CN101218545A - Pattern forming method - Google Patents

Abstract

Provided is a pattern forming method by which a fine pattern can be accurately formed by making a light quantity of each exposure unit uniform while suppressing cost, for exposure using a digital exposure apparatus having an exposure head wherein the exposure units are two-dimensionally distributed. The method at least includes a step wherein a photosensitive layer is irradiated with optical beams emitted from a light irradiation means, through a focusing optical system having a light distribution correcting means, and exposure is performed by irradiating the photosensitive layer with optical beams modulated by a light modulating means. In the pattern forming method, the exposure is performed by permitting light quantities of the optical beams applied on the light modulating means from the light irradiation means in an irradiation area to have distribution, and that the light quantity distribution of the optical beams modulated by the light modulating means is corrected to be uniform on the plane of the photosensitive layer to be exposed.

Description

Pattern formation method

Technical field

The present invention relates to the imaging and the pattern of this photographic layer exposure is formed method on photographic layer of a kind of light that will modulate by optical modulator bodies such as spatial optical modulation elements.

Background technology

The various exposure devices of using the light modulated accordingly by Digital Micromirror Device spatial optical modulation elements (SLM) such as (DMD) and pattern-information (view data) to expose were proposed in the past.

Above-mentioned DMD arranges the mirror equipment that forms two-dimensionally with a plurality of micro mirrors that the angle of reflecting surface and control signal change accordingly on semiconductor substrates such as silicon.Used in the exposure method of exposure device of digit explosure mode in the past of this DMD in utilization, use the light source that for example possesses irradiating laser, will be by the lens combination of the above-mentioned laser alignment of this light source irradiation, be disposed at the said lens system about focal position above-mentioned DMD and will be by the photohead of above-mentioned laser lens combination of imaging on scanning plane of above-mentioned DMD reflection, utilize the control signal that generates accordingly with pattern-information etc. that each micro mirror of above-mentioned DMD is carried out switch control and with above-mentioned Laser Modulation, the laser (light beam) that utilization has been modulated, on the microscope carrier that is placed in above-mentioned exposure device and the photosensitive material of printed wiring board that moves along the direction of scanning or liquid crystal display cells etc. with the pattern scan exposure.

In the aforesaid exposure method that has used the digital exposure apparatus that possesses the photohead that the unit of describing is distributed two-dimensionally, in order to form fine pattern accurately, the light quantity of the above-mentioned unit of describing evenly is very important.

But, in fact, by the light of above-mentioned photohead irradiation essential factor because of each lens combination in the above-mentioned photohead, have the problem that the light intensity of comparing periphery with the central part of optical axis reduces, irradiation respectively the light of the unit of describing pass microlens array and particularly evident in the system of the light assembled.

At this problem, the applicant had proposed following shading (shading) technology (for example with reference to patent documentation 1 and 2), promptly, mensuration is by the light intensity distributions (light quantity) of the light of above-mentioned photohead irradiation, by carrying out drive controlling in the driving of respectively the retouching plain portion mode constantly that changes above-mentioned spatial optical modulation element accordingly with this light intensity distributions, and respectively the light quantity of the unit of describing is modified to and reaches homogenising.

But, in above-mentioned patent documentation 1 and 2 the technology, have situation about processing speed being impacted because of the increase of the load on the drive control part that is carried in above-mentioned spatial optical modulation element, in addition, also have this kind exposure device because of circuit formation or the complicated situation that causes cost to rise of process software.Because the cost of the control system of electric property occupies very big ratio in the cost of device integral body,, wish to have the new technology of the load that can alleviate control system therefore for cost squeeze.

Thereby realistic situation is, in the exposure of having used the digital exposure apparatus that possesses the photohead that the unit of describing is distributed two-dimensionally, do not provide as yet a kind of can be in cost squeeze, light quantity homogenising by the respectively unit of describing that will distribute two-dimensionally, and form the pattern formation method of fine pattern accurately, so expectation further improves exploitation.

Patent documentation 1: the spy opens the 2005-22248 communique

Patent documentation 2: special hope 2005-22249 communique

Summary of the invention

Given this present invention plants present situation and finishes, and its problem is to solve above-mentioned problems in the past, the purpose below realizing.Promptly, the objective of the invention is to, a kind of pattern formation method is provided, it is in the exposure of having used the digital exposure apparatus that possesses the photohead that the unit of describing is distributed two-dimensionally, can be in cost squeeze, by the light quantity homogenising of the respectively unit of describing that will distribute two-dimensionally, and form fine pattern accurately.

As the approach that is used to address the above problem, as follows.That is,

＜1〉a kind of pattern formation method is characterized in that,

At least comprise following operation:

After the stacked pattern that has photographic layer on supporting mass on the processed matrix forms this photographic layer in the material,

The light beam that will penetrate from light irradiating means is via the light-gathering optics with light distribution correction mechanism, to have n (wherein n is the natural number 1 or more) two-dimensional arrangements retouch plain portion and with pattern-information make accordingly above-mentioned each retouch the optical modulator body that plain portion changes the optical modulation state and shine, to be exposed to this photographic layer irradiation by the light beam that above-mentioned optical modulator body is modulated

This exposure is following to be carried out, promptly, make from the light quantity of above-mentioned light irradiating means in the irradiation area of the light beam of above-mentioned optical modulator body irradiation to have distribution, the light quantity distribution of the light beam of having been modulated by above-mentioned optical modulator body is corrected for being exposed of above-mentioned photographic layer and reaches homogenising on the face.This＜1 in the record pattern formation method in, owing to utilize above-mentioned light-gathering optics with above-mentioned light quantity distribution correction mechanism, make the light quantity in the irradiation area of the light beam that above-mentioned optical modulator body shines have distribution, so that reaching the power formula of homogenising, the light quantity distribution on the plane of exposure of the light beam of having been modulated by above-mentioned optical modulator body revises, therefore retouch in the plain portion above-mentioned, the light quantity of the unit of describing respectively is modified to reaches homogenising, can carry out high-precision exposure.For example, just can form high meticulous pattern by thereafter above-mentioned photographic layer being developed.

＜2〉according to above-mentioned＜1〉the middle pattern formation method of putting down in writing, wherein, the light beam that will penetrate from light irradiating means utilizes light-gathering optics to shine to optical modulator body as the light beam that has distribution in the angle of chief ray.This＜2 in the record pattern formation method in, because the light beam that will penetrate from above-mentioned light irradiating means utilizes light-gathering optics to shine to optical modulator body as the light beam that has distribution in the angle of chief ray, therefore will make in the light quantity in the irradiation area of the light beam that above-mentioned optical modulator body shines to have distribution.Consequently, the light quantity distribution on the plane of exposure is homogenized, can carry out the exposure of very high degree of precision.For example, just can form very high meticulous pattern by thereafter above-mentioned photographic layer being developed.

＜3〉according to above-mentioned＜1〉the middle pattern formation method of putting down in writing, wherein, the light beam that will penetrate from light irradiating means utilizes light-gathering optics to shine to optical modulator body as heart light far away.This＜3 in the record pattern formation method in, because the light beam that will penetrate from above-mentioned light irradiating means utilizes above-mentioned light-gathering optics to shine to above-mentioned optical modulator body as heart light far away, aspect the homogeneity two of the light quantity distribution of light on plane of exposure that therefore just can realize the disposition far away of the light that shines to above-mentioned optical modulator body simultaneously, modulate by above-mentioned optical modulator body, can carry out the exposure of very high degree of precision.For example, just can form very high meticulous pattern by thereafter above-mentioned photographic layer being developed.

＜4〉according to above-mentioned＜3〉the middle pattern formation method of putting down in writing, wherein, light-gathering optics has light distribution correction mechanism, its by: have lens power along with first optical lens of the aspherical shape that diminishes away from optical axis center, have lens power along with second optical lens that becomes big aspherical shape away from optical axis center constitutes.This＜4 in the record pattern formation method in, because above-mentioned light-gathering optics has light distribution correction mechanism, its by: have first optical lens of lens power along with (convex lens that parallel incident beam is assembled are such) aspherical shape that diminishes away from optical axis center, has lens power along with second optical lens that becomes big (concavees lens that parallel incident beam is dispersed are such) aspherical shape away from optical axis center constitutes, therefore compare with the light of the periphery that passes above-mentioned first optical lens, near the light that passes the central authorities can realize strengthening situation away from the degree of optical axis, in addition, by utilizing first optical lens and second optical lens to reverse, just can realize telecentric optical system along the variation of the lens power of optical axis.Consequently, for the light quantity distribution of the light beam that penetrates from this telecentric optical system, compare with optical axis center, the distribution density of periphery improves, and the light quantity distribution on the plane of exposure is homogenized, can carry out the exposure of very high degree of precision.For example, just can form very high meticulous pattern by thereafter above-mentioned photographic layer being developed.

＜5〉according to above-mentioned＜1〉to＜4 in the pattern method of formationing of any record, wherein, light-gathering optics by light irradiating means in the irradiation area of the light beam that optical modulator body shines, make the light quantity of periphery compare increase with central part.This＜5 in the record pattern formation method in, since above-mentioned light-gathering optics by above-mentioned light irradiating means in the irradiation area of the light beam of above-mentioned optical modulator body irradiation, make the light quantity of periphery compare increase with central part, therefore in the irradiation area of the light beam that shines to above-mentioned optical modulator body, the light quantity that originally is lower than the periphery of central part is increased by above-mentioned light-gathering optics, and the light utilization ratio of exposure improves.

＜6〉according to above-mentioned＜1〉to＜5 in the pattern formation method of any record, wherein, optical modulator body is a spatial optical modulation element.

＜7〉according to above-mentioned＜6〉the middle pattern formation method of putting down in writing, wherein, spatial optical modulation element is Digital Micromirror Device (DMD).

＜8〉according to above-mentioned＜1〉to＜7 in the pattern method of formationing of any record, wherein, after having carried out exposing, carry out the development of photographic layer.

＜9〉according to above-mentioned＜1〉to＜8 in the pattern method of formationing of any record, wherein, after having carried out development, carry out the formation of permanent pattern.

＜10〉according to above-mentioned＜9〉the middle pattern formation method of putting down in writing, wherein, permanent pattern is a wiring pattern, the formation of this permanent pattern is at least a the carrying out that utilizes in etch processes and the coating film treatment.

＜11〉according to above-mentioned＜1〉to＜10 in the pattern formation method of any record, wherein, light irradiating means can be shone the light compositing more than two.This＜11 in the pattern of record form in the material, because of above-mentioned light irradiating means can be shone the light compositing more than two, thereby can expose with the darker exposure light of depth of focus.Consequently, can very highly carry out above-mentioned pattern is formed the exposure of material subtly.For example, just can form very high meticulous pattern by thereafter above-mentioned photographic layer being developed.

＜12〉according to above-mentioned＜1〉to＜11 in the pattern formation method of any record, wherein, light irradiating means has: a plurality of laser instruments, multimode optical fiber, will be from these a plurality of laser instruments the parallel photochemical and optically focused of the laser beam of irradiation and converge at the light source light-gathering optics of the incident end face of above-mentioned multimode optical fiber respectively.This＜12 in the record pattern formation method in, by utilizing above-mentioned light irradiating means, will be from above-mentioned a plurality of laser instruments respectively the laser beam of irradiation with above-mentioned light source light-gathering optics optically focused, converge at the incident end face of above-mentioned multimode optical fiber, just can obtain the darker light beam of high brightness and depth of focus.Consequently, can very highly carry out above-mentioned pattern is formed the exposure of material subtly.For example, just can form very high meticulous pattern by thereafter above-mentioned photographic layer being developed.

＜13〉according to above-mentioned＜1〉to＜12 in the pattern formation method of any record, wherein, photographic layer comprises bonding agent, polymerizable compound, Photoepolymerizationinitiater initiater.

＜14〉according to above-mentioned＜13〉the middle pattern formation method of putting down in writing, wherein, bonding agent has acidic groups.

＜15〉according to above-mentioned＜13〉to＜14 in the pattern formation method of any record, wherein, bonding agent is an ethylenic copolymer.

＜16〉according to above-mentioned＜13〉to＜15 in the pattern of any record form material, wherein, bonding agent contains multipolymer, this multipolymer has certain the tectonic unit at least that derives from styrene and styrene derivative.

＜17〉according to above-mentioned＜13〉to＜16 in the pattern of any record form material, wherein, the glass temperature of bonding agent (Tg) is more than 80 ℃.

＜18〉according to above-mentioned＜13〉to＜17 in the pattern formation method of any record, wherein, the acid number of bonding agent is 70～250mgKOH/g.

＜19〉according to above-mentioned＜13〉to＜18 in the pattern formation method of any record, wherein, polymerizable compound comprises certain the monomer at least with urethane groups and aryl.

＜20〉according to above-mentioned＜13〉to＜18 in the pattern formation method of any record, wherein, Photoepolymerizationinitiater initiater comprises and is selected from least a in halogenated hydrocarbon derivant, six aryl bisglyoxalines, 9 oxime derivate, organic peroxide, thio-compounds, ketonic compound, aromatic series salt and the aromatic ring alkene metal derivative class.

＜21〉according to above-mentioned＜1〉to＜20 in the pattern formation method of any record, wherein, photographic layer contains the bonding agent of 10～90 quality %, contains the polymerizable compound of 5～90 quality %.

＜22〉according to above-mentioned＜1〉to＜21 in the pattern formation method of any record, wherein, the thickness of photographic layer is 1～100 μ m.

＜23〉according to above-mentioned＜1〉to＜22 in the pattern formation method of any record, wherein, supporting mass contains synthetic resin, and is transparent.

＜24〉according to above-mentioned＜1〉to＜23 in the pattern formation method of any record, wherein, supporting mass is a strip.

＜25〉according to above-mentioned＜1〉to＜24 in the pattern method of formationing of any record, wherein, pattern formation material is a strip, is wound into drum.

＜26〉according to above-mentioned＜1〉to＜25 in the pattern method of formationing of any record, wherein, on the photographic layer of pattern formation material, form diaphragm.

Utilize the present invention, can solve problem in the past, following pattern formation method can be provided, promptly, in the exposure of having used the digital exposure apparatus that possesses the photohead that the unit of describing is distributed two-dimensionally, can be in cost squeeze, by the light quantity homogenising of the respectively unit of describing that will distribute two-dimensionally, and form fine pattern accurately.

Description of drawings

Fig. 1 is the summary pie graph of the optical system of the photohead that exposure device possessed that uses in the manufacture method of expression color filter of the present invention.

Fig. 2 is the example of partial enlarged drawing of the formation of expression Digital Micromirror Device (DMD).

Fig. 3 A is the key diagram that is used to illustrate the action of DMD shown in Figure 2.

Fig. 3 B is the key diagram that is used to illustrate the action of DMD shown in Figure 2.

Fig. 4 A is the stereographic map of the formation of expression fiber array light source.

Fig. 4 B is the vertical view of arrangement of luminous point of the laser injection part of presentation graphs 4A.

Fig. 5 is the vertical view that the formation of ripple lasing light emitter is closed in expression.

Fig. 6 is the vertical view of the formation of expression laser module.

Fig. 7 is the side view of the formation of expression laser module shown in Figure 6.

Fig. 8 is the partial side view of the formation of expression laser module shown in Figure 6.

Fig. 9 A is the synoptic diagram that schematically shows the inclination of the chief ray of the laser of irradiation on DMD.

Fig. 9 B is the synoptic diagram of expression to the distribution of the chief ray angle of the laser of the last irradiation of DMD.

Figure 10 be expression will have with shown in Fig. 9 B to DMD go up the corresponding chief ray angle of the distribution (1) of chief ray angle of laser of irradiation distribution laser to DMD go up the chart (2) of postradiation light quantity distribution, the chart (3), expression of light transmission characteristic between expression DMD-microlens array by using the laser of as above-mentioned chart (3), having adjusted to carry out image exposure with the light quantity distribution homogenising in the exposure region the chart (4) of revised state.

Figure 11 A is the pie graph of expression telecentric optical system, is the pie graph of the telecentric optical system with non-spherical lens of expression second embodiment of the present invention.

Figure 11 B is the pie graph of expression telecentric optical system, is the pie graph of telecentric optical system of the spherical lens on the basis of expression with the telecentric optical system that becomes Figure 11 A.

Embodiment

(pattern formation method)

Pattern formation method of the present invention is included in after the photographic layer that pattern is formed material is layered on the processed matrix at least, the exposure process that this photographic layer is exposed, and comprise other the operation of suitably selecting.

Above-mentioned exposure process comprises following operation at least, promptly, the light beam that will penetrate from light irradiating means is via the light-gathering optics with light distribution correction mechanism, to have n (wherein n is the natural number 1 or more) two-dimensional arrangements retouch plain portion and with pattern-information make accordingly above-mentioned each retouch the optical modulator body that plain portion changes the optical modulation state and shine, the light beam that irradiation is modulated by above-mentioned optical modulator body and exposing

This exposure is following to be carried out, promptly, make from the light quantity of above-mentioned light irradiating means in the irradiation area of the light beam of above-mentioned optical modulator body irradiation to have distribution, the light quantity distribution of the light beam of having been modulated by above-mentioned optical modulator body is corrected for being exposed of above-mentioned photographic layer and reaches homogenising on the face.

Light quantity in the irradiation area of the light beam that above-mentioned optical modulator body shines has the method for distribution from above-mentioned light irradiating means as making, be not particularly limited, can suitably select according to purpose, for example can enumerate: the light beam that will penetrate from above-mentioned light irradiating means utilizes above-mentioned light-gathering optics as first embodiment of the light beam that has distribution in the angle of chief ray to above-mentioned optical modulator body irradiation; And the light beam that will penetrate from above-mentioned light irradiating means utilizes above-mentioned light-gathering optics as second embodiment of heart light far away to the optical modulator body irradiation.

An example for the exposure device of the exposure process of pattern formation method of the present invention below will describe in the reference accompanying drawing.Exposure method in the above-mentioned exposure process will be illustrated by the explanation to above-mentioned exposure device.

[first embodiment]

The summary of＜exposure device constitutes 〉

Among Fig. 1, expression has the summary of the photohead 100 in the exposure device of being located at first embodiment to constitute.

As shown in Figure 1, photohead 100 possesses the Digital Micromirror Device (DMD) 50 that belongs to spatial optical modulation element as the light beam and the pattern-information (following be called sometimes " view data ") of institute's incident are retouched the optical modulator body that (following be expressed as sometimes " pixel ") modulates in the plain portion at each accordingly.This DMD50 is connected with the not shown controller that possesses data processing division and mirror drive control part.

In the data processing division of this controller,, generate the control signal of drive controlling as each micro mirror of the DMD50 that retouches plain portion (pixel) based on the pattern-information of being imported (view data).In addition, in the mirror drive control part, based on the control signal that in the view data handling part, generates, the angle of the reflecting surface of each micro mirror of control DMD50.

And, will narrate in the back for the control of the angle of reflecting surface.

Light incident side at DMD50 disposes: possess the fiber array light source 112 of the laser injection part that the outgoing end (luminous point) of optical fiber is formed a line along prescribed direction, the laser correction that will penetrate and the light-gathering optics 114 of optically focused on DMD, will see through the catoptron 122,124 of the laser of light-gathering optics 114 to the DMD50 reflection from fiber array light source 112 successively.

Light-gathering optics 114 by a pair of compound lens 116 of the laser focusing that will from fiber array light source 112, penetrate, with optically focused the light quantity distribution of laser be modified to the bar integrator (rod integrator) 118 that reaches homogenising and the laser that will revise light quantity distribution are gone up collector lens 120 from optically focused to DMD.

Because bar integrator 118 is that light leaded light in the integrator inner total reflection is advanced, therefore can be according to making light quantity distribution reach the mode correction laser of homogenising.

On the other hand, the light reflection side at DMD50 is provided with projection optical system.

The following formation of above-mentioned projection optical system, promptly, for with the projection on the photosensitive material of the plane of exposure of the light reflection side that is in DMD50 (this photographic layer that above-mentioned pattern is formed in the material is laminated in the laminated body that forms on the processed matrix) 134 of light source picture, and dispose the optical component of the usefulness of respectively exposing of lens combination 126, microlens array 128, objective system 130 successively towards photosensitive material 134 ground from the DMD50 side.

Here, lens combination 126 and objective system 130 are used as the magnifying optics that has made up multi-disc lens (convex lens or concavees lens etc.) as shown in Figure 1 and constitute, by will amplifying, and will be enlarged into the size of regulation by the area of the exposure region of DMD50 beam reflected on photosensitive material 134 by the sectional area of DMD50 beam reflected (light shafts).

And photosensitive material 134 is disposed at the focal position, rear of objective system 130.

Microlens array 128 as shown in Figure 1, be in each micro mirror 62 (with reference to Fig. 2) of reflection DMD50 of the laser of irradiation from fiber array light source 112, to arrange a plurality of one to one lenticules 132 two-dimensionally, integral forming and make the member of rectangular flat shape, each lenticule 132 is disposed at respectively on the optical axis of each laser beam that has seen through lens combination 126 respectively.

This microlens array 128 for example can be by making resin or optical glass mould-forming.

-optical modulator body-

As the DMD50 of an example of above-mentioned optical modulator body as shown in Figure 2, be the device that has disposed tiny mirror (micro mirror) 62 on sram cell (memory cell) 60, be a plurality of (for example 600 * 800) tiny mirror that formation is retouched plain portion (being also referred to as " pixel " or " pixel ") to be arranged with clathrate and the mirror device that constitutes with utilizing pillar supporting.

In each pixel, be provided with micro mirror 62 at topmost by pillar supporting, at the surperficial evaporation of micro mirror 62 the high material of aluminium isoreflectance is arranged.And the reflectivity of micro mirror 62 is more than 90%.

In addition, under micro mirror 62, folder is across comprising that hinge and stent strut dispose the sram cell 60 of the CMOS of the Si-gate that the production line that utilizes common semiconductor memory makes, wholely constituted by monolithic (one-piece type).

When in the sram cell 60 of DMD50, writing digital signal, will be the center with the diagonal line with respect to the scope medium dip of the substrate-side that has disposed DMD50 then at ± α degree (for example ± 10 degree) by the micro mirror 62 of pillar supporting.Fig. 3 A represent micro mirror 62 be in out state+state that the α degree tilts, Fig. 3 B represent micro mirror 62 be in off status-state that the α degree tilts.So,, just can inject of the vergence direction reflection of the light of DMD50 to each micro mirror 62 by controlling the inclination angle of micro mirror 62 of each pixel of DMD50 accordingly as illustrated in fig. 2 with picture signal.

And, among Fig. 2 the part of DMD50 is amplified, provide micro mirror 62 is controlled to be+the α degree or-example of the state of α degree.The switch control of each micro mirror 62 is to utilize the not shown controller that is connected with DMD50 to carry out.And, on the direction of micro mirror 62 folded light beams of utilizing off status, dispose absorber of light (not shown).

-light irradiating means-

Shown in Fig. 4 A, possess a plurality of (among the figure being 25) laser module 64 as the fiber array light source 112 of an example of above-mentioned light irradiating means, on each laser module 64, be coupled with an end of multimode optical fiber 30.

The other end at multimode optical fiber 30, be coupled with the optical fiber 31 of the identical and covering footpath of fibre core footpath and multimode optical fiber 30 less than multimode optical fiber 30, shown in Fig. 4 B, multiple row (being 3 row among the figure) is arranged along prescribed direction in the outgoing end (luminous point) of optical fiber 31 constitute laser injection part 68.

As multimode optical fiber 30 and optical fiber 31, no matter be that step change type (step index) optical fiber, gradient type (graded index) optical fiber and any of compound optical fiber can.For example can use the step change type optical fiber of Mitsubishi Cable Ind Ltd's system.

In the present embodiment, multimode optical fiber 30 and optical fiber 31 are step change type optical fiber, the covering footpath=125 μ m of multimode optical fiber 30, fibre core footpath=50 μ m, NA=0.2, the transmitance of incident end face coating=more than 99.5%, covering footpath=60 μ the m of optical fiber 31, fibre core footpath=50 μ m, NA=0.2.

But the covering of optical fiber 31 directly is not limited to 60 μ m.The covering of used optical fiber directly is 125 μ m in the optical fiber source in the past, yet because the covering footpath is more little, depth of focus is just dark more, so the covering of multimode optical fiber footpath is preferably below 80 μ m, more preferably below 60 μ m, further preferably below 40 μ m.

On the other hand, because the fibre core footpath needs 3～4 μ m at least, so the covering of optical fiber 31 footpath is preferably more than 10 μ m.

Laser module 64 is made of the ripple lasing light emitter (optical fiber source) that closes shown in Fig. 5.This close the ripple lasing light emitter by: arrange and to be fixed in the horizontal multimode of a plurality of (for example 7) sheet on the heating group (heat block) 10 or GaN semiconductor laser LD1, LD2, LD3, LD4, LD5, LD6 and the LD7 of single mode; With the collimation lens 11,12,13,14,15,16 and 17 that GaN based semiconductor laser instrument LD1～LD7 difference is provided with accordingly; A collector lens 20; Article one, multimode optical fiber 30 constitutes.

And the number of semiconductor laser is not defined as 7.For example, in the multimode optical fiber of covering footpath=60 μ m, fibre core footpath=50 μ m, NA=0.2, even can inject 20 semiconductor laser, can realize the essential light quantity of irradiation head, and further reduce optical fiber bar number.

The excitation wavelength of GaN based semiconductor laser instrument LD1～LD7 all is common (for example 405nm), and maximum output also all is common (being 100mW in multimode laser for example, is 30mW in single-mode laser).And, as GaN based semiconductor laser instrument LD1～LD7, also can use the laser instrument that in the wavelength coverage of 350nm～450nm, possesses above-mentioned 405nm excitation wavelength in addition.

And, will narrate in the back for the preferred wavelength scope.

Above-mentioned ripple lasing light emitter such as the Figure 6 and Figure 7 of closing is accommodated in by the optical parameter with other in packaging body 40 of case shape of top opening.Packaging body 40 possesses the packaging body lid 41 for its closure of openings is made, import sealing gas by handling the back in the degassing, the opening of packaging body 40 is sealed with packaging body lid 41, just can in by packaging body 40 and packaging body lid 41 confined spaces that form (seal cavity), the above-mentioned ripple lasing light emitter that closes hermetic be sealed.

Be fixed with base plate 42 in the bottom surface of packaging body 40, at this above base plate 42, above-mentioned heating group 10 is installed, keep lamp condenser lens 20 collector lens anchor clamps 45, keep the fiber clamp 46 of the incident end of multimode optical fiber 30.The outgoing end of multimode optical fiber 30 is pulled out outside packaging body the opening from the wall that is formed at packaging body 40.

In addition, collimation lens anchor clamps 44 are installed, are keeping collimation lens 11～17 in the side of heating group 10.On the cross wall face of packaging body 40, be formed with opening, pass this opening and will supply with the wiring 47 of drive current to the external place of packaging body to GaN based semiconductor laser instrument LD1～LD7.

And, among Fig. 6, for fear of miscellaneousization of figure, only to the GaN based semiconductor laser instrument LD7 mark in a plurality of GaN based semiconductor laser instruments numbering, and only to 17 marks of the collimation lens in a plurality of collimation lenses numbering.

Fig. 8 is the figure of front shape of the mounting portion of the above-mentioned collimation lens 11～17 of expression.

The zone that comprises optical axis that collimation lens 11～17 is made into respectively to possess aspheric round lens with parallel flat elongated the shape that cuts.The collimation lens of this elongated shape for example can be by making resin or optical glass mould-forming.Collimation lens 11～17 by so that the mode of orientation (left and right directions of Fig. 8) quadrature of the luminous point of length direction and GaN based semiconductor laser instrument LD1～LD7 be disposed in the orientation of above-mentioned luminous point with connecting airtight.

On the other hand, as GaN based semiconductor laser instrument LD1～LD7, can use following laser instrument, promptly, possesses the active layer that luminous width is 2 μ m, for example be respectively that B1～B7 gives off laser beam respectively under 10 °, 30 ° the state in the beam divergence angle of the direction parallel, rectangular direction with active layer.These GaN based semiconductor laser instruments LD1～LD7 is set in the mode that on the direction parallel with active layer luminous point is formed a line.

So the laser beam B 1～B7 that sends from each luminous point will be as described above injects each collimation lens 11～17 of elongated shape under the consistent state of the big direction that direction is consistent with length direction, beam divergence angle is little of beam divergence angle and Width (with the direction of length direction quadrature).That is to say that the width of each collimation lens 11～17 is 1.1mm, length is 4.6mm, injects the horizontal direction of their laser beam B 1～B7, the beam diameter of vertical direction is respectively 0.9mm, 2.6mm.In addition, collimation lens 11～17 focal length f separately ₁=3mm, NA=0.6, lens configuration spacing=1.25mm.

Lamp condenser lens 20 are the zones that comprise optical axis that will possess aspheric round lens with parallel flat elongated cut, and be formed in the orientation of collimation lens 11～17, just long on the horizontal direction, short shape on rectangular direction with it.The focal length f of this lamp condenser lens 20 ₂=23mm, NA=0.2.Lamp condenser lens 20 is also identical with above-mentioned collimation lens, for example can be by resin or optical glass mould-forming are made.

So in the fiber array light source 112 that constitutes, it is parallel photochemical by the collimation lens 11～17 of correspondence respectively to close the laser beam B 1, B2, B3, B4, B5, B6 and the B7 that penetrate with the diverging light state each GaN based semiconductor laser instrument LD1～LD7 of ripple lasing light emitter from formation.Parallel photochemical laser beam B 1～B7 is by lamp condenser lens 20 optically focused, is focused on the incident end face of fibre core 30a of multimode optical fiber 30.

Constitute the light source light-gathering optics by collimation lens 11～17 and lamp condenser lens 20, constitute the glistening light of waves system of closing by this light source light-gathering optics and multimode optical fiber 30.

That is, by lamp condenser lens 20 as described above optically focused laser beam B 1～B7 inject the fibre core 30a of multimode optical fiber 30 and in optical fiber, propagate, closing ripple is a laser beam B, from the optical fiber 31 of the outgoing end coupling of multimode optical fiber 30 penetrate.

In each laser module, the coupling efficiency of laser beam B 1～B7 and multimode optical fiber 30 is 0.85, (using under the situation of single-mode laser) under the situation that respectively is output as 30mW of GaN based semiconductor laser instrument LD1～LD7, be arranged in the optical fiber 31 of array-like for each bar, what can obtain to be output as 180mW (=30mW * 0.85 * 7) closes the ripple laser beam B.So the output that 25 optical fiber 31 is arranged in laser injection part 68 places of array-like is about 4.5W (=180mW * 25).

At the laser injection part 68 of fiber array light source 112, be arranged with the luminous point of high brightness like this along main scanning direction.Because the output of the optical fiber source in the past that will be coupled from the laser of single semiconductor laser and an optical fiber is low, if therefore do not arrange multiple row, then can't obtain required output, yet the employed ripple lasing light emitter that closes is owing to output is high in the present embodiment, even so row of minority, even for example 1 row also can obtain required output.

For example, in the optical fiber source in the past that semiconductor laser and optical fiber are coupled one by one, as a rule, can use the laser instrument that is output as about 30mW (milliwatt) as semiconductor laser, can use fibre core as optical fiber directly is that 50 μ m, covering directly are that 125 μ m, NA (numerical aperture) are 0.2 multimode optical fiber, if go for about 4.5W (watt) output, then 225 (15 * 15) multimode optical fibers must be finished, because the area of light-emitting zone is 3.6mm ²(1.9mm * 1.9mm), so the brightness at laser injection part 68 places is 1.25 (W/mm ²), the brightness of each bar optical fiber is 10 (W/mm ²).

Different with it, in the present embodiment, as mentioned above, owing to can obtain the output of about 4.5W with 25 multimode optical fibers, the area of the light-emitting zone at laser injection part 68 places is 0.2mm ²(0.18mm * 1.13mm), so the brightness at laser injection part 68 places just becomes 22.5 (W/mm ²), compared with the pastly can realize about 18 times high brightnessization.In addition, the brightness of each bar optical fiber is 90 (W/mm ²), compared with the pastly can realize about 9 times high brightnessization.

As constituting the above-mentioned semiconductor laser that closes the ripple lasing light emitter, preferably has near the blue laser of the excitation wavelength of 400nm.Use the words of blue laser the optically focused light beam of each lenticule 132 of microlens array 128 can be shunk.

-have the light-gathering optics of light distribution correction mechanism-

In the photohead 100 as the present embodiment of first embodiment, because above-mentioned light-gathering optics 114 is different with the light quantity distribution debugging functions that bar integrator 118 is possessed, light quantity distribution on the plane of exposure of the exposing light beam that will have been modulated by DMD50 is revised with higher uniform precisionization ground, therefore possess the light quantity that makes in the irradiation area of the laser that DMD50 shines and have the function of the distribution of regulation, specifically, possess for the laser that from fiber array light source 112, penetrates, penetrate the distribution that in the angle of chief ray, has regulation laser and to the function of DMD50 irradiation.

Here, use Fig. 9 to describe to the example of DMD50 irradiation to being somebody's turn to do the laser that in the angle of chief ray, has distribution.And, so-called chief ray (principle ray/chief ray) is meant, in optical system, pass the light (even aperture diaphragm is made as the minimum light that also can scattering ground exist) at center of the entrance pupil (or aperture diaphragm) of object space, broadly be meant the light at the center of skew ray wire harness, use the latter's the meaning here.

Fig. 9 A is the figure that schematically shows the inclination of the chief ray of the laser of irradiation on DMD50.Shown in Fig. 9 A, in the laser LB of the irradiation of the certain location P on DMD50, at the chief ray of laser LB under the oblique situation of negative (-) inclination, shown in arrow-PR, chief ray tilts to the direction of optical axis (optical axis center) X of close laser, under the oblique situation of (+) inclination just, shown in arrow+PR, tilt to direction away from the optical axis X of laser.

To be the laser that penetrates from the light-gathering optics 114 of present embodiment of expression have the figure of the example of the field of illumination irradiation on DMD50 under the state of distribution in the angle at chief ray with the distance of distance optical axis center to Fig. 9 B accordingly.Shown in Fig. 9 B, the distribution of chief ray angle for the laser of the field of illumination on DMD50 (laser radiation zone) irradiation, do not tilt and parallel at the optical axis center place of laser chief ray with optical axis, along with advancing to the periphery of field of illumination from optical axis center, chief ray at leisure to+inclination is oblique, and it is big that its inclination angle becomes at leisure, when arriving predetermined distance YA, chief ray reaches maximum (inclination maximum A) to the inclination angle of+side, when surpassing predetermined distance YA, then chief ray diminishes at leisure to the inclination angle of+side, when arriving the peripheral end of field of illumination, and the then identical distribution that becomes the inclination that does not have chief ray with optical axis center.

Have this kind distribution in the angle of the chief ray by making laser, just can the field of illumination irradiation on DMD50 compare the laser of the optical density that has improved periphery with optical axis center, that is, the laser of the luminance brightness that has improved periphery is compared in irradiation with optical axis center.

And, in making the chief ray angle of laser, have under the situation of above-mentioned distribution, size by the abundance of the inclination maximum A of chief ray decision preferably is made as more than the light quantity reduction amount of periphery, and is made as below the amount that satisfies by the disposition far away (depth of parallelism of chief ray and optical axis) of the exposing light beam of plane of exposure requirement.

Under the situation of the photohead 100 of present embodiment, because it mainly is that microlens array 128 (with reference to Fig. 1) by the projection optical system of the light reflection side that is disposed at DMD50 causes that the light quantity of the periphery of the exposing light beam of plane of exposure reduces, therefore preferably the size of above-mentioned abundance for example is set at more than the light quantity reduction amount of the periphery that produces because of this microlens array 128.

In addition, for predetermined distance YA, can reduce suitably setting of zone (revising the zone of light quantity) according to the light quantity reduction amount and the light quantity of this periphery, yet in the example shown in Fig. 9 B, when the distance of peripheral end (peripheral end of DMD50) that will be from the optical axis center to the field of illumination is made as YS, then be set at YS＞YA＞YS/2.

The action of＜exposure device 〉

Action to above-mentioned exposure device describes.

In this exposure device, when to not shown controller input image data, then controller will be based on the view data of being imported, generate drive controlling and be located at the control signal of each micro mirror 62 of the DMD50 in the photohead 100, control the angle of reflecting surface of each micro mirror 62 of DMD50 based on the control signal that is generated.

From fiber array light source 112 via light-gathering optics 114 to the illumination light (laser) of DMD50 irradiation by with the angle of the reflecting surface of each micro mirror 62 accordingly to the prescribed direction reflection and modulate, the light beam of having modulated is amplified by lens combination 126 and each lenticule 132 in being located at microlens array 128 is injected optically focused.After this, this optically focused light beam image on the plane of exposure of photosensitive material 134 by objective system 130, like this, laser by fiber array light source 112 irradiation is just carried out switch (modulation) to each pixel, photosensitive material 134 is exposed with the pixel unit (exposure region) with the roughly the same number of the use pixel count of DMD35.

As a rule, the light quantity of this light beam (light intensity) distribution will thereby make the periphery of optical axis compare reduction with central part because of lens combination, yet in the photohead 100 of present embodiment, to the DMD50 irradiation, be provided with bar integrator 118 in the light-gathering optics 114 on the light path of the light incident side that is disposed at DMD50 for the light quantity distribution homogenising of the laser that will from fiber array light source 112, penetrate.

But, even utilize this bar integrator 118, as present embodiment respectively the unit of describing utilize in the system of microlens array 128 optically focused, the optical axis periphery also becomes clearly with respect to the light intensity reduction of central part, carrying out under the situation of image exposure with high precision more, be difficult to light quantity distribution is adapted to required precision.In order to improve the correction precision of this light quantity distribution,,, therefore have the shortcoming that installation cost rises and photohead 100 maximizes because bar integrator 118 is very expensive opticses though also can consider the size of extension rod integrator 118.

Be directed to this, in the photohead 100 of present embodiment, as previously mentioned, since the laser that will inject to light-gathering optics 114 from fiber array light source 112 shown in (1) Figure 10 like that, in the angle of chief ray, has distribution, become laser and the ejaculation from light-gathering optics 114 of comparing the luminance brightness that has improved periphery with optical axis center, shine to DMD50, therefore the light quantity distribution in the laser radiation zone of DMD50 is shown in (2) among Figure 10, and the light quantity of comparing periphery with optical axis center is improved.Thus, when the light beam that utilizes DMD50 that each pixel has been carried out modulation see through as (3) among Figure 10 shown in, have like that along with from optical axis center to periphery advance and the microlens array 128 of characteristic of transit dose that reduces light when the plane of exposure of photosensitive material 134 shines, then shown in (4) among Figure 10, the light quantity distribution of the light beam on the plane of exposure just is corrected for and reaches homogenising.

As above shown in the explanation, in the exposure device of first embodiment, in a plurality of pixel portions that distribute two-dimensionally, the light quantity of the unit of describing respectively can be modified to and reach homogenising, carry out high-precision image exposure.

In addition, even be used in combination to change accordingly under the situation of technology of driving mode drive controlling constantly of each micro mirror 62 of DMD50 with light quantity distribution, because respectively the light quantity of the unit of describing is modified in advance and is reached homogenising, therefore can alleviate the load on the drive control part that is added in DMD50 and reduce influence processing speed, circuit can be constituted or the process software simplification in addition, thus can cost squeeze.

In addition, if the light quantity distribution correction mechanism that is made of optical system used in the present embodiment (light-gathering optics 114) then can utilize simple and cheap formation to realize the mechanism of above-mentioned correction light quantity distribution.

[second embodiment]

Second embodiment is following technology, promptly, in the photohead 100 of the exposure device of the first above-mentioned embodiment, by in light-gathering optics 114, setting has the telecentric optical system of non-spherical lens as above-mentioned light distribution correction mechanism, and with first embodiment in the same manner with the light quantity distribution homogenising of the light beam on the plane of exposure.

In the photohead of this second embodiment, for example in the telecentric optical system 150 that constitutes as the plano-convex lens 152,154 by 2 one group of above-mentioned light distribution correction mechanism setting shown in Figure 11 A in the light-gathering optics 114, this telecentric optical system 150 for example is disposed between bar integrator 118 and the collector lens 120.

Plano-convex lens 152,154 is set as the non-spherical lens of convex side being made the aspheric surface shape, has lens power along with first optical lens of (convex lens of parallel incident beam optically focused are such) aspherical shape that diminishes away from optical axis center and have the combination of lens power along with second optical lens that becomes big (concavees lens that parallel incident beam is dispersed are such) aspherical shape away from optical axis center.

The plano-convex lens 152 that is disposed at the light incident side (fiber array light source 112 sides) of laser is made as radius-of-curvature along with becoming big aspheric surface away from optical axis (optical axis center) X with the face shape of plane of incidence S2, in other words, be made as curved surface along with the aspheric surface that diminishes away from optical axis X, be made as exit facet S3 plane.

In addition, the plano-convex lens 154 that is disposed at the exiting side (DMD50 side) of laser is made as plane of incidence S4 plane, the face shape of exit facet S5 is made as radius-of-curvature along with the aspheric surface that diminishes away from optical axis, in other words, is made as curvature along with becoming big aspheric surface away from optical axis X.

Below, in table 1, provide the example of lens data of the telecentric optical system 150 of present embodiment, in table 2, provide an example of the aspherical surface data of the plane of incidence S2 of present embodiment and exit facet S5.

[table 1]

Lens data
					The face numbering	Radius-of-curvature	Face at interval	Refractive index (405nm)	Abbe number
OBJ	∞	25.065
					S2	15	8	1.5297	64.1
S3	∞	68.6
					S4	∞	8	1.5297	64.1
S5	-28.0	50
					IMG	∞

[table 2]

Aspherical surface data
			The face numbering	S2	S5
A	-0.00012	0.00003

In addition, above-mentioned aspherical surface data can be represented with the coefficient of the following formula (1) of representing aspherical shape.

[several 1]

$z=\frac{{\mathrm{<figure-callout\; id="2"\; label="h"\; filenames="S2006800244813E00101.png,S2006800244813E00111.png"\; state="\{\{state\}\}">h</figure-callout>}}^2/R}{1+\sqrt{1-{\mathrm{<figure-callout\; id="2"\; label="h"\; filenames="S2006800244813E00101.png,S2006800244813E00111.png"\; state="\{\{state\}\}">h</figure-callout>}}^2/{\mathrm{<figure-callout\; id="2"\; label="R"\; filenames="S2006800244813E00101.png,S2006800244813E00111.png"\; state="\{\{state\}\}">R</figure-callout>}}^2}}+A{\mathrm{<figure-callout\; id="4"\; label="h"\; filenames="S2006800244813E00101.png,S2006800244813E00111.png"\; state="\{\{state\}\}">h</figure-callout>}}^4$ Formula (1)

Above-mentioned formula defines each coefficient in (1) as followsly.

Z: from being in apart from the length (mm) of lighting the drop-down vertical line in section (plane vertical) to aspheric summit on the aspheric surface of the position of optical axis height h with optical axis

H: apart from distance (the mm) (h of optical axis ²=x ²+ y ²)

R: radius-of-curvature (curvature: 1/R)

A: aspherical surface data

Utilize above formation, in the exposure device of second embodiment, shown in Figure 11 A, among the laser LB2 that penetrates from plano-convex lens 125, focal length is along with elongated away from optical axis X.Like this, when laser LB2 arrives the plane of incidence S4 of plano-convex lens 154, compare, pass near the light of central authorities and strengthen away from the tendency of optical axis X with the light of the periphery that passes plano-convex lens 152.Like this, and compare near the central authorities of lens, the luminance brightness of periphery improves.In addition, because plano-convex lens 154 is opposite with plano-convex lens 152, therefore focal length when with these 2 plano-convex lenss, 152,154 combinations, then can form telecentric optical system along with shortening away from optical axis X.

Like this, light quantity distribution for the laser LB3 of parallelization ground ejaculation the telecentric optical system 150 that has plano-convex lens 152,154 from this, the distribution density of optical axis periphery uprises with respect to the center, in the DMD50 of illuminated this laser LB3, the light quantity of the periphery in laser radiation zone is compared with central part (optical axis center) and is obtained increasing.

Among Figure 11 B, expression becomes the ray plot of telecentric optical system 160 of spherical lens system on basis of the telecentric optical system 150 of the present embodiment that has adopted Aspheric Lens System.

In this telecentric optical system 160, the plane of incidence S2 ' of plano-convex lens 162 that is disposed at the light incident side of laser (LB1) is set as sphere, the exit facet S5 ' of plano-convex lens 164 that is disposed at the exiting side of laser (LB3 ') is set as sphere, so, in this telecentric optical system 160, the light quantity distribution of the laser LB3 ' that penetrates from exit facet S5 ' just shown in Figure 11 B, becomes the distribution of equalization haply from the optical axis center to the periphery.

Like this, in the Aspheric Lens System (telecentric optical system 150) of second embodiment, from the light quantity distribution when having used above-mentioned spherical lens system (telecentric optical system 160) more as can be known, the light quantity distribution of emitted laser improves with respect to optical axis center in the distribution density of periphery, and the light quantity of periphery is compared with optical axis center and obtained increasing.

So, identical with first embodiment, even the light beam that reason DMD50 has modulated sees through microlens array 128, and the generation periphery is with respect to the light quantity reduction of optical axis center portion, also can light quantity distribution be modified to the light beam that reaches homogenising, utilize the exposure device that possesses this telecentric optical system 150 also can carry out high-precision image exposure to the plane of exposure irradiation.

In addition, as mentioned above, because the laser that penetrates from telecentric optical system 150 is used as that heart light far away penetrates and to the DMD50 irradiation, therefore can realize simultaneously to the disposition far away of the laser of DMD50 irradiation with aspect the homogeneity two of the light quantity distribution of light beam on plane of exposure of DMD50 modulation.

In addition, identical with first embodiment, second embodiment is if the light quantity distribution correction mechanism that is made of the light-gathering optics with plano-convex lens 152,154 (telecentric optical system) of 2 one group then also can utilize simple formation to realize the mechanism of above-mentioned correction light quantity distribution.

In addition, in second embodiment, increase the light quantity of the periphery of laser, the reduction of the light utilization ratio in then can suppressing to expose by using telecentric optical system 150.Like this, because the output of the laser that penetrates is reduced, therefore can also realize the long lifetime of fiber array light source 112, to the inhibition of the contamination/degradation of the optical system that causes by high-luminance light.In addition, the maintenance frequency of fiber array light source 112 or optical system can also be reduced, thereby the maintenance cost of exposure device can be reduced.

Though more than utilize first and second embodiment that exposure process is had been described in detail, the present invention is not limited to them, can implement other variety of way within the scope of the invention.

For example, in the above-mentioned exposure device, as above-mentioned optical modulator body, though the photohead that has possessed the DMD that belongs to the spatial modulation element is illustrated, but except this kind reflection-type spatial optical modulation element, also can use infiltration type spatial optical modulation element (LCD).For example, also can use the spatial optical modulation element (SLM of MEMS (Micro Electro Mechanical Systems) type; Special Light Modulator), utilize the electric optical effect will be through the spatial optical modulation element beyond the optical element (PLZT element) of optical modulation, the liquid crystal photic gate MEMS types such as liquid crystal light gate array such as (FLC).And, so-called MEMS be meant the micron-scale that utilization obtains based on the Micrometer-Nanometer Processing Technology of IC manufacturing process sensor, actuator and with control circuit integrated the general name of fine system, the spatial optical modulation element of so-called MEMS type is meant the spatial optical modulation element by the electricapparatus action drives of having utilized electrostatic force.In addition, also can use and arrange a plurality of Grating Light Valve (GLV) and mechanism that constitute two-dimensionally.

Use in the formation of reflection-type spatial optical modulation element (GLV) or infiltration type spatial optical modulation element (LCD) at these, except above-mentioned lasing light emitter, also can use lamp etc. as light source.

In addition, as above-mentioned optical modulator body, can use possess a plurality of fiber array light source of closing the ripple lasing light emitter, will possess the optical fiber that will penetrate from the laser that the single semiconductor laser with a luminous point is injected the optical fiber source array fiber array light source, the light source (for example LD array, organic EL array etc.) that a plurality of luminous points are arranged two-dimensionally etc.

＜laminated body 〉

As the object of above-mentioned exposure, form the photographic layer that this photographic layer in the material is laminated in the laminated body that forms on the processed matrix so long as will on supporting mass, have the pattern of photographic layer, just be not particularly limited, can suitably select according to purpose.As above-mentioned laminated body, the above-mentioned pattern that can be stacked also for example forms the part that other the layer beyond the photographic layer in the material forms.

＜pattern forms material 〉

Form material as above-mentioned pattern,, just be not particularly limited, can suitably select according to purpose so long as on supporting mass, have photographic layer.

As above-mentioned photographic layer, be not particularly limited, can form the material from known pattern and suitably select, yet for example comprise bonding agent, polymerizable compound, Photoepolymerizationinitiater initiater, preferably comprise other the composition of suitably selecting.

In addition, the stacked number as photographic layer is not particularly limited, and can suitably select according to purpose, for example both can be 1 layer, also can be more than 2 layers.

" bonding agent "

As above-mentioned bonding agent, be expansile preferably for example to alkaline aqueous solution, be solubility more preferably to alkaline aqueous solution.

As alkaline aqueous solution being demonstrated swelling property or deliquescent bonding agent, for example can preferably enumerate bonding agent with acidic groups.

As above-mentioned acidic groups, be not particularly limited, can suitably select according to purpose, for example can enumerate carboxyl, sulfonic group, phosphate etc., preferred carboxyl in the middle of them.

As bonding agent with carboxyl, for example can enumerate ethylenic copolymer with carboxyl, urethane resin, polyamic acid resin, modified epoxy etc., in the middle of them, the viewpoints such as easness that dissolubility from the dissolubility to coating solvent, alkalitropism developer solution, synthetic adaptability, film rerum natura are adjusted consider preferably have the ethylenic copolymer of carboxyl.In addition, consider, go back certain multipolymer at least of optimization styrene and styrene derivative from the viewpoint of development.

Above-mentioned ethylenic copolymer with carboxyl can utilize at least (1) to have the vinyl monomer of carboxyl and (2) and can obtain with the copolymerization of the monomer of their copolymerization.As these monomers, specifically, for example can enumerate the compound put down in writing in paragraph numbering [0164]～[0205] that the spy opens the 2005-258431 communique etc.

The content of the above-mentioned bonding agent in the above-mentioned photographic layer is not particularly limited, and can suitably select according to purpose, yet for example be preferably 10～90 quality %, and more preferably 20～80 quality % are preferably 40～80 quality % especially.

When above-mentioned content during less than 10 quality %, then have alkali development or form situation with the connecting airtight property reduction of substrate (for example copper plating film laminated plate) with printed wiring board, when surpassing 90 quality %, then have the situation that the intensity of stability with respect to development time, cured film (masked film) reduces.And, above-mentioned content also can be above-mentioned bonding agent with as required and the content of the total of the high polymer binder of usefulness.

At above-mentioned bonding agent is to have under the situation of material of glass temperature (Tg), as this glass temperature, be not particularly limited, can suitably select according to purpose, yet for example from suppressing certain viewpoint consideration at least that above-mentioned pattern forms sticking excessively (tack) of material and edge-melting (edge fusion) and improves the fissility of above-mentioned supporting mass, be preferably more than 80 ℃, more preferably more than 100 ℃, be preferably especially more than 120 ℃.

When above-mentioned glass temperature during, then have the situation that mistake is sticking or edge-melting increases, the fissility of above-mentioned supporting mass worsens that above-mentioned pattern forms material less than 80 ℃.

The acid number of above-mentioned bonding agent is not particularly limited, and can suitably select according to purpose, yet for example be preferably 70～250mgKOH/g, and more preferably 90～200mgKOH/g is preferably 100～180mgKOH/g especially.

When above-mentioned acid number during less than 70mgKOH/g, then development property deficiency or resolution variation, thereby have the situation that can't high obtain permanent patterns such as wiring pattern subtly, when surpassing 250mgKOH/g, then certain deterioration at least of the anti-development fluidity of pattern and connecting airtight property, thus have the situation that can't high obtain permanent patterns such as wiring pattern subtly.

" polymerizable compound "

As above-mentioned polymerizable compound, be not particularly limited, can suitably select according to purpose, yet for example can preferably enumerate certain monomer or oligomer at least with urethane groups and aryl.In addition, they preferably have two or more polymerism bases.

As above-mentioned polymerism base; for example can enumerate ethene unsaturated link (for example the allyl of vinyl, allyl ether or the allyl ester etc. of (methyl) acryloyl group, (methyl) acrylamido, styryl, vinyl esters or vinyl ether etc. etc.), can polymerization ring-type ether (for example epoxy radicals, oxetanyl etc.) etc., optimal ethylene unsaturated link in the middle of their.

--monomer--with urethane groups

As above-mentioned monomer with urethane groups, as long as have urethane groups, just be not particularly limited, can suitably select according to purpose, for example can enumerate the compound put down in writing in paragraph numbering [0210]～[0262] that the spy opens the 2005-258431 communique etc.

--monomer--with aryl

As above-mentioned monomer with aryl, as long as have aryl, just be not particularly limited, can suitably select, for example can enumerate the ester of certain and unsaturated carboxylic acid at least of polyol compound, polyamine compound and polynary alkamine compound or acid amides etc. with aryl according to purpose.

Specifically, for example can enumerate the compound put down in writing in paragraph numbering [0264]～[0271] that the spy opens the 2005-258431 communique etc.

--other polymerizable monomer--

In the pattern formation method of the present invention, form as above-mentioned pattern in the scope that properties of materials worsens not making, also can and with the above-mentioned monomer that contains urethane groups, have the monomer polymerizable monomer in addition of aryl.

As the above-mentioned monomer that contains urethane groups, contain the polymerizable monomer beyond the monomer of aromatic rings, for example can enumerate the acid amides of unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.) and ester, unsaturated carboxylic acid and the polyamine compound of aliphatic polyol compound etc.

Specifically, for example can enumerate the compound put down in writing in paragraph numbering [0273]～[0284] that the spy opens the 2005-258431 communique etc.

The content of the polymerizable compound in the above-mentioned photographic layer for example is preferably 5～90 quality %, and more preferably 15～60 quality % are preferably 20～50 quality % especially.

When above-mentioned content during less than 5 quality %, then have the situation that film strength reduces that hides, when surpassing 90 quality %, then have the situation that edge-melting when preserving (fault of oozing out from roll end) worsens.

In addition, the content that has the polyfunctional monomer of above-mentioned polymerism base more than 2 in polymerizable compound is preferably 5～100 quality %, and more preferably 20～100 quality % are preferably 40～100 quality % especially.

" Photoepolymerizationinitiater initiater "

As above-mentioned Photoepolymerizationinitiater initiater, so long as have the ability of the polymerization that causes above-mentioned polymerizable compound, just be not particularly limited, can from known Photoepolymerizationinitiater initiater, suitably select, yet for example preferably to having photosensitive material from the ultraviolet range to visible light, both can be and produced certain effect by light activated sensitizer, and generate the activator of living radical, also can be the initiating agent that causes cationic polymerization with the kind of monomer accordingly.

In addition, above-mentioned Photoepolymerizationinitiater initiater preferably contains at least a composition that is at least about 50 molecule absorptivity that has in the scope of the about 300～800nm of wavelength.The preferred especially 330～500nm of above-mentioned wavelength.

As above-mentioned Photoepolymerizationinitiater initiater, for example can enumerate halogenated hydrocarbon derivant (for example having the material of triazine skeleton, the material of Ju You oxadiazole skeleton etc.), six aryl bisglyoxalines, 9 oxime derivate, organic peroxide, thio-compounds, ketonic compound, aromatic series salt, aromatic ring alkene metal derivative class etc.In the middle of them, consider preferably have halogenated hydrocarbon, 9 oxime derivate, ketonic compound, the six aryl bisglyoxaline based compounds of triazine skeleton with the viewpoints such as connecting airtight property of substrate from sensitivity, keeping quality and photographic layer and the printed wiring board formation of photographic layer.

As above-mentioned preferred Photoepolymerizationinitiater initiater, specifically, for example can enumerate the compound put down in writing in paragraph numbering [0288]～[0309] that the spy opens the 2005-258431 communique etc.

The content of the Photoepolymerizationinitiater initiater in the above-mentioned photographic layer is preferably 0.1～30 quality %, and more preferably 0.5～20 quality % is preferably 0.5～15 quality % especially.

" other composition "

As above-mentioned other composition, for example enumerate the compound put down in writing in paragraph numbering [0312]～[0336] that the spy opens the 2005-258431 communique etc.By suitably containing these compositions, just can adjust character such as stability that required pattern forms material, photo, dryness, film rerum natura.

The thickness of above-mentioned photographic layer is not particularly limited, and can suitably select according to purpose, yet for example be preferably 1～100 μ m, and more preferably 2～50 μ m are preferably 4～30 μ m especially.

[pattern forms the manufacturing of material]

Above-mentioned pattern forms material and for example can make as followsly.

At first, with above-mentioned various material dissolves, emulsification be scattered in water or solvent in, preparation photosensitive polymer combination solution.

Solvent as above-mentioned photosensitive polymer combination solution is not particularly limited, and can suitably select according to purpose, for example can enumerate alcohols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, sec-butyl alcohol, n-hexyl alcohol; Ketones such as acetone, MEK, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; Ester classes such as ethyl acetate, butyl acetate, n-amyl acetate, Methylsulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate and methoxy propyl yl acetate; Toluene, dimethylbenzene, benzene, ethylbenzene etc. are aromatic hydrocarbon based; Phenixin, triclene, chloroform, 1,1, halogenated hydrocarbons such as 1-trichloroethanes, methylene chloride, monochloro benzene; Tetrahydrofuran, diethyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, 1-methoxyl-ethers such as 2-propyl alcohol; Dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, sulfolane etc.They both can be used alone, also can be also with two or more.In addition, also can add known surfactant.

Then, by with above-mentioned photosensitive polymer combination solution coat on supporting mass, be dried, just can form photographic layer, make pattern and form material.

Coating process as above-mentioned photosensitive polymer combination solution, be not particularly limited, can suitably select according to purpose, for example can enumerate various coating processes such as spray-on process, rolling method, method of spin coating, slot coated method, squeezing and coating method, curtain coating, mould rubbing method, photogravure rubbing method, wire bar rubbing method, scraper rubbing method.

As the condition of above-mentioned drying, though according to each composition, solvent types, usage ratio etc. and different, yet as a rule be under 60～110 ℃ the temperature about 30 seconds～15 minutes.

" supporting mass "

As above-mentioned supporting mass, be not particularly limited, can suitably select according to purpose, yet preferably above-mentioned photographic layer can be peeled off and the good material of permeability of light, more preferably Biao Mian flatness is also good.

Preferred synthetic resin system of above-mentioned supporting mass and material transparent, for example can enumerate polyethylene terephthalate, PEN, polypropylene, tygon, cellulose triacetate, cellulose diacetate, poly-(methyl) alkyl acrylate, poly-(methyl) acrylate copolymer, Polyvinylchloride, polyvinyl alcohol (PVA), polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, the trichloroactic acid vinyl ester copolymers, teflon, poly-trifluoro-ethylene, cellulose-based film, various plastic sheetings such as nylon film, in the middle of them, preferred especially polyethylene terephthalate.They both can be used alone, also can be also with two or more.

The thickness of above-mentioned supporting mass is not particularly limited, and can suitably select according to purpose, yet for example be preferably 2～150 μ m, and more preferably 5～100mm is preferably 8～50 μ m especially.

The shape of above-mentioned supporting mass is not particularly limited, and can suitably select according to purpose, yet be preferably strip.The length of the supporting mass of above-mentioned strip is not particularly limited, and for example can enumerate 10～20, the length of 000m.

" diaphragm "

Above-mentioned pattern forms material also can form diaphragm on above-mentioned photographic layer.

As said protection film, for example can enumerate material used in above-mentioned supporting mass, paper, lamination tygon, polyacrylic paper etc., in the middle of them, preferably polyethylene film, polypropylene film.

The thickness of said protection film is not particularly limited, and can suitably select according to purpose, yet for example be preferably 5～100 μ m, and more preferably 8～50mm is preferably 10～30 μ m especially.

State in the use under the situation of diaphragm, the bonding force A of above-mentioned photographic layer and above-mentioned supporting mass and the bonding force B of above-mentioned photographic layer and diaphragm are preferably the relation of bonding force A＞bonding force B.

As the combination (supporting mass/diaphragm) of above-mentioned supporting mass and diaphragm, for example can enumerate polyethylene terephthalate/polypropylene, polyethylene terephthalate/tygon, Polyvinylchloride/cellophane, polyimide/polypropylene, polyethylene terephthalate/PEN etc.In addition, carry out surface treatment, just can satisfy the relation of aforesaid bonding force by certain side at least to supporting mass and diaphragm.The surface treatment of above-mentioned supporting mass also can be implemented in order to improve with the bonding force of above-mentioned photographic layer, for example can enumerate being coated with of undercoat, Corona discharge Treatment, flame treatment, ultraviolet treatment with irradiation, high frequency treatment with irradiation, glow discharge treatment with irradiation, plasma active treatment with irradiation, laser rays treatment with irradiation etc.

In addition, the coefficient of static friction of above-mentioned supporting mass and said protection film is preferably 0.3～1.4, and more preferably 0.5～1.2.

When above-mentioned coefficient of static friction less than 0.3 the time, then because sliding excessively, therefore have the situation that produces the volume slippage under the situation of drum making, when surpassing 1.4, then have the situation that is difficult to be wound into good drum.

Above-mentioned pattern forms material and for example preferably is wound on the volume core cylindraceous the keeping with strip coiling tubular.The length that the pattern of above-mentioned strip forms material is not particularly limited, for example can be from 10～20, suitably select in the scope of 000m.In addition, use easily in order to make the user, also can carry out cutting processing, with 100～1, the strip of the scope of 000m is made drum.And, under this situation, preferably so that above-mentioned supporting mass is in outermost mode reels.In addition, also the pattern of above-mentioned drum can be formed material with laminar cutting.In keeping, to the protection of end face, prevent that the viewpoint of edge-melting from considering, be preferably in end face barrier film (particularly the barrier film of moisture resistance, add the barrier film of drying agent) be set, packing is also preferably used the low material of moisture-penetrability in addition.

In order to adjust the cementability of said protection film and above-mentioned photographic layer, said protection film also can be carried out surface treatment.Above-mentioned surface treatment for example can form the undercoat of being made by polymkeric substance such as polysiloxane, fluorinated polyolefin, polyvinyl fluoride, polyvinyl alcohol (PVA) on the surface of said protection film.The formation of this undercoat can form down at 30～150 ℃ (preferred especially 50～120 ℃) by after the coating fluid of above-mentioned polymkeric substance is coated the surface of said protection film in dry 1～30 minute.In addition, except above-mentioned photographic layer, above-mentioned supporting mass, said protection film, also can have layers such as peel ply, adhesive linkage, light absorbing zone, sealer.

＜processed matrix 〉

As above-mentioned processed matrix (following be called sometimes " matrix "), be not particularly limited, can from material known, suitably select from the high material of surface smoothing to material with convex-concave surface, yet preferred tabular matrix (substrate), specifically, known printed wiring board be can enumerate and film with substrate (for example copper plating film laminated plate), glass plate (for example soda-lime glass plate etc.), synthetic resin, paper, sheet metal etc. formed.

Above-mentioned matrix can be formed in the laminated body that is laminated on this matrix the photographic layer in the above-mentioned pattern formation of the coincidence material and use.That is, expose, can utilize developing procedure described later just can form pattern the zone sclerosis that has exposed by the above-mentioned photographic layer that the pattern in the above-mentioned laminated body is formed material.

Above-mentioned pattern formation material can be used as displays such as printed wiring board, color filter or post material, reinforcement material, sept, next door and forms and use of many usesly with member, holograph, micromachine, proof patterns such as (proof), especially goes in the pattern formation method of the present invention.

[other operation]

As above-mentioned other operation, be not particularly limited, can enumerate the operation of from the operation that known pattern forms, suitably selecting, for example can enumerate developing procedure, etching work procedure, filming process etc.They both can use separately, also can be also with two or more.

Above-mentioned developing procedure is to utilize above-mentioned exposure process that above-mentioned photographic layer is exposed, make this photographic layer exposure zone sclerosis after, by unhardened zone is removed, and form the operation of pattern.

The method of removing as above-mentioned unhardened zone is not particularly limited, and can suitably select according to purpose, for example can enumerate the method that developer solution removes etc. of using.

As above-mentioned developer solution, be not particularly limited, can suitably select according to purpose, for example can enumerate alkaline aqueous solution, water system developer solution, organic solution etc., in the middle of them, preferred weakly alkaline aqueous solution.As the alkali composition of this weak alkaline aqueous solution, for example can enumerate lithium hydroxide, NaOH, potassium hydroxide, lithium carbonate, sodium carbonate, sal tartari, lithium bicarbonate, sodium bicarbonate, saleratus, sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, borax etc.

The pH of above-mentioned weakly alkaline aqueous solution is for example preferred about 8～12, and more preferably from about 9～11.As above-mentioned weakly alkaline aqueous solution, for example can enumerate the aqueous sodium carbonate of 0.1～5 quality % or wet chemical etc.

The temperature of above-mentioned developer solution can suitably be selected with the development coupling ground of above-mentioned photographic layer, yet for example preferred about 25 ℃～40 ℃.

Above-mentioned developer solution also can be with surfactant, defoamer, organic base (for example ethylenediamine, monoethanolamine, tetramethyl ammonium hydroxide, diethylene triamine, triethylene five amine, morpholine, triethanolamine etc.), be used to promote the organic solvent (for example alcohols, ketone, ester class, ethers, amide-type, lactone etc.) that develops etc. and use.In addition, above-mentioned developer solution both can be the water system developer solution that water or alkaline aqueous solution have been mixed with organic solvent, also can be independent organic solvent.

As above-mentioned etching work procedure, can utilize the method for from known etching processing method, suitably selecting to carry out.

As etching solution used in the above-mentioned etch processes, be not particularly limited, can suitably select according to purpose, yet for example under the situation that above-mentioned metal level is formed by copper, can enumerate copper chloride solution, ferric chloride solution, alkaline etch solution, hydrogen peroxide is etching solution etc., in the middle of them, consider preferred ferric chloride solution from the aspect of etching factor.

By after utilizing above-mentioned etching work procedure to carry out etch processes, above-mentioned pattern being removed, just can form permanent pattern on the surface of above-mentioned matrix.

As above-mentioned permanent pattern, be not particularly limited, can suitably select according to purpose, for example can preferably enumerate wiring pattern.As above-mentioned filming process, can utilize the method for from known coating film treatment, suitably selecting to carry out.

As above-mentioned coating film treatment, for example can enumerate weldering plating, watts such as plated copper films such as copper sulphate plated film, cupric pyrophosphate plated film, high fluidity welding plated film (high flow solder plating) and bathe processing such as golden plated film such as nickel plated film, hard golden plated film, soft golden plated film such as (nickelous sulfate-nickel chloride) plated film, nickel sulfamic acid.

By after utilizing above-mentioned filming process to carry out coating film treatment, above-mentioned pattern being removed, in addition by utilizing etch processes etc. will not need part to remove as required, just can be at the surface of above-mentioned matrix formation permanent pattern.

Pattern formation method of the present invention is formed at above-mentioned pattern and forms the inequality of the exploring degree that is exposed the above-mentioned pattern on the face of material or the inequality of concentration because of alleviating, suppress the distortion of the picture of imaging, and can be high meticulous and efficient form pattern well, so go for needing in the formation etc. of various patterns of high meticulous exposure, be specially adapted in the formation of high meticulous wiring pattern.

[manufacture method of printed wiring board]

Pattern formation method of the present invention goes for the manufacturing of printed wiring board, the manufacturing of the printed wiring board of (through hole) or the conductive hole hole portions such as (via hole) that is particularly useful for having through hole.Below will the manufacture method of the printed wiring board that utilizes pattern formation method of the present invention be described.

Particularly as having the manufacture method of the printed wiring board of hole portions such as through hole or conductive hole, can form pattern by carrying out following steps, promptly, (1) on the printed wiring board with hole portion as above-mentioned matrix forms with substrate, above-mentioned pattern formed material so that its photographic layer to become the position relation of above-mentioned matrix side stacked and form laminated body, (2) from the opposite side with above-mentioned matrix of above-mentioned laminated body, forming zone and hole portion to wiring pattern forms the zone and carries out rayed and photographic layer is hardened, (3) remove above-mentioned pattern from above-mentioned laminated body and form supporting mass the material, (4) photographic layer in the above-mentioned laminated body is developed, the unhardened part in this laminated body is removed.

And removing of the above-mentioned supporting mass of above-mentioned (3) also can not be to carry out between above-mentioned (2) and above-mentioned (4), but carries out between above-mentioned (1) and above-mentioned (2).

Thereafter, in order to obtain printed wiring board, as long as use above-mentioned formed pattern, utilize the method (for example known subraction or additive process (for example semi-additive process, full additive method)) of etch processes or coating film treatment to handle above-mentioned printed wiring board formation with substrate and get final product.In the middle of them, form printed wiring board, preferred above-mentioned subraction in order to utilize at industrial favourable covering method (tenting).By peeling off with the hardening resin on the substrate, in addition, under the situation of above-mentioned semi-additive process,, just can make required printed wiring board by after peeling off, again the copper film section being carried out etching with remaining in printed wiring board formation after the above-mentioned processing.In addition, multilayer printed-wiring board also can be made in the same manner with the manufacture method of above-mentioned printed wiring board.

Below, the manufacture method of having used above-mentioned pattern to form the printed wiring board with through hole of material is further specified.

At first, prepare to have through hole and with the surface with the covered printed wiring board formation of coat of metal substrate.Form as above-mentioned printed wiring board and use substrate, for example can use the copper plating film laminated base plate reach the substrate that has formed copper coating on the insulating substrates such as glass-epoxy resin or on these substrates stacked interlayer dielectric and formed the substrate (laminated base plate) of copper coating.

Then, form on the material at above-mentioned pattern and to have under the situation of diaphragm, this diaphragm is peeled off, so that the photographic layer that above-mentioned pattern forms material and above-mentioned printed wiring board formation are used backer roll crimping (stacked operation) with the mode that the surface of substrate contacts.Like this, just can be had above-mentioned printed wiring board successively and be formed the laminated body of using substrate and above-mentioned laminated body.

The stacked temperature that above-mentioned pattern forms material is not particularly limited, and for example can enumerate room temperature (15～30 ℃) or heating (30～180 ℃) down, in the middle of them, preferably heat down (60～140 ℃).

The roller pressure of above-mentioned crimping roller is not particularly limited, for example preferred 0.1～1MPa.

The speed of above-mentioned crimping is not particularly limited, preferred 1～3m/ minute.

In addition, also can form and carry out preheating, in addition, also can under reduced pressure carry out with substrate to above-mentioned printed wiring board.

The formation of above-mentioned laminated body stacked above-mentioned pattern on forming with substrate at above-mentioned printed wiring board forms the above-mentioned photographic layer of material and the method that forms, it also can be following method, promptly, to be used to make photosensitive polymer combination solution that above-mentioned pattern forms the photographic layer of material and directly coat above-mentioned printed wiring board and form surface, form by being dried with substrate.

Then, from the face irradiates light of the opposite side with matrix of above-mentioned laminated body and photographic layer is hardened.And at this moment, also (for example under the situations such as photopermeability deficiency of supporting mass) exposes after supporting mass is peeled off as required.

At this constantly, under situation about above-mentioned supporting mass not being peeled off as yet, this supporting mass peeled off on the above-mentioned laminated body (supporting mass stripping process).

Then; above-mentioned printed wiring board formation is removed with suitable developing solution dissolution with the unhardened zone of the photographic layer on the substrate; the hardened layer of formation wiring pattern formation usefulness and the metal level protection of through hole are exposed metal level (developing procedure) in above-mentioned printed wiring board formation with the surface of substrate with the pattern of hardened layer.

In addition, also can after development, utilize back heat treated or post-exposure to handle the processing of the sclerous reaction that further promotes sclerosis portion as required.Developing both can be aforesaid wet developing method, also can be the dry process development method.

Then, will form the metal level that exposes with the surface of substrate at above-mentioned printed wiring board and remove (etching work procedure) with the etching solution dissolving.The peristome of through hole is owing to covered by hardenable resin composition (masked film), do not have therefore that etching solution enters in the through hole and with the situation of the corrosion of the metal coating in the through hole, the metal coating of through hole will be residual with the shape of regulation.Like this, just can on forming with substrate, above-mentioned printed wiring board form wiring pattern.

As above-mentioned etching solution, be not particularly limited, can suitably select according to purpose, for example, under the situation that above-mentioned metal level is made of copper, can enumerate copper chloride solution, ferric chloride solution, alkaline etch solution, hydrogen peroxide is etching solution etc.In the middle of them, consider preferred ferric chloride solution from the viewpoint of etching factor.

Then, above-mentioned hardened layer as stripping film, is formed from above-mentioned printed wiring board with strong alkaline aqueous solution etc. and to remove (hardening thing is removed operation) with substrate.

Alkali composition as in the above-mentioned strong alkaline aqueous solution is not particularly limited, and for example can enumerate NaOH, potassium hydroxide etc.

The pH of above-mentioned strong alkaline aqueous solution is for example preferred about 12～14, and more preferably from about 13～14.

As above-mentioned strong alkaline aqueous solution, be not particularly limited, for example can enumerate the sodium hydrate aqueous solution of 1～10 quality % or potassium hydroxide aqueous solution etc.

In addition, printed wiring board also can be the printed wiring board that multilayer constitutes.

And above-mentioned pattern forms material not only can be used for above-mentioned etch process, also can be used for coating process.As above-mentioned coating method, for example can enumerate weldering plating, watts such as plated copper films such as copper sulphate plated film, cupric pyrophosphate plated film, high fluidity welding plated film and bathe processing such as golden plated film such as nickel plated film, hard golden plated film, soft golden plated film such as (nickelous sulfate-nickel chloride) plated film, nickel sulfamic acid.

Embodiment

Below, will utilize embodiment that the present invention is more specifically illustrated, yet the present invention is not limited to them.

(embodiment 1)

The manufacturing of-pattern formation material-

On the thick pet film of 20 μ m, coating is formed the photosensitive polymer combination solution that constitutes and is dried by following, forms the thick photographic layer of 15 μ m, makes above-mentioned pattern and forms material as above-mentioned supporting mass.

[composition of photosensitive polymer combination solution]

Methacrylic acid/methyl methacrylate/styrol copolymer (multipolymer is formed (mass ratio): 29/19/52, and the matter average molecular weight: 60,000, acid number 189) 11.8 mass parts

Polymerizable monomer 5.6 mass parts with following structural formula (1) expression

1/2 mol ratio addition product, 5.0 mass parts of hexamethylene diisocyanate and five rings oxidative ethane monomethacrylates

Ten dipropyl glycol dimethylacrylates, 0.56 mass parts

N-acridone methylquinoline 0.11 mass parts

2, two (Chloro-O-Phenyl)-4 of 2-, 4 ', 5,5 '-tetraphenyl bisglyoxaline, 2.17 mass parts

2-mercaptobenzimidazole 0.23 mass parts

Malachite green oxalates 0.02 mass parts

Leuco crystal violet 0.26 mass parts

MEK 40 mass parts

1-methoxyl-2-propyl alcohol 20 mass parts

[changing 1]

Structural formula (1)

Wherein, in the structural formula (1), m+n represents 10.

Form at above-mentioned pattern on the photographic layer of material, as the thick polyethylene film of the stacked 20 μ m of said protection film.

Then; as above-mentioned matrix; with surface grinding, washing, dry copper plating film laminated plate (no through hole; copper thickness 12 μ m) surface; when the diaphragm that above-mentioned pattern is formed material is peeled off; so that forming the photographic layer of material, this pattern uses laminating machine (MODEL8B-720-PH with the mode that above-mentioned copper plating film laminated plate contacts; great achievement laminating machine (strain) system) carries out crimping, made the laminated body that above-mentioned copper plating film laminated plate, above-mentioned photographic layer, above-mentioned pet film (supporting mass) etc. have been stacked gradually.

The crimping condition is made as: 105 ℃ of crimping roller temperature, crimping roller pressure 0.3MPa, laminate speed 1m/ minute.

The photographic layer that the pattern of above-mentioned made laminated body is formed material uses following apparatus to expose, and utilizes following method to estimate (a) exploring degree, (b) edge roughness and (c) etching.The results are shown in Table 3.

＜(a) exploring degree 〉

(1) assay method of short development time

Divest above-mentioned supporting mass from above-mentioned laminated body, above-mentioned photographic layer on the copper plating film laminated plate comprehensively with 1 quality % aqueous sodium carbonate of 30 ℃ of the air sprayings of 0.15MPa, mensuration begins dissolved the removing the required time of photographic layer to the copper plating film laminated plate from the spraying of aqueous sodium carbonate, with it as the shortest development time.

Consequently, the shortest above-mentioned development time is 10 seconds.

(2) mensuration of sensitivity

The pattern of above-mentioned made laminated body is formed the photographic layer of material, and exposure device illustrated below using from above-mentioned supporting side is with 2 ^1/2Doubly shine from 0.1mJ/cm at interval ²To 100mJ/cm ²The different light of luminous energy, with the zone sclerosis of the part of above-mentioned photographic layer.After at room temperature leaving standstill 10 minutes, divest above-mentioned supporting mass from above-mentioned laminated body, photographic layer on the copper plating film laminated plate comprehensively, 30 ℃ 1 quality % aqueous sodium carbonate with time of 2 times of the shortest development time of being tried to achieve in the spray pressure of the 0.15MPa spraying above-mentioned (1), the dissolving of unhardened zone is removed, measured the thickness of remaining hardening region.Then, the relation of the thickness of the exposure of light and hardened layer is drawn and obtain sensitivity curve.According to this sensitivity curve, the luminous energy the when thickness of hardening region is reached 15 μ ms identical with photographic layer before the exposure is as in order to harden photographic layer and essential luminous energy.

Consequently, essential luminous energy is 3.5mJ/cm for above-mentioned photographic layer is hardened ²

" exposure device "

Used the exposure device that possesses following photohead, it has: as closing the ripple lasing light emitter shown in Fig. 4 A～Fig. 8 of above-mentioned light irradiating means; Provide the DMD of skeleton diagram among Fig. 2 as above-mentioned optical modulator body, be arranged 768 groups at the micro lens array of having arranged 1024 micro mirrors on the main scanning direction on sub scanning direction, this DMD controls in the mode that only drives 1024 * 256 row wherein; Optical system shown in Figure 1.

In the above-mentioned photohead, light-gathering optics is different with the light quantity distribution debugging functions that bar integrator 118 is possessed, possess for the laser injected from fiber array light source penetrate the distribution that the angle of chief ray, has regulation laser and to the function of DMD irradiation.

In addition, the size of light quantity distribution amount is set at more than the light quantity reduction amount of the periphery that produces because of microlens array, predetermined distance YA for the optical axis center shown in distance Fig. 9 B, when the distance of peripheral end (peripheral end of DMD) that will be from the optical axis center to the field of illumination is made as YS, then be set at YS＞YA＞YS/2.

(3) mensuration of exploring degree

Make above-mentioned laminated body with method and the condition identical, room temperature (23 ℃ left standstill 10 minutes under 55%RH) with the evaluation method of the shortest development time of above-mentioned (1).From the pet film (supporting mass) of the laminated body of gained, use above-mentioned exposure device, carry out the exposure of each live width in the mode of row/space=1/1 with 1 μ m scale, be 10 μ m～50 μ m until line width.The exposure of this moment is the essential luminous energy of being measured in above-mentioned (2) for the photographic layer sclerosis that above-mentioned pattern is formed material.After at room temperature leaving standstill 10 minutes, divest pet film (supporting mass) from above-mentioned laminated body.Photographic layer on the copper plating film laminated plate comprehensively, 30 ℃ the 1 quality % aqueous sodium carbonate of 2 times time of the shortest development time of being tried to achieve in the spray pressure spraying above-mentioned (1) with 0.15MPa is removed the dissolving of unhardened zone.Utilize the surface of the copper plating film laminated plate that has the hardening resin pattern that observation by light microscope so obtains, the row of hardening resin pattern is measured not have obstruction, distortion etc. unusually and line width that can interstitial minimum, with it as the exploring degree.The numerical value of this exploring degree is the smaller the better.

＜(b) edge roughness 〉

To above-mentioned laminated body, use above-mentioned exposure device to shine with the mode of the horizontal line pattern of the direction of the direction of scanning quadrature of above-mentioned photohead and expose, in the same manner pattern is made in the zone of the part of above-mentioned photographic layer with (3) in the mensuration of above-mentioned exploring degree to form.To the line width in the pattern of gained is 5 positions arbitrarily of the row of 30 μ m, use laser microscope (VK-9500, Kyence (strain) system, 50 times on object lens) observe, try to achieve position (valley portions) poor of the position of heaving the most (mountain top portion) and depression the most in the marginal position in the visual field as absolute value, calculate the mean value at 5 observed positions, with it as edge roughness.Because the value of this edge roughness is more little, then demonstrating is good performance more, therefore preferred.The results are shown in Table 3.

＜(c) etching 〉

The above-mentioned laminated body that use forms in the mensuration of above-mentioned exploring degree with pattern, surface to the copper plating film laminated plate that exposes of this laminated body, with 36 seconds iron chloride etchant (etching solutions that contain iron chloride of 0.25MPa spraying, 40 ° of Baumes, 40 ℃ of liquid temperature), copper layer dissolving by the zone of exposing that will be not do not covered by hardened layer removed, and carried out etch processes.Then, above-mentioned formed pattern is removed, be formed in the surface possesses the wiring pattern of copper layer as above-mentioned permanent pattern printed wiring board by the sodium hydrate aqueous solution that sprays 2 quality %.Utilize the wiring pattern on this printed wiring board of observation by light microscope, measure the line width of the minimum of this wiring pattern.This minimum row width is more little, means to obtain being more high meticulous wiring pattern, and be good more aspect etching.The results are shown in Table 3.

(embodiment 2)

Except in embodiment 1, exposure device is replaced with beyond the device in the following explanation, be identically formed pattern with embodiment 1, estimated (a) exploring degree, (b) edge roughness and (c) etching.The results are shown in Table 3.

" exposure device "

Used the exposure device that possesses following photohead, it has: as closing the ripple lasing light emitter shown in Fig. 4 A～Fig. 8 of above-mentioned light irradiating means; Provide the DMD of skeleton diagram among Fig. 2 as above-mentioned optical modulator body, be arranged 768 groups at the micro lens array of having arranged 1024 micro mirrors on the main scanning direction on sub scanning direction, this DMD controls in the mode that only drives 1024 * 256 row wherein; Optical system shown in Figure 1.Between the bar integrator 118 and collector lens 120 of above-mentioned photohead shown in Figure 1,, be provided with the telecentric optical system 150 that the plano-convex lens 152,154 by 2 one group shown in Figure 11 A constitutes as above-mentioned light distribution correction mechanism.

The face shape of plane of incidence S2 of plano-convex lens 152 that is disposed at the light incident side (fiber array light source 112 sides) of laser is made into radius-of-curvature along with becoming big aspheric surface away from optical axis (optical axis center) X, in other words, be made into curvature along with the aspheric surface that diminishes away from optical axis X, exit facet S3 is made into plane.

In addition, the plane of incidence S4 of plano-convex lens 154 that is disposed at the exiting side (DMD50 side) of laser is made into plane, the face shape of exit facet S5 is made into radius-of-curvature along with the aspheric surface that diminishes away from optical axis X, in other words, is made into curvature along with becoming big aspheric surface away from optical axis X.

By using this exposure device, the light quantity distribution of the laser beam that parallelization ground penetrates from above-mentioned telecentric optical system 150 uprises with respect to optical axis center in the distribution density of periphery, illuminated among the DMD50 of this laser beam, compare with the central part (optical axis center) in laser radiation zone, the light quantity of periphery obtains increasing.Because of laser beam see through microlens array 128, produce light quantity reduction with respect to the periphery of optical axis center portion, and can to plane of exposure irradiation light quantity distribution be modified to the light beam that reach homogenising thereafter.

(embodiment 3)

Except in embodiment 1,1/2 mol ratio addition product of the hexamethylene diisocyanate of photosensitive polymer combination solution and five rings oxidative ethane monomethacrylates is replaced with beyond the compound with following structural formula (2) expression, make pattern in the same manner with embodiment 1 and form material and laminated body, form pattern, estimated (a) exploring degree, (b) edge roughness and (c) etching.The results are shown in Table 3.

And the shortest development time is 10 seconds, and essential luminous energy is 3.5mJ/cm for above-mentioned photographic layer is hardened ²

[changing 2]

Structural formula (2)

(embodiment 4)

Except in embodiment 1,1/2 mol ratio addition product of the hexamethylene diisocyanate of photosensitive polymer combination solution and five rings oxidative ethane monomethacrylates is replaced with beyond the compound with following structural formula (3) expression, make pattern in the same manner with embodiment 1 and form material and laminated body, form pattern, estimated (a) exploring degree, (b) edge roughness and (c) etching.The results are shown in Table 3.

And the shortest development time is 10 seconds, and essential luminous energy is 3.5mJ/cm for above-mentioned photographic layer is hardened ²

[changing 3]

Structural formula (3)

(embodiment 5)

Except in embodiment 1, (multipolymer is formed (mass ratio): 29/19/52 with methacrylic acid/methyl methacrylate/styrol copolymer, matter average molecular weight: 60,000, acid number 189) (multipolymer is formed (mass ratio): 8/30/37/25 to replace with methyl methacrylate/styrene/methacrylic acid benzyl ester/methacrylic acid copolymer, matter average molecular weight: 60,000, acid number 163) in addition, make pattern in the same manner with embodiment 1 and form material and laminated body, form pattern, estimated (a) exploring degree, (b) edge roughness and (c) etching.The results are shown in Table 3.

And the shortest development time is 10 seconds, and essential luminous energy is 4mJ/cm for above-mentioned photographic layer is hardened ²

(comparative example 1)

Except in the exposure device of embodiment 1, in light-gathering optics, used beyond the photohead of the formation that does not possess light distribution correction mechanism, make pattern in the same manner with embodiment 1 and form material and laminated body, form pattern, estimated (a) exploring degree, (b) edge roughness and (c) etching.The results are shown in Table 3.

And the shortest development time is 10 seconds, and essential luminous energy is 3.5mJ/cm for above-mentioned photographic layer is hardened ²

(comparative example 2)

Except in the exposure device of embodiment 2, in light-gathering optics, used beyond the photohead of the formation that does not possess light distribution correction mechanism, make pattern in the same manner with embodiment 2 and form material and laminated body, form pattern, estimated (a) exploring degree, (b) edge roughness and (c) etching.The results are shown in Table 3.

And essential luminous energy is 3.5mJ/cm for above-mentioned photographic layer is hardened ²

[table 3]

	(a) exploring degree (μ m)	(b) edge roughness (μ m)	(c) etching (μ m)
				Embodiment 1	14	1.8	24
Embodiment 2	14	1.8	24
				Embodiment 3	14	1.8	24
Embodiment 4	14	1.8	24
				Embodiment 5	14	1.8	24
Comparative example 1	15	2.1	26
				Comparative example 2	15	2.1	26

According to the result of table 3 as can be known, compare with the wiring pattern of comparative example 1 and 2, used the wiring pattern of embodiment 1～5 of the photohead that possesses light distribution correction mechanism more high meticulous, edge roughness is littler, and in addition, etching is more good.In addition we know, possessed the photohead of light distribution correction mechanism, can realize high meticulous exposure, can carry out the good exposure of efficient in addition with low-cost by use.

The industrial possibility of utilizing

Pattern formation method of the present invention is owing to can provide following pattern formation method, namely, in the exposure of having used the digital exposure apparatus that possesses the photohead that the unit of describing is distributed two-dimensionally, can be in cost squeeze, light quantity homogenising by the respectively unit of describing that will distribute two-dimensionally, and form accurately fine pattern, and needing therefore to go in the formation etc. of various patterns of exposure of fine, go for especially in the formation of wiring pattern of fine.

Claims (23)

1. a pattern formation method is characterized in that,

At least comprise following operation:

After the stacked pattern that has photographic layer on supporting mass on the processed matrix forms this photographic layer in the material,

The light beam that will penetrate from light irradiating means is via the light-gathering optics with light distribution correction mechanism, to have n (wherein n is the natural number 1 or more) two-dimensional arrangements retouch plain portion and with pattern-information make accordingly above-mentioned each retouch the optical modulator body that plain portion changes the optical modulation state and shine, to be exposed to this photographic layer irradiation by the light beam that above-mentioned optical modulator body is modulated

This exposure is following to be carried out, promptly, make from the light quantity of above-mentioned light irradiating means in the irradiation area of the light beam of above-mentioned optical modulator body irradiation to have distribution, the light quantity distribution of the light beam of having been modulated by above-mentioned optical modulator body is corrected for being exposed of above-mentioned photographic layer and reaches homogenising on the face.

2. pattern formation method according to claim 1, wherein, the light beam that will penetrate from light irradiating means utilizes light-gathering optics to shine to optical modulator body as the light beam that has distribution in the angle of chief ray.

3. pattern formation method according to claim 1, wherein, the light beam that will penetrate from light irradiating means utilizes light-gathering optics to shine to optical modulator body as heart light far away.

4. pattern formation method according to claim 3, wherein, light-gathering optics has light distribution correction mechanism, this light distribution correction mechanism by: have lens power along with first optical lens of the aspherical shape that diminishes away from optical axis center with have lens power along with second optical lens that becomes big aspherical shape away from optical axis center constitutes.

5. according to any described pattern formation method in the claim 1～4, wherein, light-gathering optics by light irradiating means in the irradiation area of the light beam of optical modulator body irradiation, make the light quantity of periphery compare increase with central part.

6. according to any described pattern formation method in the claim 1～5, wherein, optical modulator body is a spatial optical modulation element.

7. according to any described pattern formation method in the claim 1～6, wherein, after having carried out exposure, carry out the development of photographic layer.

8. according to any described pattern formation method in the claim 1～7, wherein, after having carried out development, carry out the formation of permanent pattern.

9. pattern formation method according to claim 8, wherein, permanent pattern is a wiring pattern, the formation of this permanent pattern is at least a the carrying out that utilizes in etch processes and the coating film treatment.

10. according to any described pattern formation method in the claim 1～9, wherein, light irradiating means can be shone the light compositing more than two.

11. according to any described pattern formation method in the claim 1～10, wherein, light irradiating means has: a plurality of laser instruments, multimode optical fiber, will be from these a plurality of laser instruments the parallel photochemical and optically focused of the laser beam of irradiation and converge at the light source light-gathering optics of the incident end face of above-mentioned multimode optical fiber respectively.

12. according to any described pattern formation method in the claim 1～11, wherein, photographic layer comprises bonding agent, polymerizable compound, Photoepolymerizationinitiater initiater.

13. pattern formation method according to claim 12, wherein, bonding agent has acidic groups.

14. according to any described pattern formation method in the claim 12～13, wherein, bonding agent is an ethylenic copolymer.

15. according to any described pattern formation method in the claim 12～14, wherein, the acid number of bonding agent is 70～250mgKOH/g.

16. according to any described pattern formation method in the claim 12～15, wherein, polymerizable compound comprises at least a monomer that has in urethane groups and the aryl.

17. according to any described pattern formation method in the claim 12～16, wherein, Photoepolymerizationinitiater initiater comprises and is selected from least a in halogenated hydrocarbon derivant, six aryl bisglyoxalines, 9 oxime derivate, organic peroxide, thio-compounds, ketonic compound, aromatic series salt and the aromatic ring alkene metal derivative class.

18. according to any described pattern formation method in the claim 1～17, wherein, photographic layer contains the bonding agent of 10～90 quality %, contains the polymerizable compound of 5～90 quality %.

19. according to any described pattern formation method in the claim 1～18, wherein, the thickness of photographic layer is 1～100 μ m.

20. according to any described pattern formation method in the claim 1～19, wherein, supporting mass contains synthetic resin, and is transparent.

21. according to any described pattern formation method in the claim 1～20, wherein, supporting mass is a strip.

22. according to any described pattern formation method in the claim 1～21, wherein, it is strip that pattern forms material, is wound into drum.

23., wherein, on the photographic layer of pattern formation material, form diaphragm according to any described pattern formation method in the claim 1～22.

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