～3.0 μ m, more preferably 1.0～2.5 μ m are preferably 1.0～2.0 μ m especially.
In addition, in pattern formation method of the present invention, form in the coating that utilizes resin combination under the situation of resin bed,, oxygen-proof membrane can be set further on this resin bed in order to improve the exposure sensitivity in the pattern exposure operation described later.As this oxygen-proof membrane, can enumerate and described later＜resin transfer material〉(middle layer) one in the identical oxygen-proof membrane of explanation.In addition, be not particularly limited, be preferably 0.5～3.0 μ m as the thickness of oxygen-proof membrane.
(b) utilize the attaching of laminating machine
Can use resin transfer material described later, use the roller or the flat board of heating and/or pressurization, on substrate, paste the attached resin bed that forms film like by pressing sticking or adding hot pressing.Particularly, can enumerate the spy opens flat 7-110575 communique, spy and opens that flat 11-77942 communique, spy are opened the 2000-334836 communique, the spy opens laminating machine and the laminating method of putting down in writing in the 2002-148794 communique, from the viewpoint of low foreign matter, the special method of putting down in writing in the flat 7-110575 communique of opening of preferred use.
-pattern exposure operation-
Pattern exposure utilization among the present invention is carried out based on the view data modulation plain edge relative scanning exposure method that forms two dimensional image that exposes by the limit.
In above-mentioned exposure method, (object that is called as " mask " that will use the material that does not see through exposure light or light is seen through slightly to form image is disposed on the light path of exposure light for the mask exposure that need not use in the past, make the Exposure mode of the pattern-like that photo-sensitive resin exposure in pairs should image) and so on mask, photo-sensitive resin is exposed into the Exposure mode of pattern-like.
Below above-mentioned exposure method is called " maskless exposure among the present invention ".
(explanation of light source)
Maskless exposure among the present invention uses ultrahigh pressure mercury lamp or laser instrument as light source.Ultrahigh pressure mercury lamp is to point to the discharge lamp of enclosing mercury in the quartz glass tube etc., is that the vapor pressure with mercury is set at high value, and (vapor pressure of the mercury during illumination becomes about 5MPa to the lamp of raising luminescence efficiency sometimes.W.Elenbaas:Light Sources, Philips Technical Library (light source, technology experiment chamber, Philip) 148-150).In the bright line spectrum, preferably use i ray (365nm), h ray (405nm), g ray (436nm), wherein, mainly use 365nm.
Laser is that the Light Amplificati of English connects the initial abbreviation that by Stimulated Emissi connects ofRadiati connection (utilizing the amplification of the light of being excited to penetrate of light), be to utilize the phenomenon of inducing ejaculation that in material, takes place with rotation distribution, utilize amplification, the vibration of light wave, creation coherence, monochromatic oscillator and amplifier that directivity is stronger.As exciting media, glass, liquid, pigment, gas etc. are arranged, can from these media, use known laser such as Solid State Laser (YAG laser), liquid laser, gas laser (argon laser, He-Ne laser, carbon dioxide laser, excimer laser), semiconductor laser.
Semiconductor laser is in the injection that utilizes carrier wave, and the ionization that excites/collide by electron beam, optical excitation etc. when electronics and hole flow out to the junction surface, are used the laser that penetrates the branch optical diode of coherent light and so in pn cross induction.The relevant light wavelength of this ejaculation is determined by semiconducting compound.
Wavelength of Laser is not particularly limited, and wherein, from the cost of exploring degree and laser aid, obtain the viewpoint of easness, semiconductor laser is preferably selected from the wavelength domain of 300～500nm, more preferably 340～450nm, preferred especially 405nm.
In addition, Solid State Laser can be enumerated the 532nm of YAG-SHG Solid State Laser.And then semiconductor excites Solid State Laser can enumerate 532355266nm, has the point of sensitivity, preferred 355nm from the past resist with Photoepolymerizationinitiater initiater.
Gas laser can use the 249nm of KrF laser, the 193nm of ArF laser.
In these light sources,, then, preferably select exposure wavelength to become the light source of 410nm from the viewpoint of the transmitance that improves the viewing area if consider situation about in the manufacturing process of display device, photosensitive material being exposed.
Then, the method to the modulation of the limit among the present invention plain edge relative scanning describes.
One of method that it is representative is, use DMD (Digital Micromirror Device, for example, 1987, the red Buick in Larry (ラ リ one ホ one Application ベ Star Network) doctor of Texas, USA (Texas) instrument (instruments イ Application ス Star Le メ Application Star) waited the photosemiconductor of exploitation) and so on the method for field modulator element of small mirror two-dimensional arrangements.
In this case, light from light source is radiated on the DMD by suitable optical system, come comfortable DMD to go up the reflected light of each mirror of two-dimensional arrangements,, on photographic layer, form the picture of the luminous point that is arranged in two dimension through having other optical system that lenticule is configured to the microlens array that array-like forms etc.In addition, in the present invention, preferably near the spot position of microlens array, dispose the mode that aperture (aperture) array forms.
Can be with form as described below, to exposing of photo-sensitive resin comprehensively, if that is: directly between luminous point and luminous point, do not expose, and make the picture of the luminous point of above-mentioned two-dimensional arrangements, the direction of Er Wei orientation slight inclination is shaken relatively, and the luminous point of rear row exposes between initial luminous point that is listed as and luminous point.By each mirror angle of control DMD, connect and turn-off (connection-shutoff) above-mentioned luminous point, can form picture pattern.By arrange using photohead with such DMD, substrate that can corresponding various width.
In above-mentioned DMD, the brightness of above-mentioned luminous point only turns on and off 2 grades, if but use mirror grade type modulator element, then can carry out the exposure of 256 grades.
On the other hand, other exemplary process of the method for the limit modulation plain edge relative scanning among the present invention are for using the method for polygon prism.Polygon prism (polyg connects mirror) is meant the rotating member of plane reflection face that has row around, and reflected illumination is from the light of light source on photographic layer, and catoptrical luminous point is by the rotation sweep of this level crossing.By substrate is moved relative to this direction of scanning with meeting at right angles, can comprehensively exposing to the photographic layer on the substrate.Can be by utilizing suitable method, connection is turn-offed from the intensity of light source or is controlled it as medium tone, forms picture pattern.In addition, can become multi beam, shorten sweep time by making light from light source.
Method as the modulation of the limit among the present invention plain edge relative scanning for example also can be suitable for following method.
The example that the use polygon prism of putting down in writing in the Te Kaiping 5-150175 communique is described; Obtain to the vision of record the part of the image of lower layer in the special table 2004-523101 communique (WO2002/039793), utilize the device that uses polygon prism, make the position of upper layer and the position consistency of lower layer, the example of exposure; The spy opens the example that device that the utilization of putting down in writing in the 2004-56080 communique has DMD exposes; The exposure device that possesses polygon prism, the spy that put down in writing in the special table 2002-523905 communique open the exposure device that possesses polygon prism, the spy that put down in writing in the 2001-255661 communique and open combination DMD, the LD that puts down in writing in the 2003-50469 communique, the example of multiple-exposure; The spy opens the example that the position of putting down in writing in the 2003-156853 communique that utilizes substrate changes the exposure method of exposure; The spy opens the example of the exposure method that the dislocation put down in writing in the 2005-43576 communique adjusts etc.
(relative scanning exposure)
Below relative scanning exposure is elaborated.
As the exposure method among the present invention, comprise the method for using ultrahigh pressure mercury lamp and using laser, but the preferred latter.
As the laser that uses among the present invention, can use known laser such as argon laser, He-Ne laser, semiconductor laser, carbon dioxide laser, YAG laser.
Wavelength of Laser is not particularly limited, wherein, from the viewpoint of the cost of the exploring degree of photographic layer (for example color filter etc.) and laser aid, the easness obtained, preferably select from the wavelength domain of 300～500nm, more preferably 340～450nm, preferred especially 405nm.
Beam diameter to laser is not particularly limited, wherein, and from the viewpoint of the exploring degree of photographic layer (for example color filter etc.), the 1/e of Gauss's (ガ ウ シ ア Application) light beam
2Value is preferably 5～30 μ m, more preferably 7～20 μ m.
Energy as laser beam is not particularly limited, and wherein, the viewpoint from time shutter and exploring degree is preferably 1～100mJ/cm
2, 5～20mJ/cm more preferably
2
The present invention must the correspondence image data carry out spatial light modulation to laser.For this reason, the preferred Digital Micromirror Device of using as spatial optical modulation element (DMD).
As above-mentioned exposure device, for example can use the following apparatus exposure.
[structure of image exposing apparatus]
As shown in Figure 3, this image exposing apparatus possesses laminar photosensitive material 150 absorption and remains on surperficial flat moving stage (stage) 152.Be provided with above the platform 156 in the thick plate-like that supports by 4 foots 154,2 guide rods 158 that extend along the objective table moving direction are set.Objective table 152 is configured to its major diameter direction towards the objective table moving direction, is supported for simultaneously and can utilizes guide rod 158 to move around.In addition, in this image exposing apparatus, be provided with the objective table drive unit 304 described later (with reference to Figure 17) that drives as the objective table 152 of subscan mechanism along guide rod 158.
Central portion in that platform 156 is set is provided with the door (gate) 160 of " コ " word shape, across the mobile route of objective table 152.The end of the door 160 of " コ " word shape is fixed in the two sides that platform 156 is set respectively.In this side clamping of 160 scanner 162 is set, the sensor 164 of a plurality of (for example 2) of the top of surveying photosensitive material 150 and rear end is set at opposite side.Scanner 162 and sensor 164 are installed in respectively on the door 160, the top of the mobile route that is disposed at objective table 152 of being fixed.In addition, scanner 162 and sensor 164 are connected with their not shown controller of control.
Shown in Fig. 4 and Fig. 5 (B), scanner 162 possesses a plurality of (for example 14) photohead 166 of the approximate matrix shape that is aligned to the capable n row of m (for example 3 row, 5 row).In this embodiment, according to the relation of the width of photosensitive material 150, at 4 photoheads 166 of the 3rd row configuration.In addition, when expression is arranged in each photohead of the capable n row of m, be labeled as photohead 166
Mn
The exposure range 168 that utilizes photohead 166 is for being the rectangular-shaped of minor face with the sub scanning direction.Thereby, be accompanied by moving of objective table 152, on photosensitive material 150, form the exposure area 170 of the band shape of each photohead 166.In addition, when representing to utilize the exposure area of each photohead that is arranged in the capable n row of m, be labeled as exposure area 168
Mn
In addition, as Fig. 5 (A) and (B), seamlessly arranging with the direction of sub scanning direction quadrature in order to make banded exposure area 170, each the row photohead that has been arranged in wire disposes to the orientation predetermined distance (the natural several times on the long limit of exposure range are 2 times in this example) that staggers respectively.So, at the exposure range 168 of the 1st row
11With exposure range 168
12Between the part that can not expose, can utilize the exposure range 168 of the 2nd row
21Exposure range 168 with the 3rd row
31Exposure.
As Figure 6 and Figure 7, photohead 166
11～166
MnThe Digital Micromirror Device (DMD) 50 that possesses Texas, USA (Texas) instrument company system is respectively modulated the spatial optical modulation element of the light beam of incident to each pixel as the correspondence image data.This DMD50 is connected with the controller described later 302 (with reference to Figure 17) that possesses data processing division and mirror drive control part.The data processing division of this controller 302 produces the control signal of answering each micro mirror in the control area of each photohead 166 being carried out drive controlling DMD50 based on the view data of input.In addition, for the zone that should control, aftermentioned.In addition, the mirror drive control part is based on the control signal that produces in view data portion, each photohead 166 controlled the angle of reflecting surface of each micro mirror of DMD50.In addition, to the control of the angle of reflecting surface, aftermentioned.
Light incident side at DMD50, configuration successively: the ejaculation end (luminous point) that possesses optical fiber is arranged in the fiber array light source 66 of the laser injection part of row along the direction corresponding with the long side direction of exposure range 168, the laser that correction is penetrated from fiber array light source 66, the lens that are concentrated on the DMD are 67, to the DMD50 reflecting ﹠ transmitting these lens be the mirror 69 of 67 laser.In addition, Fig. 6 shows that summarily lens are 67.
Show in detail as Fig. 7 institute, said lens is 67 to be made of structure as described below, that is: make the collector lens 71 that penetrates from fiber array light source 66 as the laser B optically focused of illumination light, be inserted into bar (rod) the shape optical integrator (opticalintegrator) (hereinafter referred to as the post integrator) 72 on the light path of the light that sees through this collector lens 71, and the place ahead that is disposed at this optical integrator 72 is the imaging len 74 of mirror 69 sides.Collector lens 71, post integrator 72 and imaging len 74 make the laser that penetrates from fiber array light source 66, become near intensity in directional light and the beam cross section by the light beam of homogenization, are incided DMD50.For the shape or the effect of this post integrator 72, describe in detail in the back.
In said lens is that the 67 laser B that penetrate reflect at mirror 69, by TIR total reflection (prism (prism)) 70, is irradiated to DMD50.In addition, in Fig. 6, omit this TIR prism 70.
In addition, in the light reflection side of DMD50, it is 51 that configuration makes the image optics in DMD50 laser light reflected B imaging on photosensitive material 150.Represent summarily that in Fig. 6 this image optics is 51, show and know clearly as Fig. 7, constitute by following structure, that is: be 52,54 the 1st image opticss systems that constitute by lens, by lens is 57,58 the 2nd image optics systems that constitute, the microlens array 55 that between these image optics systems, inserts, array of apertures 59.
Then, the beam diameter that is positioned at the laser B of each lenticule 55a is 41 μ m.
In addition, above-mentioned array of apertures 59 is that most apertures (opening) 59a that forms each lenticule 55a of corresponding microlens array 55 forms.In the present embodiment, the diameter of aperture 59a is 10 μ m.
Above-mentioned the 1st image optics is the DMD50 imaging to be zoomed into 3 times, imaging on microlens array 55.Then, the 2nd image optics system will be amplified to 1.6 times through the picture of microlens array 55, imaging on photosensitive material 150, projection.Thereby, whole for the DMD50 imaging zooms into 4.8 times, by imaging, project on the photosensitive material 150.
In addition, in this example, set prism to (prism pair) 73 between the 2nd image optics system and photosensitive material 150, move this prism to 73 by above-below direction in Fig. 7, the focus of regulating the picture on the photosensitive material 150 becomes possibility.In addition, in figure, photosensitive material 150 transmits to the subscan of arrow F direction.
As shown in Figure 8, DMD50 is on sram cell (storage unit (memory cell)) 60, and a plurality of (for example 1024 * 768) the small mirror (micro mirror) 62 that constitutes each pixel (picture point (pixel)) is aligned to the mirror device that lattice-shaped forms.In each picture point, at the micro mirror 62 of topmost setting, at the high material of surperficial AM aluminum metallization isoreflectance of micro mirror 62 by shore supports.In addition, the reflectivity of micro mirror 62 is more than 90%, and its arrangement pitches is for example 13.7 μ m at vertical and horizontal.In addition, under micro mirror 62, by the pillar that comprises the configuration of hinge (hinge) and yoke (yoke), be configured in the sram cell 60 of the CMOS of the Si-gate of making on the manufacturing line of common semiconductor memory (silic connects gate), integral body is made of monolithic (m connects olithic).
If to sram cell 60 supplied with digital signal of DMD50, then by the micro mirror 62 of shore supports, with the diagonal line substrate-side that the center disposes DMD50 relatively, tilt with the scope of ± α degree (for example ± 12 degree).Fig. 9 (A) expression micro mirror 62 be in as (connections) state of connection to+state that the α degree tilts, Fig. 9 (B) expression micro mirror 62 is in the state to-α degree inclination as (shutoff) state of shutoff.Thereby, as shown in Figure 8, by the inclination of the micro mirror 62 in each picture point of corresponding image signals control DMD50, to the laser B of DMD50 incident by vergence direction reflection to separately micro mirror 62.
In addition, Fig. 8 is the part that DMD50 is amplified in expression, micro mirror 62 is controlled as+the α degree or-example of the state of α degree.Utilize the above-mentioned controller 302 that is connected with DMD50, carry out the connection of each micro mirror 62 and turn-off control.In addition, on the direction that the micro mirror 62 laser light reflected B of off state advance, configuration absorber of light (not shown).
In addition, the preferred slight inclination of DMD50 is configured to its minor face and becomes viewpoint angle (for example 0.1 °～5 °) with sub scanning direction.Figure 10 (A) expression utilizes the track while scan of the reflected light picture (exposing light beam) 53 of each micro mirror when DMD50 is not tilted, and Figure 10 (B) expression utilizes the track while scan of the exposing light beam 53 when DMD50 is tilted.
Among the DMD50, the major diameter direction is arranged the micro lens array of a plurality of (for example 1024) micro mirror, arrange many groups (for example 756 groups) in the minor axis direction, and shown in Figure 10 (B), by DMD50 is tilted, utilize the become spacing P1 of the sweep trace when DMD50 is tilted of the spacing P2 of track while scan (sweep trace) of the exposing light beam 53 of each micro mirror narrow, can improve the exploring degree significantly.On the other hand, the pitch angle of DMD50 is small, so that the sweep trace W2 of DMD50 when tilting, the sweep trace W1 when DMD50 is tilted is roughly the same.
In addition, also become utilize that different micro lens arrays is overlapping, on the identical sweep trace of exposure (multiple-exposure).Like this, by making its multiple-exposure, the pettiness amount that can control the exposure position of relative positioning mark (alignmentmark) can realize high meticulous exposure.In addition, by little a spot of exposure position control, can the section of not having connect the connection eye between a plurality of photoheads that are arranged in main scanning direction poorly.
In addition, even replace making DMD50 to tilt, and stagger predetermined distance to the direction of sub scanning direction quadrature, each micro lens array is configured to staggered, also can obtain same effect.
Shown in Figure 11 A, fiber array light source 66 possesses a plurality of (for example 14) laser module 64, an end of multimode optical fiber 30 combines with each laser module 64.At the other end of multimode optical fiber 30, and clad (clad) diameter identical with core diameter and multimode optical fiber 30 combines less than the optical fiber 31 of multimode optical fiber 30.Know clearly as Figure 11 B and to show, the end of optical fiber 30 opposition sides of multimode optical fiber 31, along with the main scanning direction of sub scanning direction quadrature, arrange 7, be arranged in 2 row, constitute laser injection part 68.
Shown in Figure 11 B, 2 back up pads 65 that the laser injection part 68 that is made of the end of multimode optical fiber 31 is had an even surface sandwich, fixing.In addition, for the light of protecting multimode optical fiber 31 penetrates end face, be preferably in transparent fenders such as this end face configuration glass.The light of multimode optical fiber 31 penetrates end face owing to the optical density height, thus collect dust easily, easy deterioration, but, can prevent that dust from adhering to end face by the aforesaid fender of configuration, can also slow down deterioration in addition.
In this example, as shown in figure 12, the head portion of the laser emitting side of the multimode optical fiber 30 that optical fiber 31 that the clad diameter about long 1～30cm is little and clad diameter are big, coaxial combination.These optical fiber 30,31 are under the state of separately mandrel unanimity, and the incident end face by making optical fiber 31 and the ejaculation end face of optical fiber 30 are bonding, and combination.As mentioned above, the diameter of the core 31a of optical fiber 31 is identical size with the diameter of the core 30a of multimode optical fiber 30.
As multimode optical fiber 30 and optical fiber 31, also can be suitable for any one of step index (step index) type optical fiber, graded index (graded index) type optical fiber and compound optical fiber.For example, can use the step index type optical fiber of Mitsubishi Cable Ind Ltd's system.In this example, multimode optical fiber 30 and optical fiber 31 are step index type optical fiber, and multimode optical fiber 30 is clad diameter=125 μ m, core diameter is 50 μ m, NA=0.2, and the transmitance of incident end face coating=more than 99.5%, optical fiber 31 is clad diameter=60 μ m, and core diameter is 50 μ m, NA=0.2.
Wherein, the clad diameter of optical fiber 31 is not limited to 60 μ m.The clad diameter of a lot of optical fiber that use in the optical fiber source in the past is 125 μ m, but since the more little then depth of focus of clad diameter become dark more, so the clad diameter of multimode optical fiber be preferably below the 80 μ m, more preferably below the 60 μ m.On the other hand, under the situation that is single-mode fiber, it is 3～4 μ m that core diameter needs at least, so the clad diameter of optical fiber 31 is preferably more than the 10 μ m.In addition, from the point of joint efficiency, preferably make the core diameter of optical fiber 30 consistent with the core diameter of optical fiber 31.
The oscillation wavelength of GaN based semiconductor laser instrument LD1～LD7 all common (for example 405nm), maximum output also all common (for example multimode laser is 100mW, and single-mode laser is about 50mW).In addition, as GaN based semiconductor laser instrument LD1～LD7, in the scope of 350nm～450nm, can use the laser of the oscillation wavelength beyond above-mentioned 405nm.
As Figure 14 and shown in Figure 15, the above-mentioned ripple LASER Light Source of closing is with other optical parameters, is incorporated in the container (package) 40 of case shape of top opening.Container 40 possesses makes to become the container cover 41 that covers this opening, after handling in the degassing, imports sealing gas, with the opening of container cover 41 covered containers 40, seals the above-mentioned ripple LASER Light Source of closing in the space (seal cavity) airtightly closing of being formed by them.
At the bottom surface of container 40 fixed base (base) plate 42, the fiber support thing 46 in this incident end of the above-mentioned heating square 10 of installation, the collector lens stilt (holder) 45 that keeps collector lens 20 and maintenance multimode optical fiber 30 above substrate 42.Draw outside container from the opening that the wall at container 40 forms the ejaculation end of multimode optical fiber 30.
In addition, collimator lens stilt 44 is installed, is kept collimator lens 11～17 at this in the side of heating square 10.On the cross wall face of container 40, form opening, drawn outside the container to the wiring 47 that GaN based semiconductor laser instrument LD1～LD7 supplies with drive current by this opening.
In addition, in Figure 15,, in a plurality of GaN based semiconductor laser instruments, only give mark numbering on the GaN based semiconductor laser instrument LD7, in a plurality of collimator lens, only give mark numbering on the collimator lens 17 for fear of numerous and diverseization of figure.
Figure 16 is the figure of front shape of the mounting portion of the above-mentioned collimator lens 11～17 of expression.
On the other hand, as GaN based semiconductor laser instrument LD1～LD7, can use to possess the active layer that luminous width is 2 μ m, for example be the laser that 10 °, 30 ° state is sent out laser B1～B7 respectively with the extended corner of the direction at the direction parallel with active layer, right angle.These GaN based semiconductor laser LD1～LD7 is adapted to luminous point and arranges 1 row in the direction parallel with active layer.
Thereby, the laser B1～B7 that sends from each luminous point, as mentioned above, each collimator lens 11～17 at relative elongated shape, the direction that expanded-angle is big is consistent with length direction, under the direction that expanded-angle the is little state consistent with cross direction (with the direction of length direction quadrature), and incident.In other words, the width of each collimator lens 11～17 is 1.1mm, and length is 4.6mm, incides the horizontal direction of their laser B1～B7, the beam diameter of vertical direction is respectively 0.9mm, 2.6mm.In addition, collimator lens 11～17 is respectively, focal length f
1=3mm, NA=0.6, lens configuration spacing=1.25mm.
The parallel plane of collector lens 20 usefulness will possess the zone that comprises optical axis of aspheric round lens slenderly cuts, and forms orientation in collimator lens 11～17, is that horizontal direction is long, in the short shape of direction rectangular with it.This collector lens 20 is focal length f
2=23mm, NA=0.2.This collector lens 20 also can form by for example module shaping resin or optical glass.
Then, with reference to Figure 17, the electric structure in this routine image exposing apparatus is described.As shown here, modulation circuit 301 is connected with whole control part 300, and the controller 302 of control DMD50 is connected with this modulation circuit 301.In addition, the LD driving circuit 303 of driving laser module 64 is connected with whole control part 300.And then the objective table drive unit 304 that drives above-mentioned objective table 152 is connected with this integral body control part 300.
[work of image exposing apparatus]
Then, the work to above-mentioned image exposing apparatus describes.In each photohead 166 of scanner 162, the GaN based semiconductor laser instrument LD1～LD7 (with reference to Figure 13) that closes the ripple LASER Light Source that constitutes fiber array light source 66 is respectively with laser B1, B2, B3, B4, B5, B6 and the B7 of the ejaculation of diverging light state, and is parallel photochemical by the collimator lens 11～17 of correspondence respectively.Parallel photochemical laser B1～B7 is by collector lens 20 optically focused, brings together on the incident end face of the core 30a of multimode optical fiber 30.
In this example, constitute light-gathering optics system, constitute with multimode optical fiber 30 by this light-gathering optics system and close the ripple optical system by collimator lens 11～17 and collector lens 20.
That is, utilize collector lens 20 as described above the laser B1～B7 of optically focused incide the core 30a of this multimode optical fiber 30, propagate in the optical fiber, close ripple to 1 a laser B, penetrate from the optical fiber 31 that combines with the ejaculation end of multimode optical fiber 30.
In each laser module, laser B1～B7 is 0.9 to the joint efficiency of multimode optical fiber 30, under the situation that respectively is output as 50mW of GaN based semiconductor laser instrument LD1～LD7, to the optical fiber 31 that is arranged in array-like, what can obtain exporting 315mW (=50mW * 0.9 * 7) respectively closes ripple laser B.Thereby whole 14 root multimode fibers 31 can obtain the laser B of the output of 4.4W (=0.315W * 14).
When carrying out image exposure, the view data of corresponding exposing patterns is input to the controller 302 of DMD50 from modulation circuit shown in Figure 17 301, is remembered at frame memory (framememory) temporarily.This view data is the data with the concentration of each pixel of 2 values (having or not of the record of point (dot)) expression composing images.
At the objective table 152 of surface adsorption photosensitive material 150, utilize objective table drive unit 304 shown in Figure 17, along guide rail 158, with constant speed, from the upstream side of door 160 side shifting downstream.Objective table 152 is during by door 160 times, if utilize the sensor 164 that is installed on door 160 to detect the top of photosensitive material 150, the view data of being remembered in frame memory is divided into multirow, read successively, based on the view data that reads at data processing division, produce control signal respectively at each photohead 166.Then, utilize the mirror drive control part,,, control is connected/turn-offed to each micro mirror of DMD50 at each photohead based on the control signal that produces.In addition, in the case of this example, the above-mentioned micro mirror that becomes 1 pixel portions is of a size of 14 μ m * 14 μ m.
If to DMD55 irradiating laser B, when the micro mirror of DMD50 was on-state, it was 54,58 that the laser that is reflected utilizes lens, imaging on photosensitive material 150 from fiber array light source 66.Like this, the laser that penetrates from fiber array light source 66 is switched on/turn-offs in each pixel, and photosensitive material 150 exposes at the pixel cell (exposure range 168) with the roughly the same number of the use pixel count of DMD50.In addition, photosensitive material 150 is by moving with constant speed with objective table 152, and photosensitive material 150 utilizes scanner 162 to carry out subscan to the reverse direction of objective table moving direction, at each photohead 166, forms banded exposure area 170.
In addition, in this example, as Figure 18 (A) and (B), DMD50 has arranged the micro lens array of 1024 micro mirrors to main scanning direction, arrange 768 groups to sub scanning direction, but in this example, utilize controller 302 to be controlled to be only micro lens array (for example 1024 * 256 row) driving of some.
In this case, also can shown in Figure 18 (A), use the micro lens array of the central portion that is disposed at DMD50, also can shown in Figure 18 (B), use the micro lens array of the end that is disposed at DMD50.In addition, in a part of micro mirror, produce under the situation of defective, also can suitably change to use and not produce the micro lens array that the micro lens array etc. of defective uses according to situation.
There is the limit in the data processing speed of DMD50, owing to be directly proportional with the pixel count that uses, determines the modulating speed of per 1 row, so by only using the micro lens array of a part, accelerate the modulating speed of per 1 row.On the other hand, continuously relatively under the situation of the Exposure mode of plane of exposure moving exposure head, do not need all to use the pixel of sub scanning direction.
If utilize the subscan of the photosensitive material 150 of scanner 162 to finish, detect the rear end of photosensitive material 150 with sensor 164, objective table 152 utilizes objective table drive unit 304 so, along guide rail 158, revert to the initial point of the upstream side that is positioned at door 160, again along guide rail 158, from the upstream side of door 160 downstream side move with constant speed.
Then, illumination optical system as described below shown in Figure 7 is described, this illumination optical system is made of fiber array light source 66, collector lens 71, post integrator (rod integrator) 72, imaging len 74, catoptron 69 and TIR prism 70, to the laser B of DMD50 irradiation as illumination light.For example for forming the light transmission bar of square column, in the process of advancing in laser B portion's total reflection within it, intensity distributions is by homogenization in the beam cross section of this laser B for post integrator 72.Wherein, incident end face, ejaculation end face coating antireflection film at post integrator 72 improve transmitance.As mentioned above, as long as can make as intensity homogenization to heavens respectively in the beam cross section of the laser B of illumination light, the heterogeneity of illumination light intensity is disappeared, the high-accuracy image of exposure becomes possibility on photosensitive material.
At this, Figure 19 represents to measure the result of flatness of the reflecting surface of the micro mirror 62 that constitutes DMD50.In with figure, represent to link the equal height position of reflecting surface with level line, isocontour spacing is 5nm.Wherein, be 2 diagonals of micro mirror 62 with x direction shown in the figure and y direction, micro mirror 62 is the center with the turning axle that extends to the y direction, as described above rotation.In addition, Figure 20 (A) and (B) represent respectively along the height and position displacement of the reflecting surface of the micro mirror 62 of above-mentioned x direction, y direction.
As above-mentioned Figure 19 and shown in Figure 20, on the reflecting surface of micro mirror 62, have distortion, and if pay special attention to the catoptron central portion, the distortion of 1 diagonal (y direction) is greater than the distortion of another diagonal (x direction) so.So the shape in the spot position of the laser B of the lenticule 55a of microlens array 55 optically focused may deform.
In the image exposing apparatus of present embodiment, in order to prevent the problems referred to above, the lenticule 55a of microlens array 55 becomes and different in the past special shapes.Below this point is elaborated.
It (B) is respectively the front shape of the whole microlens array 55 of expression in detail and the figure of side view that (A) of Figure 21 reaches.In these figure, also mark the size of each several part of microlens array 55, their unit is mm.In the present embodiment, at first illustrated as this figure with reference to Figure 18, the micro mirrors 62 of 1024 * 256 row of DMD50 are driven, and are corresponding therewith, microlens array 55 constitute transversely arranged 1024 lenticule 55a be listed in vertically on be set up in parallel into 256 row.Wherein, in figure, represent with i, vertically representing with k the putting in order of microlens array 55 of transverse direction.
In addition, Figure 22 (A) reaches front shape and the side view of (B) representing 1 lenticule 55a in the above-mentioned microlens array 55 respectively.Wherein, in figure, in conjunction with the level line of expression lenticule 55a.The end face of the light emitting side of each lenticule 55a becomes the aspherical shape of the aberration that the distortion of the reflecting surface of revising above-mentioned micro mirror 62 causes.More specifically, in the present embodiment, lenticule 55a becomes toric lens (toric lens), the radius of curvature R x=-0.125mm of the direction of corresponding above-mentioned x direction on the optics, the radius of curvature R y=-0.1mm of the direction of corresponding above-mentioned y direction.
Thereby the spot condition of the laser B in the cross section parallel with above-mentioned x direction and y direction is substantially respectively as (A) of Figure 23 and (B).In other words, if in the relatively more parallel cross section with the x direction with the cross section parallel with the y direction in, the radius-of-curvature of the lenticule 55a in the latter's the cross section is littler, it is shorter that focal length becomes.
In addition, the face shape of the lenticule 55a that uses in the above-mentioned simulation is represented with following formula 1.
[several 1]
Wherein, in following formula, the curvature of Cx:x direction (=1/Rx), the curvature of Cy:y direction (=1/Ry), the distance apart from lens axis O of X:x directional correlation, the distance apart from lens axis O of Y:y directional correlation.
Comparison diagram 24a～d and Figure 25 a～d are as can be known, in the present embodiment, by making lenticule 55a become focal length in the cross section parallel, can suppress near the distortion of the beam shape this spot position less than the toric lens of the focal length in the cross section parallel with the x direction with the y direction.If like this, can there be the shifting ground meticulousr image that on photosensitive material 150, exposes to become possibility so.In addition, also as can be known in the present embodiment shown in Figure 24 a～d, the zone that beam diameter is little is wideer, and promptly the depth of focus is bigger.
In addition, under the distortion magnitude relationship of the central portion of the x of lenticule 62 direction and y directional correlation and above-mentioned opposite situation, if lenticule is made of the toric lens of the focal length in the cross section parallel with the x direction less than the focal length in the cross section parallel with the y direction, can there be the shifting ground meticulousr image that on photosensitive material 150, exposes to become possibility equally so.
In addition, near the array of apertures 59 that is disposed at the spot position of microlens array 55 is configured to the light of this each aperture 59a incident through the lenticule 55a corresponding with it.That is,, can prevent that light from not corresponding with it adjacent lenticule 55a to each aperture 59a incident, can improve extinction ratio by this array of apertures 59 is set.Wherein, these array of apertures 59 preferred disposition are in the focal position of microlens array 55.If like this, can prevent light incident more reliably from not corresponding adjacent lenticule 55a with it.
If the diameter of the aperture 59a of the array of apertures 59 that will be provided with for above-mentioned purpose originally is reduced to a certain degree, the effect of the distortion of the beam shape in the spot position of the lenticule 55a that also can be inhibited.But in this case, the light quantity of being blocked by array of apertures 59 becomes too much, and the light utilization ratio reduces.Relative therewith, lenticule 55a is under the situation of aspherical shape, because shading light not, so also can keep high light utilization ratio.
In addition, in the present embodiment, that be suitable for is the lenticule 55a of the different toric lens of the curvature of the x direction of 2 diagonals of corresponding micro mirror 62 on the optics and y direction, as being with shown in isocontour front shape, the side view that Figure 28 (A), (B) represent respectively, also can be suitable for the distortion of corresponding micro mirror 62, the lenticule 55 ' that the toric lens that the curvature of the xx direction of 2 edge directions of the micro mirror 62 of corresponding rectangle and yy direction differs from one another on the optics constitutes.
In addition, in the present embodiment, lenticule 55a becomes aspherical shape 2 times, but by adopting the more aspherical shape of high order (4 times, 6 times), can further optimize beam shape.And then, also can adopt consistent each other and so on the lens shape of the curvature of the above-mentioned x direction of distortion of reflecting surface of corresponding micro mirror 62 and y direction.Below the example of such lens shape is elaborated.
The lenticule of representing respectively among (A) of Figure 29, (B) 55 with isocontour front shape, side view "; the curvature of x direction and y direction is equal to each other; in addition, and this curvature becomes the curvature that corresponding distance h from the lens center is revised the curvature Cy of spherical lens.That is, become this lenticule 55 " the spherical lens shape on basis of lens shape, for example adopt shape with following formula (formula 2) regulation lens height (the optical axis direction position of lens curved surface) z.
[several 2]
Wherein, under the situation of above-mentioned curvature Cy=(1/0.1mm), to concerning the march linearize between lens height z and the distance h, as shown in figure 30.
Then, corresponding distance h from the lens center is as shown in the formula the curvature Cy that revises above-mentioned spherical lens shape shown in (formula 3), as lenticule 55 " lens shape.
[several 3]
Mathematical formulae 3
In this (formula 3), the meaning of z is identical with (formula 2), at this, uses 4 ordered coefficients a and 6 ordered coefficients b, revises curvature Cy.Wherein, above-mentioned curvature Cy=(1/0.1mm) 4 ordered coefficients a=1.2 * 10
3, 6 ordered coefficients a=5.5 * 10
7Situation under, to concerning the march linearize between lens height z and the distance h, as shown in figure 31.
In addition, in the embodiment described above, the end face of the light emergence face of lenticule 55a is aspheric surface (anchor ring), if but be that sphere, the opposing party are that the lenticule of cylindrical shape face constitutes microlens array by a side of 2 light transmission end faces, also can obtain the effect identical with above-mentioned embodiment.
And then, in the embodiment described above, the aspherical shape of the aberration that the lenticule 55a of microlens array 55 causes for the distortion of the reflecting surface of revising micro mirror 62, but replace adopting such aspherical shape, make each lenticule that constitutes microlens array, have the index distribution of the aberration that the distortion of the reflecting surface of revising micro mirror 62 causes, also can obtain same effect.
Such lenticule 155a's is one for example shown in Figure 26.Reaching (B) with figure (A) is to represent the front shape of this lenticule 155a and the figure of side view respectively, and as shown in the figure, the outer shape of this lenticule 155a is the parallel flat shape.Wherein, as mentioned above with the x among the figure, y direction.
In addition, Figure 27 (A) and (B) spot condition of the laser B during expression summarily utilizes in the cross section parallel with above-mentioned x direction and y direction of this lenticule 155a.This lenticule 155a has the index distribution that increases successively to foreign side from optical axis O, and in figure, the dotted line shown in lenticule 155a is interior represents that its refractive index begins to change wherein from optical axis O with the equidistant of regulation.As shown in the figure, if in the relatively more parallel cross section with the x direction with the cross section parallel with the y direction in, the side in the latter's the cross section, the ratio of the variations in refractive index of lenticule 155a is bigger, it is shorter that focal length becomes.Even use the microlens array that constitutes by such refractive index distribution lens, identical with the situation of above-mentioned microlens array 55, can obtain same effect.
In addition, as Figure 22 and lenticule 55a shown in Figure 23 in front, be shaped as in the aspheric lenticule at face, also can cooperate to give aforesaid index distribution, utilize face shape and index distribution both sides, revise the aberration that the distortion of the reflecting surface of micro mirror 62 causes.
Then, the image exposing apparatus to another embodiment among the present invention describes.The image exposing apparatus of present embodiment is compared with reference to the image exposing apparatus of Fig. 2～16 explanations with the front, replaces microlens array 55 shown in Figure 7, uses microlens array 255 shown in Figure 32, in addition, forms substantially the samely.Below this microlens array 255 is elaborated.
As illustrated with reference to Figure 19 and Figure 20 in front, there be distortion at the reflecting surface of the micro mirror 62 of DMD50, and should the existence of distortion variable quantity begin to become big trend successively to periphery from the center of micro mirror 62.So, the periphery of 1 diagonal (y direction) of micro mirror 62 distortion variable quantity, bigger than the periphery distortion variable quantity of other diagonals (x direction), it is remarkable that above-mentioned trend also becomes.
The image exposing apparatus of present embodiment is suitable for microlens array 255 shown in Figure 32 in order to address the above problem.In this microlens array 255, the lenticule 255a that is adapted to array-like has circular lens openings.Therefore, as mentioned above,,, can prevent the warpage in the spot position of the laser B of optically focused not by lenticule 255a optically focused at the periphery of the reflecting surface of the big micro mirror 62 of the distortion laser light reflected B of four sides portion particularly.Like this, can there be the shifting ground higher meticulous image of exposure to become possibility at photosensitive material 150.
In addition, in the present embodiment, shown in figure, at the back side from the transparent component 255b of the maintenance lenticule 255a of microlens array 255 (its usually and lenticule 255a become one), promptly form the opposing face of the face of lenticule 255a, state with the exterior lateral area of the lens openings of imbedding a plurality of lenticule 255a separated from one another forms light-proofness mask 255c.By such mask 255c is set, the periphery of the reflecting surface of micro mirror 62 especially the laser light reflected B of four sides portion in this absorption, block, so can prevent the warpage of the laser B of optically focused more reliably.
In the present invention, lenticular opening shape is not limited to aforesaid circle, for example shown in Figure 33, also can be suitable for and be set up in parallel the microlens array 455 that a plurality of lenticule 455a with elliptical openings form or be set up in parallel microlens array 555 that a plurality of lenticule 555a with opening of polygon (being quadrilateral at this) form etc. as shown in figure 34.Wherein, above-mentioned lenticule 455a and 555a are the lens that the part of common rotational symmetry spherical lens are cut into circular or polygonal shape, have the light-focusing function identical with common rotational symmetry spherical lens.
And then, in the present invention, can also be suitable for as Figure 35 (A), (B) and the microlens array (C).With the microlens array 655 shown in the figure (A), in the side that the laser B of transparent component 655b penetrates, be set up in parallel a plurality of lenticule 655as identical each other closely, form the mask 655c identical in a side of laser B incident and form with aforementioned mask 255c with above-mentioned lenticule 55a, 455a and 555a.Wherein, the mask 255 of Figure 32 forms at the Outboard Sections of lens openings, and relative therewith, this mask 655c is located in the lens openings.In addition, with the microlens array 755 shown in the figure (B), in the side that the laser B of transparent component 755b penetrates, ground separated from one another is also established and a plurality of lenticule 755a, forms mask 755c and form between these lenticules 755a.In addition, with the microlens array 855 of figure shown in (C),, with the state of contacting with each other and establish a plurality of lenticule 855a, form mask 855c at the periphery of each lenticule 855a and form in the side that the laser B of transparent component 855b penetrates.
In addition, aforementioned mask 655c, 755c and 855c all similarly have circular opening with aforementioned mask 255c, and like this, lenticular opening is defined as circle.
Particularly on the lens face of the micro mirror 855a shown in Figure 35 (C), form in the structure of mask 855c, lenticule 855a has aforesaid aspherical shape or index distribution, on this basis, under the situation of the image space of setting the 1st image optics system (lens for example shown in Figure 7 are 52,54) on the lens face of lenticule 855a, it is high especially that the light utilization ratio becomes, can be with more high-intensity light exposure photosensitive material 150.That is, in this case, utilize the 1st image optics system, the parasitic light that makes anaclasis become the distortion of the reflecting surface of micro mirror 62 to cause converges in 1 point at the image space of this optical system, and the light utilization ratio improves.
In addition, in the above-described embodiment, be suitable for LASER Light Source as light source, but be not limited thereto in the present invention, for example also can use lamp source such as mercury lamp to the spatial optical modulation element irradiates light.
In addition, in the above-described embodiment, prevented to constitute the reduction of the extinction ratio that the micro mirror 62 of DMD50 causes, but in the exposure device of the spatial optical modulation element beyond using DMD, a plurality of and establish under the situation that the pixel of this spatial optical modulation element forms, also can be suitable for the reduction that the present invention prevents this extinction ratio.
-developing procedure-
Developer solution as using is not particularly limited, can use the spy to open to put down in writing in the flat 5-72724 communique etc. known developer solution.In addition, developer solution preferably carries out the developer solution of the developing operation of lysotype, for example, contains the developer solution of the compound of pKa=7～13 with the concentration of 0.05～5mol/L, but also can add on a small quantity with glassware for drinking water blended organic solvent is arranged.
As blended organic solvent being arranged, can enumerate methyl alcohol, ethanol, isopropyl alcohol, n-propanol, butanols, diacetone alcohol, glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol one n-butyl ether, benzylalcohol, acetone, methyl ethyl ketone, cyclohexanone, 6-caprolactone, gamma-butyrolacton, dimethyl formamide, dimethyl acetamide, hexamethyl phosphoramide, ethyl lactate, methyl lactate, epsilon-caprolactams, N-Methyl pyrrolidone with glassware for drinking water.The concentration of this organic solvent is usually at 0.1～30 quality %.
In addition, in developer solution, can further add known surfactant.Surfactant concentrations is preferably in the scope of 0.01～10 quality %.
As the mode of developing, can use stirring (パ De Le) to develop, spray and develop, spray ﹠amp; Known method such as rotation is developed, infiltration development.
At this, illustrate that above-mentioned spray develops, can blow developer solution by utilizing the resin bed of spray after exposure, remove uncured portion.In addition, preferably before development, utilize spray to wait the low akaline liquid of dissolubility that blows resin bed, remove thermoplastic resin, middle layer etc.In addition, preferably after developing, utilize spray to blow washing agent etc.,, remove the development residue on one side on one side with scourings such as brushes.
Can use known cleaning fluid as cleaning fluid, preferably (contain phosphate silicate non-ionic surfactant defoamer stabilizing agent, trade name " T-SD1 (Fujiphoto) system ") or (containing sodium carbonate phenoxy group oxygen ethene is surfactant, trade name " T-SD2 (Fujiphoto system ").
The fluid temperature of developer solution is preferably 20～40 ℃, and the pH of developer solution is preferably 8～13 in addition.
In addition, the optimal way of developing procedure is illustrated in greater detail, as developing trough, the preferred use is provided with roller path etc., and substrate is moved horizontally.In order to prevent to be subjected to the damage of above-mentioned roller path, preferred formation photoresist on substrate.Substrate size surpasses under 1 meter the situation, if the horizontal feed substrate can be detained developer solution near the substrate center, there are the difference of developing in substrate center and peripheral part.For fear of this difference, preferably make the oblique inclination of substrate.The angle of inclination is preferably 5 °～30 °.
In addition, in order to obtain the developing result of homogeneous, the pure water of preferably before development, spraying, wetting photo-sensitive resin.In addition,, after development,, roughly remove excess liquid, implement washing again to substrate featheriness air in order to obtain the more developing result of homogeneous.And then, in order to obtain not having the high-quality picture of residue, before washing,,, spray ultrapure water with the pressure about 3～10MPa from the UHV (ultra-high voltage) washer jet, remove residue.If under the state that adheres to water droplet on the substrate, be delivered directly to the back operation, can pollute back each device in the operation so, perhaps residual contamination vestige on substrate, thus not preferred, so, preferably utilize squeegee etc. to get rid of and anhydrate, remove unnecessary water or water droplet.
After the experience developing procedure, can resin bed be solidified by operations such as experience post-exposure or thermal treatments, obtain pattern.
-post-exposure operation-
The viewpoints such as control that reduce from the film of the control of the concave-convex surface of the control of the hardness of the control of the cross sectional shape of image, image, image, image, preferably develop and thermal treatment between implement post-exposure.As the light source that post-exposure is used, can enumerate the ultrahigh pressure mercury lamp, high-pressure sodium lamp, metal halide lamp of record in the paragraph numbering 0074 that the spy opens the 2005-3861 communique etc.The summary of slave unit and economize the viewpoint of electric power, post-exposure preferably do not shine directly on the substrate by exposed mask etc. from the light of the light source of ultrahigh pressure mercury lamp or metal halide lamp etc.As required, can implement from the two sides, exposure in this case also can be in the above: 100～2000mJ/ square centimeter, below: in the scope of 100～2000mJ/ square centimeter, suitably regulate according to above-mentioned control purpose.
-heat treatment step-
By the experience heat treatment step, the monomer or the crosslinking chemical that contain in the above-mentioned photo-sensitive resin are reacted, thereby guarantee the hardness of pattern.The scope that heat treated temperature is preferred 150 ℃～250 ℃.During less than 150 ℃, hardness can become insufficient sometimes, when surpassing 250 ℃, coloring resin may take place, and excitation worsens.Preferred 10 minutes～150 minutes of heat treatment period.During less than 10 minutes, hardness tends to deficiency, when surpassing 150 ℃, coloring resin may take place, and excitation worsens.In addition, heat treated condition optimization is suitably selected according to the composition of photo-sensitive resin.
And then, preferably after forming whole patterns, carry out final thermal treatment, make the hardness stabilization.In this case, from the point of hardness, preferably implement with the temperature (for example 240 ℃) that improves.
＜photosensitive polymer combination 〉
Then, the resin combination that uses in pattern formation method of the present invention is described.
As this resin combination, preferably contain the photosensitive resin combination of (1) resin, (2) monomer or oligomer, (3) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system, (4) polymerization inhibitor.And then, when forming color filter, preferably wherein also contain the photosensitive polymer combination of (5) colorant.
Below the composition of these (1)～(5) is described successively.
(1) resin
As (following abbreviate as sometimes " bonding agent (binder) " of the resin among the present invention.), preferably have the alkali soluble polymer of carboxylic acid group or carboxylate group isopolarity base at side chain.As its example, can enumerate the spy open clear 59-44615 communique, special public clear 54-34327 communique, special public clear 58-12577 communique, special public clear 54-25957 communique, spy open clear 59-53836 communique and special open put down in writing in the clear 59-71048 communique and so on methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc.In addition, also can enumerate the cellulose derivative that side chain has the carboxylic acid group.In addition, also can preferably use material to polymkeric substance addition cyclic acid anhydride with hydroxyl.In addition, as more preferred example, the multiple copolymer of (methyl) acrylic acid benzyl ester of putting down in writing in No. 4139391 instructions of United States Patent (USP) and (methyl) acrylic acid multipolymer or (methyl) acrylic acid benzyl ester and (methyl) acrylic acid and other monomers.These binder polymers with polar group can use separately or use with the state that forms the composition of property polymkeric substance and usefulness with common film, the content of all solids composition of resin combination is generally 20～50 quality % relatively, is preferably 25～45 quality %.
(2) monomer or oligomer
As monomer among the present invention or oligomer, preferably have 2 above ethene unsaturated double-bonds, the monomer or the oligomer of addition polymerization take place under the irradiation of light.As such monomer and oligomer, can enumerate in molecule, have at least 1 can addition polymerization ethene unsaturated group, boiling point be the compound more than 100 ℃ under normal pressure.As its example, can enumerate monofunctional acrylate or simple function methacrylates such as polyglycol one (methyl) acrylate, polypropylene glycol one (methyl) acrylate and (methyl) acrylic acid phenoxy group ethyl ester; Polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the trimethylolethane trimethacrylate acrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl alcohol two (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, hexanediol two (methyl) acrylate, trimethylolpropane tris (acryloyl group propoxyl group) ether, three (acryloyl group ethoxy) isocyanates; On polyfunctional alcohols such as trimethylolpropane or glycerine after addition of ethylene oxide or the epoxypropane, the polyfunctional acrylic ester or the multifunctional methacrylates such as material of (methyl) acroleic acid esterification again.
And then can also enumerate special public clear 48-41708 communique, special public clear 50-6034 communique and the special urethane acrylate class of putting down in writing in the clear 51-37193 communique of opening; The spy opens the polyester acrylate class of putting down in writing in clear 48-64183 communique, special public clear 49-43191 communique and the special public clear 52-30490 communique; As polyfunctional acrylic ester or the methacrylates such as epoxy acrylate class of epoxy resin with (methyl) acrylic acid resultant of reaction.
Wherein, preferred trimethylolpropane triacrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate.
In addition, can also preferably enumerate the spy and open " the polymerizable compound B " that puts down in writing in the flat 11-133600 communique.
These monomers or oligomer can use or mix two or more uses separately, and the content of all solids composition of resin combination is generally 5～50 quality % relatively, is preferably 10～40 quality %.
(3) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system
As the method that resin combination is solidified, can use Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system in the present invention.Photoepolymerizationinitiater initiater is the compound of the spike of the polymerization of initiation multi-functional monomer described later under irradiation (the being also referred to as exposure) effect that can be created in luminous ray, ultraviolet ray, far ultraviolet, electron ray, X ray isoradial as used herein, can suitably select from known Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system.
As Photoepolymerizationinitiater initiater, as long as have the ability of the polymerization that causes above-mentioned polymerizable compound, be not particularly limited, can from known Photoepolymerizationinitiater initiater, suitably select, for example preferably to having photosensitive Photoepolymerizationinitiater initiater from the ultraviolet range to visible light, can produce the activator of living radical for producing certain effect, also can cause the initiating agent of cationic polymerization for the kind of corresponding monomer with light activated sensitizer.
In addition, above-mentioned Photoepolymerizationinitiater initiater preferably contains a kind at least at about 300～800nm (composition that more preferably has about 50 molar extinction coefficient in 330～500nm) the scope at least.
As above-mentioned Photoepolymerizationinitiater initiater, for example can enumerate halogenated hydrocarbon derivant (for example having the halogenated hydrocarbon derivant triazine skeleton, Ju You oxadiazole skeleton etc.), phosphine oxygen, six aryl di-imidazolines, 9 oxime derivate, organic peroxide, sulfocompound, ketonic compound, aromatic series salt, ketoxime ether etc.
As above-mentioned halogenated hydrocarbon compound with triazine skeleton, for example can enumerate if Lin Dengzhu, Bull.Chem.Soc.Japan, the compound, the spy that put down in writing open the J.Org.Chem. of the compound put down in writing in No. 3337024 instructions of compound, Deutsche Bundespatent of putting down in writing in the clear 53-133428 communique, F.C.Schaefer etc. in No. 1388492 instructionss of compound, BrP of 42,2924 (1969) records; Compound, the spy that compound, the spy that compound, the spies of 29,1527 (1964) records open the record of clear 62-58241 communique opens flat 5-281728 communique record opens the compound etc. of No. 4212976 communique record of compound, United States Patent (USP) of flat 5-34920 communique record.
And then, can also enumerate the vicinal polyketals De ニ Le compound of putting down in writing in No. 2367660 instructions of United States Patent (USP), the accidental cause ether compound of putting down in writing in No. 2448828 instructions of United States Patent (USP), the aromatic series accidental cause compound of putting down in writing in No. 2722512 instructions of United States Patent (USP) with α-hydrocarbon replacement, the polynucleation quinone compound of putting down in writing in No. 3046127 instructions of United States Patent (USP) and No. 2951758 instructions of United States Patent (USP), the spy opens the organoboron compound of putting down in writing in the 2002-229194 communique, free-radical generating agent, the triarylsulfonium salt salt of antimony hexafluoride or hexafluorophosphate (for example with), salt compound (for example (phenyl thio-phenyl) diphenyl sulfonium salt etc.) (is effective as cationic polymerization initiators), the international salt compound that discloses record in the 01/71428th trumpeter's volume (pamphlet) etc.
As above-mentioned if Lin Dengzhu, Bull.Chem.Soc.Japan, 42, the compound of 2924 (1969) records for example can be enumerated 2-phenyl-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-chlorphenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-three)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-methoxyphenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(2, the 4-dichlorophenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2,4,6-three (trichloromethyl)-1,3, the 5-triazine, 2-methyl-4, two (trichloromethyl)-1,3 of 6-, the 5-triazine, 2-n-nonyl-4, two (trichloromethyl)-1,3 of 6-, 5-triazine and 2-(α, α, β-three chloroethyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-etc.
As the compound of putting down in writing in No. 1388492 instructions of above-mentioned BrP, for example can enumerate 2-styryl-4, two (trichloromethyl)-1 of 6-, 3,5-triazine, 2-(4-methyl styrene base)-4, two (trichloromethyl)-1,3 of 6-, 5-triazine, 2-(4-methoxyl-styrene)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-methoxyl-styrene)-4-amino-6-trichloromethyl-1,3,5-triazine etc.
Open the compound of putting down in writing in the clear 53-133428 communique as above-mentioned spy; for example can enumerate 2-(4-methoxyl-naphthalene-1-acyl group)-4; two (trichloromethyl)-1 of 6-; 3, the 5-triazine; 2-(4-ethoxy-naphthalene-1-acyl group)-4, two (trichloromethyl)-1 of 6-; 3; the 5-triazine; 2-[4-(2-ethoxyethyl group)-naphthalene-1-acyl group]-4, two (trichloromethyl)-1,3 of 6-; the 5-triazine; 2-(4; 7-dimethoxy-naphthalene-1-acyl group)-4, two (trichloromethyl)-1,3 of 6-; 5-triazine and 2-(acenaphthene is (ア セ Na Off ト)-5-acyl group also)-4; two (the trichloromethyl)-1,3,5-triazines of 6-etc.
As the compound of putting down in writing in No. 3337024 instructions of above-mentioned Deutsche Bundespatent, for example can enumerate 2-(4-styryl phenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-(4-methoxyl-styrene) phenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(1-naphthyl ethenylidene phenyl)-4, two (trichloromethyl)-1,3 of 6-, the 5-triazine, 2-chlorostyrene base phenyl-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-thiophene-2-ethenylidene phenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-thiophene-3-ethenylidene phenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-furans-2-ethenylidene phenyl)-4, two (trichloromethyl)-1,3 of 6-, 5-triazine and 2-(4-coumarone-2-ethenylidene phenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-etc.
J.Org.Chem. as above-mentioned F.C.Schaefer etc.; The compound of 29,1527 (1964) records for example can be enumerated 2-methyl-4, two (the trisbromomethyl)-1,3,5-triazines, 2 of 6-, 4,6-three (trisbromomethyl)-1,3,5-triazine, 2,4,6-three (two bromomethyls)-1,3,5-triazine, 2-amino-4-methyl-6-three (bromomethyl)-1,3,5-triazine and 2-methoxyl-4-methyl-6-trichloromethyl-1,3,5-triazines etc.
Open the compound of putting down in writing in the clear 62-58241 communique as above-mentioned spy, for example can enumerate 2-(4-phenylacetylene base phenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-naphthyl-1-ethylphenyl-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-(4-three ethinyls) phenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-(4-methoxyphenyl) ethynyl phenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-(4-isopropyl phenyl ethinyl) phenyl)-4, two (trichloromethyl)-1,3 of 6-, the 5-triazine, 2-(4-(4-ethylphenyl ethinyl) phenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-etc.
Open the compound of putting down in writing in the flat 5-281728 communique as above-mentioned spy, for example can enumerate 2-(4-trifluoromethyl)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine, 2-(2, the 6-difluorophenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(2, the 6-dichlorophenyl)-4, two (trichloromethyl)-1,3 of 6-, 5-triazine, 2-(2, the 6-dibromo phenyl)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine etc.
Open the compound of putting down in writing in the flat 5-34920 communique as above-mentioned spy, for example can enumerate 2, two (trichloromethyl)-6-[4-(N of 4-, N-di ethoxy carbonyl methylamino)-and the 3-bromophenyl]-1,3, trihalomethyl group-s-triaizine compounds and then 2,4 of putting down in writing in 5-triazine, No. 4239850 instructions of United States Patent (USP), 6-three (trichloromethyl)-s-triazine, 2-(4-chlorphenyl)-4, two (the trisbromomethyl)-s-triazines of 6-etc.
As the compound of putting down in writing in No. 4212976 instructions of above-mentioned United States Patent (USP).For example can enumerate compound (2-trichloromethyl-5-phenyl-1,3 for example, 4-oxadiazole, the 2-trichloromethyl-5-(4-chlorphenyl)-1 of Ju You oxadiazole skeleton, 3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-trisbromomethyl-5-phenyl-1,3,4-oxadiazole, 2-trisbromomethyl-5-(2-naphthyl)-1,3, the 4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxyl-styrene)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxy styryl)-1,3,4-oxadiazole, 2-three bromos (プ ロ メ) methyl-5-styryl-1,3,4-oxadiazole etc.) etc.
As the 9 oxime derivate that preferably uses in the present invention, for example can enumerate 3-benzoyl imino group fourth-2-ketone, 3-acetate imino group fourth-2-ketone, 3-propionyloxy imino group fourth-2-ketone, 2-acetate imino group penta-3-ketone, 2-acetate imino group-1-phenyl third-1-ketone, 2-benzoyl imino group-1-phenyl third-1-ketone, 3-(4-tosyl oxygen) imino group fourth-2-ketone and 2-ethoxy carbonyl oxyimino group-1-phenyl third-1-ketone etc.
In addition; as the Photoepolymerizationinitiater initiater beyond above-mentioned; can enumerate acridine derivatives (9-phenylacridine for example; 1; 7-two (9; 9 '-acridinyl) heptane etc.); N-phenylglycine etc.; poly-halogen compounds (carbon tetrabromide for example; phenyl trisbromomethyl sulfone; phenyl trichloromethyl ketone etc.); Coumarins (3-(2-coumarone formoxyl)-7-diethyl amino coumarin for example; 3-(2-coumarone formoxyl)-7-(1-pyrrolidinyl) cumarin; 3-benzoyl-7-diethyl amino coumarin; 3-(2-methoxybenzoyl)-7-diethyl amino coumarin; 3-(4-dimethylamino benzoyl)-7-diethyl amino coumarin; 3; 3 '-carbonyl two (5; 7-two-positive propoxy cumarin); 3; 3 '-carbonyl two (7-diethyl amino coumarin); 3-benzoyl-ayapanin; 3-(2-furoyl)-7-diethyl amino coumarin; 3-(4-diethylamino cinnamoyl)-7-diethyl amino coumarin; 7-methoxyl-3-(3-pyridine radicals carbonyl) cumarin; 3-benzoyl-5; 7-dipropoxy cumarin; 7-benzotriazole-2-acyl group cumarin; also have the spy to open flat 5-19475 number; Te Kaiping 7-271028 number; the spy opens 2002-363206 number; the spy opens 2002-363207 number; the spy opens 2002-363208 number; the spy opens the coumarin compound of record in the 2002-363209 communique etc. etc.); amine (4-dimethylamino ethyl benzoate for example; 4-Dimethylaminobenzene n-buty formate; 4-dimethylamino benzoic acid phenethyl ester; 4-dimethylamino benzoic acid 2-phthalimido ethyl ester; 4-dimethylamino benzoic acid methacryloxyethyl ester; cyclopentane two (4-dimethylamino benzoate); 3-dimethylamino benzoic acid phenethyl ester; the cyclopentane ester; the 4-dimethylaminobenzaldehyde; 2-chloro-4-dimethylaminobenzaldehyde; 4-dimethylamino benzylalcohol; ethyl (4-dimethylamino benzoyl) acetic acid esters; 4-piperidyl acetophenone; 4-dimethylamino benzoin; N; N-dimethyl-4-dimethyl methyl aniline; N; N-diethyl-3-phenetidine; tribenzylamine; dibenzyl aniline; N-methyl-N-phenylbenzyl amine; 4-bromo-N; the N-dimethylaniline; tridodecylamine; amino glimmering hydro carbons (ODB; ODBII etc.); crystal violet lactone; leuco crystal violet etc.); acyl group phosphine oxygen class (for example two (2; 4; 6-trimethylbenzene formyl)-the phenyl phosphine oxygen; two (2; 6-dimethoxy benzoyl)-2; 4; 4-trimethyl-amyl group phenyl phosphine oxygen; LucirinTPO etc.); aromatic hydrocarbons alkene metal derivative class (for example two (η 5-2; 4-cyclopentadienyl-1-acyl group)-two (2,6-difluoro 3-(1H-pyrroles-1-acyl group)-phenyl) titanium; η 5-cyclopentadienyl-η 6-cumenyl-iron (1+)-hexafluorophosphate (1-) etc.); the spy opens clear 53-133428 communique; special public clear 57-1819 communique; with compound of putting down in writing in 57-6096 communique and No. 3615455 instructions of United States Patent (USP) etc.
As above-mentioned ketonic compound, for example can enumerate Benzophenone, 2-methylbenzene ketone, 3-methylbenzene ketone, 4-methylbenzene ketone, 4-methoxybenzene ketone, the 2-Win4692, the 4-Win4692,4-bromobenzene ketone, 2-carboxyl Benzophenone, 2-ethoxy carbonyl Benzophenone, benzophenonetetracarboxylic acid or its tetramethyl ester, 4,4 '-two (dialkyl amido) Benzophenone class (for example 4,4 '-two (dimethylamino) Benzophenone, 4,4 '-two (dicyclohexyl amino) Benzophenone, 4,4 '-two (diethylamino) Benzophenone, 4,4 '-two (dihydroxy ethyl amino) Benzophenone, 4-methoxyl-4 '-dimethylamino Benzophenone, 4,4 '-two (dihydroxy ethyl amino) Benzophenone, 4-dimethylamino Benzophenone, 4-dimethylamino acetophenone, dibenzoyl, anthraquinone, 2-tert-butyl group anthraquinone, 2-methylanthraquinone, phenanthrenequione, xanthone, thioxanthones, 2-chloro-thioxanthones, 2, the 4-diethyl thioxanthone, Fluorenone, 2-benzyl-dimethylamino-1-(4-morpholino phenyl)-1-butanone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino-1-acetone, 2-hydroxy-2-methyl [4 (1-methyl ethylene) phenyl] propyl alcohol oligomer, benzoin, benzoin ethers (benzoin methylether for example, benzoin ethyl ether, the benzoin propyl ether, benzoin iso-propylether, the benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro-acridine ketone, N-methylacridine ketone, N-butyl acridone, N-butyl-chloro-acridine ketone etc.
As the content of above-mentioned Photoepolymerizationinitiater initiater, all solids composition in the above-mentioned relatively photosensitive composite is preferably 0.1～50 quality %, 0.5～30 quality % more preferably, preferred especially 1～20 quality %.
If use the content of recently representing above-mentioned Photoepolymerizationinitiater initiater with the quality of above-mentioned polymerizable compound, be preferably Photoepolymerizationinitiater initiater/polymerizable compound=0.01～0.2, more preferably 0.02～0.1, be preferably 0.03～0.08 especially.If surpass this scope, can produce the development residue so, play perhaps takes place be out of order, if less than this scope, can not obtain sufficient sensitivity so sometimes.
In addition, in order to adjust luminous sensitivity or the wavelength photoreceptor when above-mentioned photographic layer exposes described later, except above-mentioned Photoepolymerizationinitiater initiater, can also add sensitizer.
Above-mentioned sensitizer can suitably be selected according to luminous ray or the ultraviolet light visible light laser etc. as light irradiating means described later.
Above-mentioned sensitizer becomes excited state under the effect of active energy ray, can produce useful bases such as free radical or acid by interact (for example energy moves, electronics moves etc.) with other materials (for example free radical generating agent, acid-producing agent etc.).
As above-mentioned sensitizer; be not particularly limited; can from known sensitizer, suitably select according to purpose; for example can enumerate known Ppolynuclear aromatic class (pyrene for example; penta-1-alkene-3-alkynes; 9; the 10-benzophenanthrene); oxa anthracenes (fluorescein for example; tetrabromofluorescein; erythromycin; rhodamine B; Luo Si agar (ロ one ズ ベ Application ガ Le)); cyanine class (indoles carbocyanine for example; the thiophene carbocyanine; the oxa-carbocyanine); part cyanines class (part cyanines for example; carbonyl part cyanines); thiazide (thionine for example; methylenum careuleum; toluidine blue); acridine (acridine orange for example; chloroflavin; acridine yellow); anthraquinone class (for example anthraquinone); this overstates mother's (ス Network ア リ ウ system) class (for example this overstates mother); acridine ketone (acridone for example; chloro-acridine ketone; N-methylacridine ketone; N-butyl acridone; N-butyl-chloro-acridine ketone etc.); Coumarins (3-(2-coumarone formoxyl)-7-diethyl amino coumarin for example; 3-(2-coumarone formoxyl)-7-(1-pyrrolidinyl) cumarin; 3-benzoyl-7-diethyl amino coumarin; 3-(2-methoxybenzoyl)-7-diethyl amino coumarin; 3-(4-dimethylamino benzoyl)-7-diethyl amino coumarin; 3; 3 '-carbonyl two (5; 7-two-positive propoxy cumarin); 3; 3 '-carbonyl two (7-diethyl amino coumarin); 3-benzoyl-ayapanin; 3-(2-furoyl)-7-diethyl amino coumarin; 3-(4-diethylamino cinnamoyl)-7-diethyl amino coumarin; 7-methoxyl-3-(3-pyridine radicals carbonyl) cumarin; 3-benzoyl-5; 7-dipropoxy cumarin etc.; in addition, can also enumerate the spy opens flat 5-19475 number; Te Kaiping 7-271028 number; the spy opens 2002-363206 number; the spy opens 2002-363207 number; the spy opens 2002-363208 number; the spy opens and waits coumarin compound of putting down in writing in each communique etc. for 2002-363209 number).
As the combination of above-mentioned Photoepolymerizationinitiater initiater and above-mentioned sensitizer, for example can enumerate the spy and open the electronics mobile model initiation system combinations of putting down in writing in the 2001-305734 communique such as [(1) electronics supply-type initiating agent and sensitizing dyestuff, (2) electronics acceptance type initiating agent and sensitizing dyestuff, (3) electronics supply-type initiating agent, sensitizing dyestuff and electronics acceptance type initiating agents (ternary initiating agent)].
As the content of above-mentioned sensitizer, the whole compositions in the above-mentioned relatively photosensitive composite are preferably 0.05～30 quality %, and more preferably 0.1～20 quality % is preferably 0.2～10 quality % especially.If this content is less than 0.05 quality %, the sensitivity to active energy ray so sometimes reduces, and exposure process expends time in, and throughput rate reduces, if surpass 30 quality %, above-mentioned sensitizer is played out from above-mentioned photographic layer when preserving so sometimes.
Above-mentioned Photoepolymerizationinitiater initiater can use separately a kind or and with more than 2 kinds.
More preferred example as above-mentioned Photoepolymerizationinitiater initiater, can enumerate in exposure described later the composite photoinitiator of laser, the above-mentioned phosphine oxygen class of combination, above-mentioned alpha-aminoalkyl ketone that can corresponding wavelength 405nm, above-mentioned halogenated hydrocarbon compound with triazine skeleton and the amines as sensitizer described later, six aryl di-imidazolinium compounds, perhaps dichloro titanium alkene (チ ノ セ Application) etc.
(4) polymerization inhibitor
The γ value of the photo-sensitive resin among the present invention can be passed through kind or its amount control of the polymerization inhibitor of use.In addition, polymerization inhibitor is that the polymerization of playing producing from above-mentioned Photoepolymerizationinitiater initiater under the effect of above-mentioned exposure causes the free radical composition, implement hydrogen supply (or being subjected to hydrogen), energy supply (or being subjected to energy), power supply (or being subjected to electronics) etc., make polymerization cause the free radical inactivation, forbid the material of the effect that polymerization causes.
As above-mentioned polymerization inhibitor, can enumerate and have the right compound of isolated electron (oxygen for example, nitrogen, sulphur, compounds such as metal), has the compound (for example aromatics) of pi-electron etc., viewpoint from control γ value, particularly, the compound that preferably has the phenol hydroxyl, phenothiazine phenoxazine etc. has the compound of imino group, compound with nitro, has nitroso compound, compound with aromatic rings, compound with heterocycle has the compound (comprising the coordination compound with organic compound) of metallic atom etc.Wherein, preferred especially from having the compound of phenol hydroxyl, that selects in the phenothiazine, phenoxazine is at least a.
As above-mentioned compound with phenol hydroxyl, be not particularly limited, can suitably select according to purpose, for example preferably have the compound of 2 phenol hydroxyls at least.At least have in the compound of 2 phenol hydroxyls at this, at least 2 phenol hydroxyls can be substituted on same aromatic rings, also can be substituted on same intramolecular distinct fragrance ring.
The above-mentioned compound that has 2 phenol hydroxyls is at least for example more preferably used the compound of following structural formula (1) expression.
[changing 1]
Structural formula (1)
In the said structure formula (1), Z represents substituting group, and m represents the integer more than 2, and n represents the integer more than 0.This m and n are preferably the integer of m+n=6.In addition, n is under the situation of the integer more than 2, and above-mentioned Z can be same to each other or different to each other.
In addition, if above-mentioned m less than 2, exploring degree possible deviation so.
As the above-mentioned substituting group of representing with Z; for example can enumerate carboxyl; sulfo group; cyano group halogen atom (fluorine atom for example; the chlorine atom; bromine atoms); hydroxyl; the alkoxy carbonyl of carbon number below 30 (methoxycarbonyl group for example; carbethoxyl group; benzyloxycarbonyl group); the aryloxycarbonyl (for example phenyloxycarbonyl) of carbon number below 30; the alkyl sulfonyl-amino carbonyl of carbon number below 30 (mesyl amino carbonyl for example; the octyl group sulfonyl amino carbonyl); aryl sulfonyl amino carbonyl (for example tosyl amino carbonyl); the amide group sulfonyl of carbon number below 30 (Benzamido sulfonyl for example; the acetamido sulfonyl; pivaloyl amido sulfonyl); the alkoxy of carbon number below 30 (methoxyl for example; ethoxy; benzyloxy; the phenoxy group ethoxy; the benzene ethoxy); the arylthio of carbon number below 30; alkylthio group (thiophenyl for example; methyl mercapto; ethylmercapto group; dodecane sulfenyl etc.); the aryloxy group of carbon number below 30 (phenoxy group for example; to toloxyl; the 1-naphthoxy; 2-naphthoxy etc.); nitro; the alkyl of carbon number below 30; alkyl oxy carbonyl oxygen (methoxy carbonyl oxygen base for example; stearic oxygen base carbonyl oxygen base; phenoxy group ethoxy carbonyl oxygen base); aryloxy group carbonyl oxygen base (phenoxy group carbonyl oxygen base for example; chlorophenoxy carbonyl oxygen base); the allyloxy of carbon number below 30 (acetoxyl group for example; propionyloxy etc.); the acyl group of carbon number below 30 (acetyl group for example; propiono; benzoyl group); carbamyl (carbamyl for example; N; the N-formyl-dimethylamino; morpholino carbonyl; piperidino carbonyl etc.); sulfamoyl (sulfamoyl for example; N, N-dimethylamino sulfonyl; the morpholino sulfonyl; piperidyl sulfonyl etc.); the alkyl sulphonyl of carbon number below 30 (methyl sulphonyl for example; trifluoromethyl sulfonyl; ethylsulfonyl; the butyl sulfonyl; the dodecyl sulfonyl); aryl sulfonyl (benzenesulfonyl for example; tosyl; the naphthalene sulfonyl base; the pyridine sulfonyl; the quinoline sulfonyl); the aryl of carbon number below 30 (phenyl for example; dichlorophenyl; toluyl groups; anisyl; the diethylamino phenyl; the acetyl-amino phenyl; the methoxycarbonyl phenyl; hydroxyphenyl; uncle's octyl phenyl; naphthyl etc.); substituted-amino is (for example amino; the alkyl amino dialkyl amido; arylamino; ammonia diaryl base; acyl amino etc.); replace phosphate (phosphono) base (phosphate for example; the diethyl phosphate; the diphenylphosphine acidic group); heterocyclic radical (pyridine radicals for example; quinolyl; furyl; thienyl; tetrahydrofurfuryl; pyrazolyl isoxazolyl; isothiazolyl; imidazole radicals oxazolyl; thiazolyl; pyridazinyl; pyrimidine radicals; pyrazinyl; triazolyl; tetrazole radical benzoxazolyl; benzimidazolyl; isoquinolyl; the thiadiazole base; the morpholino base; piperidyl; indyl; isoindolyl; thiomorpholine is for base); urea groups (methyl urea groups for example; the dimethyl urea groups; phenyl urea groups etc.); sulfamoyl amino (for example dipropyl sulfamoyl amino etc.); alkoxycarbonyl amido (for example carbethoxyl group amino etc.); aryloxycarbonyl amino (for example phenyloxycarbonyl amino etc.); aryl sulfonyl (for example phenyl sulfonyl etc.); silicyl (trimethoxysilyl for example; triethoxysilyl etc.); siloxy (for example trimethylsiloxy etc.) etc.
As compound with above-mentioned structural formula (1) expression, for example can enumerate alkyl catechol (catechol for example, resorcinol, 1, the 4-p-dihydroxy-benzene, the 2-methyl catechol, the 3-methyl catechol, the 4-methyl catechol, the 2-ethylcatechol, the 3-ethylcatechol, the 4-ethylcatechol, 2-propyl group catechol, 3-propyl group catechol, 4-propyl group catechol, 2-normal-butyl catechol, 3-normal-butyl catechol, 4-normal-butyl catechol, the 2-tert-butyl catechol, the 3-tert-butyl catechol, the 3-tert-butyl catechol, 3,5-ditertiarybutyl catechol etc.), alkyl-resorcin (2-methylresorcinol for example, cresorcinol, the 2-ethyl resorcinol, the 4-ethyl resorcinol, 2-propyl group resorcinol, 4-propyl group resorcinol, the 2-n-butyl resorcinol, the 4-n-butyl resorcinol, the 2-tert-butyl resorcin, 4-tert-butyl resorcin etc.), alkyl p-dihydroxy-benzene (methyl hydroquinone for example, the ethyl p-dihydroxy-benzene, the propyl group p-dihydroxy-benzene, TBHQ, 2,5 di tert butyl hydroquinone etc.), pyrogallol, phloroglucin etc.
In addition, above-mentioned compound with phenol hydroxyl for example also is preferably the compound that the aromatic rings that has 1 above-mentioned phenol hydroxyl is at least used the concatenating group binding of divalent each other.
As the concatenating group of above-mentioned divalent, for example can enumerate and have 1～30 carbon atom, oxygen atom, nitrogen-atoms, sulphur atom, SO, SO
2Deng base.Above-mentioned sulphur atom, oxygen atom, SO and SO
2Also directly combination.
Above-mentioned carbon atom and oxygen atom also can have substituting group, as this substituting group, for example can enumerate the substituting group of representing with Z in above-mentioned structural formula (1).
In addition, above-mentioned aromatic rings also can have substituting group, as this substituting group, for example can enumerate the substituting group of representing with Z in above-mentioned structural formula (1).
As above-mentioned object lesson with compound of phenol hydroxyl, the sterically hindered phenolic compound that known bisphenol compound, the spy who can enumerate bisphenol-A, bisphenol S, bis-phenol M, uses in heat sensitive paper as developer open the bisphenol compound put down in writing in the 2003-305945 communique, use as antioxidant etc.In addition, can also enumerate 4-metoxyphenol, 4-methoxyl-2-Viosorb 110, betanaphthol, 2,6-di-t-butyl-4-cresols, gaultherolin, hydroxyl diethyl have substituent monohydric phenol compound etc. for aniline etc.
As above-mentioned commercially available product, can enumerate the bisphenol compound of Honshu chemical company system with compound of phenol hydroxyl.
As above-mentioned compound with imino group, be not particularly limited, can suitably select according to purpose, for example the compound of preferred molecular weight more than 50, the more preferably compound of molecular weight more than 70.
Above-mentioned compound with imino group preferably has the ring texture that is replaced by imino group.As this ring texture, be preferably the product of any one generation condensation at least of aromatic rings and heterocycle, the product of the condensation of aromatic rings generation more preferably.In addition, in the above-mentioned ring texture, also can have oxygen atom, nitrogen-atoms, sulphur atom.
As above-mentioned object lesson, can enumerate phenothiazine, phenoxazine, dihydro azophenlyene, quinhydrones or replace the compound of these compounds by the substituting group of representing with Z in the above-mentioned said structure formula (1) with compound of imino group.
As the above-mentioned compound with ring texture that is replaced by imino group, a preferred part has the bulky amine derivant of bulky amine (ヒ Application ダ one De ア ミ Application).
As above-mentioned bulky amine, for example can enumerate the spy and open the bulky amine of putting down in writing in the 2003-246138 communique.
As above-mentioned compound with nitro or above-mentionedly have a nitroso compound, be not particularly limited, can suitably select according to purpose, for example preferred molecular weight is the compound more than 50, more preferably molecular weight is the compound more than 70.
As above-mentioned compound or above-mentioned object lesson, can enumerate the chelate of nitrobenzene, nitroso compound and aluminium etc. with nitroso compound with nitro.
As above-mentioned compound with aromatic rings, be not particularly limited, can suitably select according to purpose, for example preferred above-mentioned aromatic rings is by having the compound that the right substituting group of isolated electron (substituting group that for example has oxygen atom, nitrogen-atoms, sulphur atom etc.) replaces.
As the object lesson of compound, for example can enumerate the above-mentioned compound (for example methylenum careuleum, crystal violet etc.) that the compound of phenol hydroxyl, above-mentioned compound, a part with imino group have the aniline skeleton that has with above-mentioned aromatic rings.
As above-mentioned compound with heterocycle, be not particularly limited, can suitably select according to purpose, for example be preferably and have the compound that this heterocycle has the right atom of isolated electrons such as nitrogen, oxygen, sulphur.
As above-mentioned object lesson, be not particularly limited pyrimidine, quinoline etc. with compound of heterocycle.
As above-mentioned compound with metallic atom, be not particularly limited, can suitably select according to purpose.
As above-mentioned metallic atom, so long as the metallic atom that has an affinity with the free radical that produces from above-mentioned polymerization initiator gets final product, be not particularly limited, can suitably select according to purpose, for example, can enumerate copper, aluminium, titanium etc.
In above-mentioned polymerization inhibitor, from the point of the pattern that can obtain high asperratio, especially preferably have at least 2 phenol hydroxyls compound, have the aromatic rings that is replaced by imino group compound, have the compound of the heterocycle that is replaced by imino group.Particularly, preferred alkyl catechol, phenothiazine, phenoxazine, bulky amine, dihydronaphthalene or their derivant.
Above-mentioned polymerization inhibitor usually in commercially available polymerizable compound trace contain, and in the present invention, from improving the viewpoint of exploring degree, make its contain with commercially available above-mentioned polymerizable compound in the different polymerization inhibitor of polymerization inhibitor that contains.Thereby above-mentioned polymerization inhibitor is preferably the compound except the monohydric phenol based compounds such as 4-metoxyphenol that contain in order to give stability in commercially available above-mentioned polymerizable compound.
In addition, form in the manufacturing process of material, also can in photosensitive composite solution, add above-mentioned polymerization inhibitor in advance at pattern.
Content as above-mentioned polymerization inhibitor, viewpoint in the scope that the γ value is controlled at above-mentioned hope, monomer in the above-mentioned relatively photo-sensitive resin and oligomer amount are preferably 0.005～0.5 quality %, more preferably 0.01～0.4 quality % is preferably 0.02～0.2 quality % especially.
In addition, the content of above-mentioned polymerization inhibitor is represented the content except the monohydric phenol based compounds such as 4-metoxyphenol that contain in order to give stability in commercially available above-mentioned polymerizable compound.
(5) colorant
As the colorant among the present invention, in the resin combination of R (red), preferred C.I. paratonere (C.I.P.R.) 254 is in the resin combination of G (green), preferred C.I. naphthol green (C.I.P.G.) 36, in the resin combination of B (indigo plant), preferred C.I. alizarol saphirol (C.I.P.B.) 15:6.
In addition, except above-mentioned pigment, can also enumerate the known dyestuff of following record.Pigment etc.In addition, when using the pigment in this known colorant, it is disperseed equably in resin combination, thus particle diameter be preferably below the 0.1 μ m, below the preferred especially 0.08 μ m.
As above-mentioned known dyestuff or pigment, look material, the spy that for example can preferably enumerate record in paragraph numbering [0038]～[0040] that the spy opens the 2005-17716 communique opens the colorant of record in the pigment of record in paragraph numbering [0068]～[0072] of 2005-361447 communique and special paragraph numbering [0080]～[0088] of opening the 2005-17521 communique etc.
In the present invention, and with the preferred compositions of the pigment of above-mentioned record, when being C.I. paratonere 254, can enumerate combination with C.I. paratonere 177, C.I. paratonere 224, C.I. pigment yellow 13 9 or C.I. pigment Violet 23, when being the C.I. pigment green 36, can enumerate combination with C.I. pigment yellow 150, C.I. pigment yellow 13 9, C.I. pigment yellow 185, C.I. pigment yellow 13 8 or C.I. pigment yellow 180, be the C.I. pigment blue 15:, can enumerate combination at 6 o'clock with C.I. pigment Violet 23 or C.I. pigment blue 60.
Wherein, like this and C.I. paratonere 254, C.I. pigment green 36, C.I. pigment blue 15 in the pigment of time spent: 6 content, C.I. paratonere 254 are preferably more than the 80 quality %, are preferably especially more than the 90 quality %.C.I. pigment green 36 is preferably more than the 50 quality %, is preferably especially more than the 60 quality %.C.I. pigment blue 15: 6 are preferably more than the 80 quality %, are preferably especially more than the 90 quality %.
Above-mentioned pigment optimization at first becomes dispersion liquid.This dispersion liquid can be by adding and be distributed to organic solvent described later (or vehicle) and prepare being pre-mixed composition that above-mentioned pigment and pigment dispersing agent obtain.Vehicle is meant the medium part that makes pigment dispersing when coating is in liquid condition, is included as liquid state and combines with above-mentioned pigment to reinforce the part (bonding agent) of filming and with the composition (organic solvent) of its dissolved dilution.The dispersion machine that uses during as the above-mentioned pigment of dispersion, be not particularly limited, for example can enumerate and make work towards storehouse nation, " topical reference book of pigment ", first published, towards storehouse bookstore, 2000, kneader (kneader), roller mill (roll mill), vertical ball mill (attritor), Ultra-micro-grinding machine (super mill), dissolver (dissolver), homogeneous mixer (homomixer), the puddle mixer known dispersion machines such as (sand mill) of record in 438 pages.And then also can grind by the machinery of 310 pages of records of the document, it is broken to utilize friction force to carry out micro mist.
The preferred number average bead diameter of the colorant that uses among the present invention (pigment) is 0.001～0.1 μ m, more preferably 0.01～0.08 μ m.If the pigment number average bead diameter is less than 0.001 μ m, then big, the cohesion easily that becomes of particle surface energy quantitative change, the pigment dispersing difficulty that becomes stably keeps the disperse state difficulty that also becomes simultaneously, and is not preferred.In addition, if the pigment number average bead diameter surpasses 0.1 μ m, then produce the elimination of the polarized light that pigment causes, contrast reduces, and is not preferred.In addition, described in this manual " particle diameter " is meant that the electron micrograph image of particle becomes the diameter of bowlder of the same area, and " number average bead diameter " is meant a lot of particles are asked above-mentioned particle diameter, its mean value of 100.
In addition, diminish, can realize by the jitter time of regulating the pigment dispersing thing in order to make particle diameter.Dispersion can be used the known dispersion machine of above-mentioned record, as jitter time, is preferably 10～30 hours, and then is preferably 18～30 hours, most preferably is 24～30 hours.If jitter time was less than 10 hours, pigment particle size is big so sometimes, and the separating of polarized light that generation pigment causes disappears, and contrast reduces.On the other hand, if surpass jitter time 30 hours, the viscosity of dispersion liquid may rise so, thereby coating becomes difficult.
(other adjuvants)
-solvent-
In the resin combination in the present invention, except mentioned component, also can be further with an organic solvent.As representative examples of organic, can enumerate methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetic acid esters, cyclohexanone, cyclohexanol, hexone, ethyl lactate, methyl lactate, caprolactam etc.
-surfactant-
Forming under the situation of color filter, in order to realize high color purity, each color of pixel thickened in the past, and the thickness that has a pixel is uneven and directly be identified as the problem of irregular colour.So the thickness when need optimizing the formation (coating) of resin bed of the thickness that directly influences pixel changes.
In the present invention, from the thickness that may be controlled to homogeneous, prevent from the viewpoint composition of coating uneven (irregular colour that the thickness change causes) from this resin combination, preferably to contain suitable surfactant effectively.As above-mentioned surfactant, can enumerate preferably that the spy opens the 2003-337424 communique, the spy opens disclosed surfactant in the flat 11-133600 communique.
-thermal polymerization inhibitor-
Resin combination of the present invention preferably contains thermal polymerization inhibitor.Example as this thermal polymerization inhibitor, can enumerate quinhydrones, quinhydrones monomethyl ether, p methoxy phenol, two-tert-butyl group-to pyrogallol, tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole, phenothiazine etc.
-ultraviolet light absorber-
In resin combination of the present invention, also can contain ultraviolet light absorber as required.As ultraviolet light absorber, except the spy opens the compound of putting down in writing in the flat 5-72724 communique, can also enumerate salicylate system, Benzophenone system, benzotriazole system, cyanoacrylate system, nickel chelate system, bulky amine system etc.
Particularly; can enumerate phenyl salicylic acid esters; salicylic acid 4-tert-butyl-phenyl ester; 2; 4-di-tert-butyl-phenyl-3 '; 5 '-two-uncle-4 '-Para Hydroxy Benzoic Acid ester; salicylic acid 4-tert-butyl-phenyl ester; 2; the 4-dihydroxy benaophenonel; 2-hydroxyl-4-methoxybenzene ketone; 2-hydroxyl-4-n-octyloxy Benzophenone; 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole; 2-(the 2 '-hydroxyl-3-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole; ethyl-2-cyano group-3; 3-diphenylacrylate ester; 2; 2 '-hydroxyl-4-methoxybenzene ketone; nickel dibutyl dithiocaarbamate salt; two (2; 2; 6; 6-tetramethyl-4-pyridine)-sebacate; 4-tert-butyl-phenyl salicylate; the salicylic acid phenylester; 4-hydroxyl-2; 2; 6; 6-tetramethyl piperazine condensation thing; succinic acid-two (2; 2; 6; 6-tetramethyl-4-piperidines thiazolinyl)-ester; 2-[2-hydroxyl-3; two (α, the α-Er Jiajibianji) phenyl of 5-]-the 2H-benzotriazole; 7-{[4-chloro-6-(diethylamino)-5-triazine-2-acyl group] amino }-3-phenyl cumarin etc.
In addition, in the resin combination in the present invention, except above-mentioned adjuvant, can also contain the spy and open " the bonding auxiliary agent " put down in writing in the flat 11-133600 communique or other adjuvants etc.
＜resin transfer material 〉
Then, the resin transfer material that uses in the pattern formation method of the present invention is described.
As resin transfer material, preferred spy opens the resin transfer material of putting down in writing in the flat 5-72724 communique, promptly uses the film of the type that becomes one to form.As the structure example of this one-piece type film, can enumerate the structure that stacks gradually interim supporter/thermoplastic resin/middle layer/resin bed/protective film.
In addition, the resin bed in this resin transfer material utilizes above-mentioned resin combination setting.
-interim supporter-
Interim supporter as in the photosensitive transfer printing material must have flexibility, even also significant deformation, contraction or elongation can not take place under pressurization or pressurization and heating.As the example of so interim supporter, can enumerate pet film, cellulose triacetate film, plasticon, polycarbonate film etc., wherein, preferred especially two-way stretch pet film.
Thickness to interim supporter is not particularly limited, and is generally the scope of 5～200 μ m, and the scope of 10～150 μ m is favourable at points such as operation easily, versatilities, and is preferred especially.In addition, interim supporter can also can contain dyestuff silicon, alumina sol, chromic salts, zirconates etc. for transparent.
-thermoplastic resin-
As the composition that uses in the thermoplastic resin, preferred spy opens the organic polymer material of putting down in writing in the flat 5-72724 communique, especially preferably from the about organic polymer material below 80 ℃ of softening point that utilizes Vickers Vicat method (particularly, utilizing the polymkeric substance softening point measurement method of U.S. material test method(s) ASTMD1235), select.Particularly, can enumerate tygon, polyolefin such as polypropylene, the ethylene copolymer that ethene and vinyl acetate or its are saponified and so on, the multipolymer of ethene and acrylate or its are saponified, Polyvinylchloride, the multipolymer of vinyl chloride and vinyl acetate and saponified and so on vinyl chloride copolymer thereof, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, the styrol copolymer that the multipolymer of styrene and (methyl) acrylate or its are saponified and so on, polyvinyl toluene, the vinyl toluene copolymer that the multipolymer of vinyltoluene and (methyl) acrylate or its are saponified and so on, poly-(methyl) acrylate, (methyl) acrylate copolymer of (methyl) butyl acrylate and vinyl acetate etc., vinyl acetate co-polymer nylon, copolymerization nylon, N-alkoxy methyl nylon, the organic polymers such as polyamide of N-dimethylamino nylon and so on.
-middle layer-
In above-mentioned resin transfer material, the mixing of the composition in order to prevent to apply a plurality of overlay and during the preservation after the coating preferably is provided with the middle layer.As this middle layer, the preferred use the spy opened the oxygen-proof membrane of putting down in writing as " separating layer " in the flat 5-72724 communique with blocking-up oxygen function, and in this case, sensitivity improves during exposure, and the time load of exposure machine reduces, and throughput rate improves.
As this oxygen-proof membrane, preferably demonstrate the hypoxemia permeability, be dispersed or dissolved in the film of water or aqueous alkali, can from known film, suitably select.Wherein, the combination of special preferably polyethylene alcohol and polyvinylpyrrolidone.
-protective film-
Not contaminated or damage preferably is provided with thin protective film when preserving in order to protect on resin bed.Protective film can be made of or materials similar identical with interim supporter, but must separate with resin bed easily.As the protective film material, for example silicone paper, polyolefin or ptfe sheet are suitable material.
The method for making of-resin transfer material-
Resin transfer material among the present invention can be made by process as described below, that is: by coating on interim supporter and the dry coating liquid (thermoplastic resin coating liquid) that is dissolved with the adjuvant of thermoplastic resin, thermoplastic resin is set, the solution of coating on thermoplastic resin then, the dry intermediate layer material that constitutes by the solvent that does not dissolve thermoplastic resin, with the solvent coating of not dissolving the middle layer, the resin bed of dry resin composition, be provided with then.
In addition; the thin slice that preparation is provided with the thin slice in thermoplastic resin and middle layer and is provided with resin bed on protective film on above-mentioned interim supporter; by mutual applying middle layer with resin bed and it is contacted; and then prepare the thin slice that on above-mentioned interim supporter, is provided with the thin slice of thermoplastic resin and on protective film, is provided with resin bed and middle layer again;, with the middle layer and being contacted, it also can make by mutual applying thermoplastic resin.
In addition, in resin transfer material, as the thickness of the resin bed of resin combination, preferred 1.0～5.0 μ m are 1.0～4.0 μ m more preferably, are preferably 1.0～3.0 μ m especially.
In addition, the preferred thickness of each layer is not particularly limited as other, and thermoplastic resin is preferably 2～30 μ m, and the middle layer is preferably 0.5～3.0 μ m, and protective film is preferably 4～40 μ m.
In addition, coating in the manufacture method of above-mentioned resin transfer material, can utilize as in above-mentioned＜pattern formation method〉in (resin bed formation operation) one in cited known applying device etc. carry out, in the present invention, the preferred especially applying device (machine of applying is removed in the slit) that uses slot-shaped nozzle that utilizes carries out.
＜substrate 〉
The substrate that uses in pattern formation method of the present invention for example can be enumerated known glass plate such as the soda-lime glass plate that uses transparency carrier, have the monox tunicle on the surface, low-expansion glass, nothing (n connection) alkali glass, quartz glass or plastic sheeting etc.
In addition, aforesaid substrate can adhere to resin combination or resin transfer material well by carrying out coupling processing in advance.As this coupling processing, can preferably use the spy to open the method for 2000-39033 communique record.In addition, the thickness as substrate is not particularly limited, but common preferred 700～1200 μ m.
＜color filter, structured material and liquid crystal indicator 〉
The pattern that utilizes said method to form on substrate is the pattern that uses in color filter or the structured materials such as gap material or flange.Color filter with this pattern is particularly preferred in the liquid crystal display cells (liquid crystal indicator), be not particularly limited as this liquid crystal display cells, can adopt ECB (electronic birefringence) (Electrically Controlled Birefringence), TN (twisted-nematic) (Twisted Nematic), IPS (plate internal conversion) (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), OCB (optical compensation curved) (OpticallyCompensatory Bend), STN (supertwist is to row) (Supper Twisted Nematic), VA (homeotropic alignment) (Vertically Aligned), HAN (mixing collimation) (Hybrid AlignedNematic) to row, the various display modes of GH (host and guest) (Guest Host) and so on can be preferred for big picture display device such as personal display of notebook or TV monitor etc.
[embodiment]
Below utilize embodiment that the present invention is further elaborated, but the present invention is not as long as its purport of insurmountability is limited by these embodiment.In addition, so long as not explanation especially in advance, " part " reaches " % " is quality standard.
In the present embodiment, be that the center is elaborated with the transfer printing, but in the present invention, also can use coating processs such as slit coating machine to implement.
The making of-colour filtering chip basic board-
The making of＜photosensitive resin transfer material 〉
On the interim supporter of the pet film of thick 75 μ m (the interim supporter of PET), use slot-shaped nozzle, the thermoplastic resin coating liquid that coating, dry following prescription H1 constitute.Then, the middle layer coating liquid that coating on the obstruction thermoplastic resin, dry following prescription P1 constitute, stacked middle layer (oxygen-proof membrane).And then the photo-sensitive resin that the composition of coating on this middle layer, dry following table 1 record constitutes is with applying liquid (composition 1), stacked photo-sensitive resin.Like this, the thermoplastic resin of dry film thickness 15 μ m, the middle layer of dry film thickness 1.6 μ m and the photo-sensitive resin of dry film thickness 3.0 μ m are set on the interim supporter of PET, on photo-sensitive resin, press sticking protective film (thick 12 μ m polypropylene films).
[table 1]
| | | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | ||
| Photo-sensitive resin is with applying | Prescription | 1 | | Prescription 3 | Prescription 4 | | Prescription 6 | |
| | 120 | 120 | 120 | 120 | 120 | 120 | 120 | |
| 1-methoxyl-2-propyl-acetic acid ester | 456 | 456 | 456 | 456 | 456 | 456 | 456 | |
| Methyl ethyl ketone | 243 | 243 | 243 | 243 | 243 | 243 | 243 | |
| | 17 | 17 | 17 | 17 | 17 | 17 | 17 | |
| Bonding agent-1 | 80 | 80 | 80 | 80 | 80 | 80 | 80 | |
| DPHA liquid | 79 | 79 | 79 | 79 | 79 | 79 | 79 | |
| Initiating | 2.2 | 2.2 | 2.2 | 2.2 | 2.2 | 2.2 | 2.2 | |
| Polymerization inhibitor (※) | 0.100 | 0.06 | 0.2 | 0.08 | 0.1 | 0.1 | 0.5 | |
| | 0.86 | 0.86 | 0.86 | 0.86 | 0.86 | 0.86 | 0.86 | |
| | 17 | 17 | 17 | 17 | 17 | 17 | 17 | |
| Classes of colored pigments | CIPR254 | CIPG36 | CIPB15: 6 | Carbon black | CIPR254 | CIPR254 | CIPR254 |
(unit: part)
*The polymerization inhibitor that uses respectively in embodiment 1～4 and the comparative example 1～3 is recorded in table 3.
At this, the photo-sensitive resin of putting down in writing in the above-mentioned table 1 is described with the preparation that applies liquid.
Photo-sensitive resin obtains by process as described below with coating liquid, that is: measure the coloring pigment of the amount of above-mentioned table 1 record, mix down in 24 ℃ of temperature (± 2 ℃), 150r.p.m. stirred 10 minutes, then, measure the 1-methoxyl-2-propyl-acetic acid ester of the amount of above-mentioned table 1 record, methyl ethyl ketone, methyl alcohol, bonding agent-1, DPHA liquid, initiating agent 1, polymerization inhibitor (polymerization inhibitor that record is used in table 3), surfactant 1, illuminating colour 1, under 25 ℃ of temperature (± 2 ℃), add successively, at 40 ℃ of temperature (± 2 ℃), 150r.p.m. following stirring 30 minutes.
The concrete condition that in the above-mentioned table 1 in the composition of record each formed is as described below.Wherein, as described later to the introduction of surfactant 1.
*The composition of bonding agent 1
Methacrylic acid/ALMA multipolymer
(=20/80[mol ratio], molecular weight 36,000)
*The composition of DPHA liquid
Dipentaerythritol acrylate
(containing polymerization inhibitor MEHQ 500ppm, trade name: KAYARAD DPHA, Japanese chemical drug (strain) system) ... 76 parts
Propylene glycol monomethyl ether acetic acid esters ... 24 parts
In addition, as initiating agent, use 2, two (trichloromethyl)-6-[4-(N of 4-, the two di ethoxy carbonyl methylaminos of N-)-the 3-bromophenyl]-s-triazine (with the pure medicine of light (strain) system), as illuminating colour 1, use than cut Li Apia Bole (PVC Network ト リ ア ピ ユ ア Block Le)-BOH-M (hodogaya chemical (strain) system).
[the thermoplastic resin prescription H1 of coating liquid]
Methyl alcohol ... 11.1 part
Propylene glycol monomethyl ether acetic acid esters ... 6.4 part
Methyl ethyl ketone ... 52.4 part
Methyl methacrylate/2-ethylhexyl acrylate/methacrylic acid benzyl ester/methacrylic acid copolymer ... 5.83 part
[copolymerization than (mol ratio)=55/11.7/4.5/28.8, weight-average molecular weight=100,000,70 ℃ of Tg ]
Styrene/acrylic acid co-polymer ... 13.6 part
[copolymerization than (mol ratio)=63/37, weight-average molecular weight=10,000,100 ℃ of Tg ]
2, two [4-(methacryloxy polyethoxy) phenyl] propane (Xin Zhong village chemical industry (strain) system) of 2-... 9.1 part
*Surfactant 1:
The F-780-F of Mick method section (メ ガ Off ア Star Network) (big Japanese ink chemical industry (strain) system)
[composition]
C
6F
13CH
2CH
2OCOCH=CH
2(40 parts) and
H (OCH (CH
3) CH
2)
7OCOCH=CH
2(55 parts) and
H (OCH
2CH
2)
7OCOCH=CH
2(5 parts)
Multipolymer (weight-average molecular weight 30,000) ... 30 parts
Methyl ethyl ketone ... 70 parts
[the middle layer prescription P1 of coating liquid]
Polyvinyl alcohol (PVA) ... 2.1 part
(PVA-205 (saponification degree=88%), (strain) carat happy (Network レ ラ) system)
Polyvinylpyrrolidone ... 0.95 part
(PVP, K-30; ISP Japan (ア イ エ ス ピ one ジ ヤ パ Application) Co., Ltd.'s system)
Methyl alcohol ... 44 parts
Distilled water ... 53 parts
As mentioned above, stacked interim supporter, thermoplastic resin, middle layer (oxygen-proof membrane) and photo-sensitive resin are made the photosensitive resin transfer material that constitutes duplexer.
The making of＜colour filtering chip basic board 〉
Utilize spray, on the alkali-free glass substrate of 680 * 880mm size ejection 20 seconds adjusted be 25 ℃ glass washing agent liquid, clean with rotating brush simultaneously with nylon hair, after the pure water spray Cleaning for High Capacity, utilize spray, spray to its silane coupling agent liquid (N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane 0.3% aqueous solution, trade name: KBM603, SHIN-ETSU HANTOTAI's chemical industry (strain) system) 20 seconds, the pure water spray Cleaning for High Capacity.Prepare heating arrangement with substrate, heated this substrate 2 minutes down at 100 ℃.
Then; peel off the protective film of above-mentioned photosensitive resin transfer material; use laminator LamicII type [(strain) Hitachi industry (イ Application ダ ス ト リ イ ズ) system] then; make the photo-sensitive resin that exposes contact coincidence, minute carry out stacked with 130 ℃ of rubber-surfaced roll temperature, line pressure 100N/cm, transporting velocity 2.2m/ with the surfaces of above-mentioned 2 minutes substrate of 100 ℃ of heating.Then, peel off the interim supporter of PET, be transferred on the glass substrate.
After the transfer printing, utilize laser to carry out pattern exposure.Particularly,, under atmospheric environment, use following pattern to form device, above-mentioned photo-sensitive resin and photohead are relatively moved, with wavelength 405nm, 80mJ/cm to the above-mentioned photo-sensitive resin on the base material
2Exposure expose, form pattern.
-pattern formation device-
(exposure device that is: closes the ripple LASER Light Source shown in Fig. 1～16 to use the pattern with structure as described below to form device as above-mentioned light irradiating means; As above-mentioned optical modulator body, the micro lens array of arranging 1024 micro mirrors at main scanning direction shown in Figure 180 is controlled so as to the DMD50 that only drive 768 * 356 row in sub scanning direction is arranged 600 groups above-mentioned optical modulator body; Lenticule shown in Figure 36 is arranged in the microlens array 472 of array-like and makes photoimaging by this microlens array in the optical system 480,482 of above-mentioned photographic layer.
In addition, be disposed at the light that near the spot position of microlens array 55 array of apertures 59 is configured to only pass through to each aperture 59a incident the lenticule 55a corresponding with it.
Like this, utilize following method, the photo-sensitive resin behind the pattern exposure is implemented development treatment.
At first; with 30 ℃ of 50 seconds, flat burner pressure 0.04MPa; using triethanolamine is that developer solution (will contain triethanolamine 30 quality % with pure water; polypropylene glycol, glycerine monostearate, polyoxyethylene sorbitan monostearate, stearyl ether amount to 0.1%; trade name: T-PD2 (Fujiphoto (strain) system) is diluted to the liquid of 12 times (mixing with the ratio of 11 parts of pure water with 1 part of T-PD2)); spray development, remove thermoplastic resin and middle layer.Then, blow above the substrate to this, get rid of after the liquid, utilize spray to blow pure water 10 seconds, carry out pure water and clean, blow, the liquid that reduces on the substrate accumulates.
Then, using carbonic acid Na is that developer solution (will contain the sodium bicarbonate of 0.38 mol, the sodium carbonate of 0.47 mol, 5% nekal, anionic surfactant, defoamer and stabilizing agent with pure water; Trade name: T-CD1 (Fujiphoto (strain) system) is diluted to 5 times liquid), with 29 ℃, pyramid type nozzle pressure 0.15MPa, spray and developed 30 seconds, develop and remove photo-sensitive resin, obtain pattern image.
Then, with pure water washing agent (is contained phosphate silicate non-ionic surfactant, defoamer and stabilizing agent; Trade name: T-SD1, Fujiphoto (strain) system) is diluted to 10 times and use, under 33 ℃, with the pyramid type nozzle pressure is 0.02MPa, with spray ejection 20 seconds, and then utilizes the rotating brush with nylon hair, the image that wiping forms is removed residue, is deceived the image of (K).Then, to this substrate, from the two sides, use ultrahigh pressure mercury lamp, with 500mJ/cm
2Exposure, carry out post-exposure, then with 220 ℃ of thermal treatments 15 minutes.
(embodiment 2～4 and comparative example 1～3)
In embodiment 1, photo-sensitive resin is changed to prescription 2～7 respectively with the prescription that applies liquid, and the exposure energy profile of the laser of thickness, the exposure of utilizing laser and the use of the photo-sensitive resin of the polymerization inhibitor that uses, formation changed to record in the table 3 respectively, in addition, utilize the method identical, the pattern of formation embodiment 2～4 and comparative example 1～3 with embodiment 1.
(embodiment 5)
In embodiment 1, do not add coloring pigment and add following pigment 1 (17 parts), and then add 0.5 part illuminating colour 1, in addition, make photosensitive material similarly to Example 1, use method similarly to Example 1, form the pattern (post) of embodiment 5.
*The composition of pigment 1
30% methyl isobutyl ketone of silica sol disperses thing
(trade name: MIBK-ST, daily output chemical industry (strain) system)
(embodiment 6)
In embodiment 1, do not add coloring pigment and add above-mentioned pigment 1 (17 parts), and then add 0.5 part illuminating colour 1, and then replacement pyrogallol, use phenoxazine as polymerization inhibitor, in addition, make photosensitive material similarly to Example 1, use method similarly to Example 1, form the pattern (post) of embodiment 6.
For the exposure energy profile that makes the exposure device in above embodiment, the comparative example changes, change conditions such as laser beam.This condition is stated table 2 as follows.
[table 2]
| Laser beam diameter (μ m) (1/e 2) | Lenticule focal length (μ m) | |
| | 15 | 0.1 |
| | 10 | 0.1 |
| Embodiment 3 | 10 | 0.2 |
| Embodiment 4 | 13 | 0.1 |
| | 15 | 0.1 |
| Embodiment 6 | 15 | 0.1 |
| Comparative example 1 | 15 | 0.1 |
| Comparative example 2 | 30 | 0.1 |
| Comparative example 3 | 10 | 0.1 |
The mensuration of-γ-
Each photo-sensitive resin to the foregoing description and comparative example utilizes said method, makes the curve map (curve map shown in Figure 1) of the relation between the survival rate Y of thickness after expression exposure energy E and the development, tries to achieve E
50Slope (the Y of the straight line of ± Δ E
50+ Δ-Y
50-Δ)/(log E
50+ Δ-logE
50-Δ) value.
(evaluation)
[pattern form]
Utilize following method to estimate the shape of the above-mentioned pattern that obtains.
Observe shape with laser microscope VK-9500 (Ji Ensi (キ one エ Application ス) system), measure simultaneously with the length on one side of the face (bottom) of the substrate contacts of pattern and with the length of the discontiguous opposing face of substrate (top), the rate of change of the pattern dimension of trying to achieve and setting.The side that any one change in size of top or bottom is big is as the value of this change of shape.
Zero: almost do not have change of shape (less than 10%)
Δ: the change of shape more than 10%, less than 20% (allowed band)
*: the change of shape more than 20% (allowed band is outer)
The results are shown in Table 3.
[sensitivity]
To the photo-sensitive resin of the photosensitive transfer printing material in the duplexer of above-mentioned preparation, use above-mentioned pattern to form device, irradiation is from 0.1mJ/cm
2, with 2
1/2Doubly at interval, to 200mJ/cm
2The different light (laser of wavelength 405nm) of luminous energy, expose, a part of zone of above-mentioned photo-sensitive resin is solidified.At room temperature, after leaving standstill 10 minutes, utilize above-mentioned development treatment, uncured zone is removed in dissolving, measures the thickness of residual consolidation zone.Then, the relation between the thickness of the exposure of light and cured layer is plotted figure, obtain sensitivity curve.From this sensitivity curve, the thickness of consolidation zone is become 95% luminous energy when above of photoresist bed thickness before the exposure as the sensitivity of photo-sensitive resin.
[table 3]
| Polymerization inhibitor | Thickness (μ m) | Amount of exposure (mJ/cm 2) | γ | Energy profile | Pattern form (rate of change) | | |
| Embodiment | |||||||
| 1 | Pyrogallol | 3.0 | 30 | 1.5 | 50 | ○ (3％) | 25 |
| | Phenothiazine | 2.5 | 24 | 5 | 20 | ○ (2％) | 20 |
| Embodiment 3 | Catechol | 2.5 | 36 | 2.3 | 30 | ○ (3％) | 30 |
| Embodiment 4 | 2,3-hydroxyl naphthalene | 2.0 | 24 | 8.7 | 30 | ○ (4％) | 20 |
| | Pyrogallol | 3.5 | 33 | 1.5 | 50 | ○ (3％) | 27 |
| Embodiment 6 | Phenoxazine | 3.5 | 33 | 1.4 | 50 | ○ (3％) | 25 |
| Comparative example 1 | P-matulane hydrochloride | 2.0 | 30 | 0.8 | 50 | × (20％) | 25 |
| Comparative example 2 | 3-mercaptopropionic acid-2-ethylhexyl | 3.0 | 30 | 0.9 | 8 | × (23％) | 25 |
| Comparative example 3 | Phenothiazine | 2.5 | 120 | 16 | 50 | ○ (1％) | 100 |
Phenoxazine: Northeast chemistry (strain) system
Pyrogallol: Northeast chemistry (strain) system
Phenothiazine: Tokyo changes into industry (strain) system
Catechol: Northeast chemistry (strain) system
2,3-hydroxyl naphthalene: and the pure pharmaceutical worker's industry of light (strain) system
P-matulane hydrochloride: and the pure pharmaceutical worker's industry of light (strain) system
3-mercaptopropionic acid-2-ethylhexyl: and the pure pharmaceutical worker's industry of light (strain) system
Such as table 3 record, part dissolving etc. takes place in pattern that comparative example 1 and 2 obtains, can not obtain desirable shape.Relative therewith, in embodiment 1～6, can obtain the pattern of excellent in shape.In addition, in the numerical value of γ was 16 comparative example 3, pattern form can obtain good result, but sensitivity is insufficient.
Claims (9)
1. a pattern formation method is characterized in that, it is the pattern formation method that forms the pattern of color filter parts at least through the following stated operation, that is:
The photo-sensitive resin that forms the photo-sensitive resin that is made of photosensitive polymer combination on substrate forms operation;
With respect to described photo-sensitive resin, the limit is carried out relative scanning based on view data modulation plain edge and is exposed, and forms the pattern exposure operation of two dimensional image; With
The developing procedure that the described photo-sensitive resin that has exposed is developed,
The γ of described photo-sensitive resin is 1～15, and
The exposure energy profile of the exposure device that uses in described pattern exposure operation is 10～50,
Wherein said γ is: the survival rate of the thickness the when exposure energy in the time will carrying out pattern exposure to the photo-sensitive resin of certain thickness is made as E, exposure back development treatment is made as under the situation of Y, with the relation curveization between the survival rate of exposure energy E and thickness, in this curve, the survival rate Y of thickness becomes 50% point, and (survival rate at this point is made as Y
50, exposure energy is made as E
50) in E
50Slope (the Y of the straight line of ± Δ E
50+ Δ-Y
50-Δ)/(logE
50+ Δ-logE
50-Δ) value, described exposure energy profile is: the exposure energy E in the time of will carrying out pattern exposure to the photo-sensitive resin of certain thickness is made as 100%, with the related curveization between the location coordinate of exposure area and this E, in this curve, exposure energy becomes 50% point, and (coordinate at this point is made as P
50, exposure energy is made as E
50) in the slope (E of straight line
50+ Δ-E
50-Δ)/(P
50+ Δ-P
50-Δ) value.
2. pattern formation method according to claim 1 is characterized in that,
Described pattern exposure utilizes laser explosure device to carry out, and described exposure device possesses: light irradiating means; Optical modulator body, it has a plurality of acceptance from the light of described light irradiating means and the drawing section that penetrates; Microlens array, it is arranged with lenticule, and this lenticule has the aspheric surface of the aberration that the distortion that can revise the outgoing plane in the described drawing section causes.
3. pattern formation method according to claim 1 is characterized in that,
Described photosensitive polymer combination contains resin, monomer or oligomer, Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system and polymerization inhibitor.
4. pattern formation method according to claim 3 is characterized in that,
Described polymerization inhibitor is to be selected from compound with phenol hydroxyl, phenothiazine Ji at least a in the phenoxazine.
5. pattern formation method according to claim 3 is characterized in that,
With respect to the content of described monomer and oligomer, the content of described polymerization inhibitor is in the scope of 0.005～0.5 quality %.
6. a color filter is characterized in that,
Use any described pattern formation method manufacturing in the claim 1～5.
7. a structured material is characterized in that,
Use any described pattern formation method manufacturing in the claim 1～5.
8. a liquid crystal indicator is characterized in that,
Possesses the described color filter of claim 6.
9. a liquid crystal indicator is characterized in that,
Possesses the described structured material of claim 7.
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| JP2006137821 | 2006-05-17 | ||
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103293881A (en) * | 2013-05-24 | 2013-09-11 | 京东方科技集团股份有限公司 | Developing solution component |
| CN105611124A (en) * | 2015-12-18 | 2016-05-25 | 广东欧珀移动通信有限公司 | Image sensor, imaging method, imaging device and electronic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103293881A (en) * | 2013-05-24 | 2013-09-11 | 京东方科技集团股份有限公司 | Developing solution component |
| CN103293881B (en) * | 2013-05-24 | 2015-11-25 | 京东方科技集团股份有限公司 | A kind of developer solution component is preparing the application in colored filter |
| US10197912B2 (en) | 2013-05-24 | 2019-02-05 | Boe Technology Group Co., Ltd. | Method for manufacturing color photoresist pattern in color filter |
| CN107431020A (en) * | 2015-03-27 | 2017-12-01 | 东丽株式会社 | The effective photosensitive polymer combination of film crystal, cured film, thin film transistor (TFT), liquid crystal display device or organic el display, the manufacture method of cured film, the manufacture method of thin film transistor (TFT) and the manufacture method of liquid crystal display device or organic el display |
| CN105611124A (en) * | 2015-12-18 | 2016-05-25 | 广东欧珀移动通信有限公司 | Image sensor, imaging method, imaging device and electronic device |
| CN105611124B (en) * | 2015-12-18 | 2017-10-17 | 广东欧珀移动通信有限公司 | Imaging sensor, imaging method, imaging device and terminal |
| CN108469717A (en) * | 2017-02-23 | 2018-08-31 | 旭化成株式会社 | Photosensitive polymer combination and photoresist laminated body |
| CN108469717B (en) * | 2017-02-23 | 2021-08-20 | 旭化成株式会社 | Photosensitive resin composition and photosensitive resin laminate |
| CN112368646A (en) * | 2018-07-10 | 2021-02-12 | 应用材料公司 | Dynamic imaging system |
| CN112368646B (en) * | 2018-07-10 | 2024-06-04 | 应用材料公司 | Dynamic imaging system |
| CN113126449A (en) * | 2021-03-16 | 2021-07-16 | 合肥众群光电科技有限公司 | Laser direct-writing photoetching system and method for green oil photoetching |
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Application publication date: 20071121 |