CN101263425B

CN101263425B - Pattern forming material, pattern forming apparatus and pattern forming method

Info

Publication number: CN101263425B
Application number: CN2006800338399A
Authority: CN
Inventors: 南一守; 佐藤守正
Original assignee: Asahi Chemical Co Ltd
Current assignee: Asahi Kasei Corp
Priority date: 2005-09-14
Filing date: 2006-08-25
Publication date: 2012-06-13
Anticipated expiration: 2026-08-25
Also published as: TWI411880B; JP2007079128A; JP4966528B2; WO2007032195A1; CN101263425A; TW200722918A

Abstract

The invention aims at providing a pattern forming material which little suffers from area defects, fog caused by a color developer, and break of unexposed film and exhibits high resolution, high tent film strength, and excellent removability after pattern formation and which can form finer patterns; a pattern forming apparatus provided with the material; and a pattern forming process by use of the material. The invention provides a pattern forming material having a photosensitive layer which comprises a binder, a polymerizable compound, a photopolymerization initiator, a fused heterocyclic compound, a polymerization inhibitor, a color developer and an organic solvent, wherein the binder has an acid value of 50 to 400mgKOH/g and a mass-average molecular weight of 10,000 to 100,000; the polymerizable compound is a compound having a urethane group and/or a compound having an aryl group; and the organic solvent is at least one member selected from among ketones, alcohols and ethers with the content thereof being 0.5% by mass or below.

Description

Pattern becomes material and pattern apparatus for converting and pattern formation method

Technical field

The present invention relates to a kind ofly be suitable for the pattern that dry film photoresist (dryfilmresist) (DFR) waits and become material and possess this pattern to become the pattern apparatus for converting of material and use said pattern to become the pattern formation method of material.

Background technology

When forming permanent pattern such as wiring pattern, use be to become material through the pattern that coating on supporter, dry sensation photosensitive resin composition form photographic layer.Manufacturing approach as said permanent pattern; For example on the matrix of the copper plating film laminated plate that forms said permanent pattern etc.; Range upon range of said pattern becomes the material cambium layer to fold body, the said photographic layer in this duplexer is made public, after this exposure; The said photographic layer of developing forms pattern, forms said permanent pattern through carrying out etch processes etc. then.

Become material that following described proposal is arranged to said pattern: in order to improve bin stability or to improve the exploring degree and in said photosensitive polymer combination, add phenol property hydroxyl, aromatic rings, heterocycle or have the polymerization inhibitor (with reference to patent documentation 1～4) of the compound of imino group.But, in this case, do not have open yet or propose the point of the relevant reduction that can suppress sensitivity or the dry film photoresist of high sensitivity through the remaining quantity that reduces organic solvent.

In addition, to DFR, except improving sensitivity, also need the fissility etc. after pattern forms.

Thereby; Do not provide as yet at present a kind of superficial failure few, can prevent the breaking less of the light fog that developer causes, unexposed film, the exploring degree is high, masked film intensity height and the pattern fissility after forming is good, the pattern that can form high meticulous pattern becomes material and possess this pattern to become the pattern apparatus for converting of material and use said pattern to become the pattern method of formationing of material, needs further improvement to develop.

Patent documentation 1: the spy opens the 2000-268211 communique

Patent documentation 2: the spy opens the 2003-29399 communique

Patent documentation 3: the spy opens the 2004-4527 communique

Patent documentation 4: the spy opens the 2004-4528 communique

Summary of the invention

The present invention proposes in view of said present situation just, is problem with said each problem, the following purpose of realization that solves in the past.That is, the present invention provide a kind of superficial failure few, can prevent the breaking less of the light fog that developer causes, unexposed film, the exploring degree is high, masked film intensity height and the pattern fissility after forming is good, the pattern that can form higher meticulous pattern becomes material and possess this pattern to become the pattern apparatus for converting of material and use said pattern to become the pattern formation method of material.

Means as solving said problem are described below, that is,

< 1>a kind of pattern becomes material, it is characterized in that,

Have supporter and the photographic layer on this supporter forms, this photographic layer includes (A) bonding agent, (B) polymerizable compound, (C) Photoepolymerizationinitiater initiater, (D) assorted compound ring series that contracts, (E) polymerization inhibitor, (F) developer and (G) organic solvent,

(A) acid number of bonding agent is 50～400mgKOH/g, and the matter average molecular weight is 10,000～100,000,

(B) polymerizable compound include (b1) have the compound of urethane groups and (b2) have the compound of aryl and (b3) have the polyalkylene oxide hydrocarbon chain compound at least any one,

(G) organic solvent is at least a for what from ketone, alcohols and ethers, select, and remaining quantity is below the 0.5 quality %.Become in the material in this < 1>described pattern; Acid number and weight-average molecular weight through the bonding agent that includes in the regulation photographic layer; And the compound that not only includes in the regulation polymerizable compound; The compound and the content that are contained of regulation organic solvent also, can form superficial failure few, can prevent the breaking less of the light fog that developer causes, unexposed film, the exploring degree is high, masked film intensity height and the pattern fissility after forming well, higher meticulous pattern.

< 2>become material according to < 1>described pattern, wherein,

(A) the I/O value of bonding agent is 0.35～0.60.

< 3>become material according to < 1>or < 2>described pattern, wherein,

(B) polymerizable compound includes the compound with polyalkylene oxide hydrocarbon chain, this polyalkylene oxide hydrocarbon chain have ethylidene and propyl group at least any one.

< 4>become material according to any described pattern in < 1 >～< 3 >, wherein,

(D) the assorted compound ring series that contracts comprises from assorted contract ring system ketonic compound, quinoline compound and acridine compound, select at least a.

< 5>become material according to any described pattern in < 1 >～< 4 >; Wherein, (E) polymerization inhibitor for from the compound that has 2 above phenol property hydroxyls at least, have by the compound of the substituted aromatic rings of imino group, have at least a by what select the compound of the substituted heterocycle of imino group and the bulky amine compound.

< 6>become material according to any described pattern in < 1 >～< 5 >, wherein, and then contain dyestuff, reductive agent and the hydrogen donor compound that includes compound with triallyl methane skeleton.

< 7>become material according to any described pattern in < 1 >～< 6 >, wherein, (G) organic solvent be methyl ethyl ketone, cyclohexanone, methyl alcohol, methyl propanediol and tetrahydrofuran at least any one.

< 8>become material according to any described pattern in < 6 >～< 7 >, wherein, the dyestuff that includes the compound with triallyl methane skeleton is the allyl sulphonic acid compound.

< 9>become material according to any described pattern in < 6 >～< 8 >, wherein, reductive agent is 1-phenyl-3-pyrazolidone.

<10>According to<1>～<9>In any described pattern become material; Wherein, For photographic layer, under this photographic layer of exposure and the situation of developing, the least energy of light that do not change, that in said exposure, use is 0.1～20mJ/cm to the thickness of exposed portion that makes this photographic layer in this exposure and after developing ²

< 11>become material according to each described pattern in < 1 >～< 10 >, wherein, the relative alkaline aqueous solution of bonding agent shows swellability or dissolubility.

< 12>become material according to any described pattern in < 1 >～< 11 >, wherein, bonding agent contains multipolymer, and this multipolymer has any one the structural unit at least that derives from styrene and styrene derivative.

< 13>become material according to any described pattern in < 1 >～< 12 >, wherein, the glass transition temperature of bonding agent is more than 80 ℃.

< 14>become material according to any described pattern in < 1 >～< 13 >, wherein, polymerization inhibitor is at least a for what from aromatic rings, heterocycle, imino group and phenol property hydroxyl, select.

< 15>become material according to any described pattern in < 1 >～< 14 >, wherein, said polymerization inhibitor is to be selected from least a in catechol, phenothiazine, phenoxazine, bulky amine and their derivant.

< 16>according to any described pattern formation method in < 1 >～< 15 >, wherein, relative polymerizable compound, the content of polymerization inhibitor is 0.005～0.5 quality %.

< 17>become material according to any described pattern in < 1 >～< 16 >; Wherein, Photoepolymerizationinitiater initiater contains from halogenated hydrocarbons derivant, phosphine oxide (phosphine oxide), six aryl di-imidazoles, 9 oxime derivate, organic peroxide, thio-compounds, ketonic compound, acylphosphine oxide compound, aromatic series salt, reaches select the ketoxime ether at least a.

< 18>become material according to any described pattern in < 1 >～< 17 >, wherein, Photoepolymerizationinitiater initiater contains six aryl di-imidazoles.

< 19>become material according to any described pattern in < 1 >～< 18 >, wherein, the thickness of photographic layer is 1～100 μ m.

< 20>become material according to any described pattern in < 1 >～< 19 >, wherein, supporter is microscler thing.

< 21>become material according to any described pattern in < 1 >～< 20 >, wherein, it is microscler thing that pattern becomes material, and is rolled into the roller shape.

< 22>become material according to any described pattern in < 1 >～< 21 >, wherein, become on the photographic layer in the material to have protective film in pattern.

< 23>become material according to any described pattern in < 1 >～< 22 >; Wherein, On photographic layer, have protective film, this protective film contains from acrylic resin, ethene-copolymerization of propylene resin and pet resin, select at least a.

< 24>a kind of pattern apparatus for converting is characterized in that, possess < 1 >～< 23>in any described pattern become material,

At least have: but the light irradiating means of irradiates light; With modulation from the light of this light irradiating means, and the optical modulator body that becomes the photographic layer in the material to make public to said pattern.In these < 24>described pattern apparatus for converting, said light irradiating means is to said optical modulator body irradiates light.Said optical modulator body is modulated the light of accepting from said light irradiating means.Utilize said optical modulator body to make the said relatively photographic layer exposure of light of modulation.For example, if develop said photographic layer afterwards, then form high meticulous pattern.

< 25>according to said < 24>described pattern apparatus for converting; Wherein, The pattern signal generation mechanism that optical modulator body further has based on formed pattern-information generation control signal forms; To generating the control signal that mechanism produced by pattern signal, to modulating from the light of light irradiating means irradiation.In the pattern apparatus for converting of record, said optical modulator body generates mechanism through having said pattern signal in these < 25 >, from the light of said light irradiating means irradiation to the control signal that should pattern signal generates mechanism and produce and modulated.

< 26>according to any described pattern apparatus for converting in said < 24 >～< 25 >; Wherein, Optical modulator body has n drawing section and forms, and the pattern-information that can corresponding will form is controlled less than n said drawing section what from this n drawing section, dispose continuously arbitrarily.In the pattern apparatus for converting of in these < 26 >, putting down in writing; Through corresponding pattern-information; Control less than n drawing section arbitrarily what dispose continuously in the drawing section of the n from said optical modulator body, thereby modulated at high speed from the light of said light irradiating means.

< 27>according to any described pattern apparatus for converting in said < 24 >～< 26 >, wherein, optical modulator body is a spatial optical modulation element.

< 28>according to said < 27>described pattern apparatus for converting, wherein, spatial optical modulation element be DMD (digitalmicromirrordevice) (DMD).

< 29>according to any described pattern apparatus for converting in said < 26 >～< 28 >, wherein, drawing section is a micro mirror.

< 30>according to any described pattern apparatus for converting in said < 24 >～< 29 >, wherein, light irradiating means can the two or more light of compound irradiation.In these < 30>in the pattern apparatus for converting of record, can the two or more light of compound irradiation through said light irradiating means, can utilize the darker exposure light of the depth of focus to make public.As a result, can highly become material to make public to said pattern subtly.For example, if after said photographic layer is developed, then can form high meticulous pattern.

< 31>according to any described pattern apparatus for converting in said < 24 >～< 30 >; Wherein, thus light irradiating means has multiple laser instrument, multimode optical fiber and will carry out the light-gathering optics system that optically focused is incorporated into said multimode optical fiber from the laser that this multiple laser instrument shines respectively.In the pattern apparatus for converting of in these < 31 >, putting down in writing; Said light irradiating means combines through utilizing said light-gathering optics system can thereby the laser that shine respectively from said multiple laser instrument be assembled with said multimode optical fiber, can make public with the darker exposure light of the depth of focus.As a result, can highly become material to make public to said pattern subtly.For example, if after said photographic layer is developed, then can form high meticulous pattern.

< 32>a kind of pattern formation method is characterized in that, comprises at least becoming this photographic layer in the material to carry out step of exposing to any pattern of stating in said < 1 >～< 23 >.In the pattern formation method of record, the said relatively pattern of exposure becomes material to carry out in these < 32 >.For example, if after said photographic layer is developed, then can form high meticulous pattern.

< 33 >, wherein, on matrix, become material to heat and carrying out in any one at least of pressurizeing is range upon range of, make public to pattern according to < 32>described pattern method of formationing.

< 34>according to any described pattern method of formationing in < 32 >～< 33 >, wherein, making public is based on the pattern-information that will form, and carries out with decent.

< 35>according to any described pattern method of formationing in < 32 >～< 34 >, wherein, exposure is based on the pattern-information that will form and after generating control signal, the light that use is modulated according to this control signal carries out.In this < 35>described pattern formation method, control signal forms information based on formed pattern and is generated, and light is according to this control signal and modulated.

< 36>according to any described pattern formation method in < 32 >～< 35 >; Wherein, exposure is to use the light irradiating means of irradiates light and based on the pattern-information that will form the optical modulator body of modulating from the light of said light irradiating means irradiation is carried out.

< 37>according to < 36>described pattern formation method; Wherein, Exposure is after utilizing the optical modulator body light modulated; See through and to be arranged with that lenticular microlens array carries out, said lenticule has the aspheric surface of the aberration that the distortion of the outgoing plane that can revise the drawing section in the said optical modulator body causes.In the pattern formation method of record, the light that utilizes said optical modulator body modulation is through seeing through the said aspheric surface in the said microlens array in these < 37 >, and the aberration that the distortion of the outgoing plane in the said drawing section causes is able to revise.As a result, can be suppressed at the distortion that pattern becomes the picture that becomes on the material, the high exposure of carrying out this pattern is become material subtly.For example, if after said photographic layer is developed, then can form high meticulous pattern.

< 38>according to < 37>described pattern formation method, wherein, aspheric surface is a double-curved surface.In these < 38 >, in the pattern formation method of record, be double-curved surface, can revise the aberration that the distortion of the emitting surface in the said drawing section causes effectively, can be suppressed at the distortion that pattern becomes the picture that becomes on the material effectively through making said aspheric surface.As a result, the high exposure of carrying out said pattern is become material subtly.For example, if after said photographic layer is developed, then can form high meticulous pattern.

< 39>according to any described pattern formation method in said < 32 >～< 38 >, wherein, exposure is carried out via array of apertures.In these < 39 >, in the pattern formation method of record,, can improve extinction ratio through making public via said array of apertures.As a result, can highly make public subtly.For example, if after said photographic layer is developed, can form high meticulous pattern.

< 40>according to any described pattern formation method in said < 32 >～< 39 >, wherein, exposure is when exposure light and photographic layer are relatively moved, to carry out.In these < 40 >, in the pattern formation method of record,, can make public at high speed through when the light that carries out said modulation and said photographic layer are relatively moved, making public.For example, if after said photographic layer is developed, then can form high meticulous pattern.

< 41>according to any described pattern formation method in said < 32 >～< 40 >, wherein, exposure is that carry out in a part of zone of relative photographic layer.

< 42 >, wherein, after having carried out exposure, carry out the development of photographic layer according to any described pattern formation method in < 32 >～< 41 >.In these < 42 >, in the pattern formation method of record,, can form high meticulous pattern through after having carried out said exposure, said photographic layer being developed.

< 43 >, wherein, after having carried out development, form permanent pattern according to < 42>described pattern formation method.

< 44>according to < 43>described pattern method of formationing, wherein, permanent pattern is a wiring pattern, the formation of this permanent pattern be utilize etch processes and plating processing any one carries out at least.

Utilize the present invention; Can solve problem in the past, the pattern that superficial failure is few, can prevent the breaking less of the light fog that developer causes, unexposed film, the exploring degree is high, masked film intensity height and the pattern fissility after forming is good, can form higher meticulous pattern becomes material and possesses this pattern to become the pattern apparatus for converting of material and use said pattern to become the pattern formation method of material.

Embodiment

(pattern becomes material)

Pattern of the present invention becomes material to have supporter and the photographic layer on this supporter at least, other layers of also can have protective film, suitably selecting.

< photographic layer >

Said photographic layer includes the assorted compound ring series that contracts of (A) bonding agent, (B) polymerizable compound, (C) Photoepolymerizationinitiater initiater, (D), (E) polymerization inhibitor, (F) developer and (G) organic solvent, contains other compositions that dyestuff, reductive agent etc. are suitably selected as required.Wherein, the range upon range of number of said photographic layer can be 1 layer, also can be for more than 2 layers.

In addition, under the situation that said photographic layer is made public, develops, the least energy of the light that does not change in the front and back of this development as the thickness of the exposed portion of this photographic layer is preferably 0.1～20mJ/cm ², 0.5～10mJ/cm more preferably ², be preferably 1～8mJ/cm especially ²

If said least energy is less than 0.1mJ/cm ², photographic fog then takes place in treatment process sometimes, if surpass 20mJ/cm ², the required time that then makes public sometimes is elongated, and processing speed is slack-off.

At this; Said " least energy of the thickness of exposed portion that makes photographic layer light that do not change, that in said exposure, use in this exposure and after developing " is meant so-called development sensitivity, and the energy (exposure) of the light that uses for example can the said exposure when expression makes public to said photographic layer utilizes the curve map (curve of sensitivity) of the relation between the thickness of said cured layer of said development treatment generation to try to achieve with following said exposure.

The thickness of said cured layer increases and increases along with said exposure, become then with said exposure before the roughly the same and constant of thickness of said photographic layer.Said development sensitivity is the value that the minimum exposure amount when becoming constant through the thickness that reads said cured layer is tried to achieve.

Difference between the thickness of the said photographic layer before the thickness of said cured layer and the said exposure be in ± 1 μ m time, thinks that the thickness of said cured layer is by the exposure and the change of developing.

Determination of thickness method as the said photographic layer before said cured layer and the said exposure; Not special restriction; Can suitably select according to purpose; For example can enumerate and use determining film thickness device, surface roughness measurement machine (for example サ one Off コ system 1400D, Tokyo Precision Co., Ltd system) etc. to carry out method for measuring etc.

-(A) bonding agent-

The acid number of said bonding agent is 50～400mgKOH/g, is preferably 75～300mgKOH/g, more preferably 100～250mgKOH/g.

If said acid number is less than 50mgKOH/g; Development property deficiency then; Perhaps the exploring degree is poor, may not obtain patterns such as wiring pattern subtly by height, if surpass 400mgKOH/g; Then the anti-development fluidity of pattern and adhering any one variation at least can not obtain permanent patterns such as wiring pattern by height sometimes subtly.

Matter average molecular weight in the molecular weight of said bonding agent is 10,000～100,000, is preferably 30,000～80,000.

If said matter average molecular weight is less than 10,000, then film strength is not enough easily, is difficult to sometimes in addition stably make, if surpass 100,000, then development property reduces sometimes.

As the higher limit of said I/O value, for example, be preferably 0.60, more preferably 0.58 from any one the viewpoint at least of further raising exploring degree and covering property.

As the lower limit of said I/O value, for example, be preferably 0.35, more preferably 0.40 from improving the viewpoint of development property.

As the method for the I/O value of regulating said bonding agent, the kind of monomer that can be through suitable selection formation multipolymer and the polymerization when making this monomer polymerization than (content) any one is adjusted to for example 0.35～0.60 scope at least.

Said I/O value is to treat also the value of the polarity of the various organic compounds that are called as (inorganic value)/(organic value) from organic notion angle, is that one of method is expressed by the functional group of setup parameter in each functional group.As said I/O value, particularly, at organic conceptional diagram (first Tian Shansheng work, three publish (1984) altogether); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1 the 1st～16 (1954 years); 719～725 of No. the 10th, field the 11st volumes of chemistry (nineteen fifty-seven); Fragrance magazine No. the 34th, (Off レグラ Application スジヤ one Na Le) the 97th～111 (1979 years); Specified in No. 50 the 79th～82 documents such as (1981) of fragrance magazine (Off レグラ Application スジヤ one Na Le).

The notion of said I/O value is divided into the organic property group of representing covalency and the inorganic nature group of representing ionic link property with the character of compound, all organic compound object locations is determined on per 1 on the quadrature coordinate that is named as arbor and no arbor.

Said inorganic value is meant with the hydroxyl to be standard, and the various substituting groups that organic compounds is had or key etc. are the value that benchmark quantizes to the size of the influence power of boiling point with the hydroxyl.Particularly; If the distance between the boiling curve of carbon number boiling curve about 5, straight chain alcohol and linear paraffin is about 100 ℃; So the influence power of 1 hydroxyl is decided to be 100 with numerical value; Based on this numerical value, be the substituent inorganic value that organic compound has to the value that the influence power of boiling point quantizes with various substituting groups or various keys etc.For example, the inorganic value of-COOH base is 150, and the inorganic value of two keys is 2.Thereby the inorganic value of certain organic compound is meant the summation of the inorganic value of various substituting groups that this compound has or key etc.

Said organic value is meant, is unit with intramolecular methylene, the value that the carbon atom of representing this methylene is confirmed as standard the influence power of boiling point.Promptly; The straight chain saturation alkane compound whenever adds 1 carbon and mean value that boiling point rises is 20 ℃ at carbon number about 5～10; So with it is standard; The organic value of 1 carbon atom is decided to be 20, is standard with it, is organic value with various substituting groups or key etc. to the value that the influence power of boiling point quantizes.For example, nitro (NO ₂) organic value be 70.

Said I/O value is more near 0, shows more to be the organic compound of nonpolar (hydrophobicity, organic property big), and is big more, shows it is polarity (water wettability, inorganic nature big) organic compound more.

One example of the computing method of said I/O value below is described.

(multipolymer is formed (mol ratio): I/O value 2/5/3) is to try to achieve through calculating following formula (inorganic value of said multipolymer)/(organic value of said multipolymer) behind inorganic value that calculates this multipolymer with following method and the organic value to methacrylic acid/methyl methacrylate/styrol copolymer.

The inorganic value of said multipolymer calculates through the summation of trying to achieve (inorganic value of said methacrylic acid) * (mol ratio of said methacrylic acid), (inorganic value of said methyl methacrylate) * (mol ratio of said methyl methacrylate) and (said cinnamic inorganic value) * (said cinnamic mol ratio).

Said methacrylic acid has 1 carboxyl, and said methyl methacrylate has 1 ester group, and said styrene has 1 aromatic rings, so

The inorganic value of said methacrylic acid: 150 (inorganic value of carboxyl) * 1 (number of carboxyl)=150,

The inorganic value of said methyl methacrylate: 60 (inorganic value of ester group) * 1 (number of ester group)=60,

Said cinnamic inorganic value: 15 (inorganic value of aromatic rings) * 1 (number of aromatic rings)=15,

Thereby the inorganic value of said multipolymer utilizes following formula: 150 * 2 (mol ratio of methacrylic acid)+60 * 5 (mol ratio of methyl methacrylate)+15 * 3 (cinnamic mol ratio) are calculated and are calculated as 645.

The organic value of said multipolymer calculates through the summation of trying to achieve (organic value of said methacrylic acid) * (mol ratio of said methacrylic acid), (organic value of said methyl methacrylate) * (mol ratio of said methyl methacrylate) and (said cinnamic organic value) * (said cinnamic mol ratio).

Said methacrylic acid has 4 carbon atoms, and said methyl methacrylate has 5 carbon atoms, and said styrene has 8 carbon atoms, so

The organic value of said methacrylic acid: (carbon number)=80,20 (organic value of carbon atom) * 4,

The organic value of said methyl methacrylate: (carbon number)=100,20 (organic value of carbon atom) * 5,

Said cinnamic organic value: (carbon number)=160,20 (organic value of carbon atom) * 8.

Thereby the organic value of said multipolymer utilizes following formula: 80 * 2 (mol ratio of said methacrylic acid)+100 * 5 (mol ratio of said methyl methacrylate)+160 * 3 (said cinnamic mol ratio) are calculated and are calculated as 1140.

Thereby the I/O value of said multipolymer is judged as 645 (inorganic value of said multipolymer)/1140 (organic value of said multipolymer)=0.566.

Said bonding agent needs only said I/O value in said numerical range, and not special restriction can suitably be selected according to purpose, for example also can have acidic groups.

As said bonding agent, acid number and matter average molecular weight do not limit as long as in said scope especially, and for example preferred aqueous alkali relatively is a swellability, and more preferably alkaline aqueous solution is a solubility relatively.In addition, also can in bonding agent, contain the polymerism base.

Demonstrate swellability or deliquescent bonding agent as relative alkaline aqueous solution, for example can preferably enumerate bonding agent with acidic groups.

As said acidic groups, not special restriction can suitably be selected according to purpose, for example can enumerate carboxyl, sulfonic group, phosphate etc., wherein preferred carboxyl.

As bonding agent with carboxyl; For example can enumerate ethylenic copolymer with carboxyl, urethane resin, polyamic acid resin, modified epoxy etc.; Wherein, From viewpoints such as easy degree, preferably has the ethylene copolymer of carboxyl to the adjusting of the dissolubility that applies solvent, dissolubility, synthetic adaptability, film physical property to alkaline developer.In addition, from the viewpoint of development property, go back any one the multipolymer at least of optimization styrene and styrene derivative.

Said ethylene copolymer with carboxyl can utilize at least (1) have carboxyl vinyl monomer, and (2) can obtain with the copolymerization of the monomer of their copolymerizations.As these monomers, particularly, can enumerate the compound of record in paragraph numbering [0164]～[0201] that the spy opens the 2005-258431 communique and [0203]～[0205] etc.

As the content of the said bonding agent in the said photographic layer, not special restriction can suitably not selected according to purpose, but for example preferred 10～90 quality %, more preferably 20～80 quality %, preferred especially 40～80 quality %.

If said content is less than 10 quality %; Alkali-developable or form adhesiveness reduction then with substrate (for example copper plating film laminated plate) with printed-wiring board (PWB); If surpass 90 quality %, then the stability of development time or the intensity of cured film (masked film) may reduce relatively.In addition, said content also can for as required with the total content of the macromolecule binding material of said bonding agent and usefulness.

Said bonding agent is to have under the situation of material of glass transition temperature; As this glass transition temperature, not special restriction can suitably be selected according to purpose; But become any one the viewpoint at least of fissility of the fusion of viscosity (tack), edge and the said supporter of material from for example said pattern; Be preferably more than 80 ℃, more preferably more than 100 ℃, be preferably especially more than 120 ℃.

If said glass transition temperature less than 80 ℃, then possibly said pattern become the viscosity of material to increase, the fissility variation of said supporter.

-(B) polymerizable compound-

As said polymerizable compound, include (b1) have the compound of urethane groups and (b2) have aryl compound at least any one, contain compound, other polymerizable compounds as required and form with polyalkylene oxide hydrocarbon compound.In addition, they preferably have polymerism base more than 2 kinds.

As said polymerism base; For example can enumerate ethene property unsaturated link (vinyl such as (methyl) acryloyl group, (methyl) acrylamido, styryl, vinyl acetate or vinethene for example; Allyl such as allyl ether or allyl ester etc.), ring-type ether (for example epoxy radicals, oxetanyl etc.) that can polymerization etc.; Wherein, optimal ethylene property unsaturated link.

The monomer of urethane groups---(b1) have---

As said monomer with urethane groups, as long as have urethane groups, not special restriction can suitably not selected according to purpose, for example can enumerate the compound of paragraph numbering [0210]～[0262] record that the spy opens the 2005-258431 communique etc.

The content of compound in said polymerizable compound with said urethane groups is preferably below the 70 quality %, 20～60 quality % more preferably, and then be preferably 30～50 quality %.If said content surpasses 70 quality %, variation sometimes such as exploring, adhesiveness then.

The monomer of aryl---(b2) have---

As said compound with aryl; As long as have aryl; Not special restriction can suitably not selected according to purpose, for example can enumerate ester or the acid amides etc. of any one and the unsaturated carboxylic acid at least of polyol compound, polyamine compound and polynary alkamine compound with aryl.

Particularly, can enumerate the compound etc. of paragraph numbering [0264]～[0271] record that the spy opens the 2005-258431 communique.

The said content of compound in said polymerizable compound with aryl is preferably below the 70 quality %, 20～60 quality % more preferably, and then be preferably 30～50 quality %.If said content surpasses 70 quality %, variation sometimes such as exploring, adhesiveness, covering property then.

---compound---with polyalkylene oxide hydrocarbon chain

Also can become to contain compound in the material in pattern of the present invention with polyalkylene oxide hydrocarbon chain.

As said compound with polyalkylene oxide hydrocarbon chain, not special restriction can be monofunctional monomer, also can be polyfunctional monomer.

As said monofunctional monomer, for example can preferably enumerate the compound of following structural formula (i) expression.

[changing 1]

structural formula (i)

In said structural formula (i), R ¹Expression hydrogen atom or methyl.

X representes that carbon number is 2～6 alkylidene, compares with ring texture, more preferably has chain structure.The chain alkylidene also can have side chain.As this alkylidene, for example can enumerate ethylidene, propylidene, tetramethylene, pentylidene, hexa-methylene etc., wherein, preferred ethylidene and propylidene.

N is 1～30 integer, and n is under the situation more than 2, a plurality ofly (X-O-) is same to each other or different to each other, (under the situation about X-O-) differing from one another, for example can preferably enumerates the combination of ethylidene and propylidene etc.

As R ², for example can enumerate alkyl, aryl, aralkyl etc., these groups also can and then be substituted base and replace.

As said alkyl, be 1～20 alkyl as carbon number, for example can enumerate methyl, ethyl, propyl group, hexyl, cyclohexyl, 2-ethylhexyl, dodecyl, cetyl, octadecyl etc.This alkyl can have substituting group, also can have side chain or ring structure.

As said aralkyl, for example can enumerate benzyl, phenethyl etc.This aralkyl also can have substituting group.

As said aryl, for example can enumerate phenyl, naphthyl, tolyl, xylyl, ethylphenyl, methoxyphenyl, propyl group phenyl, butyl phenyl, tert-butyl-phenyl, octyl phenyl, nonyl phenyl, chlorphenyl, cyano-phenyl, dibromo phenyl, tribromo phenyl, xenyl, benzyl phenyl, alpha-alpha-dimethyl-benzyl phenyl etc.This aryl also can have substituting group.

As the substituting group in said alkyl, aralkyl and the aryl, for example can enumerate halogen atom, aryl, alkenyl, alkoxy, cyanic acid etc.

As said halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms etc.

The preferred total carbon atom number of said aryl is 6～20, more preferably 6～14.As this aryl, for example can enumerate phenyl, naphthyl, anthryl, anisyl etc.

As said alkenyl, preferred total carbon atom number is 2～10, more preferably 2～6.As this alkenyl, for example can enumerate ethinyl, propenyl, bytyry etc.

As said alkoxy, can branching, preferred total carbon atom number is 1～10, more preferably 1～5.As this alkoxy, for example can enumerate methoxyl, ethoxy, propoxyl group, 2-methyl propoxyl group, butoxy etc.

As the compound of said structural formula (i) expression, particularly, can enumerate compound that following structural formula representes etc.Wherein, in the following formula, R representes hydrogen atom or methyl.N representes 1～30 integer, and m and L represent the integer more than 1 respectively, and m+L representes 1～30 integer.Me representes methyl, and Bu representes butyl.

[changing 2]

[changing 3]

In addition, in the compound with polyalkylene oxide hydrocarbon chain, as any one the compound at least with ethylidene and propylidene, the number that can also preferably enumerate ethylidene or propylidene is 10～30 polyglycol, polypropylene glycol.

Said compound with polyalkylene oxide hydrocarbon chain can use a kind separately, also can be also with more than 2 kinds.

As said polyfunctional monomer, the number that for example can enumerate ethylene glycol bisthioglycolate (methyl) acrylic ester, ethylidene is that the number of 2～30 polyglycol two (methyl) acrylic ester (for example diglycol two (methyl) acrylic ester, triethylene glycol two (methyl) acrylic ester, tetraethylene glycol two (methyl) acrylic ester, polyglycol #400 dimethylacrylate, polyglycol #600 dimethylacrylate, polyglycol #1000 dimethylacrylate etc.), propylene glycol two (methyl) acrylic ester, propenyl is 2～18 polypropylene glycol two (methyl) acrylic ester (for example DPG two (methyl) acrylic ester, tripropylene glycol two (methyl) acrylic ester, four propylene glycol two (methyl) acrylic ester, ten DPG two (methyl) acrylic ester etc.), has two (methyl) acrylic ester (compound of for example in International Publication the 01/98832nd trumpeter's volume, putting down in writing etc.), polytetramethylene glycol two (methyl) acrylic ester etc. of the alkylene glycol chain of 1 glycol chain/propylene glycol chain at least respectively.

Wherein, from the viewpoints such as easy degree of its acquisition, preferred ethylene glycol bisthioglycolate (methyl) acrylic ester, propylene glycol two (methyl) acrylic ester, has two (methyl) acrylic ester etc. of the alkylene glycol chain of 1 glycol chain/propylene glycol chain at least respectively.

The said content of compound in said polymerizable compound with polyalkylene oxide hydrocarbon chain is preferably below the 40 quality %, 1～30 quality % more preferably, and then be preferably 1～25 quality %.If said content is less than 0.1 quality %, then the effect of fissility or development latitude improvement becomes insufficient sometimes, if surpass 40 quality %, and variation sometimes such as exploring, adhesiveness, covering property then.

---other polymerizable compounds---

Pattern of the present invention becomes material also can use the polymerizable compound beyond the said polymerizable compound.For example can enumerate the acid amides etc. of ester, unsaturated carboxylic acid and the polyamine compound of unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.) and aliphatic polyol compound.

Particularly, can enumerate the compound etc. of paragraph numbering [0273]～[0283] record that the spy opens the 2005-258431 communique.

As the content of the polymerizable compound in the said photographic layer, for example preferred 5～90 quality %, more preferably 15～60 quality %, preferred especially 20～50 quality %.

If said content is 5 quality %, then hiding film strength may reduce, if surpass 90 quality %, the edge fusion (from the fault of oozing out of roll end) when then preserving may worsen.

-(C) Photoepolymerizationinitiater initiater-

As said Photoepolymerizationinitiater initiater; As long as have the ability of the polymerization that causes said polymerizable compound; Not special restriction can suitably be selected from known Photoepolymerizationinitiater initiater, but for example preferred to from the ultraviolet range to the luminous ray, having the Photoepolymerizationinitiater initiater of photosensitivity; Can also can cause the initiating agent of cationic polymerization for the kind of corresponding monomer for by the light activated assorted compound ring series or with sensitizer certain effect takes place, produce the active agent of living radical of contracting.

In addition, said Photoepolymerizationinitiater initiater preferably contains a kind of composition that in the scope of about 300～800nm, has about 50 molecule absorptivity at least at least.Said wavelength is 330～500nm more preferably.

As said Photoepolymerizationinitiater initiater, for example can enumerate halogenated hydrocarbons derivant (for example having the derivant of triazine skeleton, the derivant of Ju You oxadiazole skeleton etc.), phosphine oxide, six aryl di-imidazoles, 9 oxime derivate, organic peroxide, thio-compounds, ketonic compound, acylphosphine oxide, aromatic series salt, ketoxime ether etc.As the Photoepolymerizationinitiater initiater beyond the said 9 oxime derivate, particularly, for example can enumerate the compound of record in paragraph numbering [0288]～[0299] that the spy opens the 2005-258431 communique and paragraph numbering [0305]～[0309] etc.

As said 9 oxime derivate, for example can enumerate 3-benzoyloxy imino group butane-2-ketone, 3-acetyl group imino group butane-2-ketone, 3-propionyloxy imino group butane-2-ketone, 2-acetoxyl group imino group pentane-3-ketone, 2-acetoxyl group imino group-1-phenyl-propane-1-ketone, 2-benzoyloxy imino group-1-phenyl-propane-1-ketone, 3-(4-tosyloxy) imino group butane-2-ketone, 2-ethoxy carbon acyloxy imino group-1-phenyl-propane-1-ketone etc.

As the content of the Photoepolymerizationinitiater initiater in the said photographic layer, be preferably 0.1～30 quality %, 0.5～20 quality % more preferably, preferred especially 0.5～15 quality %.

-(D) the assorted compound ring series that contracts-

As the said assorted compound ring series that contracts; For exposure sensitivity or the wavelength photoreceptor of stating after adjusting when photographic layer makes public; Perhaps when exposure, the said photographic layer of development; Make the viewpoint of the least energy (sensitivity) of the said light that the thickness of the exposed portion of this photographic layer do not change from raising before and after this development, add.Through and with the said compound ring series that contracts of mixing, for example can be easy as can the least energy (sensitivity) of said photographic layer be adjusted into 0.1～20mJ/cm ²

The said assorted compound ring series that contracts preferred corresponding as after luminous ray or the suitable compound of ultraviolet laser and visible light laser etc. of the light irradiating means stated.

The said assorted compound ring series that contracts becomes excited state under the effect of active energy ray, can produce useful bases such as free radical or acid through interact (for example energy moves, electronics moves etc.) with other materials (for example free-radical generating agent, acid producing agent etc.).

In addition, the assorted compound ring series that contracts is not only in order to improve the sensitivity of photographic layer, but also plays the function as the Photoepolymerizationinitiater initiater of the polymerization of trigger monomer under optical excitation.

The said assorted compound ring series that contracts is meant the polycyclic compound that in ring, has assorted element, preferably in said ring, contains nitrogen-atoms.

As the said assorted compound ring series that contracts, for example preferably contain from assorted contract ring system ketonic compound, quinoline compound, acridine compound, select at least a.

As the said assorted compound ring series that contracts, particularly, for example can enumerate acridone, chloro-acridine ketone, N-methylacridine ketone, N-butyl acridone, N-butyl-acridone compounds such as chloro-acridine ketone; 3-(2-coumarone formoxyl)-7-diethyl amino coumarin, 3-(2-coumarone formoxyl)-7-(1-pyrrolidinyl) cumarin, 3-benzoyl-7-diethyl amino coumarin, 3-(2-methoxybenzoyl)-7-diethyl amino coumarin, 3-(4-dimethylamino benzoyl)-7-diethyl amino coumarin, 3; 3 '-carbonyl two (5; 7-two-positive propoxy cumarin), 3; 3 '-carbonyl is two-(7-diethyl amino coumarin), 3-benzoyl-ayapanin, 3-(2-furoyl)-7-diethyl amino coumarin, 3-(4-diethylamino cinnamoyl)-7-diethyl amino coumarin, 7-methoxyl-3-(3-pyridine radicals carbonyl) cumarin, 3-benzoyl-5; 7-dipropoxy cumarin, 7-benzotriazole-2-basic note legumin, 7-diethylin-4-methylcoumarin also have the special flat 5-19475 communique, spy opened to open flat 7-271028 communique, spy and open 2002-363206 communique, spy and open 2002-363207 communique, spy and open the coumarin compound etc. that 2002-363208 communique, spy are opened record in the 2002-363209 communique etc. in addition.

As said quinoline compound; Particularly, for example can enumerate quinoline, 9-hydroxyl-1,2-EEDQ-2-ketone, 9-ethoxy-1; 2-EEDQ-2-ketone, 9-dibutyl amino-1,2-EEDQ-2-ketone, oxine, thiooxine, quinoline-2-carbonic acid etc.

As said acridine compound, particularly, for example can enumerate 9-phenylacridine, 1, two (9,9 '-acridinyl) heptane of 7-etc.

In the said assorted compound ring series that contracts, more preferably in ring, contain the nitrogen element.As the compound that contains the nitrogen element at said ring, can preferably enumerate said acridine compound, by the substituted coumarin compound of amino, acridone compound etc.Wherein, preferred especially acridone compound.

As the said assorted compound ring series that contracts, so preferred said acridone, by the substituted cumarin of amino, 9-phenylacridine etc., wherein, preferred especially said acridone.

As the combination of said Photoepolymerizationinitiater initiater and the said assorted compound ring series that contracts, for example can enumerate the spy and open the electronics mobile model initiator system combinations of putting down in writing in the 2001-305734 communique such as [(1) electronics supply-type initiating agent and sensitizing dyestuff, (2) electronics acceptance type initiating agent and sensitizing dyestuff, (3) electronics supply-type initiating agent, sensitizing dyestuff and electronics acceptance type initiating agents (ternary initiator system)].

The above-mentioned assorted content of compound ring series in said photographic layer that contracts is preferably 0.05～30 quality %, and more preferably 0.1～20 quality % is preferably 0.2～10 quality % especially.If this content is less than 0.05 quality %, the sensitivity to active energy ray reduces so sometimes, and exposure process expends time in, and throughput rate reduces, if surpass 30 quality %, the above-mentioned assorted compound ring series that contracts is separated out from above-mentioned photographic layer when preserving so sometimes.

Except said assorted contracting the compound ring series, also can add other sensitizers as required.

-(E) polymerization inhibitor-

As said polymerization inhibitor, not special restriction can suitably be selected according to purpose.

Said polymerization inhibitor causes the free radical composition for the polymerization that under the effect of above-mentioned exposure, produces from above-mentioned Photoepolymerizationinitiater initiater; Implement hydrogen supply (or receiving hydrogen), energy supply (or receiving ability), power supply (or receiving electronics) etc.; Play making polymerization cause the free radical inactivation, forbid the effect that polymerization causes.

As above-mentioned polymerization inhibitor; Can enumerate and have the right compound of isolated electron (compound that for example has oxygen, nitrogen, sulphur, metal etc.), have the compound (for example aromatics) of pi-electron etc., particularly, preferably have the compound of phenol property hydroxyl; Compound with imino group; Compound with nitro has nitroso compound, has the compound of aromatic rings; Compound with heterocycle has the compound (comprising the coordination compound with organic compound) of metallic atom etc.Wherein, preferably have the compound of phenol property hydroxyl, have the compound of imino group, have the compound of aromatic rings, have the compound of heterocycle.

As above-mentioned compound with phenol property hydroxyl, not special restriction can suitably be selected according to purpose, for example preferably has the compound of 2 phenol property hydroxyls at least.At least have in the compound of 2 phenol property hydroxyls at this, at least 2 phenol property hydroxyls can be substituted on same aromatic rings, also can on same intramolecular distinct fragrance ring, be substituted.

The compound that the above-mentioned compound that has 2 phenol property hydroxyls is at least for example more preferably represented with following structural formula.

[changing 4]

In the said structure formula, Z representes substituting group, and m representes the integer more than 2.N representes the integer more than 0.This m and n are preferably integer and m+n=6.In addition, n is under the situation of the integer more than 2, and above-mentioned Z can be same to each other or different to each other.

In addition, if above-mentioned m less than 2, exploring degree possible deviation so.

As above-mentioned substituting group; For example can enumerate acyl group (for example acetyl group, propiono, benzoyl group) below 30 of acyloxy (for example acetoxyl group, propionyloxy etc.) below 30 of alkyl below 30 of aryloxy group below 30 of arylthio below 30 of alkoxy (for example methoxyl, ethoxy, benzyloxy, phenoxy group ethoxy, benzene ethoxy) below 30 of amide group sulfonyl (for example Benzamido sulfonyl, acetamido sulfonyl, pivaloyl amido sulfonyl) below 30 of alkyl sulfonyl-amino carbonyl (for example mesyl amino carbonyl, octyl group sulfonyl amino carbonyl) below 30 of aryloxycarbonyl (for example phenyloxycarbonyl) below 30 of alkoxy carbonyl (for example methoxycarbonyl group, carbethoxyl group, benzyloxycarbonyl group) below 30 of carboxyl, sulfo group, cyanic acid, halogen atom (for example fluorine atom, chlorine atom, bromine atoms), hydroxyl, carbon number, carbon number, carbon number, aryl sulfonyl amino carbonyl (for example tosyl amino carbonyl), carbon number, carbon number, carbon number, alkylthio group (for example thiophenyl, methyl mercapto, ethylmercapto group, dodecane sulfenyl etc.), carbon number (for example phenoxy group, to toloxyl, 1-naphthoxy, 2-naphthoxy etc.), nitro, carbon number, alkyl oxy carbonyl oxygen (for example methoxy carbonyl oxygen base, stearic oxygen base carbonyl oxygen base, phenoxy group ethoxy carbonyl oxygen base), aryloxy group carbonyl oxygen base (for example phenoxy group carbonyl oxygen base, chlorophenoxy carbonyl oxygen base), carbon number, carbon number, carbamyl (for example carbamyl, N; N-formyl-dimethylamino, morpholino carbonyl, piperidino carbonyl etc.), aryl (for example phenyl, dichlorophenyl, toluyl, anisyl, diethylamino phenyl, acetyl-amino phenyl, methoxycarbonyl phenyl, hydroxyphenyl, uncle's octyl phenyl, naphthyl etc.), substituted-amino (for example amino, alkyl amino, dialkyl amido, arylamino, ammonia diaryl base, acyl amino etc.) below 30 of alkyl sulphonyl (for example mesyl, trifluoromethyl sulfonyl, ethylsulfonyl, butyl sulfonyl, dodecyl sulfonyl) below 30 of sulfamoyl (for example sulfamoyl, N, N-dimethylamino sulfonyl, morpholino sulfonyl, piperidyl sulfonyl etc.), carbon number, aryl sulfonyl (for example benzenesulfonyl, tosyl, naphthalene sulfonyl base, pyridine sulfonyl, quinoline sulfonyl), carbon number, replace phosphate (phosphono) (for example phosphate, diethyl phosphate, diphenylphosphine acidic group), heterocyclic radical (for example pyridine radicals, quinolyl, furyl, thienyl, tetrahydrofurfuryl, pyrazolyl, isoxazolyl, isothiazolyl, imidazole radicals, oxazolyl, thiazolyl, pyridazinyl, pyrimidine radicals, pyrazinyl, triazolyl, tetrazole radical, benzoxazolyl, benzimidazolyl, isoquinolyl, thiadiazolyl group, morpholino base, piperidyl, piperazinyl, indyl, isoindolyl, thiomorpholine are for base), urea groups (for example methyl urea groups, dimethyl urea groups, phenyl urea groups etc.), sulfamoyl amino (for example dipropyl sulfamoyl amino etc.), alkoxycarbonyl amido (for example carbethoxyl group amino etc.), aryloxycarbonyl amino (for example phenyloxycarbonyl amino etc.), alkyl sulphinyl (for example methylsulfinyl etc.), aryl sulfonyl kia (for example phenyl sulfinyl etc.), silicyl (for example trimethoxysilyl, triethoxysilyl etc.), siloxy (for example trimethylsiloxy etc.) etc.

As the compound of representing with above-mentioned structural formula; For example can enumerate alkyl catechol (for example catechol, resorcinol, 1; 4-p-dihydroxy-benzene, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propyl group catechol, 3-propyl group catechol, 4-propyl group catechol, 2-normal-butyl catechol, 3-normal-butyl catechol, 4-normal-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, 3; 5-ditertiarybutyl catechol etc.), alkyl-resorcin (for example 2-methylresorcinol, cresorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl group resorcinol, 4-propyl group resorcinol, 2-n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcin, 4-tert-butyl resorcin etc.), alkyl p-dihydroxy-benzene (for example methyl hydroquinone, ethyl p-dihydroxy-benzene, propyl group p-dihydroxy-benzene, TBHQ, 2,5 di tert butyl hydroquinone etc.), pyrogallol, phloroglucin etc.

In addition, above-mentioned compound with phenol property hydroxyl for example also is preferably the compound that the aromatic rings that has 1 above-mentioned phenol property hydroxyl at least links with the concatenating group of divalent each other.

As the concatenating group of above-mentioned divalent, for example can enumerate and have 1～30 carbon atom, oxygen atom, nitrogen-atoms, sulphur atom, SO, SO ₂Deng group.Above-mentioned sulphur atom, oxygen atom, SO and SO ₂Also can directly combine.

Above-mentioned carbon atom and oxygen atom also can have substituting group, as this substituting group, for example can enumerate the Z in above-mentioned structural formula.

In addition, above-mentioned aromatic rings also can have substituting group, as this substituting group, for example can enumerate the Z in above-mentioned structural formula.

As above-mentioned object lesson with compound of phenol property hydroxyl, the sterically hindered phenolic compound that known bisphenol compound, the spy who can enumerate bisphenol-A, bisphenol S, bis-phenol M, in heat sensitive paper, uses as developer open the bisphenol compound put down in writing in the 2003-305945 communique, use as antioxidant etc.In addition, can also enumerate 4-methoxyl phenol, 4-methoxyl-2-dihydroxy benaophenonel, betanaphthol, 2,6-di-t-butyl-4-cresols, gaultherolin, hydroxyl diethyl have substituent monohydric phenol compound etc. for aniline etc.

As above-mentioned commercially available article, can enumerate the bisphenol compound of Honshu chemical company system with compound of phenol property hydroxyl.

As above-mentioned compound with imino group, not special restriction can suitably be selected according to purpose, for example the compound of preferred molecular weight more than 50, the more preferably compound of molecular weight more than 70.

Above-mentioned compound with imino group preferably has by the substituted ring texture of imino group.As this ring texture, be preferably the product of any one generation condensation at least of aromatic rings and heterocycle, the product of the condensation of aromatic rings generation more preferably.In addition, in the above-mentioned ring texture, also can have oxygen atom, nitrogen-atoms, sulphur atom.

As above-mentioned object lesson, can enumerate phenothiazine 、 phenoxazine, dihydro azophenlyene, quinhydrones or replace the compound of these compounds by the Z in the above-mentioned said structure formula (37) with compound of imino group.

By the substituted compound with ring texture of imino group, a preferred part has the bulky amine derivant of bulky amine (ヒ Application ダ one De アミ Application) as above-mentioned.

As above-mentioned bulky amine, for example can enumerate the spy and open the bulky amine of putting down in writing in the 2003-246138 communique.

Have nitroso compound as above-mentioned compound with nitro or above-mentioned, not special restriction can suitably not selected according to purpose, and for example preferred molecular weight is the compound more than 50, and more preferably molecular weight is the compound more than 70.

As above-mentioned compound or above-mentioned object lesson, can enumerate the chelate of nitrobenzene, nitroso compound and aluminium etc. with nitroso compound with nitro.

As above-mentioned compound with aromatic rings, not special restriction can suitably be selected according to purpose, and for example preferred above-mentioned aromatic rings is by having the substituted compound of the right substituting group of isolated electron (substituting group that for example has oxygen atom, nitrogen-atoms, sulphur atom etc.).

As the object lesson of compound, for example can enumerate the above-mentioned compound (for example methylenum careuleum, crystal violet etc.) that the compound of phenol property hydroxyl, above-mentioned compound, a part with imino group have the aniline skeleton that has with above-mentioned aromatic rings.

As above-mentioned compound with heterocycle, not special restriction can suitably be selected according to purpose, for example is preferably to have the compound that this heterocycle has the right atom of isolated electrons such as nitrogen, oxygen, sulphur.

As above-mentioned object lesson with compound of heterocycle, not special restriction can be enumerated and given a tongue-lashing pyridine, quinoline etc.

As above-mentioned compound with metallic atom, not special restriction can suitably be selected according to purpose.

As above-mentioned metallic atom, so long as the metallic atom that has an affinity with the free radical that produces from above-mentioned polymerization initiator get final product, do not limit especially, can suitably not select according to purpose, for example, can enumerate copper, aluminium, titanium etc.

In above-mentioned polymerization inhibitor; The preferred compound that has 2 phenol property hydroxyls at least, have by the compound of the substituted aromatic rings of imino group, have by the compound of the substituted heterocycle of imino group, preferred especially imino group constitutes compound, the bulky amine compound of the part of ring texture.Particularly, preferred catechol, phenothiazine 、 phenoxazine, bulky amine or their derivant.

Above-mentioned polymerization inhibitor usually in commercially available polymerizable compound trace contain, and in the present invention, from improving the viewpoint of exploring degree, make its contain with commercially available above-mentioned polymerizable compound in the different polymerization inhibitor of polymerization inhibitor that contains.Thereby above-mentioned polymerization inhibitor is preferably the compounds the monohydric phenol based compound such as 4-methoxyl phenol except containing in commercially available above-mentioned polymerizable compound in order to give stability.

In addition, become in the manufacturing process of material, also can in photosensitive polymer combination solution, add above-mentioned polymerization inhibitor in advance in pattern.

As the content of above-mentioned polymerization inhibitor, the said polymerizable compound of above-mentioned relatively photographic layer is preferably 0.005～0.5 quality %, and more preferably 0.01～0.4 quality % is preferably 0.02～0.2 quality % especially.If said content is less than 0.005 quality %, then the exploring degree may reduce, if surpass 0.5 quality %, the sensitivity to active energy ray reduces so sometimes.

In addition, the content of above-mentioned polymerization inhibitor is represented the content the monohydric phenol based compound such as 4-methoxyl phenol except containing in commercially available above-mentioned polymerizable compound in order to give stability.

-(F) developer-

But give video (printing function) for the said photographic layer after exposure, also can add said developer.

As said developer, for example can enumerate the compound of record in paragraph numbering [0320]～[0321] that the spy opens the 2005-258431 communique etc.

As the content of said developer in said photographic layer, be preferably 0.01～20 quality %, more preferably 0.05～10 quality % is preferably 0.1～5 quality % especially.In addition, the content of content in said photographic layer as said halogen compounds is preferably 0.001～5 quality, more preferably 0.005～1 quality %.

-(G) organic solvent-

Coating liquid when forming and add said organic solvent in order to prepare photographic layer.

The remaining quantity of said organic solvent in said photographic layer is below the 0.5 quality %, is preferably below the 0.45 quality %, more preferably below the 0.4 quality %, is preferably especially below the 0.35 quality %.If said remaining quantity surpasses 0.5 quality %, then fissility reduces, and masked film intensity also dies down.

As said organic solvent, at least a for what from ketone, alcohols and ethers, select.

As said ketone, for example can enumerate acetone, methyl ethyl ketone, hexone, cyclohexanone, isobutyrone etc.

As said alcohols, for example can enumerate methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, sec-butanols, n-hexyl alcohol, methyl propanediol, 1-methoxyl-2-propyl alcohol etc.

As said ethers, for example can enumerate tetrahydrofuran, diethyl ether, glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether etc.

In said organic solvent, owing to methyl ethyl ketone, cyclohexanone, methyl alcohol, tetrahydrofuran, the remaining quantity of propylene glycol monomethyl ether when forming photographic layer tail off, so preferred.

Also have, these organic solvents also can use a kind of separately, can also more than 2 kinds and use.In addition, also can add known surfactant.

-other compositions-

As said other compositions; For example can enumerate dyestuff, reductive agent, hydrogen donor, sensitizer, plastifier, colorant etc., and then also can and use to the adhesion promoter of matrix surface and other auxiliary agent classes (for example pigment, conductive particle, filling agent, foam-breaking agent, fire retardant, levelling agent, peel off promoter, anti-oxidant, spices, thermal cross-linking agent, surface tension modifier, chain-transferring agent etc.).Through suitably containing these compositions, the pattern that can regulate needs becomes character such as the stability of material, photograph property, printing property, film rerum natura.

-dyestuff-

Add said dyestuff for the operability that improves the identification of inspection during coated surfaces etc., preferably do not make the coated surfaces of said photographic layer and the dyestuff that the exposure sensitivity reduces.

As said dyestuff, preferred absorbing wavelength is big with difference between the absorbing wavelength of utilizing after the chromogenic reagent, exposure wavelength does not have the dyestuff of absorption relatively.

In addition, as the absorbing wavelength of dyestuff, the identification of said photographic layer when inspection is outstanding, demonstrates the not green of stimulation applications person's vision, thus preferred, preferably have maximum absorption wavelength at 500～650nm.

As said dyestuff; As long as this dyestuff is the methyl ethyl ketone lysate of 0.5 quality % is that filtration pressure in the 0.45 μ m filtrator is the dyestuff below the 0.3MPa in the aperture; Not special restriction can suitably be selected according to purpose, is preferably the compound with triallyl methane skeleton.In addition, said dyestuff is preferably ionic dye, this ionic dye negative ion (counter anion) is especially preferably had for example aromatic acid, carbonic acid, phosphoric acid etc.

As said aromatic acid, for example can enumerate naphthalene sulfonic acids, phenylbenzimidazole sulfonic acid etc., wherein,, can preferably enumerate naphthalene sulfonic acids from deliquescent viewpoint.

As said compound with triallyl methane skeleton; The operability of, identification when the coated surfaces of inspection said photographic layer outstanding from the dissolubility of relative organic solvent etc. remarkably, does not make the coated surfaces of this photographic layer and the viewpoint that the exposure sensitivity reduces; The preferred allyl sulphonic acid compound that uses, preferred especially naphthalene sulfonic acids compound.

As said naphthalene sulfonic acids compound, for example can preferably enumerate Victoria's ethereal blue NAPS.

" solubleness of organic solvent relatively "

The methyl ethyl ketone lysate of the preferred 0.5 quality % of said dyestuff is that the filtration pressure in the 0.45 μ m filtrator is below the 0.3MPa in the aperture.This filtration pressure can be measured with being described below.Wherein, being determined under room temperature, the atmospheric condition of filtration pressure carried out.

(1) with 0.5 quality % dyestuff is dissolved in the methyl ethyl ketone solution.

(2) at syringe (テ Le モ corporate system, SS-20ESZ; Diameter 1.5cm, long 9.5cm) goes up that to connect the aperture be filtrator (ADVANTEC corporate system, the DISMIC of 0.45 μ m; 25HP045AN), via this filtrator, filter the methyl ethyl ketone lysate that is filled in the illuminating colour 0.5 quality % in the syringe.The filter velocity of this moment is the 50cc/ branch.

When (3) carrying out said filtration, act on the pressure of syringe with the tensimeter instrumentation, as the filtration pressure of illuminating colour 0.5 quality % methyl ethyl ketone lysate.

Through making said filtration pressure is below the 0.3MPa, and the dissolubility of the organic solvent of illuminating colour is outstanding relatively, and the surface of photographic layer or exposure sensitivity are reduced, and in addition, is difficult to produce the not residue of dissolved matter.If said filtration pressure surpasses 0.3MPa, and is then poorly soluble, dissolved matter does not cause the generation of the superficial failure of photographic layer, the reduction of exposure sensitivity sometimes, perhaps becomes the residue of illuminating colour takes place easily.

Whole compositions of the said relatively photographic layer of the content of said dyestuff are preferably 0.001～20 quality %, and more preferably 0.03～3 quality % is preferably 0.05～0.1 quality % especially.If said content is less than 0.001 quality %, then colour rendering reduces, and the identification when becoming the shortage surface inspection if surpass 20 quality %, then can not confirm to utilize the colour developing of developer sometimes.

---reductive agent and hydrogen donor compound---

As said reductive agent; So long as can get final product with radical reaction, the reductive agent that can suppress the colour developing of said developer; Not special restriction; Can suitably select according to purpose, for example can enumerate methoxyl phenol, quinhydrones, alkyl replacement quinhydrones, catechol, alkyl replacement catechol, phenothiazine, pyrogallol and 1-phenyl-3-pyrazolidone etc.Wherein, preferred 1-phenyl-3-pyrazolidone.

As said hydrogen donor compound, not special restriction for example can be enumerated and had-compound of SH base, have-CH ₂The compound of X-(X=R) base (R representes to include any one the substituting group of O, N and S) etc.

Have-the basic compound of SH as said, for example can enumerate the compound that following structural formula is represented.

[changing 5]

Have-CH as said ₂The compound of X-(X=R) base for example can be enumerated N-phenylglycine, dimethylamino cinnamic acid, dimethylaminobenzaldehyde etc.

In these hydrogen donor compounds, from the viewpoint identical with said reductive agent, preferred N-phenylglycine.

---sensitizer---

Above-mentioned sensitizer can according to after state suitably select as the luminous ray of light irradiating means or ultraviolet light visible light laser etc.

Above-mentioned sensitizer becomes excited state under the effect of active energy ray, can produce useful bases such as free radical or acid through interact (for example energy moves, electronics moves etc.) with other materials (for example free radical generating agent, acid-producing agent etc.).

As above-mentioned sensitizer, not special restriction can suitably not selected according to purpose from known sensitizer, for example can enumerate the spy and open the compound put down in writing in paragraph numbering [0313]～[0314] of 2005-258431 communique etc.

As the content of said sensitizer in said photographic layer, be preferably 0.05～30 quality %, more preferably 0.1～20 quality % is preferably 0.2～10 quality % especially.

If said content is less than 0.05 quality %, then sometimes to the sensitivity reduction of active energy ray, exposure process expends time in, and throughput rate reduces, if surpass 30 quality %, then when preserving, separates out from said photographic layer sometimes.

-plastifier-

In order to control the film rerum natura (flexible) of said photographic layer, also can add said plastifier.

As said plastifier, for example can enumerate the spy and open the compound put down in writing in the paragraph numbering [0318] of 2005-258431 communique etc.

As the content of said plastifier in said photographic layer, be preferably 0.1～50 quality %, more preferably 0.5～40 quality % is preferably 1～30 quality % especially.

-colorant-

As said colorant; Not special restriction; Can suitably select according to purpose; For example can enumerate known pigment or dyestuffs such as redness, green, blueness, yellow, purple, magenta, cyanogen look, black; Particularly, can enumerate that Victoria's pure blue B O (C.I.42595), (alkalescence) Chinese scholartree yellow (C.I.41000), liposoluble (fat) ?HB (C.I.26150), Monot rely special yellow GT (C.I. pigment Yellow 12), permanent yellow GR (C.I. pigment yellow 17), permanent yellow HR (C.I. pigment yellow 83), permanent carmine FBB (C.I. pigment red 146), advertisement poster paratonere ESB (C.I. pigment violet 1 9), permanent red jewel FBH (C.I. paratonere 11), the pink B of Fa Siteer Soviet Union pula (C.I. pigment red 81), sodium Si Telaer fast blue (C.I. pigment blue 15), Monot rely special hard firm ?B (C.I. face material ?1), carbon black.

In addition; As making the preferred said colorant of color filter, for example can enumerate C.I. Pigment Red 97, C.I. pigment red 122, C.I. pigment red 149, C.I. paratonere 168, C.I. paratonere 177, C.I. paratonere 180, C.I. paratonere 192, C.I. pigment red 21 5, C.I. pigment Green 7, C.I. pigment green 36, C.I. pigment blue 15: 1, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. alizarol saphirol 22, C.I. pigment blue 60, C.I. alizarol saphirol 64, C.I. pigment yellow 13 9, C.I. pigment yellow 83, C.I. pigment Violet 23, spy open the middle colorant of putting down in writing in (0138)～(0141) of 2002-162752 communique etc.As the mean grain size of said colorant, not special restriction can suitably be selected according to purpose, below the for example preferred 5 μ m, more preferably below the 1 μ m.In addition, during color filter manufacturing,, be preferably below the 0.5 μ m as said mean grain size.

---adhesion promoter---

For adhesiveness or the pattern that improves each interlayer becomes the adhesiveness between material and the matrix, can in each layer, use known so-called adhesion promoter.

As said adhesion promoter, for example can enumerate the spy and open the compound put down in writing in the paragraph numbering [0326] of 2005-258431 communique etc.

As the content of said adhesion promoter in said photographic layer, be preferably 0.001 quality %～20 quality %, more preferably 0.01～10 quality % is preferably 0.1 quality %～5 quality % especially.

Said photographic layer for example also can contain organosulfur compound, superoxide, redox based compound, azo or the diazo-compounds in J. コ one サ one work " ライトヤ Application シテイ Block システ system ズ " the 5th chapter, put down in writing, photo-reduction property pigment, organohalogen compound etc.

Particularly, for example can enumerate the spy and open the compound put down in writing in paragraph numbering [0329]～[0333] of 2005-258431 communique etc.

---surfactant---

In order to improve the surface inequality that produces when said pattern of the present invention becomes material making, can and use known surfactant.

As said surfactant, can be that surfactant, kation are that surfactant, nonionic are suitably to select surfactant, amphoteric surfactant, the fluorochemical surfactant etc. for example from negative ion.

As the content of said surfactant in said photographic layer, be preferably 0.001～10 quality %.If said content less than 0.001 quality %, then can not obtain the effect of surfaction sometimes, if surpass 10 quality %.Then adhesiveness reduces sometimes.

To the not special restriction of the thickness of said photographic layer, can suitably select for example preferred 1～100 μ m, more preferably 2～50 μ m, preferred especially 4～30 μ m according to purpose.

As said supporter, not special restriction can suitably be selected according to purpose, preferably can peel off the permeability good supporting body of said photographic layer and light, and then more preferably surperficial flatness is good.

Particularly, for example can enumerate the spy and open the mode put down in writing in paragraph numbering [0342]～[0348] of 2005-258431 communique etc.

< other layers >

As said other layers, not special restriction can suitably be selected according to purpose, for example can enumerate layers such as cushion, restraining barrier, peel ply, adhesive linkage, light absorbing zone, sealer.Said pattern becomes material can have 1 layer in these layers separately, also can have more than 2 layers, in addition, also can have layer of the same race more than 2 layers.

The light exposure that said pattern of the present invention becomes the said photographic layer in the material preferably to be described below; That is: have n the optical modulator body of accepting from the light of light irradiating means and the drawing section that penetrates in utilization; After the light of modulation from said light irradiating means, through being arranged with the light of aspheric lenticular microlens array with aberration that the distortion that can revise the outgoing plane in the said drawing section causes.After state the concrete condition of said light irradiating means, said drawing section, said optical modulator body, said aspheric surface, said lenticule and said microlens array.

[pattern becomes the manufacturing approach of material]

Said pattern becomes the material manufacturing that for example can be described below.

At first, make material dissolves, the emulsification that contains in said photographic layer and other layers be scattered in water or organic solvent in, preparation applies liquid.

Wherein, as said organic solvent, described in the explanation that becomes material in pattern of the present invention.

Then, can on said supporter, apply said coating liquid, make its drying, form each layer, make pattern and form material.For example, can on supporter, apply and dry dissolving, emulsification or the photosensitive polymer combination solution that disperses the composition of said photographic layer to form, form photographic layer,, make pattern and form material through forming protective film above that.

Coating method as said coating liquid; Not special restriction; Can suitably select according to purpose, for example can enumerate that gunite, rolling method, spin-coating method, gap coating method, extrusion coated method, curtain are coated with method, mould is coated with known coating methods such as method, intaglio rubbing method, wire bar rubbing method, air knife Tu Fa.

As the condition of said drying, according to the kind of each composition, solvent, usage ratio etc. and different, but usually about being 30 second～15 minute under 60～110 ℃ the temperature.

Because pattern of the present invention becomes the superficial failure of material few, can prevent the breaking less of the light fog that developer causes, unexposed film, the exploring degree is high, masked film intensity height and the pattern fissility after forming is good; So can be preferred for manufacturing usefulness, holographic photography, the micromachine of the liquid crystal structure member such as formation usefulness, color filter, post material, timber, distance piece, next door of the permanent pattern such as formation usefulness, wiring pattern of various patterns; The pattern of pull etc. forms to be used etc., particularly can be preferred for the formation of high meticulous wiring pattern.In addition, can also be preferred for pattern formation method of the present invention and pattern apparatus for converting.

(pattern apparatus for converting and pattern formation method)

Pattern apparatus for converting of the present invention possesses said pattern of the present invention and becomes material, has light irradiating means and optical modulator body at least.

Pattern formation method of the present invention comprises exposure process at least, also comprises other operations of suitable selection.

In addition, through explanation to said pattern formation method of the present invention, clear and definite said pattern apparatus for converting of the present invention.

[exposure process]

Said exposure process is the operation that becomes the photographic layer in the material to make public to pattern of the present invention.Said pattern of the present invention becomes material as stated.

As the object of exposure, so long as said pattern becomes the photographic layer in the material to get final product, not special restriction can suitably be selected according to purpose, and for example, thereby the duplexer that preferably becomes material to form to the said pattern of formation on matrix carries out.

As said matrix; Not special restriction; Can be from material known, suitably select to matrix from the high base material of surface smoothing property with surface that convex-concave is arranged, preferred tabular matrix (substrate), particularly; Can enumerate known printed-wiring board (PWB) forms with substrate (for example copper plating film laminated plate), glass plate (for example soda-lime glass plate etc.), synthetic resin property film, paper, sheet metal etc.; Wherein, from the outstanding point of adhesiveness of the material of internal cupric, preferred said copper plating film laminated plate.。

As the formation method of said duplexer, not special restriction can suitably not selected according to purpose, preferably on said matrix, heat and pressurize at least a the time range upon range of said pattern become material.

As said heating-up temperature, not special restriction can suitably be selected according to purpose, but for example preferred 15～180 ℃, more preferably 60～140 ℃.

As the pressure of said pressurization, not special restriction can suitably be selected according to purpose, but for example preferred 0.1～1.0MPa, more preferably 0.2～0.8MPa.

As any one the device at least that carries out said heating and pressurization, not special restriction can suitably not selected according to purpose, for example can preferably enumerate laminating machine (great achievement laminating machine corporate system for example, VP-II) etc.

As said exposure, not special restriction can suitably be selected according to purpose, can enumerate digit explosure, analogue exposure etc., wherein, and the digit preference exposure.

As digit explosure, not special restriction can suitably not selected according to purpose, for example is preferably based on the pattern that will form and the information generating control signal, uses should control signal and modulated light carries out.

As the mechanism of said digit explosure, not special restriction can suitably not selected according to purpose, for example can enumerate the light irradiating means of irradiates light, based on the pattern-information that will form to the optical modulator body modulated from the light of this light irradiating means irradiation etc.

-optical modulator body-

As said optical modulator body, as long as can light modulated, not special restriction can suitably not selected according to purpose, for example preferably has n drawing section.

As the optical modulator body with said n drawing section, not special restriction can suitably be selected according to purpose, for example the preferable space optical modulation element.

As said spatial optical modulation element, for example can enumerate the spatial optical modulation element (SLM of DMD (DMD), MEMS (microelectromechanical systems (Micro Electro Mechanical Systems)) type; Spatial light modulator (Space Light Modulator)), utilize the electrooptics effects modulation to see through the optical element (PLZT element), liquid crystal light shutter (FLC) etc. of light, wherein, can preferably enumerate DMD.

In addition, said optical modulator body preferably has the pattern signal generation mechanism that generates control signal based on the pattern-information that will form.In this case, the corresponding said pattern signal generation of the said optical modulator body control signal that mechanism generated is come light modulated.

As said control signal, not special restriction can suitably be selected according to purpose, for example can preferably enumerate digital signal.

As said optical modulator body and the pattern apparatus for converting that contains said optical modulator body, for example can enumerate the spy and open the mechanism that puts down in writing in paragraph numbering [0016]～[0047] of 2005-258431 communique etc.

< light irradiating means >

As said light irradiating means; Not special restriction; Can suitably select according to purpose; For example can enumerate (surpassing) high-pressure sodium lamp, xenon lamp, carbon arc lamp, Halogen lamp LED, manifolder and known light source such as fluorescent tube, LED, semiconductor laser or mechanism that can the light of compound irradiation more than 2 kinds such as use, wherein, mechanism that preferably can the light of compound irradiation more than 2 kinds.

As light from said light irradiating means irradiation; For example undertaken under light-struck situation by supporter; Can enumerate through the electromagnetic wave of this supporter and employed Photoepolymerizationinitiater initiater of activation or sensitizer, from the ultraviolet to the luminous ray, electron beam, X ray, laser etc.; Wherein, preferred laser, the laser of more preferably compound light more than 2 kinds (below be sometimes referred to as " closing ripple laser ").In addition, after peeling off supporter, carry out also can using same light under light-struck situation.

As said wavelength from the ultraviolet to the luminous ray, for example preferred 300～1,500nm, more preferably 320～800nm, preferred especially 330nm～650nm.

As said Wavelength of Laser, for example preferred 200～1,500nm, more preferably 300～800nm, and then preferred 330～500nm, preferred especially 400～450nm.

As shining said mechanism of closing ripple laser, for example preferably have a plurality of laser instruments, multimode optical fiber and will carry out optically focused from the laser that these a plurality of laser instruments shine respectively and make it be incorporated into the mechanism of the light-gathering optics system of said multimode optical fiber.

Below can shine mechanism's (fiber array light source) of closing ripple laser to said, for example can enumerate the method for record in paragraph numbering " 0130 "～" 0177 " that the spy opens the 2005-316431 communique etc.

< microlens array >

Said exposure preferably makes said modulated light carry out through microlens array, and then also can carry out through array of apertures, image optics system etc.

As said microlens array; Not special restriction; Can suitably select according to purpose, for example can preferably enumerate the aspheric lenticule with aberration that the distortion that can revise the outgoing plane in the said drawing section causes is arranged the microlens array that forms.

As said aspheric surface, not special restriction can suitably be selected according to purpose, for example is preferably double-curved surface.

In addition; As said microlens array, said array of apertures and said image optics system etc., for example can enumerate the spy and open the mechanism that puts down in writing in paragraph numbering [0051]～[0063], paragraph numbering [0065], paragraph numbering [0070]～[0073] and paragraph numbering [0083]～[0088] of 2005-258431 communique etc.

< other optics systems >

In pattern formation method of the present invention, also can with other optics system and usefulness of from known optics system, suitably selecting, for example can enumerate the light quantity distribution correction optics system that constitutes by a pair of compound lens etc.

Said light quantity distribution correction optics system changes the width of light beam that respectively penetrates the position; Thereby the width of light beam that makes periphery is relatively near the ratio of the width of light beam of the central part of optical axis; Littler at emitting side than light incident side; To DMD irradiation during, be modified into roughly homogeneous in the light quantity distribution of plane of illumination from the parallel beam of light irradiating means.

As said light quantity distribution correction optics system, particularly, for example can enumerate the spy and open the mechanism that puts down in writing in paragraph numbering [0090]～[0105] of 2005-258431 communique etc.

[other operations]

As said other operations, not special restriction can be enumerated the operation of suitably selecting in the operation from known pattern forms, and for example can enumerate developing procedure, etching work procedure, plating operation etc.They can use a kind separately, also can be also with more than 2 kinds.

Said developing procedure is through utilizing said exposure process said pattern to be become photographic layer in the material make public and making after the exposed areas of this photographic layer solidifies, and removes uncured zone and develops, and forms the operation of pattern.

Said developing procedure for example can preferably utilize developing mechanism to implement.

As said developing mechanism, can use developer solution to develop, not special restriction can suitably not selected according to purpose, for example can enumerate the said developer solution of spraying mechanism, apply said developer solution mechanism, impregnated in the mechanism of said developer solution etc.They can use separately a kind or and with more than 2 kinds.

In addition, said developing mechanism also can comprise the developer solution exchange mechanism that exchanges said developer solution, the developer solution feed mechanism of supplying with said developer solution etc.

As said developer solution, not special restriction can suitably be selected according to purpose, for example can enumerate alkalies, water system developer solution, organic solvent etc., wherein, and the preferred weakly alkaline WS.As the alkali composition of this alkalescent liquid, for example can enumerate lithium hydroxide, NaOH, potassium hydroxide, lithium carbonate, sodium carbonate, sal tartari, lithium bicarbonate, soda mint, saleratus, sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, borax etc.

As the pH of the said weakly alkaline WS, for example preferably be about 8～12, be more preferably 9～11.As the said weakly alkaline WS, for example can enumerate aqueous sodium carbonate or wet chemical of 0.1～5 quality % etc.

As the temperature of said developer solution, development property that can corresponding said photographic layer is suitably selected, and for example preferably is about 25 ℃～40 ℃.

Said developer solution also can with surfactant, foam-breaking agent, organic base (for example ethylenediamine, monoethanolamine, TMAH, diethylenetriamine, triethylene five amine, morpholine, triethanolamine etc.) or be used to promote organic solvent (for example alcohols, ketone, ester class, ethers, amide-type, lactone etc.) that develops etc.In addition, said developer solution can be the water system developer solution of mixed water or aqueous alkali and organic solvent, can be separately organic solvent also.

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

As the etching solution that uses in the said etch processes; Not special restriction can suitably be selected according to purpose, is for example formed under the situation of said metal level by copper; Can enumerate copper chloride solution, liquor ferri trichloridi, alkaline etching solution, hydrogen peroxide is etching solution etc.; Wherein, from the point of etching factor (etchingfactor), preferred liquor ferri trichloridi.

Through utilizing said etching work procedure to remove said pattern after carrying out etch processes, can on the surface of said matrix, form permanent pattern.

As said permanent pattern, not special restriction can suitably be selected according to purpose, for example can enumerate wiring pattern etc.

As said plating operation, can utilize the method for the suitable selection of from known plating is handled, suitably selecting to carry out.

Handle as said plating; For example can enumerate copper platings such as copper sulphate plating, cupric pyrophosphate plating; Scolding tin platings such as high fluidity (high flow) scolding tin plating; Watt is bathed (nickelous sulfate-nickel chloride) plating, nickel platings such as nickel sulfamic acid, processing such as golden plating such as hard (hard) golden plating, soft golden plating.

Can be through removing said pattern after handling utilizing said plating operation to carry out plating, also further do not need part through removing as required in addition, at the surface of said matrix formation permanent pattern with etch processes etc.

[manufacturing approach of printed-wiring board (PWB) and color filter]

The manufacturing that said pattern formation method of the present invention can be preferred for printed wiring board particularly has manufacturing and the manufacturing of color filter of the printed-wiring board (PWB) of hole portions such as reach through hole or through hole.Below an example of the method for making of the manufacturing approach of the printed-wiring board (PWB) that utilizes pattern formation method of the present invention and color filter is described.

The manufacturing approach of-printed-wiring board (PWB)-

Particularly as having the manufacturing approach of the printed-wiring board (PWB) of hole portions such as reach through hole or through hole; Can be on the printed-wiring board (PWB) with hole portion as said matrix form with substrate through (1), the position that becomes said matrix side with this photographic layer concerns that range upon range of said pattern becomes material, forms duplexer; (2) with said matrix opposition side rayed is carried out in the zone of needs from said duplexer; Photographic layer is solidified, and (3) are removed said pattern from said duplexer and are become supporter, cushion and restraining barrier the material, and develop to the photographic layer in the said duplexer (4); Remove the uncured portion in this duplexer, form pattern.

In addition, removing of the said supporter in said (3) also can replace between said (2) and said (4), carrying out and between said (1) and said (2), carry out.

Then; In order to obtain printed-wiring board (PWB); As long as utilize to use said established pattern, etch processes or plating are handled said printed-wiring board (PWB) and are formed method with substrate (for example known subtract (subtractive) method or add (additive) method (for example false add (semiadditive) method, add (full additive) method entirely)) and handle and get final product.Wherein, form printed-wiring board (PWB), preferred said subtraction in order to go up favourable protuberance (tenting) operation with industry.Peel off said processing back printed-wiring board (PWB) and form with cured resin remaining on the substrate, in addition under the situation of said half add, can be through peeling off a laggard step etching copper film section, the printed-wiring board (PWB) of manufacturings needs.In addition, multilayer printed circuit board also can likewise be made with the manufacturing approach of said printed-wiring board (PWB).

Then, to using said pattern to become the manufacturing approach of the printed-wiring board (PWB) with reach through hole of material to further specify.

At first, the printed-wiring board (PWB) that prepare to have reach through hole, the surface is covered by metallization layer forms uses substrate.Use substrate as said printed-wiring board (PWB) formation, for example can use the substrate that on insulating substrates such as copper plating film laminated plate and glass-epoxy, forms the copper plating layer, or form the substrate (multilayer board) of copper plating layers at these substrate laminated interlayer dielectrics.

Then, become under the situation that has protective film on the material in said pattern, peel off this protective film, use backer roll, the said pattern of crimping becomes the photographic layer in the material, makes it contact (range upon range of operation) with printed-wiring board (PWB) formation with the surface of substrate.Like this, can be had said printed-wiring board (PWB) successively and formed duplexer with substrate and said duplexer.

Become the range upon range of temperature of material as said pattern, not special restriction for example can be enumerated room temperature (15～30 ℃) or heating (30～180 ℃) down, wherein, preferably heat down (60～140 ℃).

As the roll-in of said crimping roller, not special restriction, for example preferred 0.1～1MPa.

As the speed of said crimping, not special restriction, preferred 1～3m/ minute.

In addition, also can the said printed-wiring board (PWB) formation of preheating use substrate, or under reduced pressure range upon range of.

The formation of said duplexer also can form at said printed-wiring board (PWB) and become material with the said pattern of substrate laminated; Perhaps through directly applying on forming with the surface of substrate at said printed-wiring board (PWB) and dry said pattern becomes photosensitive polymer combination solution that made uses etc., in said printed-wiring board (PWB) formation with substrate laminated photographic layer, restraining barrier, cushion and supporter.

Then, from face said duplexer and opposition side matrix, irradiates light solidifies photographic layer.In addition, at this moment, make public after also can (for example the inadequate situation of the photopermeability of supporter is inferior) peels off said supporter, cushion and restraining barrier as required.

At the moment, under the situation on still unstripped said supporter, cushion and restraining barrier, peel off said supporter, cushion and restraining barrier (stripping process) from said duplexer.

Then; Remove said printed-wiring board (PWB) with suitable dissolves and form uncured zone with the photographic layer on the substrate; Form the cured layer of wiring pattern formation usefulness and the metal level of reach through hole and protect pattern, form on the surface with substrate at said printed-wiring board (PWB) and expose metal level (developing procedure) with cured layer.

In addition, also can after development, utilize back heat treated or post-exposure to handle as required, further promote the processing of the curing reaction of solidified portion.Development can be aforesaid wet development method, also can be dried development method.

Then, remove the metal level (etching work procedure) that on the surface of said printed-wiring board (PWB) formation, exposes with the etching solution dissolving with substrate.The peristome of reach through hole is covered by curable resin composition (masked film), so etching solution can not get into the coat of metal in the reach through hole internal corrosion reach through hole, and the remaining shape of the coat of metal of reach through hole for regulation.Like this,, said printed-wiring board (PWB) forms wiring pattern on forming with substrate.

As said etching solution; Not special restriction can suitably not selected according to purpose, under the situation that for example said metal level is formed by copper; Can enumerate copper chloride solution, liquor ferri trichloridi, alkaline etching solution, hydrogen peroxide is etching solution etc.; Wherein, from the point of etching factor, preferred liquor ferri trichloridi.

Then, as with strong alkali aqueous solution etc., said cured layer as stripping film, is formed from said printed-wiring board (PWB) and to remove (solidfied material is removed operation) with substrate.

As the alkali composition in the said strong alkali aqueous solution, not special restriction for example can be enumerated NaOH, potassium hydroxide etc.

As the pH of said strong alkali aqueous solution, for example preferably be about 12～14, be more preferably 13～14.

As said strong alkali aqueous solution, not special restriction for example can be enumerated sodium hydrate aqueous solution or the potassium hydroxide aqueous solution of 1～10 quality % etc.

In addition, printed-wiring board (PWB) also can be the printed-wiring board (PWB) of sandwich construction.

In addition, said pattern becomes material not only can in said etching process, use, and can also in the plating process, use.As said plating method; For example can enumerate copper platings such as copper sulphate plating, cupric pyrophosphate plating; Scolding tin platings such as high fluidity (high flow) scolding tin plating; Watt is bathed (nickelous sulfate-nickel chloride) plating, nickel platings such as nickel sulfamic acid, golden platings such as hard (hard) golden plating, soft golden plating etc.

The manufacturing approach of-color filter-

On the matrix of glass substrate etc.; The said pattern of the present invention of fitting becomes the photographic layer in the material; Become material to peel off under the situation on supporter, cushion and restraining barrier from this pattern; Charged said supporter (film) may receive uncomfortable electric shock (shock) with human body, perhaps exists in problems such as adhering to dust on the charged said supporter.So, preferably on said supporter, conductive layer is set, perhaps implement to give the processing of electric conductivity to said supporter self.In addition, with the said supporter of cushion opposition side on be provided with under the situation of said conductive layer, the hydrophobic polymer layer preferably is set in order to improve traumatic resistance.

Then, the pattern that make that the pattern with red photographic layer that said photographic layer is coloured to red, green, blue, ? respectively becomes material, pattern with green photographic layer becomes material, has a blue photographic layer becomes material to become material with the pattern with black photosensitive layer.The pattern that use has the said red photographic layer that red pixel uses becomes material, after the range upon range of red photographic layer of said matrix surface forms duplexer, decent is made public, develops, and forms red pixel.Form after the red pixel, heat said duplexer, uncured portion is solidified.Green, blue pixel is also likewise carried out with it, form each pixel.

The formation of said duplexer can become material in the said pattern of said glass substrate laminated; Perhaps also can be through on the surface of said glass substrate, directly applying and dry said pattern becomes photosensitive polymer combination solution that made uses etc., thus at said glass substrate laminated photographic layer, restraining barrier, cushion and supporter.In addition, under the situation of three kinds of pixels of configuration red, green, blue, also can be configuration as inlaying type, triangle type, 4 pixel arrangement types etc. and so on.

The pattern that has the ?color sensation photosphere of stating in the face laminated that is formed with said pixel becomes material, and a side that never forms pixel is carried out back-exposure, development, forms black matrix.Can should deceive the duplexer of matrix through adding thermosetting, uncured portion is solidified, make color filter.

Said pattern formation method of the present invention is owing to use said pattern of the present invention to become material; So can be preferred for manufacturing, holographic photography, the micromachine of the liquid crystal structure member such as formation, color filter, post material, timber, distance piece, next door of the permanent pattern such as formation, wiring pattern of various patterns; The manufacturing of pull etc. can be preferred for forming high meticulous wiring pattern especially.Pattern apparatus for converting of the present invention becomes material owing to possess said pattern of the present invention; So can be preferred for the manufacturing of the liquid crystal structure member such as formation, color filter, post material, timber, distance piece, next door of the permanent pattern such as formation, wiring pattern of various patterns; Holographic photography, micromachine; The manufacturing of pull etc. can be preferred for the formation of high forming fine wiring pattern especially.

Embodiment

Below utilize embodiment to further explain of the present invention, but the present invention not limit by these.

(embodiment 1)

As said supporter, (eastern レ corporate system 16FB50), applies and dryly forms the photographic layer of thick 18 μ m by the following photosensitive composite solution that constitutes of forming, and makes said pattern and becomes material to the pet film of thick 16 μ m.

[composition of photosensitive polymer combination solution]

Methyl methacrylate/styrene/methacrylic acid multipolymer (multipolymer is formed (quality %): 19/52/29, and the matter average molecular weight: 60,000, acid number 189mgKOH/g, I/O value: 0.55): 139.6 mass parts

The polymerizable compound of following structural formula (1) expression (the first industrial drugmaker system, GX8702c): 44.33 mass parts

The polymerizable compound of following structural formula (2) expression (the first industrial drugmaker system, BPEM-10F): 44.33 mass parts

The polymerizable compound (East Asia Synesis Company system, アロニ Star Network ス M270) of following structural formula (3) expression: 6.37 mass parts

Polyglycol #1000 dimethylacrylate (Xin Zhong village chemistry, NK エステ Le 23G): 16.75 mass parts

As 2 of Photoepolymerizationinitiater initiater, two (the o-chlorphenyls)-4,4 ', 5 of 2-, 5 '-tetraphenyl di-imidazoles: 18.5 mass parts

N-butyl chloride acridone as the assorted compound ring series that contracts: 0.99 mass parts

As polymerization inhibitor De phenoxazine: 0.032 mass parts

LCV as developer: 1.10 mass parts

Methyl ethyl ketone as the organic solvent of ketone: 327.4 mass parts

Propylene glycol monomethyl ether as the organic solvent of ethers: 304.9 mass parts

Cyclohexanone as the organic solvent of ketone: 58.1 mass parts

Methyl alcohol as the organic solvent of alcohols: 36.3 mass parts

The naphthalene sulfonate of Victoria's ethereal blue: 0.186 mass parts

1-phenyl-3-pyrazolidone: 0.022 mass parts

N-phenylglycine as hydrogen donor compound: 0.370 mass parts

Fluorine be surfactant (big Japanese ink corporate system, F780F): 0.78 mass parts

The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 0.30 quality %.

[changing 6]

structural formula (1)

Wherein, in the said structural formula (1), m+n representes 20.Wherein, the compound of said structural formula (1) expression is the example with polymerizable compound of urethane groups.

[changing 7]

structural formula (2)

Wherein, in the said structural formula (2), m+n representes 10.Wherein, the compound of said structural formula (2) expression is the example with polymerizable compound of aryl.

[changing 8]

structural formula (3)

Wherein, in the said structural formula (3), n representes 12.Wherein, the compound of said structural formula (3) expression is the example with compound of polyalkylene oxide hydrocarbon chain.

< evaluation of superficial failure >

Under amber light, observe coated surfaces, estimate the superficial failure of coated surfaces at the said photographic layer that obtains.As the evaluation method of said superficial failure, count every 1m ²In the surface of photographic layer less than the number of the superficial failure of 40 μ m and the number of the superficial failure more than the 40 μ m.Based on this number, utilize following evaluation criterion to estimate superficial failure property.The result is as shown in table 1.

-evaluation criterion-

Zero ... Less than 20, and the above superficial failure of 40 μ m demonstrates outstanding coated surfaces less than 3 less than the superficial failure of 40 μ m.

△ ... Superficial failure less than 40 μ m is more than 20, less than 50, and the above superficial failure of 40 μ m is that coated surfaces is slightly poor more than 3, less than 30, does not become the problem in the practicality.

* ... Less than the superficial failure of 40 μ m is more than 50 or the superficial failure more than the 40 μ m is more than 30, the coated surfaces extreme difference.

< evaluation of the photographic fog of developer >

Pattern in the said relatively duplexer becomes the photographic layer of material, utilize spectrophotometer (Shimadzu Seisakusho Ltd.'s system, MPS-200); Measure the dullness (OD) of 550nm, if this dullness below 0.4, then is zero; If surpass 0.4, then be *, the photographic fog of evaluation developer.Result such as table 1 are not.

Become in said pattern the photographic layer laminated of material as the polyethylene film of the thick 25 μ m of said protective film (タ system ボリ corporate system, GF-1).Then, as said matrix, grind, wash the surface; (diameter is 1,2,3,4,5 and each 30 in the hole portion of 6mm at the copper plating film laminated plate of drying; Amount to 180 of openings, the thick 12 μ m of copper) the surface on, Yi Bian peel off the protective film that said pattern becomes material; Use laminating machine (MODEL8B-720-PH on one side; Great achievement laminating machine (strain) system) crimping makes said pattern form the photographic layer that draws and contacts with said copper plating film laminated plate, and preparation stacks gradually the duplexer of said copper plating film laminated plate, said photographic layer, said pet film (supporter).

The crimping condition is 105 ℃ of crimping roller temperature, crimping roller pressure 0.3MPa, laminate speed 1m/ branch.

< evaluation of unexposed film rupture >

Then, to the copper plating film laminated plate in the said duplexer, with said crimping condition; To two sides laminated photosensitive layer, in addition, likewise carry out with said duplexer; Prepare the duplexer of the evaluation usefulness of unexposed film rupture, (25 ℃, 50%RH) the following duplexer that obtains certainly is 5 in room temperature.From this keeping after duplexer, peel off supporter, the counting peel off the number of breaking behind the photographic layer of said bore portion, carry out the evaluation of unexposed film rupture.At said diameter is in each hole portion of 1～6mm, and the diameter of the largest hole portion in the hole portion of not breaking fully in 30 holes is the value of unexposed film rupture.The result lists in table 1.

-developing procedure-

Peel off pet film (supporter) from said duplexer, the said photographic layer on the copper plating film laminated plate comprehensively, utilize the pressure of 0.15MPa, sprays 30 ℃ 1 quality % aqueous sodium carbonate, dissolve and remove uncured zone.Then, wash, drying, form permanent pattern.

Wherein, measure and to remove the needed time of photographic layer on the copper plating film laminated plate to dissolving from beginning to spray aqueous sodium carbonate, with it as the shortest development time.This shortest development time is short more, and development property runs off look.

Be formed with relatively said permanent pattern duplexer comprehensively, implements 160 ℃, 30 minutes heat treated, solidify the surface of permanent pattern, the raising film strength.The result of this permanent pattern of visualization does not see bubble on the surface of permanent pattern.

In addition, relatively formed the printed-wiring board (PWB) of said permanent pattern,, carried out gold-platedly, carried out water soluble flux then and handle according to conventional method.Then, in 5 seconds of dipping in being set at 260 ℃ solder bath, 3 times repeatedly, washing removes deflux.

< exploring degree >

(1) mensuration of sensitivity

Pattern in the said relatively duplexer becomes the photographic layer of material, from pet film (supporter) side, uses the pattern apparatus for converting as the LASER Light Source with 405nm of said light irradiating means, with 2 ^1/2Doubly shine 0.1mJ/cm at interval ²～100mJ/cm ²The different light of luminous energy, make public, a part of zone of said photographic layer is solidified.At room temperature left standstill 10 minutes; Peel off pet film (supporter) from duplexer then; Photographic layer on the copper plating film laminated plate comprehensively; Spray to press 0.15MPa, spray aqueous sodium carbonate (30 ℃, 1 quality %), injecting time is 2 times of the shortest development time of in said developing procedure, trying to achieve.Uncured zone is removed in dissolving, measures the thickness of residual consolidation zone.Then, the relation between the thickness of the exposure of light and cured layer is plotted curve map, obtain curve of sensitivity.Can know that from the curve of sensitivity that obtains like this luminous energy the when thickness of consolidation zone is become 15 μ m makes photographic layer solidify necessary luminous energy as being used to.The result is as shown in table 1.

(2) mensuration of exploring degree

At room temperature (23 ℃ 55%RH) left standstill said duplexer 10 minutes.From the pet film (supporter) of the duplexer that obtains, use said pattern apparatus for converting, with line (line)/space (space)=1/1; From the wide 5 μ m of line (line)～20 μ m; With per 1 μ m, carry out the exposure of each live width, from live width 20 μ m～50 μ m; With per 5 μ m, carry out the exposure of each live width.The exposure of this moment becomes the necessary luminous energy of photographic layer of material for the said pattern that is solidificated in said (1) mensuration.After at room temperature leaving standstill 10 minutes, peel off pet film (supporter) from said duplexer.With comprehensive injection of spray pressing the photographic layer of 0.15MPa on the copper plating film laminated plate as (30 ℃ of the aqueous sodium carbonates of said developer solution; 1 quality %); Injecting time is to utilize 2 times of the shortest development time of trying to achieve in the said method, and uncured zone is removed in dissolving.The surface of the copper plating film laminated plate of the band solidified resin pattern that obtains like this with observation by light microscope, in the line of solidified resin pattern, measure not have obstruction, unusual minimum feature such as the crust that wrinkles, with it as the exploring degree.The numerical value of this exploring degree is more little to be good more.The result is as shown in table 1.

< covering property >

Copper plating film laminated plate in the duplexer that the evaluation of said unexposed film rupture is used replaces the copper plating film laminated plate for the reach through hole with 200 diameter 2mm; In addition; Likewise make the evaluation of covering property with said duplexer and use duplexer; The condition held of room temperature (23 ℃, relative humidity 55%) 10 minutes.Then, from the pet film (supporter) of the duplexer of said making, use said pattern apparatus for converting, comprehensively the making public of the photographic layer in this duplexer.The exposure of this moment is to make the said pattern that (2) are measured in the evaluation of said exploring degree become the photographic layer of material to solidify necessary luminous energy.After at room temperature leaving standstill 10 minutes, peel off pet film (supporter) from said duplexer.With the aqueous sodium carbonate (30 ℃, 1 quality %) of comprehensive injection of spray pressing the said photographic layer of 0.15MPa on said copper plating film laminated plate as said developer solution, injecting time is 2 times of the shortest development time of in said developing procedure, trying to achieve.The cured layer that on the reach through hole peristome, forms (masked film) in the said copper plating film laminated plate that obtains like this with microscopic examination peel off or defective such as breakage have or not the incidence of counting defective.The result is as shown in table 1.

< mensuration of splitting time >

Under method identical and condition, make said duplexer with the evaluation of said development property, room temperature (23 ℃, 55%RH) under, left standstill 10 minutes.From the pet film (supporter) of the duplexer that obtains, use said pattern apparatus for converting, carry out blanket exposure.The exposure of this moment is the necessary luminous energy of photographic layer that the said pattern that is solidificated in said mensuration becomes material.After at room temperature leaving standstill 10 minutes, peel off pet film (supporter) from said duplexer.With the aqueous sodium carbonate (30 ℃, 1 quality %) of comprehensive injection of spray pressing the said photographic layer of 0.15MPa on the copper plating film laminated plate as said developer solution, injecting time is 2 times of the shortest development time of in said developing procedure, trying to achieve.After the drying, upright dipping substrate is measured the time up to film is peeled off fully in the sodium hydrate aqueous solution of 3 quality %.This time lacks and more is good.The result is as shown in table 1.

(embodiment 2)

In embodiment 1, replace cyclohexanone as the organic solvent of said ketone, use tetrahydrofuran as the organic solvent of ethers, in addition, likewise carry out with embodiment 1, make pattern and form material and duplexer.Wherein, the remaining quantity that obtains the organic solvent in the photographic layer is 0.30 quality %.

< evaluation >

The pattern that use obtains becomes material, likewise carries out with embodiment 1, estimates the breaking of superficial failure, the photographic fog of developer, unexposed film, sensitivity, exploring degree, covering property and splitting time.The result is as shown in table 1.

(embodiment 3)

In embodiment 1, with bonding agent become methyl methacrylate/styrene/methacrylic acid multipolymer (multipolymer is formed (quality %): 46/31/23, matter average molecular weight: 60; 000; Acid number 150mgKOH/g, the I/O value: 0.63), in addition; Likewise carry out with embodiment 1, make pattern and form material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 0.30 quality %.

< evaluation >

(embodiment 4)

In embodiment 1, the composition of organic solvent is changed with being described below, in addition, likewise carry out with embodiment 1, make pattern and form material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 0.40 quality %.

Methyl ethyl ketone as the organic solvent of ketone: 227.4 mass parts

Propylene glycol monomethyl ether as the organic solvent of ethers: 327.4 mass parts

Cyclohexanone as the organic solvent of ketone: 79.0 mass parts

Methyl alcohol as the organic solvent of alcohols: 58.1 mass parts

< evaluation >

(embodiment 5)

In embodiment 1; Do not contain the polymerizable compound of said structural formula (40) expression and the polymerizable compound of polyglycol #1000 dimethylacrylate and said structural formula (38) expression and the polymerizable compound of structural formula (39) expression and contain 55.89 mass parts altogether; In addition; Likewise carry out with embodiment 1, make pattern and form material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 0.30 quality %.

< evaluation >

(embodiment 6)

In embodiment 1, supporter is become the pet film of thick 16 μ m, and (eastern レ corporate system 16QS52), in addition, is likewise carried out with embodiment 1, makes pattern and forms material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 0.30 quality %.

< evaluation >

(embodiment 7)

In embodiment 1, supporter is become the mylar of thick 16 μ m, and (Mitsubishi Chemical Ind's system R-340G), in addition, is likewise carried out with embodiment 1, makes pattern and forms material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 0.30 quality %.

< evaluation >

(embodiment 8)

In embodiment 1, protective film is become the polypropylene film of thick 12 μ m, and (the special paper company of prince system E-501), in addition, is likewise carried out with embodiment 1, makes pattern and forms material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 0.30 quality %.

< evaluation >

(embodiment 9)

In embodiment 6, protective film is become the polypropylene film of thick 20 μ m, and (the special paper company of prince system E-200), in addition, is likewise carried out with embodiment 6, makes pattern and forms material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 0.30 quality %.

< evaluation >

The pattern that use obtains becomes material, likewise carries out with embodiment 6, estimates the breaking of superficial failure, the photographic fog of developer, unexposed film, sensitivity, exploring degree, covering property and splitting time.The result is as shown in table 1.

(comparative example 1)

In embodiment 1, the composition of organic solvent is changed with being described below, in addition, likewise carry out with embodiment 1, make pattern and form material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 1 quality %.

Methyl ethyl ketone as the organic solvent of ketone: 127.4 mass parts

Propylene glycol monomethyl ether as the organic solvent of ethers: 404.9 mass parts

Cyclohexanone as the organic solvent of ketone: 158.1 mass parts

Methyl alcohol as the organic solvent of alcohols: 36.3 mass parts

< evaluation >

(comparative example 2)

In comparative example 1, the composition of organic solvent is changed with being described below, in addition, likewise carry out with comparative example 1, make pattern and form material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 0.80 quality %.

Propylene glycol monomethyl ether as the organic solvent of ethers: 350 mass parts

Cyclohexanone as the organic solvent of ketone: 100 mass parts

Methyl alcohol as the organic solvent of alcohols: 149.3 mass parts

< evaluation >

(comparative example 3)

[composition of organic solvent]

Methyl ethyl ketone as the organic solvent of ketone: 227.4 mass parts

Cyclohexanone as the organic solvent of ketone: 94.4 mass parts

Methyl alcohol as the organic solvent of alcohols: add

< evaluation >

(comparative example 4)

In comparative example 1, with bonding agent become methyl methacrylate/styrene/methacrylic acid multipolymer (multipolymer is formed (quality %): 46/31/23, matter average molecular weight: 60; 000; Acid number 150mgKOH/g, I/O value: 0.63): 139.58 mass parts, in addition; Likewise carry out with comparative example 1, make pattern and form material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 1 quality %.

< evaluation >

(comparative example 5)

In comparative example 1; With polymerizable compound become have only following structural formula (39) expression polymerizable compound (the first industrial drugmaker system, BPEM-10F) 111.78 mass parts, in addition; Likewise carry out with comparative example 1, make pattern and form material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 1 quality %.

[changing 9]

structural formula (39)

< evaluation >

(comparative example 6)

In comparative example 1, the 1-phenyl-3-that does not add as reductive agent gives a tongue-lashing oxazolidone, in addition, likewise carries out with comparative example 1, makes pattern and forms material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 1 quality %.

< evaluation >

(comparative example 7)

In comparative example 1, do not add phenoxazine as polymerization inhibitor, in addition, likewise carry out with comparative example 1, make pattern and form material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 1 quality %.

< evaluation >

(comparative example 8)

In comparative example 1, will become the diethylin benzophenone as the N-butyl chloride acridone of the assorted compound ring series that contracts, in addition, likewise carry out with comparative example 1, make pattern and form material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 1 quality %.

< evaluation >

(comparative example 9)

In comparative example 1, the naphthalene sulfonate of Victoria's ethereal blue is become peacock green, in addition, likewise carry out with comparative example 1, make pattern and form material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 1 quality %.

< evaluation >

(comparative example 10)

In comparative example 1, do not add N-phenylglycine, in addition, likewise carry out with comparative example 1, make pattern and form material and duplexer.The remaining quantity of the organic solvent in the photographic layer that wherein, obtains is 1 quality %.

< evaluation >

[table 1]

	Organic solvent content (quality %)	Superficial failure	The photographic fog of developer	Break (mm) of unexposed film	Sensitivity (mJ/cm ²)	Exploring degree (μ m)	Covering property	Splitting time (second)
									Embodiment 1	0.30	○	○	6	8	15	0％	21
Embodiment 2	0.30	○	○	6	8	15	0％	21
									Embodiment 3	0.30	○	○	5	8	18	1％	23
Embodiment 4	0.40	○	○	3	10	15	1％	25
									Embodiment 5	0.30	○	○	5	10	15	3％	25
Embodiment 6	0.30	○	○	6	8	15	0％	21
									Embodiment 7	0.30	○	○	6	8	15	0％	21
Embodiment 8	0.30	○	○	6	8	15	0％	21
									Embodiment 9	0.30	○	○	6	8	15	0％	21
Comparative example 1	1	○	○	1	15	18	2％	28
									Comparative example 2	0.80	○	○	2	13	17	2％	26
Comparative example 3	1	○	○	1	15	17	1％	28
									Comparative example 4	1	○	○	1	15	25	2％	26
Comparative example 5	1	○	○	1	15	15	35％	28
									Comparative example 6	1	○	×	1	10	17	3％	28
Comparative example 7	1	○	×	1	10	30	2％	28
									Comparative example 8	1	○	○	1	20	20	2％	28
Comparative example 9	1	×	○	1	20	17	1％	28
									Comparative example 10	1	○	○	1	22	18	2％	28

Can judge from the result of table 1; Pattern at embodiment 1～9 becomes in the material; In photographic layer, contain at least a organic solvent of from ketone, alcohols and ethers, selecting; And its remaining quantity is below 0.5 quality %, so superficial failure is few, can prevent the breaking less of the light fog that developer causes, unexposed film, the exploring degree is high, masked film intensity height and the pattern fissility after forming is good, can form higher meticulous pattern.Particularly be below the 0.35 quality % at the remaining quantity of organic solvent, the I/O value of bonding agent is 0.35～0.60, contain the embodiment 1,2 of the compound with polyalkylene oxide hydrocarbon chain and 6～9 pattern becomes in the material as polymerizable compound, be judged as superficial failure few, can prevent the breaking less of the light fog that developer causes, unexposed film, the exploring degree is high, masked film intensity is strong and the fissility of pattern after forming is good, can form higher meticulous pattern.On the other hand, the pattern of comparative example 1～10 becomes material to be judged as, and breaking of unexposed at least film is many, the masked film weak strength, the fissility after pattern forms is poor, even and in other assessment items, mostly than embodiment difference, can not form high meticulous pattern.

Utilizability on the industry

Pattern of the present invention become the superficial failure of material few, can prevent the breaking less of the light fog that developer causes, unexposed film, the exploring degree is high, masked film intensity height and the pattern fissility after forming is good, the pattern that can form higher meticulous pattern becomes material.So; Can be preferred for manufacturing, holographic photography, the micromachine of the liquid crystal structure member such as formation, color filter, post material, timber, distance piece, next door of the permanent pattern such as formation, wiring pattern of various patterns; The manufacturings of pull etc. particularly can be preferred for the formation of the meticulous wiring pattern of height.

In addition; Pattern apparatus for converting of the present invention possesses said pattern of the present invention and becomes material; So can be preferred for the manufacturing of the liquid crystal structure member such as formation, color filter, post material, timber, distance piece, next door of the permanent pattern such as formation, wiring pattern of various patterns; Holographic photography, micromachine, the manufacturing of pull etc. can be preferred for the formation of high forming fine wiring pattern especially.

Pattern formation method of the present invention becomes material owing to possess said pattern of the present invention; So can be preferred for the manufacturing of the liquid crystal structure member such as formation, color filter, post material, timber, distance piece, next door of the permanent pattern such as formation, wiring pattern of various patterns; Holographic photography, micromachine; The manufacturings of pull etc. etc. can be preferred for the formation of high forming fine wiring pattern especially.

Claims

1. a pattern becomes material, it is characterized in that,

Have supporter and the photographic layer on this supporter; This photographic layer comprises the assorted compound ring series that contracts of (A) bonding agent 40～80 quality %, (B) polymerizable compound, (C) Photoepolymerizationinitiater initiater, (D), (E) polymerization inhibitor, (F) developer, N-phenylglycine and (G) organic solvent

(B) polymerizable compound comprises (b1) and has the compound of urethane groups and (b2) have at least a in the compound of aryl,

(D) the assorted compound ring series that contracts comprises from assorted contract ring system ketonic compound, quinoline compound and acridine compound, select at least a, and the said assorted content of compound ring series in said photographic layer that contracts is 0.05～30 quality %,

(G) organic solvent is at least a for what from ketone, alcohols and ethers, select, and remaining quantity is below the 0.5 quality %.

2. pattern according to claim 1 becomes material, wherein,

(A) the I/O value of bonding agent is 0.35～0.60.

3. pattern according to claim 1 becomes material, wherein,

(B) polymerizable compound comprises the compound with polyalkylene oxide hydrocarbon chain, and this polyalkylene oxide hydrocarbon chain has at least a of ethylidene and propylidene.

4. pattern according to claim 1 becomes material, wherein,

(C) Photoepolymerizationinitiater initiater contains from halogenated hydrocarbons derivant, phosphine oxide, six aryl di-imidazoles, 9 oxime derivate, organic peroxide, thio-compounds, ketonic compound, acylphosphine oxide compound, aromatic series salt and ketoxime ether, select at least a.

5. pattern according to claim 1 becomes material, wherein,

(E) polymerization inhibitor for from the compound that has 2 phenol property hydroxyls at least, have by the compound of the substituted aromatic rings of imino group, have at least a by what select the compound of the substituted heterocycle of imino group and the bulky amine compound.

6. pattern according to claim 1 becomes material, wherein,

And then comprise dyestuff and the reductive agent that includes compound with triallyl methane skeleton.

7. pattern according to claim 1 becomes material, wherein,

(G) organic solvent is at least a of methyl ethyl ketone, cyclohexanone, methyl alcohol, methyl propanediol and tetrahydrofuran.

8. pattern according to claim 6 becomes material, wherein,

The dyestuff that includes the compound with triallyl methane skeleton is the allyl sulphonic acid compound.

9. pattern according to claim 6 becomes material, wherein,

Reductive agent is 1-phenyl-3-pyrazolidone.

10. pattern according to claim 1 becomes material, wherein,

For photographic layer, under this photographic layer of exposure and the situation of developing, the least energy of light that do not change, that in said exposure, use is 0.1～20mJ/cm to the thickness of exposed portion that makes this photographic layer in this exposure and after developing ²

11. pattern according to claim 2 becomes material, wherein,

The relative alkaline aqueous solution of bonding agent shows swellability or dissolubility.

12. pattern according to claim 11 becomes material, wherein,

Bonding agent comprises multipolymer, and this multipolymer has any one the structural unit at least that derives from styrene and the styrene derivative.

13. pattern according to claim 11 becomes material, wherein,

The glass transition temperature of bonding agent is more than 80 ℃.

14. a pattern apparatus for converting is characterized in that,

Possess the described pattern of claim 1 and become material,

At least have: but the light irradiating means of irradiates light; With the modulation from the light of this light irradiating means and the optical modulator body that becomes the photographic layer in the material to make public to said pattern.

15. a pattern formation method is characterized in that,

At least comprise the operation that becomes this photographic layer in the material to make public to the described pattern of claim 1.

16. pattern formation method according to claim 15, wherein,

Exposure is based on the pattern-information that will form and after generating control signal, uses the light modulated according to this control signal to carry out.

17. pattern formation method according to claim 15, wherein,

Exposure is after utilizing the optical modulator body light modulated, and lenticular microlens array carries out via being arranged with, and said lenticule has the aspheric surface of the aberration that the distortion of the outgoing plane that can revise the drawing section in the said optical modulator body causes.

18. pattern formation method according to claim 17, wherein,

Aspheric surface is a double-curved surface.

19. pattern formation method according to claim 15, wherein,

After making public, carry out the development of photographic layer.

20. pattern formation method according to claim 19, wherein,

After developing, carry out the formation of permanent pattern.