CN101135852B - Pattern forming material and method - Google Patents

Abstract

The object of the present invention is to provide a pattern forming material which can form high elaborated pattern with high sensitivity, high resolution, adhesiveness and sensitiveness, and excellent stability and less developing draff, and provide a pattern forming method using the pattern forming material. The present invention provides a pattern forming material which is composed of a photosensitive layer formed by photosensitive composition at least including bond, polymerized compound and photopolymerization initiating agent on a support, wherein, the bond includes a polymer with an I/O value of 0.300-0.650 and the photopolymerization initiating agent includes hexa-aryl group two imidazole compounds with hydrophilicity group, and provides a pattern forming method using the pattern forming material.

Description

Pattern becomes material and pattern formation method

Technical field

The present invention relates to a kind of dry film photoresist (dryfilmresist) pattern (DFR) that is applicable to becomes material and uses said pattern to become the pattern formation method of material.

Background technology

In the field of printed circuit substrate, at first copper-clad laminates is formed the wiring pattern of copper usually with DFR.At this moment, use the bonding agent that constitutes by the photosensitive composite that contains bonding agent, polymerizable compound and Photoepolymerizationinitiater initiater etc. to form with material (opening the 2004-252421 communique) with reference to International Publication the 01/071428th trumpeter's volume and spy.

Become the exposure of material to make public with mask usually to said pattern; But in recent years from viewpoints such as throughput rate, exploring degree, the maskless exposure device that utilizes laser that use DMD (digitalmicromirrordevice) (DMD) waits is also by in the positive research and development.

Become in the material in said pattern,, proposed to use in the Photoepolymerizationinitiater initiater in photosensitive composite the pattern of six aryl di-imidazoles of possess hydrophilic property base to become material (with reference to special table 2002-507004 communique) in order to lower the development residue.

But as six aryl di-imidazolium compoundss with this water wettability base, from realizing the viewpoint of high sensitivityization, preferred use further has the compound of chlorine atom, even but in this case, even surpass 20mJ/cm when carrying out digit explosure ²Sensitivity also may not be high, so in the pattern that obtains, also there is the problem of exploring degree and adhesiveness variation.

On the other hand; Under the situation of six aryl di-imidazoles of use possess hydrophilic property base; Placed about 7 days if will contain the coating liquid of the photosensitive composite that in bonding agent, uses hydrophilic polymers, then LCV developers such as (leuco crystal violet) can develop the color the result gradually; Pattern becomes the sensitivity of material to reduce, and the ageing stability of sensitivity is poor.In addition, have the crystallinity height of six aryl di-imidazoles of chlorine atom, the coating liquid that contains the photosensitive composite that uses this six aryl di-imidazoles can be separated out crystallization when the low temperature keeping, can cause also that thus sensitivity reduces.

Thereby; Do not provide still at present that a kind of ageing stability that can form high sensitivity and high-resolution, adhesiveness and sensitivity is outstanding, the development residue is few, the pattern of high meticulous pattern becomes material and uses this pattern to become the pattern method of formationing of material, remain further improvement to be developed.

Summary of the invention

The present invention proposes in view of this present situation just, is problem with said each problem, the following purpose of realization that solves in the past.That is, the object of the present invention is to provide a kind of pattern that can form the pattern that ageing stability is outstanding, the development residue is few, height is meticulous of high sensitivity and high-resolution, adhesiveness and sensitivity to become material and use this pattern to become the pattern formation method of material.

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

On supporter, have the photographic layer that constitutes by the photosensitive composite that contains bonding agent, polymerizable compound and Photoepolymerizationinitiater initiater at least and form,

It is 0.300～0.650 polymkeric substance that said bonding agent contains the I/O value, and said Photoepolymerizationinitiater initiater contains six aryl di-imidazolium compoundss of possess hydrophilic property base.

< 2>become material according to < 1>described pattern, wherein, six aryl di-imidazoles (ヘ キ サ ア リ-Le PVC イ ミ ダ ゾ-Le) the water wettability base that compound had is an alkoxy.

< 3>become material according to < 2>described pattern, wherein, alkoxy is a methoxyl.

< 4>become material according to any described pattern in < 1 >～< 3 >, wherein, the I/O value is that the glass temperature (Tg) of 0.300～0.650 polymkeric substance is more than 80 ℃.

< 5>become material according to any described pattern in < 1 >～< 4 >; Wherein, The I/O value is that 0.300～0.650 polymkeric substance contains multipolymer, and this multipolymer has any one the structural unit at least that derives from styrene, styrene derivative and (methyl) acrylic acid benzyl ester.

< 6>become material according to any described pattern in < 1 >～< 5 >, wherein, the I/O value is that 0.300～0.650 polymer is alkali-soluble (ア Le カ リ solubility) or swellability (swelling).

< 7>become material according to any described pattern in < 1 >～< 6 >, wherein, polymerizable compound contains any one the monomer at least with urethane groups and aryl.

< 8>become material according to any described pattern in < 1 >～< 7 >, wherein, polymerizable compound contains monomer of (propylene oxide) base that has epoxypropane.

< 9>become material according to any described pattern in < 1 >～< 8 >, wherein, contain sensitizer.

< 10>become material according to < 9>described pattern, wherein, sensitizer is the assorted ring system ketonic compound that contracts.

< 11>become material according to any described pattern in < 1 >～< 10 >, wherein, contain compound with NH base.

< 12>become material according to any described pattern in < 1 >～< 11 >, wherein, contain 10～90 quality % bonding agents, contain 5～90 quality % polymerizable compounds.

< 13>become material according to any described pattern in < 1 >～< 12 >, wherein, supporter contains synthetic resin and is transparent.

< 14>become material according to any described pattern in < 1 >～< 13 >, wherein, supporter is long chi shape.

< 15>become material according to any described pattern in said < 1 >～< 14 >, it is long chi shape, and is rolled into the roller shape and forms.

< 16>become material according to any described pattern in said < 1 >～< 15 >, wherein, have protective film on the photographic layer.

< 17>become material according to any described pattern in said < 1 >～< 16 >, wherein, the thickness of photographic layer is 1～100 μ m.

< 18>a kind of pattern formation method is characterized in that, comprises at least becoming the photographic layer in the material to make public to any described pattern in < 1 >～< 17 >.

< 19>according to < 18>described pattern formation method, wherein, exposure does not use photomask to carry out.

< 20>according to < 18>or < 19>described pattern formation method, wherein, exposure is when exposure light and photographic layer are relatively moved, to carry out.

< 21>according to < 19>or < 20>described pattern formation method; Wherein, Exposure is to make any at least one of the photohead that possesses light irradiating means and optical modulator body at least and said photographic layer to move, and the light that penetrates from said light irradiating means with the corresponding pattern-information modulation of said optical modulator body of lateral dominance, limit shine from said photohead and carries out simultaneously.

< 22>according to said < 21>described pattern formation method, wherein, optical modulator body can corresponding pattern-information, to controlling less than n said drawing section arbitrarily of configuration continuously from n drawing section.

< 23>according to said < 21>or < 22>described pattern formation method, wherein, optical modulator body is a spatial optical modulation element.

< 24>according to said < 23>described pattern method, wherein, spatial optical modulation element is DMD (DMD).

< 25>according to any described pattern formation method in said < 21 >～< 24 >, wherein, exposure is carried out through the hole array.

< 26>according to any described pattern formation method in said < 21 >～< 25 >, wherein, light irradiating means can the two or more light of compound irradiation.

< 27>according to any described pattern formation method in said < 21 >～< 26 >; 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 coupling in said multimode optical fiber from the laser beam that this multiple laser instrument shines respectively.

< 28>according to said < 27>described pattern formation method, wherein, Wavelength of Laser is 350～420nm.

< 29 >, wherein, after having carried out exposure, carry out the development of photographic layer according to any described permanent pattern formation method in said < 18 >～< 28 >.

< 30>according to said < 29>described pattern formation method, wherein, after having carried out developing, carry out that etch processes and plating handle at least any one.

< 31>a kind of pattern is characterized in that, utilizes any described pattern formation method formation in said < 18 >～< 30 >.

It is on supporter, to have the photographic layer that is made up of the photosensitive composite that contains bonding agent, polymerizable compound and Photoepolymerizationinitiater initiater at least to form that pattern of the present invention becomes material; It is 0.300～0.650 polymkeric substance that said bonding agent contains the I/O value, and said Photoepolymerizationinitiater initiater contains at least a six aryl di-imidazolium compoundss of possess hydrophilic property base.As a result, can form the pattern that ageing stability is outstanding, the development residue is few, height is meticulous of high sensitivity and high-resolution, adhesiveness and sensitivity.

Pattern formation method of the present invention is owing to use said pattern of the present invention to become material, and the ageing stability of high sensitivity and high-resolution, adhesiveness and sensitivity is outstanding, the development residue is few, high meticulous pattern so can form.Particularly, can form pattern in high productivity ground through not using the direct patterning of photomask.

Embodiment

(pattern becomes material)

The photographic layer that the photosensitive composite that said pattern of the present invention becomes material on supporter, to have the composition that contains regulation constitutes forms, and other layers of suitably selecting such as range upon range of cushion form as required.

< photographic layer >

Said photographic layer is made up of the photosensitive composite that is described below; That is: contain bonding agent, polymerizable compound and Photoepolymerizationinitiater initiater at least; Preferably contain sensitizer and have NH base compound at least any one, contain other compositions of suitably selecting as required.

-Photoepolymerizationinitiater initiater-

As said Photoepolymerizationinitiater initiater, contain at least a six aryl di-imidazolium compoundss of possess hydrophilic property base.

Six aryl di-imidazolium compoundss are generally 2,4, and 5-triphenyl imidazole radicals dimer is known as Photoepolymerizationinitiater initiater.As the photosensitive composite that uses this compound, for example at the United States Patent (USP) the 3rd of No. the 3rd, 479,185, the United States Patent (USP) of Chambers, Chang etc.; 549, No. 367 instructionss, the 3rd, 684, No. 557 instructionss of United States Patent (USP) of Cescon, the United States Patent (USP) the 4th of Dessauer; The United States Patent (USP) the 4th of 252, No. 887 instructionss and the 4th, 331, No. 783, Chamber etc.; The United States Patent (USP) the 4th of the 4th, 410, No. 621 instructionss of United States Patent (USP) of 264, No. 708 instructionss, Wada etc., Tanaka etc.; Disclosed in the 4th, 622, No. 286 instructionss of United States Patent (USP) of 459, No. 349 instructionss, Sheets.

In the present invention, from reducing the viewpoint of development residue, use six aryl di-imidazolium compoundss of possess hydrophilic property base.At this, the water wettability base is meant the base that can be easily associates with water.

As the water wettability base in the six aryl di-imidazolium compoundss with said water wettability base, not special restriction can suitably be selected according to purpose, for example; Can enumerate dialkyl aminos such as hydroxyl, diethylin and dipropyl amido, carboxylic acid group and their Arrcostab, alkoxys such as methoxyl and ethoxy; Acid amides, and salt etc., wherein; From highly sensitive point, preferred alkoxy, preferred especially methoxyl.In addition, the six aryl di-imidazolium compoundss that have these water wettability bases can use a kind of separately or and with two or more.

From the viewpoint of further raising sensitivity, six aryl di-imidazolium compoundss with said water wettability base preferably have 1 chlorine atom at least, more preferably have 2 chlorine atoms.As six aryl di-imidazolium compoundss, for example can preferably enumerate 2,2 ', 5-three-(Chloro-O-Phenyl)-4-(3, the 4-Dimethoxyphenyl)-4 ' with said water wettability base; 5 '-diphenyl-di-imidazoles, 2,2 ', 4,4 '-four-(Chloro-O-Phenyl)-5; 5 '-two-(3, the 4-Dimethoxyphenyl)-di-imidazoles, 2,2 '-two-(Chloro-O-Phenyl)-4,4 '; 5,5 '-four-(m-methoxyphenyl)-1,2-di-imidazoles, 2,2 '-two (2-ethoxyl phenenyl)-4; 4 ', 5,5 '-tetraphenyl-1,1 '-di-imidazoles etc.Wherein, preferred especially 2,2 ', 5-three-(Chloro-O-Phenyl)-4-(3, the 4-Dimethoxyphenyl)-4 ', 5 '-diphenyl-di-imidazoles.Six aryl di-imidazolium compoundss of said possess hydrophilic property base are usually with the oxidative coupling preparation that replaces the triphenyl imidazoles.For the preparation that replaces the triphenyl imidazoles, be disclosed in the 4th, 331, No. 783 instructionss of United States Patent (USP) of the 3rd, 784, No. 557 instructionss of United States Patent (USP), Dessauer of Cescon.For oxidative coupling, be documented in the BULL.Chem.Soc.Japan33 of Hayashi etc., in 565 (1960), the Angew.Chem.73 of Zimmerman etc., 808 (1961).For 2,2 ', 5-three-(Chloro-O-Phenyl)-4-(3, the 4-Dimethoxyphenyl)-4 ', the preparation of 5 '-diphenyl-di-imidazoles is documented in the 4th, 622, No. 286 instructionss of United States Patent (USP) of Sheets.Six aryl di-imidazolium compoundss of said possess hydrophilic property base can do not separate completely and the situation of purifying under use the reaction mixture that contains this compound more than a kind.As such reaction mixture, as putting down in writing in the 4th, 622, No. 286 instructionss of United States Patent (USP) of Sheets; For containing 2,2 ', 5-three-(Chloro-O-Phenyl)-4-(3, the 4-Dimethoxyphenyl)-4 '; The potpourri, particularly 2-(Chloro-O-Phenyl)-4 of 5 '-diphenyl-di-imidazoles, 5-diphenyl-imidazole and 2,4-pair-(Chloro-O-Phenyl)-5-[3; The 4-Dimethoxyphenyl]-the oxidative coupling product of imidazoles, can use resultant of reaction is 2,2 ', 5-three-(Chloro-O-Phenyl)-4-(3; The 4-Dimethoxyphenyl)-4 ', 2,4 of 5 '-diphenyl-di-imidazoles, the dimeric potpourri of 5-triphenyl imidazole radicals.

Six aryl di-imidazolium compoundss of said possess hydrophilic property base also can supply to use with the body compound with hydrogen.Supply and body as said hydrogen, for example can enumerate organic mercaptans such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, tertiary amine, N-phenylglycine; 1,1-dimethyl-3,5-dioxo cyclohexane, ether; Ester, alcohol contains any one the compound at least of allylic hydrogen, benzylic hydrogens etc.; Acetal, acetaldehyde, acid amides etc.Supply and body about said hydrogen, in No. the 3rd, 390,996, the United States Patent (USP) of MacLachlan, set forth.

In addition, as said Photoepolymerizationinitiater initiater, for example also can further contain the compound of record in " 0288 "～" 0309 " that the spy opens the 2005-258431 communique etc.

The content of said Photoepolymerizationinitiater initiater is preferably 0.1～30 quality % in said photosensitive composite, more preferably 0.5～20 quality % is preferably 0.5～15 quality % especially.

-bonding agent-

As said bonding agent, be that the I/O value is 0.300～0.650 polymkeric substance.Wherein, in the present invention, " (methyl) acrylic acid " is meant that " acrylic acid " reaches any one of " methacrylic acid ".

As the I/O value is 0.300～0.650 polymkeric substance, as long as I/O value is 0.300～0.650, does not then limit especially, can suitably select according to purpose.If said I/O value surpasses 0.650, then adhesiveness reduces, and perhaps edge roughness (edge roughness) becomes big.

As the higher limit of I/O value, for example from any one the viewpoint at least of further raising exploring degree and covering property, more preferably 0.630, be preferably 0.600 especially.

As the lower limit of I/O value, for example from improving the viewpoint of development property, more preferably 0.350, be preferably 0.400 especially.

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 in 0.300～0.650 scope at least.

Said I/O value be also be called as (inorganic value)/(organic value) treat the value of the polarity of various organic compounds from organic notion angle, be 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-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-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 compound is had or key etc. are to the value of the magnitude numerical valueization of the influence power of boiling point.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 sum total 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 nonpolar (hydrophobicity, organic property big) organic compound, and is big more, shows (water wettability, the inorganic nature big) organic compound that is polarity 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 mol ratio of the mol ratio of the inorganic value * said methacrylic acid of the inorganic value of said multipolymer through trying to achieve said methacrylic acid, the inorganic value * said methyl methacrylate of said methyl methacrylate and the total incompatible calculating of 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 calculates following formula: 150 * 2 (mol ratio of methacrylic acid)+60 * 5 (mol ratio of methyl methacrylate)+15 * 3 (cinnamic mol ratio) and be calculated as 645.

The mol ratio of the mol ratio of the organic value * said methacrylic acid of the organic value of said multipolymer through trying to achieve said methacrylic acid, the organic value * said methyl methacrylate of said methyl methacrylate and the total incompatible calculating of said cinnamic organic value * said cinnamic mol ratio.

Said methacrylic acid has 4 carbon numbers, and said methyl methacrylate has 5 carbon numbers, and said styrene has 8 carbon numbers, 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 1,140.

Thereby the I/O value of said multipolymer is judged as 645 (inorganic value of said multipolymer)/1,140 (organic value of said multipolymer)=0.566.

At said bonding agent is to have under the situation of material of glass temperature, and this glass temperature is so long as more than 80 ℃, then not special restriction can suitably be selected according to purpose, more preferably more than 100 ℃, is preferably especially more than 115 ℃.

If said glass temperature is less than 80 ℃, then the stickability (tack) of the said photographic layer of possibility can increase, perhaps when making pattern formation material; The fissility variation of said photographic layer and said supporter; In addition, when changing exposure, separate the change that looks like etc. and may become big.

As said I/O value is 0.300～0.650 bonding agent, for example contains multipolymer, and this multipolymer is preferably has the multipolymer of any one structural unit at least that derives from styrene and styrene derivative.In addition; Except any one the structural unit at least that derives from said styrene and styrene derivative; As the combination of the composition of copolymerization, for example more preferably contain at least (methyl) acrylic acid and (methyl) alkyl acrylate combination, contain (methyl) acrylic acid and (methyl) alkyl acrylate and (methyl) acrylic acid benzyl ester combination, contain the combination of (methyl) acrylic acid and (methyl) acrylic acid benzyl ester.

As the alkyl of said (methyl) alkyl acrylate, special preferable methyl, ethyl.

Examples of the I / O value of 0.300 ~ 0.650 and the glass transition temperature of 80 ℃ or more of the binder, for example, methacrylic acid / methyl methacrylate / styrene / methyl methacrylate, benzyl group ester copolymer (copolymer composition (mass ratio): 25/8/30/37), methacrylic acid / methyl methacrylate / styrene / methacrylic acid benzyl ester (copolymer composition (mass ratio) : 23/8/15/54), methacrylic acid / methyl methacrylate / styrene / methacrylic acid benzyl ester (copolymer composition (mass ratio): 29/16/35/20), methyl acrylate / methyl methacrylate / styrene / ethyl acrylate copolymer (Copolymer composition (mass ratio): 25/25/39/11), methacrylic acid / methyl methacrylate / styrene / acrylic acid ethyl ester copolymer (copolymer composition (mass ratio): 25/25/45/5), methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer (Copolymer composition (mass ratio): 25 / 10/45/20), methacrylic acid / methyl acrylate, cyclohexyl acrylate / methacrylate, 2 - ethylhexyl acrylate copolymer (Copolymer composition (mass ratio): 25/70/5), methacrylic acid / methyl yl acrylate, cyclohexyl acrylate / methacrylate, 2 - ethylhexyl acrylate copolymer (Copolymer composition (mass ratio): 23/70/7), methacrylic acid / styrene / methyl acrylate copolymer (Copolymer composition ( mass ratio): 25/60/15), methacrylic acid / styrene / methyl acrylate copolymer (Copolymer composition (mass ratio): 25/50/25), methacrylic acid / styrene / methyl acrylate copolymer matter (copolymer composition (mass ratio): 29/61/10), methacrylic acid / styrene / ethyl acrylate copolymer (Copolymer composition (mass ratio): 23/60/17), methacrylic acid / benzene ethylene / ethyl acrylate copolymer (Copolymer composition (mass ratio): 29/61/10), methacrylic acid / styrene / ethyl acrylate copolymer (Copolymer composition (mass ratio): 25/70/5) , methacrylic acid / styrene copolymer (copolymerization composition ratio (mass ratio): 20/80), methacrylic acid / styrene copolymer (copolymerization composition ratio (mass ratio): 28/72), methacrylic acid / styrene copolymer (copolymerization composition ratio (mass ratio): 32/68), methacrylic acid / styrene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 25 / 65/10), methacrylic acid / styrene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 30/61/9), methacrylic acid / styrene / methacrylic acid 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 29/60/11), methacrylic acid / styrene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 29/47/24), methacrylic acid / methyl methacrylate / styrene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 25/22/40 / 13), methacrylic acid / methyl methacrylate / styrene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 29/15/47/9), methacrylic acid / methyl methacrylate / styrene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 29/18/50/3), methacrylic acid / methyl methacrylate / Benzyl ethylene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 25/15/40/20), methacrylic acid / methyl methacrylate / styrene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 25/15/35/25), methacrylic acid / styrene / methyl acrylate, cyclohexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 31/64/5), methacrylic acid / styrene / methyl acrylate, cyclohexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 25/15/60), methacrylic acid / methyl methacrylate / Benzyl ethylene / butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/27/46/2), methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer (of Copolymerization composition ratio (mass ratio): 29/15/50/6), methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/27 / 36/12), methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/13/38/20), methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/5/31/35), methacrylic acid / methyl methacrylate / styrene copolymer (of Copolymerization composition ratio (mass ratio): 25/29/46), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 20/53/27), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 29/19/52), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio) : 30/13/57), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 28/13/59), methacrylic acid / methyl methacrylate / Benzyl ethylene copolymer (copolymerization composition ratio (mass ratio): 32/8/60), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 29/31/40) , methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 25/41/34) and methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization component ratio (mass ratio): 20/56/24), methacrylic acid / styrene / methyl methacrylate, benzyl ester (copolymer composition (mass ratio): 30/15/55), methacrylic acid / styrene / benzyl methacrylate copolymer (Copolymer composition (mass ratio): 30/25/45) and methacrylic acid / methyl styrene / methacrylic acid benzyl ester (copolymer composition (mass ratio) : 30/15/55) and so on.

Among them, methacrylic acid / methyl methacrylate / styrene / methacrylic acid benzyl ester (copolymer composition (mass ratio): 25/8/30/37), methacrylic acid / methyl methacrylate acrylate / styrene / methacrylic acid benzyl ester (copolymer composition (mass ratio): 29/16/35/20), methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer ( Copolymer composition (mass ratio): 25/25/39/11), methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer (Copolymer composition (mass ratio): 25/25/45 / 5), methacrylic acid / styrene / methyl acrylate copolymer (Copolymer composition (mass ratio): 25/60/15), methacrylic acid / styrene / methyl acrylate copolymer (Copolymer composition (mass ratio ): 29/61/10), methacrylic acid / styrene / ethyl acrylate copolymer (Copolymer composition (mass ratio): 29/61/10), methacrylic acid / styrene / ethyl acrylate copolymer ( Copolymer composition (mass ratio): 25/70/5), methacrylic acid / styrene copolymer (copolymerization composition ratio (mass ratio): 20/80), methacrylic acid / styrene copolymer (copolymerization component ratio (mass ratio): 28/72), methacrylic acid / styrene copolymer (copolymerization composition ratio (mass ratio): 32/68), methacrylic acid / styrene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 25/65/10), methacrylic acid / styrene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 30/61 / 9), methacrylic acid / styrene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 29/60/11), methacrylic acid / methyl methacrylate / Benzyl ethylene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 25/22/40/13), methacrylic acid / methyl methacrylate / styrene / methyl acrylate, 2 - ethylhexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 29/15/47/9), methacrylic acid / methyl methacrylate / styrene / methyl acrylate, 2 - ethylhexyl acrylate copolymer ( Copolymerization composition ratio (mass ratio): 29/18/50/3), methacrylic acid / styrene / methyl acrylate, cyclohexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 31/64/5). methacrylic acid / styrene / methyl acrylate, cyclohexyl acrylate copolymer (copolymerization composition ratio (mass ratio): 25/15/60), methacrylic acid / methyl methacrylate / styrene / methyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/27/46/2), methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer (copolymerization composition ratio (mass ratio) : 29/15/50/6), methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/27/36/12), methyl acrylate / methyl methacrylate / styrene / butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/13/38/20), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 25/29/46), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 20/53/27), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 29/19/52), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 30/13/57), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 28/13/59), methacrylic acid / methacrylic acid ester / styrene copolymer (copolymerization composition ratio (mass ratio): 32/8/60), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 29 / 31/40), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 25/41/34), methacrylic acid / styrene / methacrylic acid benzyl ester copolymer matter (copolymer composition (mass ratio): 30/15/55), methacrylic acid / styrene / methyl methacrylate, benzyl ester (copolymer composition (mass ratio): 30/25/45) and methyl acrylic acid / methyl styrene / methacrylic acid benzyl ester (copolymer composition (mass ratio): 30/15/55).

And then, more preferably methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer (multipolymer is formed (mass ratio): 29/16/35/20), methacrylic acid/methyl methacrylate/styrene/acrylic ethyl ester multipolymer (multipolymer is formed (mass ratio): 25/25/45/5), methacrylic acid/styrene/acrylic methyl terpolymer (multipolymer is formed (mass ratio): 29/61/10), methacrylic acid/styrene/acrylic ethyl ester multipolymer (multipolymer is formed (mass ratio): 25/70/5), methacrylic acid/styrol copolymer (copolymerization ratio of components (mass ratio): 32/68), methacrylic acid/styrene/methacrylic acid 2-ethylhexyl ester copolymer (copolymerization ratio of components (mass ratio): 30/61/9), methacrylic acid/styrene/methacrylic acid 2-ethylhexyl ester copolymer (copolymerization ratio of components (mass ratio): 29/60/11), methacrylic acid/methyl methacrylate/styrene/methacrylic acid 2-ethylhexyl ester copolymer (copolymerization ratio of components (mass ratio): 29/15/47/9), methacrylic acid/methyl methacrylate/styrene/methacrylic acid 2-ethylhexyl ester copolymer (copolymerization ratio of components (mass ratio): 29/18/50/3), methacrylic acid/styrene/methacrylic acid cyclohexyl ester multipolymer (copolymerization ratio of components (mass ratio): 31/64/5), methacrylic acid/methyl methacrylate/styrene/methacrylic acid butyl ester multipolymer (copolymerization ratio of components (mass ratio): 25/27/46/2), methacrylic acid/methyl methacrylate/styrene/methacrylic acid butyl ester multipolymer (copolymerization ratio of components (mass ratio): 29/15/50/6), methacrylic acid/methyl methacrylate/styrol copolymer (copolymerization ratio of components (mass ratio): 25/29/46), methacrylic acid/methyl methacrylate/styrol copolymer (copolymerization ratio of components (mass ratio): 20/53/27), methacrylic acid/methyl methacrylate/styrol copolymer (copolymerization ratio of components (mass ratio): 29/19/52), methacrylic acid/methyl methacrylate/styrol copolymer (copolymerization ratio of components (mass ratio): 30/13/57), methacrylic acid/methyl methacrylate/styrol copolymer (copolymerization ratio of components (mass ratio): 28/13/59), methacrylic acid/methyl methacrylate/styrol copolymer (copolymerization ratio of components (mass ratio): 32/8/60), methacrylic acid/methyl methacrylate/styrol copolymer (copolymerization ratio of components (mass ratio): 29/31/40), methacrylic acid/methyl methacrylate/styrol copolymer (copolymerization ratio of components (mass ratio): 25/41/34), methacrylic acid/styrene/methacrylic acid benzyl ester multipolymer (multipolymer is formed (mass ratio): 30/15/55), methacrylic acid/styrene/methacrylic acid benzyl ester multipolymer (multipolymer is formed (mass ratio): 30/25/45) and methacrylic acid/methyl styrene/methacrylic acid benzyl ester multipolymer (multipolymer is formed (mass ratio): 30/15/55).

As said bonding agent, as long as said I/O value and said glass temperature in said numerical range, then do not limit especially, can suitably select according to purpose, for example preferred alkalies relatively is a swellability, more preferably alkalies is a solubility relatively.

Demonstrate the bonding agent of swellability or solubility as relative alkalies, can preferably enumerate the bonding agent that for example has acidic groups.

Acid number as said bonding agent; As long as said I/O value is in said numerical range; Then not special restriction can suitably be selected according to purpose, and the acid number of said bonding agent for example is preferably 100～250mgKOH/g; More preferably 120～220mgKOH/g is preferably 150～220mgKOH/g especially.

If said acid number is less than 100mgKOH/g, development property deficiency then, perhaps the exploring degree is poor, may not obtain high meticulous pattern.

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 vinyl 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, also any one the multipolymer at least of optimization styrene and styrene derivative.

Said vinyl 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 vinyl copolymer, for example can enumerate compound that the spy opens record in " 0164 "～" 0205 " of 2005-258431 communique 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-clad laminates) 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.

The six at least a aryl di-imidazolium compoundss of said possess hydrophilic property base and I/O value be 0.300～0.650 polymkeric substance content ratio as be preferably 1: 10 with mass ratio～1: 1, more preferably 1: 30～1: 2, be preferably 1: 20～1: 4 especially.

-polymerizable compound-

As the said polymerizable compound in the said photosensitive composite, not special restriction can suitably not selected according to purpose, for example can preferably enumerate any one monomer or the oligomer at least with urethane groups and aryl.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.

---monomer---with urethane groups

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 etc. that the spy opens " 0210 "～" 0262 " record of 2005-258431 communique.

---monomer---with aryl

As said monomer 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 " 0264 "～" 0271 " record that the spy opens the instructions of 2005-258431 communique.

---other polymerizable monomers---

In said photosensitive composite, in the scope that does not make the characteristic degradation that utilizes the photographic layer that this photosensitive composite forms, can also and with the said monomer that contains urethane groups, contain the monomer polymerizable monomer in addition of aryl.

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

Particularly, can enumerate the compound etc. that the spy opens " 0273 "～" 0284 " record of 2005-258431 communique.

More than, in illustrative polymerizable compound,, preferably contain monomer at least with epoxypropane base from having as the effect on the effect of foam-breaking agent, can forming the viewpoint of higher meticulous pattern.

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

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

In addition, as the content that has the polyfunctional monomer of 2 the above polymerism bases in the polymerizable compound in the photographic layer, preferred 5～100 quality %, more preferably 20～100 quality %, preferred especially 40～100 quality %.

-sensitizer-

Sensitivity) or wavelength photoreceptor in order to regulate to (the corresponding Japanese:,, can also add sensitizer of the exposure sensitivity in the exposure of photographic layer except said Photoepolymerizationinitiater initiater.

Can according to as after luminous ray or ultraviolet laser and the visible light laser of the light irradiating means stated wait and suitably select said sensitizer.

Said 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 the combination of Photoepolymerizationinitiater initiater and said sensitizer, for example can enumerate the spy and open the electronics mobile model initiation system combinations of putting down in writing in the 2001-305734 communique such as [(1) electronics supply-type initiating agent and sensitizing dyestuff, (2) electronics acceptance type initiating agent and sensitizing dyestuff, (3) electronics supply-type initiating agent, sensitizing dyestuff and electronics acceptance type initiating agent (ternary cause system)].

As said sensitizer; Not special restriction; Can from known sensitizer, suitably select; For example can enumerate known Ppolynuclear aromatic class (Bi 、 perylene, 9 for example; The 10-benzophenanthrene), oxa anthracenes (for example luciferin, tetrabromofluorescein, tetraiodofluorescein, rhodamine B, RB), cyanine glycoside (for example indoles carbocyanine, sulfo-carbocyanine, oxa-carbocyanine), merocyanine class (for example merocyanine, carbonyl merocyanine), thiazide (for example thionine, methylenum careuleum, toluidine blue), acridine (for example acridine orange, chloroflavin, acridine yellow, 9-phenylacridine, 1; 7-two (9; 9 '-acridinyl) heptane), (for example acridone, chloro-acridine ketone, N-methylacridine ketone, N-butyl acridone, N-butyl-chloro-acridine ketone (for example 2-chloro-10-butyl acridone etc.) etc., Coumarins (for example can be enumerated 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 to anthraquinone class (for example anthraquinone), Si Kuamu (ス Network ア リ ウ system) type (for example Si Kuamu (ス Network ア リ ウ system)), acridine ketone; 3 '-carbonyl two (5; 7-two-positive propoxy cumarin), 3; 3 '-carbonyl two (7-diethyl amino coumarin), 3-benzoyl-ayapanins, 3-(2-furoyl)-7-diethyl amino coumarin, 3-(4-diethylamino cinnamoyl)-7-diethyl amino coumarin, 7-methoxyl-3-(3-pyridine radicals carbonyl) cumarin, 3-benzoyl-5; 7-dipropoxy cumarin etc.; Also have in addition and specially open flat 5-19475 number, spy and open flat 7-271028 number, spy and open 2002-363206 number, spy and open 2002-363207 number, spy and open 2002-363208 number, spy and the coumarin compound put down in writing in each communique etc. such as open 2002-363209 number), thioxanthene ketone (thioxanthones, isopropyl thioxanthone, 2; 4-diethyl thioxanthone, 1-chloro-4-propoxyl group thioxanthones, QuantacureQTX etc.) etc.; Wherein, optimization aromatic ring or heterocycle contract behind the ring compound (compound ring series contracts) and with any one substituted amine compound of at least 2 aromatic hydrocarbon rings and fragrant heterocycle.

In the said compound ring series that contracts, more preferably assorted contract ring system ketonic compound (acridone based compound, thioxanthones based compound, coumarin series compounds) and acridine based compound.In the said assorted ring system ketonic compound that contracts, preferred especially acridone compound, thioxanthones compound.

The sensitizer that the light that any one substituted amine compound of at least 2 aromatic hydrocarbon rings of said usefulness and fragrant heterocycle is preferably the wavelength domain of relative 330～450nm has absorption maximum, for example can enumerate disubstituted amido benzophenone based compound, relatively the amino on the phenyl ring have on the carbon atom of contraposition heterocyclic radical as substituent disubstituted amido-benzene compounds, have the substituent disubstituted amido-benzene compounds that contains the sulfonyl imino group on the carbon atom of amino on the phenyl ring relatively and form the disubstituted amido-benzene compounds of hydroxyquinoline skeleton and will have at least 2 aromatic rings and be incorporated into the compound that the disubstituted amido-benzene such as compound of the structure of nitrogen-atoms have as part-structure in contraposition.

Said sensitizer can use a kind of separately or and with two or more.

The content of said sensitizer, whole compositions of photosensitive composite are preferably 0.01～4 quality % relatively, and more preferably 0.02～2 quality % is preferably 0.05～1 quality % especially.

If said content is less than 0.01 quality %, sensitivity so sometimes reduces, if surpass 4 quality %, the shape of pattern can worsen so sometimes.

-have the compound of NH-

In order to improve covering (tent) property in the established pattern and to reduce the development residue, can add compound with NH base.

As the compound with said NH base, not special restriction can suitably be selected according to purpose, for example can enumerate the heterogeneous ring compound that contains NH, the sulfonamide compounds that contains NH etc.Wherein, preferably contain the benzotriazole skeleton compound, contain the benzimidazole skeleton compound, contain the compound of benzsulfamide skeleton.

Particularly, for example can enumerate benzotriazole, carboxyl benzotriazole, dibutylamino methylbenzotrazole, dibutylamino carboxyl benzotriazole, benzimidazole, benzsulfamide, toluenesulfonamide, butyl benzene sulfonamide etc.In addition, contain compound of NH etc. in the thermal polymerization inhibitor of stating after also can adding.

The compound of the said NH of having base can use a kind of separately or and with two or more, from the viewpoint of the raising of light-proofness, preferred toluenesulfonamide, from the viewpoint of the minimizing of development residue, preferred benzotriazole based compound such as carboxyl benzotriazole.

The content of the compound with NH base in the said photosensitive composite for example is preferably 0.001～5 quality %, more preferably 0.002～3 quality %.

-other compositions-

As other compositions in the said photosensitive composite; For example can enumerate known thermal polymerization inhibitor, surfactant, plastifier, developer, colorant etc., and then also can and use the adhesion promoter of matrix surface and other assistant 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 move agent etc.).Through suitably containing these compositions, can regulate the character such as stability, photograph property, printing property, film physical property of the said photographic layer (said pattern becomes material) that needs.

---thermal polymerization inhibitor---

Said thermal polymerization inhibitor can prevent the thermal polymerization or the polymerization through time ground of the said polymerizable compound in the said photographic layer that is made up of said photosensitive composite, so also can add.

As said thermal polymerization inhibitor; For example 4-metoxyphenol, quinhydrones, alkyl or aryl replace quinhydrones, tert-butyl catechol, pyrogaelol, 2-Viosorb 110,4-methoxyl-2-Viosorb 110, stannous chloride, phenothiazine, tetrahydrochysene quinone, naphthylamines, betanaphthol, 2; 6-di-t-butyl-4-cresols, 2, the chelate of 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), pyridine, nitrobenzene, dinitro benzene, picric acid, 4-toluidine, methylenum careuleum, copper and organic sequestering agent reactant, gaultherolin and phenothiazine, nitroso compound, nitroso compound and Al etc.

As the content of said thermal polymerization inhibitor, said relatively polymerizable compound, preferred 0.001～5 quality %, more preferably 0.005～2 quality %, preferred especially 0.01～1 quality %.

If this content is less than 0.001 quality %, the stability when then preserving sometimes can reduce, if surpass 5 quality %, then the sensitivity meeting of relative activity energy line reduces.

-plastifier-

In order to control the film physical property (flexible) of the photographic layer that constitutes by said photosensitive composite, also can add said plastifier.

As said plastifier, for example can enumerate phthalates such as phthalic acid dimethyl ester, dibutyl phthalate, diisobutyl phthalate, dibutyl phthalate (DHP), dioctyl phthalate, dicyclohexyl phthalate, phthalic acid tricosyl ester, butyl benzyl phthalate, diisooctyl phthalate, phthalic acid diphenyl, diallyl phthalate, phthalic acid octyl group capryl ester; Glycol ester classes such as triethylene-glycol diacetate, tetraethylene glycol diacetate esters, phthalic acid dimethyl glucose ester, phthalic acid ethyl phthalyl ethyl ester, O-phthalic acid methyl phthalyl ethyl ester, O-phthalic acid butyl phthalyl butyl ester, diglycol dicaprylate; Phosphoric acid ester such as phosphoric acid trimethylbenzene phenolic ester, triphenyl phosphate; Amide-types such as 4-toluenesulfonamide, benzsulfamide, N-n-butylbenzene sulfonamide, N-normal-butyl acetamide; Fatty acid dibasic acid ester classes such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, dioctyl azelate, dibutyl maleate; Triethyl citrate, ATBC, glycerol triacetate, butyl laurate, 4,5-diethoxy cyclohexane-1, glycols such as polyglycol, polypropylene glycol such as 2-dicarboxylic acid dioctyl ester.

The content of said plastifier, whole compositions of said relatively photosensitive composite, preferred 0.1～50 quality %, more preferably 0.5～40 quality %, preferred especially 1～30 quality %.

---developer---

For but the said photographic layer after exposure is given video (printing function) and is added said developer.

As said developer, for example can enumerate aminotriaryl methanes classes such as three (4-dimethylaminophenyl) methane (LCV), three (4-diethylin phenyl) methane, three (4-dimethylamino-2-aminomethyl phenyl) methane, three (4-diethylin-2-aminomethyl phenyl) methane, two (4-dibutyl amino phenyl)-[4-(2-cyano ethyl) methylamino phenyl] methane, two (4-dimethylaminophenyl)-2-quinolyl methane, three (4-dipropyl aminocarbonyl phenyl) methane; 3, two (the dimethylamino)-9-phenyl yanthines of 6-, 3-amino-amino xanthines such as 6-dimethylamino-2-methyl-9-(2-chlorphenyl) xanthine; 3, two (diethylamino)-9-(the 2-ethoxy carbonyl phenyl) thioxanthenes, 3 of 6-, amino thioxanthene classes such as two (dimethylamino) thioxanthenes of 6-; 3, two (diethylin)-9 of 6-, 10-dihydro-9-phenylacridine, 3, two (benzylamino)-9 of 6-, amino such as 10-dihydro-9-methylacridine-9,10-acridan class; 3, two (the amino phenoxazine classes such as diethylin) phenoxazine of 7-; 3, amino phenothiazines such as two (ethylamino-) phenthiazones of 7-; 3, two (the diethylin)-5-hexyls-5 of 7-, amino dihydrophenazine classes such as 10-dihydrophenazine; Aminophenyl methane classes such as two (4-dimethylaminophenyl) anilino-methane; Amino-the 4 '-dimethylamino diphenylamine of 4-, 4-amino-α, β-amino hydrocinnamic acid classes such as dicyano hydrocinnamic acid methyl esters; 1-(2-naphthyl)-hydrazine classes such as 2-phenyl hydrazine; 1, two (ethylamino-)-2 of 4-, the amino-2 of 3-dihydroanthracene quinones, 3-dihydroanthracene quinones; N, N-diethyl-phenethyl phenyl aminess such as 4-phenethyl aniline; 10-acetyl group-3, two (dimethylamino) phenothiazine etc. of 7-contain the acyl derivative of the colourless pigment of alkaline NH; Three (4-diethylin-2-tolyl) though ethoxy carbonyl terpane etc. do not have can oxidation hydrogen can be oxidized to the no tinctorial pattern compound of color-developing compounds; Colourless indigo-blue pigment; Like United States Patent (USP) 3,042, No. 515 and the same the 3rd; The organic amine that can be oxidized to colour developing shape and so on of record in 042, No. 517 (for example 4,4 '-ethylenediamine, diphenylamine, N; The N-dimethyl is for propylamine, 4; 4 '-methylene diamine triphenylamine, N-acetyl group carbazole), wherein, triarylmethane based compounds such as preferred LCV.

And then in order to make said shadow colour developing etc., known usually said developer and the halogen compounds of making makes up.

As said halogen compounds, for example can enumerate halogenated hydrocarbons (for example carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, bromo pentane, isoamyl bromide, iodopentane, bromination isobutylene, butyl iodide, diphenyl methyl bromine, carbon trichloride, 1,2-ethylene dibromide, 1,1; 2,2 ,-tetrabromoethane, 1,2-two bromo-1; 1,2-trichloroethanes, 1,2,3-tribromopropane, 1; 2,3,4-tetrabromobutane, tetrachloro cyclopentene, hexachlorocyclopentadiene, dibromo cyclohexane, 1; 1,1-three chloro-2, two (4-chlorphenyl) ethane of 2-etc.); Halogen alcoholic compound (for example 2,2,2-ethapon, ethobrom, 1,3-two chloro-2-propyl alcohol, 1,1,1, the amino isopropyl alcohol of-trichloro-2-propanol, two (iodine hexa-methylene), acetone-bromoform, 2,2,3-three neoprenes-1,4-glycol etc.); Halogen carbonyls (for example 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, perbrome-acetone, 1,1,3,3-tetrachloroacetone, 1,1,1-trichloroacetone, 3,4-two bromo-2-butanols, 1,4-two chloro-2-butanols-dibromo cyclohexanol etc.); Halogen ether compound (for example 2-bromoethyl methyl ether, 2-bromoethyl ether, two (2-bromoethyl) ether, 1,2-dichloroethyl ether etc.); Halogen ester compounds (for example bromoethyl acetate, ethyl trichloroacetate, trichloroacetic acid trichloro ethyl ester, 2, the homopolymer of 3-dibromopropyl acrylic ester and multipolymer, dibromo-propionic acid trichloro ethyl ester, α, β-dichloropropylene acetoacetic ester etc.); Halogen amide compound (for example chloroacetamide, acetbromamide, dichloro acetamide, trichloroacetamide, tribromoacetamide, three chloroethyl trichloroacetamides, 2-bromine Isopropamide, 2; 2,2-trichlorine propionamide, N-chlorosuccinimide, N-bromosuccinimide etc.); Compound (for example trisbromomethyl phenyl sulfone, 4-nitrobenzophenone trisbromomethyl sulfone, 4-chlorphenyl trisbromomethyl sulfone, tricresyl phosphate 2,3 a dibromo propyl ester etc.), 2 with sulphur or phosphorus, two (trichloromethyl) 6-Phenyltriazoles of 4-etc.In organohalogen compound, preferably have the halogen compounds of 2 above halogen atoms that combine with same carbon atom, more preferably on 1 carbon atom, have the halogen compounds of 3 halogen atoms.Said organohalogen compound can use a kind of separately or and with two or more.Wherein, preferred trisbromomethyl phenyl sulfone, 2, two (trichloromethyl) 6-Phenyltriazoles of 4-.

The content of said developer, whole compositions of photosensitive composite are preferably 0.01～20 quality % relatively, and more preferably 0.05～10 quality % is preferably 0.1～5 quality % especially.In addition, the content of said halogen compounds, whole compositions of photosensitive composite are preferably 0.001～5 quality, more preferably 0.005～1 quality % relatively.

---colorant-

As said colorant, not special restriction can suitably not selected according to purpose, for example can enumerate known pigment or dyestuffs such as redness, green, blueness, yellow, purple, peony, dark green, black.Particularly, can enumerate Victoria's pure blue B O (C.I.42595), (alkalescence) Chinese scholartree yellow (C.I.41000), liposoluble (fat) ?HB (C.I.26150), single shallow (モ ノ ラ イ ト) 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 ?.

---dyestuff---

In order to improve operability or to give storage stability, also can in said photosensitive composite, use dyestuff.

As said dyestuff; Can enumerate bright green (for example its sulfate), eosin, ethyl violet, Erythrosin B, methyl green, crystal violet, basic fuchsin (basic fuchsin), phenolphthalein, 1; 3-diphenyl triazine, alizarin red S, thymol phthalein, crystal violet 2B, quinaldine red, RB, rice tower Neil-Huang, the yellow phthalein of thymol, xylenol blue, methyl orange, orange IV, diphenyl junket (チ ロ) carbarsone, 2; 7-dichlorofluorescein, paramethyl red, Congo red, benzopurpurine 4B, Alpha-Naphthyl-red, Nile blue A, phenacetolin (Off エ Na セ タ リ Application), methyl violet, peacock green, paramagenta, oil blue #603 (オ リ エ Application ト chemical industrial company system), rhodamine B, rhodamine 6G, Victoria's pure blue B O etc.; Wherein, preferred cationic dyestuff (for example peacock green oxalates, peacock green sulfate etc.).As this dye of positive ion to negative ion, so long as the residue of organic acid or mineral acid gets final product, for example can enumerate the residue (negative ion) of bromic acid, acid iodide, sulfuric acid, phosphoric acid, oxalic acid, methane-sulforic acid, toluenesulfonic acid etc. etc.

The content of said dyestuff, whole compositions of said relatively photosensitive composite are preferably 0.001～10 quality %, and more preferably 0.01～5 quality % is preferably 0.1～2 quality % especially.

---adhesion promoter---

For the adhesiveness that improves the photographic layer that forms with this photosensitive composite (when becoming material as said pattern and the adhesiveness of other layers or with the adhesiveness of matrix); In said photosensitive composite, can in each layer, use known so-called adhesion promoter.

As said adhesion promoter, for example can preferably enumerate the spy and open flat 5-11439 communique, spy and open the adhesion promoter that flat 5-341532 communique and special is opened record in the flat 6-43638 communique etc.

The content of said adhesion promoter, whole compositions of said relatively photosensitive composite are preferably 0.001 quality %～20 quality %, and more preferably 0.01～10 quality % is preferably 0.1 quality %～5 quality % especially.

In addition, said photosensitive composite for example also can contain just like organosulfur compound, superoxide, redox based compound, azo or the diazo-compounds put down in writing in J. コ-サ-work " photosensitive system (light sensitive systems ラ イ ト セ Application シ テ イ Block シ ス テ system ズ) " the 5th chapter, photo-reduction property pigment, organohalogen compound etc.

As organosulfur compound, for example can enumerate di-n-butyl disulfide, benzyl disulfide thing, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, benzenethiol, ethyl methenyl choloride sulfenic acids ester, 2-mercaptobenzimidazole etc.

As said superoxide, for example can enumerate di-tert-butyl peroxide, dibenzoyl peroxide, peroxidating methyl ethyl ketone.

Said redox compound is the compound that constitutes of superoxide and reductive agent, can enumerate ferrous ion and persulfuric acid ion, ferric ion and superoxide etc.

As said azo and diazo-compounds, for example can enumerate α, α '-azoisobutyronitrile, 2-azo be two-the diazonium class of 2-methylbutyronitrile, 4-aminodiphenylamine.

As said photo-reduction property pigment, for example can enumerate RB, iodeosin, eosin, acridine yellow, lactochrome, thionine.

---surfactant---

In order to improve the planar inequality that when forming said photographic layer, produces, said photosensitive composite can add 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.

If said content less than 0.001 quality %, then can not obtain the effect of planar improvement sometimes, if surpass 10 quality %.Then adhesiveness reduces sometimes.

As said surfactant; Except above-mentioned surfactant; As the surfactant of fluorine system, also can preferably enumerate to contain the above fluorine atom of 40 quality % and have and be incorporated into the high molecular surfactant that is had as the copolymerization composition by the acrylic ester of the substituted fluorine fatty group of fluorine or methacrylate from the hydrogen atom of at least 3 carbon atoms of non-binding terminal number with carbochain 3～20.

Said photographic layer is become the not special restriction in the position that is provided with in the material in said pattern.Can suitably select according to purpose, be laminated in usually on the said supporter.As said photographic layer, can be single or multiple lift.

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.

<supporter >

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, more preferably the flatness good supporting body on surface.

-turbidity value-

The turbidity value of said supporter, the turbidity value of the light of 405nm is preferably below 5.0% relatively, more preferably below 3.0%, is preferably below 1.0% especially.If said turbidity value surpasses 5.0%, the amount of light scatter in the then said photographic layer increases, and the exploring degree when asking fine pitch (fine pitch) reduces sometimes or harmful effects such as adhesiveness reduces, the edge roughness change is big take place.

In addition, total light penetration of the light of the relative 405nm of said supporter is preferably more than 86%, more preferably more than 87%.

As the assay method of said turbidity value and total light penetration, not special restriction can suitably be selected according to purpose, for example can enumerate the method for following explanation.

At first, total light penetration is measured in (1).Assay method as said total light penetration; Not special restriction; Can suitably select according to purpose, (for example Shimadzu Seisakusho Ltd.'s corporate system UV-2400) is carried out method for measuring for example can to enumerate the spectrophotometer that uses integrating sphere and can shine the light of 405nm.(2) in the assay method of said total light penetration, except not using said integrating sphere, carry out with the assay method of said total light penetration identically, measure the parallel rays transmitance.Then; (3) calculate from following calculating formula: the diffusion light transmitance that " said total light penetration-said parallel rays transmitance " tries to achieve, (4) can be from following calculating formulas: " said diffusion light transmitance/said total light penetration * 100 " tried to achieve said turbidity value.

The thickness of the working sample when wherein, trying to achieve said total light penetration and said turbidity value is 16 μ m.

Said supporter also can at least simultaneously apply inert particulate.Said inert particulate preferably applies at the face opposite with the face that forms said photographic layer.

As said inert particulate; For example can enumerate cross-linked polymer particle, inorganic particle (for example lime carbonate, calcium phosphate, monox, porcelain earth, talcum, titania, aluminium oxide, barium sulphate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide etc.), organic fine particles (for example two 22 phosphoamides (ヘ キ サ メ チ レ Application PVC ス ベ ヘ Application ア ミ De) of hexa-methylene, the bimonthly osmanthus of hexa-methylene acid amides, N; N '-two stearyl terephthalamides, silicone, calcium oxalate etc.), produce during polyester separate out particle etc.; Wherein, preferred monox, lime carbonate, two 22 phosphoamides of hexa-methylene.

The said particle of separating out for example is meant through utilizing conventional method to make and separates out particle with what alkaline metal or alkali earth metallic compound were separated out in reaction system as the system generation polymerization of ester exchange catalyst, also can be to make it separate out particle through adding terephthalic acids when said ester exchange reaction or the polycondensation reaction.In said ester exchange reaction or polycondensation reaction, also can there be more than one of phosphorus compounds such as phosphoric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, acid phosphate ester, phosphorous acid, Trimethyl phosphite, triethyl phosphite, tributyl phosphite.

As the mean grain size of said inert particulate, be preferably 0.01～2.0 μ m, 0.02～1.5 μ m more preferably, and then be preferably 0.03～1.0 μ m, be preferably 0.04～0.5 μ m especially.

If the mean grain size of said inert particulate is less than 0.01 μ m, then said pattern becomes the carrier wave property of material to worsen sometimes, contains said inert particulate in order to obtain carrier wave property through excessive, and the turbidity value of said supporter can rise.In addition, if the mean grain size of said inert particulate surpasses 2.0 μ m, the scattering of light that then makes public causes that sometimes the exploring degree reduces.

As the coating method of said inert particulate, not special restriction can suitably be selected according to purpose.For example can enumerate after creating the synthetic resin made membrane of said supporter, apply the method for the coating liquid that contains said inert particulate with known method.In addition, also can fusion contain the synthetic resin of said inert particulate,, be shaped becoming on the synthetic resin made membrane of said supporter from the die head ejection.And then the method that also can utilize the spy to open to put down in writing in the 2000-221688 communique forms.

The thickness that contains the overlay of said inert particulate in the said supporter is preferably 0.02～3.0 μ m, and more preferably 0.03～2.0 μ m is preferably 0.04～1.0 μ m especially.

The synthetic resin made membrane that becomes said supporter is preferably transparent, for example is preferably the vibrin made membrane, is preferably biaxially oriented polyester film especially.

As said vibrin; For example can enumerate polyethylene terephthalate, PEN, gather (methyl) acrylate copolymer, gather (methyl) alkyl acrylate, tygon-2; 6-naphthoic acid ester, polytetramethylene terephthalate, polytetramethylene-2,6-naphthoic acid ester etc.They can use a kind of separately or and with two or more.

As the resin beyond the said vibrin, for example can enumerate polypropylene, tygon, Triafol T, cellulose diacetate, PVC, polyvinyl alcohol (PVA), polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride vinyl acetate co-polymer, teflon, gather trifluoro-ethylene, cellulose-based resin, nylon resin etc.They can use a kind of separately or and with two or more.

Said synthetic resin made membrane can be made up of one deck, also can be made up of two-layer above layer.Under two-layer above layer situation about constituting, the layer of distance perspective photosphere position farthest preferably contains said inert particulate.

In addition, said synthetic resin made membrane, the viewpoint from mechanical strength property and optical characteristics is preferably biaxially oriented polyester film.

To the not special restriction of the double orientation method of said biaxially oriented polyester film, can suitably select according to purpose.For example; Can utilize the method preparation that is described below, that is: with said vibrin melt extrusion flakiness shape, carry out quenching; Make non-stretched film; When this non-stretched film is carried out two-way stretch, draft temperature is made as 85～145 ℃, will vertically reaches horizontal stretching ratio and be made as 2.6～4.0 times, as required, utilize 150～210 ℃ of heat fixations to carry out the film after the two-way stretch.

Said two-way stretch can be for through to vertical or horizontal stretching non-stretched film, as monodirectional tension film, then to two-way stretch method successively horizontal or this monodirectional tension film of longitudinal stretching; Also can be for simultaneously to two-way stretch method vertically and this non-stretched film of cross directional stretch the time.In addition, as required, said biaxially oriented film also can further stretch to vertically reaching horizontal any at least direction.

As the thickness of said supporter, not special restriction can suitably not selected according to purpose, for example preferred 2～150 μ m, more preferably 5～100 μ m, preferred especially 8～50 μ m.

As the shape of said supporter, preferably long chi shape can be suitably selected in not special restriction according to purpose.As the length of the supporter of said long chi shape, not special restriction for example can not enumerate 10～20, the long chi shape of 000m length.

< other layers >

Become other layers in the material as said pattern, not special restriction can suitably be selected, and for example also can have layers such as cushion, oxidation prevention layer (PC layer), peel ply, adhesive linkage, light absorbing zone, sealer.These layers can have a kind of separately, also can have two or more.In addition, also can on said photographic layer, have protective film.

-cushion-

As said cushion, not special restriction can suitably be selected according to purpose, can be swellability or solubility to alkalies, also can be for insoluble.

The relative alkalies of said cushion is under the situation of swellability or solubility; As said thermoplastic resin, for example can enumerate multipolymer, styrene and (methyl) acrylic ester and (methyl) acrylic acid multipolymer etc. of saponified, (methyl) acrylic ester and (methyl) acrylic ester of saponified, (methyl) acrylate copolymer of gathering (methyl) acrylic ester, (methyl) butyl acrylate and vinyl acetate etc. etc. of saponified, vinyltoluene and (methyl) acrylate copolymer of saponified, styrene and (methyl) acrylate copolymer of ethene and acrylate copolymer.

As the not special restriction of the softening point (Vicat) of in this case thermoplastic resin, can suitably select according to purpose, for example be preferably below 80 ℃.

As said softening point is the thermoplastic resin below 80 ℃; Except above-mentioned thermoplastic resin; Can also enumerate that (Japanese plastics industry connects alliance in " plastics performance brief guide "; All Japan plastics forming industry Colaesce meeting is write, and the census of manufacturing can be issued, distribution on October 25 nineteen sixty-eight) softening point to be about in the organic polymer below 80 ℃ alkalies be the soluble thermoplastic resin.In addition, be in the organic polymer material more than 80 ℃ at softening point, also can actual softening point be dropped to below 80 ℃ in this organic polymer material, adding the various plastifier that have mutual solubility with this organic polymer material.

In addition; The relative alkalies of said cushion is under the situation of swellability or solubility; Become the interlayer bonding force of material as said pattern, not special restriction can suitably not selected according to purpose; For example in the interlayer bonding force of each layer, the interlayer bonding force between preferred said supporter and the said cushion is minimum.Through becoming such interlayer bonding force, can be after only peeling off said supporter from said duplexer and said photographic layer being made public via said cushion, with the developer solution of alkalescence this photographic layer is developed.In addition, can also stay said supporter, after said photographic layer is made public, only peel off said supporter, this photographic layer developed with alkaline developer solution from said duplexer.

Control method as said interlayer bonding force; Not special restriction; Can suitably select according to purpose, for example can enumerate the method for in said thermoplastic resin, adding known polymkeric substance, supercooling material, adhering to modifying agent, surfactant, release agent etc.

As said plastifier; Not special restriction; Can suitably select according to purpose, for example can enumerate alcohols or ester classes such as polypropylene glycol, polyglycol, dioctyl phthalate, dibutyl phthalate (DHP), dioctyl phthalate, dibutyl phthalate, phosphoric acid trimethylbenzene phenolic ester, tricresyl phosphate diphenyl, phosphoric acid xenyl diphenyl; Amide-types such as toluenesulfonamide etc.

The relative alkalies of said cushion is under the insoluble situation, and as said thermoplastic resin, for example can enumerate principal ingredient is with the multipolymer of ethene as necessary copolymerization composition.

As with the multipolymer of ethene as necessary copolymerization composition, do not limit especially, can suitably not select according to purpose, for example can enumerate ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA) etc.

The relative alkalies of said cushion is under the insoluble situation; Become the interlayer bonding force of material as said pattern, not special restriction can suitably not selected according to purpose; For example in the interlayer bonding force of each layer, the bonding force between preferred said photographic layer and the said cushion is minimum.Through becoming such interlayer bonding force, can after only peeling off said supporter and cushion from said duplexer, said photographic layer is made public, this photographic layer be developed with alkaline developer solution.In addition, can also stay said supporter, after said photographic layer is made public, only peel off said supporter and said cushion, this photographic layer developed with alkaline developer solution from said duplexer.

Control method as said interlayer bonding force; Not special restriction; Can suitably select according to purpose; For example can enumerate the method for in said thermoplastic resin, adding various polymkeric substance, supercooling material, adhering to modifying agent, surfactant, release agent etc., the method for the adjusting ethylene copolymer composition and division in a proportion of below explaining etc.

To with said ethene as the ethylene copolymer composition and division in a proportion in the multipolymer of necessary copolymerization composition, not special restriction can suitably not selected according to purpose, for example preferred 60～90 quality %, more preferably 60～80 quality %, preferred especially 65～80 quality %.

The copolymerization of said ethene such as the fruit less than 60 quality %; Interlayer bonding force between then said cushion and the said photographic layer uprises; Peel off at the interface that is difficult to sometimes between this cushion and this photographic layer, if surpass 90 quality %, then because the interlayer bonding force between said cushion and the said photographic layer becomes too small; So be very easy to peel off between this cushion and this photographic layer, be difficult to make the pattern that comprises said cushion sometimes and become material.

To the not special restriction of the thickness of said cushion, can suitably select for example preferred 5～50 μ m, more preferably 10～50 μ m, preferred especially 15～40 μ m according to purpose.

If said thickness is less than 5 μ m, then concavo-convex in the surface of matrix or the concavo-convex tracing ability of bubble etc. reduced can not form high meticulous permanent pattern sometimes, if surpass 50 μ m, then produces the unfavorable conditions such as drying load increase on making sometimes.

-oxidation prevention layer (PC layer)-

Said oxidation prevention layer preferably is that principal ingredient forms usually with the polyvinyl alcohol (PVA), is preferably the tunicle of thickness about 0.5～5 μ m.

-protective film-

Said protective film prevents the contaminated or damage of said photographic layer, has the function of protection.

Said protective film is become the not special restriction in the position that is provided with in the material in said pattern, can suitably select, on said photographic layer, be provided with usually according to purpose.

As said protective film, for example can enumerate the protective film that in said supporter, uses, silicone paper, range upon range of have tygon, polyacrylic paper, polyolefin or polytetrafluoroethylsheet sheet etc., wherein, preferably polyethylene film, polypropylene film.

As the thickness of said protective film, for example preferred 5～100 μ m, more preferably 8～30 μ m can be suitably selected in not special restriction according to purpose.

Use under the situation of said protective film, the bonding force A of said photographic layer and said supporter, be preferably the relation of bonding force A＞bonding force B with the bonding force B of said photographic layer and protective film.

As the combination (supporter/protective film) of said supporter and protective film, for example can enumerate polyethylene terephthalate/polypropylene, polyethylene terephthalate/tygon, PVC/cellophane, polyimide/polypropylene, polyethylene terephthalate/polyethylene terephthalate etc.In addition, through surface treatment supporter and protective film at least one, can satisfy the relation of aforesaid bonding force.The surface treatment of said supporter also can be used to improve with the bonding force of said photographic layer implement, and for example can enumerate being coated with of undercoat, Corona discharge Treatment, flame treatment, ultraviolet treatment with irradiation, high frequency treatment with irradiation, glow discharge treatment with irradiation, active plasma treatment with irradiation, laser light irradiation processing etc.

In addition, the coefficient of static friction as between said supporter and the said protective film is preferably 0.3～1.4, and more preferably 0.5～1.2.

If said coefficient of static friction less than 0.3, then owing to sliding excessively, under the situation that becomes the roller shape, volume may take place depart from,, may be difficult to be rolled into good roller shape if surpass 1.4.

Said protective film also can carry out surface treatment in order to regulate the cementability between said protective film and the said photographic layer.Said surface treatment for example forms the undercoat that is made up of polymkeric substance such as polysiloxane, fluorinated polyolefin, PVF, polyvinyl alcohol (PVA) on the surface of said protective film.The formation of this undercoat can be passed through after the coating liquid of the said polymkeric substance of surface applied of said protective film, and it was formed down at 30～150 ℃ in dry 1～30 minute.Preferred especially 50～120 ℃ of the temperature of said drying.

[pattern becomes the method for making of material]

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

At first, with the material dissolves that contains in the said photographic layer, emulsification be scattered in water or solvent in, the preparation pattern photosensitive polymer combination solution that becomes material to use.

As said solvent, not special restriction can suitably be selected according to purpose, for example can enumerate alcohols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, sec-butyl alcohol, n-hexyl alcohol; Ketones such as acetone, methyl ethyl ketone, hexone, cyclohexanone, isobutyrone; Ester classes such as ethyl acetate, butyl acetate, n-amyl acetate, dimethyl suflfate, ethyl propionate, dimethyl phthalate, ethyl benzoate and methoxy propyl yl acetate; Toluene, xylene, benzene, ethylbenzene etc. are aromatic hydrocarbon based; Phenixin, triclene, chloroform, 1,1, halogenated hydrocarbons such as 1-trichloroethanes, methylene chloride, monochloro-benzene; Tetrahydrofuran, diethyl ether, glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxyl-ethers such as 2-propyl alcohol; Dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, sulfolane etc.They can use separately a kind or and with more than 2 kinds.In addition, also can add known surfactant.

Then, can on said supporter, apply said photosensitive composite solution, make its drying, form photographic layer, make pattern and form material.

Coating method as said photosensitive composite solution; 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 be about 30 seconds～15 minutes under 60～110 ℃ the temperature usually.

(photosensitive laminate)

Said photosensitive laminate be on matrix, have said photographic layer of the present invention at least, range upon range of other layers of suitably selecting according to purpose form.

-matrix-

Said matrix should become be formed with photographic layer be processed matrix or transfer printing has pattern of the present invention to become the transfer printing body of the photographic layer at least of material; Not special restriction; Can suitably select according to purpose, for example can to matrix, select arbitrarily from the high matrix of surface smoothing property with surface that convex-concave is arranged.Preferred tabular matrix can use so-called substrate.Particularly, can enumerate known printed-wiring board (PWB) manufacturing with substrate, glass plate (for example soda-lime glass plate etc.), synthetic resin property film, paper, sheet metal etc.

[manufacturing approach of photosensitive laminate]

Manufacturing approach as said photosensitive laminate; As first mode; Can enumerate in the surface applied of said matrix and the method for dry said photosensitive polymer combination solution; As second mode, can enumerate to the photographic layer at least in the photosensitive film of the present invention heat and pressurize at least a, and transfer printing simultaneously and then range upon range of method.

It is on said matrix, to apply and dry said photosensitive polymer combination solution that said first mode is divided the manufacturing approach of photosensitive laminate, thereby forms photographic layer.

As said coating and dry method; Not special restriction; Can suitably select according to purpose, for example preferred on the surface of said matrix, make material dissolves, the emulsification that contains in the said photographic layer or be scattered in water or solvent; Preparation photosensitive composite solution, thus directly apply and the range upon range of method of dry this solution.

As the not special restriction of the solvent of said photosensitive composite solution, can suitably select according to purpose, can enumerate with said photosensitive film in the identical solvent that uses.They can use a kind of separately or and with two or more.In addition, also can add known surfactant.

As said coating method and drying condition, not special restriction can suitably not selected according to purpose, and carries out under identical method of in said photosensitive film, using and the condition.

The manufacturing approach of the photosensitive laminate of said second mode is the folded photosensitive film of the present invention of at least one side's boundary layer that the Surface Edge at said matrix heats and pressurizes.Wherein, said photosensitive film has under the situation of said protective film, preferably peels off this protective film, thereby overlapping said photographic layer carries out range upon range of on said matrix.

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, not special restriction can suitably not selected according to purpose, for example can preferably enumerate laminating machine (for example MODEL8B-720-PH, great achievement laminating machine (strain) system) etc.

Pattern of the present invention becomes material and said photosensitive laminate owing to can form the pattern that ageing stability is outstanding, the development residue is few, height is meticulous of high sensitivity and high-resolution, adhesiveness and sensitivity; 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 various patterns; The manufacturings of pull etc. can be preferred for pattern apparatus for converting of the present invention and pattern formation method especially.

(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 such as developing procedure of suitable selection.

In addition, said pattern apparatus for converting of the present invention communicates with the explanation of said permanent pattern formation method of the present invention and is clear and definite in addition.

[exposure process]

Said exposure process is the operation that photographic layer of the present invention is made public.The material of said photographic layer of the present invention and matrix as stated.

Object as said exposure; So long as said photographic layer gets final product; Not special restriction can suitably be selected according to purpose, for example; As stated, thus preferably become the photographic layer in the photosensitive laminate that material forms to carry out to the folded pattern of at least one side's boundary layer of heating in the matrix top and pressurizeing.

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 said analogue exposure, not special restriction can suitably be selected according to purpose, for example can enumerate the photomask by the pattern with regulation, the method for using (surpassing) high-pressure sodium lamp, xenon lamp, Halogen lamp LED etc. to make public.

As digit explosure; So long as the exposure of need not said photomask carrying out gets final product; Not special restriction can suitably not selected according to purpose, and the photohead that possesses light irradiating means and optical modulator body at least and any at least of said photographic layer are moved; Simultaneously, thus utilize the light that the corresponding pattern-information modulation of said optical modulator body penetrates from said light irradiating means and from said photohead said photographic layer shone simultaneously and make public.

As the light source that uses in the said digit explosure; Get final product near infrared light source so long as send from ultraviolet; Not special restriction can suitably not selected according to purpose, for example can use the known light sources such as fluorescent tube or laser of (surpassing) high-pressure sodium lamp, xenon lamp, carbon arc lamp, Halogen lamp LED and used in copy machines lamp; Wherein preferred (surpassing) high-pressure sodium lamp, more preferably laser.

(surpassing) high-pressure sodium lamp is the discharge lamp of sealing mercury in silica glass tube etc., and the vapor pressure of mercury is set in the device that high value improves luminescence efficiency.In the bright line spectrum, can use with ND filtrator etc. and have only the bright line spectrum of a kind of wavelength, also can use light with multiple bright line spectrum.

" laser " of said laser is that the initial of Light Amplification by Stimulated Emission ofRadiation (utilizing the amplification of the light of being excited to penetrate of light) is called for short.As the device that sends said laser, be to be utilized in the phenomenon of inducing ejaculation that takes place in the material with rotation distribution, utilize amplification, the vibration of light wave, creation coherence, monochromatic oscillator and amplifier that directivity is stronger.

As the exciting media of said laser, crystallization, glass, liquid, pigment, gas etc. are arranged, can from these media, use known laser such as Solid State Laser, liquid laser, gas laser, semiconductor laser.

Particularly,, Ar ion laser (364nm, 351nm), Kr ion laser (356nm, 351nm), He-Cd laser (325nm) can be enumerated,, YAG laser, YVO can be enumerated as Solid State Laser as gas laser ₄Laser (1,064nm) YAG laser or YVO ₄2 times of ripples (532nm) of laser, 3 times of ripples (355nm), 4 times of ripples (266nm), waveguide wavelength conversion element and AlGaAs, the semi-conductive combination of InGaAs (380～400nm), the combination of waveguide wavelength conversion element and AlGaInP or AlGaAs semiconductor t (300～350nm), AlGaInN (350～470nm) etc.As preferred laser wherein,, can enumerate AlGaInN semiconductor laser (commercially available InGaN based semiconductor laser 375nm or 405nm) 355nm laser for high output aspect throughput rate from the cost aspect.

Said Wavelength of Laser for example is preferably 200～1,500nm, and 300～800nm more preferably, and then be preferably 330～500nm, be preferably 350～420nm especially.

-optical modulator body-

As said optical modulator body, representative method can be enumerated preferably has n drawing section, and corresponding said pattern-information is controlled the method for said drawing section.Particularly, can enumerate the spatial optical modulation element (SLM of DMD (DMD), MEMS (microelectromechanical systems (Micro Electro MechanicalSystems)) type; Spatial light modulator (Spece LightModulator)), 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.

Use under the situation of said DMD, be radiated on the said DMD by appropriate optical system, come comfortable DMD to go up the reflected light of each mirror of two-dimensional arrangements,, on photographic layer, form the picture of the luminous point that is arranged in two dimension through other optical system etc. from the light of light source.Can be with the form that is described below; To making public of photographic layer comprehensively; If that is: directly between luminous point and luminous point, do not make public; And make the picture of the luminous point of above-mentioned two-dimensional arrangements, and the direction of the orientation slight inclination of two dimension is shaken relatively, and the luminous point of rear row makes public between the luminous point of initial row and luminous point.Said DMD is through each mirror angle of control, and the above-mentioned luminous point of connection-shutoff (ON-OFF) can form picture pattern.Through arrange using photohead with so said DMD, substrate that can corresponding various width.

In above-mentioned DMD, the brightness of above-mentioned luminous point only turns on and off 2 grades, if but use mirror grade type spatial modulation element, then can carry out the exposure of 256 grades.

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.

On the other hand, other exemplary process of said optical modulator body can be enumerated the method for using polygon prism.At this, polygon prism (polygon mirror) is meant the rotating member of the plane reflection face that has row around.Reflected illumination is from the light of light source on photographic layer for said polygon prism, and catoptrical luminous point is by the rotation sweep of this level crossing.Through substrate is moved relative to this direction of scanning with meeting at right angles, can comprehensively making public to the photographic layer on the substrate.Then, can form picture pattern through connection-shutoff from the intensity of light source or control it as medium tone.At this moment, can become multi beam, shorten sweep time through making light from light source.

As optical modulator body of the present invention, except above-mentioned, can also enumerate the spy and open the example that the use polygon prism put down in writing in the flat 5-150175 communique is described; Obtain to the vision of record the part of the image of lower layer in the special table 2004-523101 communique (International Publication the 2002/039793rd trumpeter's volume), utilize the device that uses polygon prism, make the position of upper layer and the position consistency of lower layer, the example of exposure; The spy opens the example that device that the utilization of putting down in writing in the 2004-56080 communique has DMD makes public; The exposure device that possesses polygon prism, the spy who puts down in writing in the special table 2002-523905 communique opens the example that the exposure device that possesses polygon prism, the spy that put down in writing in the 2001-255661 communique open the combination DMD that puts down in writing in the 2003-50469 communique, LD, multiple-exposure; The spy opens the example that the position of putting down in writing in the 2003-156853 communique that utilizes substrate changes the exposure method of exposure; The spy opens the example etc. of the exposure method of the dislocation adjustment of putting down in writing in the 2005-43576 communique.

-light irradiating means-

As said light irradiating means is the illuminating method of light; Not special restriction; Can suitably select said exposure light source according to purpose, preferably enumerate compound and then shine the light more than 2 kinds, especially preferably enumerate the laser (closing ripple laser) of the compound light more than 2 kinds of irradiation from these light sources.

As the said illuminating method that closes ripple laser; Not special restriction; Can suitably select according to purpose; For example can preferably enumerate utilize have multiple LASER Light Source, multimode optical fiber and carry out optically focused and make its mechanism in the compound light-gathering optics system of said multimode optical fiber from the laser that this multiple LASER Light Source shines respectively, constitute the method that ripple laser is closed in also irradiation.

To the beam diameter of said laser, not special restriction can suitably be selected according to purpose, from the viewpoint of dark color from the exploring degree in next door, at the 1/e of Gauss (Gaussian) light beam ²Be preferably 5～30 μ m under the value, more preferably 7～20 μ m.

In the present invention, preferred correspondence image pattern carries out spatial light modulation to laser.Thereby, the preferred for this reason said DMD that uses as spatial optical modulation element.

As exposure device with said optical modulator body and said light irradiating means; For example can use the spy to open 2005-222039 communique, spy and open the device that 2005-258431 communique, spy are opened record in the 2006-30966 communique etc., but the exposure device among the present invention not limit by its.

[other operations]

As said other operations, not special restriction can be enumerated in the operation from known pattern forms and suitably selected, and for example can enumerate developing procedure, etching work procedure, plating operation, curing process etc.

-developing procedure-

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, can suitably select according to the development property of said photographic layer, for example preferably be about 25～40 ℃.

Said developer solution also can with surfactant, foam-breaking agent, organic base (for example ethylenediamine, monoethanolamine, tetramethyl amine oxyhydroxide, diethylene triamine, 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.

-etching work procedure-

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.In addition, also can use known sand-blast.

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

-plating operation-

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 slow) 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 metal line pattern (circuit) with etching lift-off processing etc.

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

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

Manufacturing approach as printed-wiring board (PWB) with hole portions such as reach through hole or through holes; 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 its 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 the supporter 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-clad laminates 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, peel off this protective film, use backer roll, press sticking said pattern to become the photographic layer in the material, make it contact (range upon range of operation) with the surface of substrate with printed-wiring board (PWB) formation in said pattern.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 extrusion coater, not special restriction, for example preferred 0.1～1MPa.

As the sticking speed of said pressure, 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 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 as required.

At the moment, under the situation of unstripped said supporter still, peel off said supporter (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, the coat of metal of reach through hole becomes the shape of remaining 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 backflow property (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.

Pattern apparatus for converting of the present invention and pattern formation method are because preferred use said pattern of the present invention 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 various patterns, the manufacturing of pull etc.

Embodiment

Below utilize embodiment that the present invention is explained more specifically, but the present invention not limit by these.

(embodiment 1)

-pattern become the manufacturing of material-

As said supporter; (eastern レ corporate system 16FB50), applies also dry by the following photosensitive composite solution that constitutes of forming to the PET of thick 16 μ m (polyethylene terephthalate) film; Form the photographic layer of thick 30 μ m; Then,, make said pattern and become material at the thick polyethylene film of this photographic layer laminated 25 μ m with laminating machine.

[composition of photosensitive composite solution]

Methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer (multipolymer is formed (mass ratio): 25/8/30/37, and the matter average molecular weight: 68,800, Tg:105 ℃) ... 17.5 mass parts

The polymerizable monomer of representing with following formula M-1 ... 6.0 mass parts

1/2 mol ratio addition product of decamethylene diisocyanate and Fourth Ring oxygen ethene monomethyl acrylic ester ... 6.0 mass parts

Trimethylolpropane epoxy pronane modification triacrylate (East Asia Synesis Company system, ア ロ ニ Star Network ス M-310) ... 2.0 mass parts

The sensitizer of representing with following formula S-1 ... 0.09 mass parts

2,2 ', 5-three-(Chloro-O-Phenyl)-4-(3; The 4-Dimethoxyphenyl)-4 '; (Photoepolymerizationinitiater initiater utilizes 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole and 2 to 5 '-diphenyl-di-imidazoles; The compound that the oxidative coupling of 4-pair-(Chloro-O-Phenyl)-5-[3, the 4-Dimethoxyphenyl]-imidazoles is made (with reference to special table 2002-507004 communique)) ... 2.2 mass parts

Toluenesulfonamide ... 1.0 mass parts

Carboxyl benzotriazole ... 0.01 mass parts

The peacock green oxalates ... 0.02 weight portion

LCV ... 0.29 weight portion

The 30 quality % concentration article (methyl ethyl ketone solution) of F780F (big Japanese ink (strain) system) ... 0.05 mass parts

Methyl ethyl ketone ... 40 mass parts

1-methoxyl-2-propyl alcohol ... 20 mass parts

Wherein, (multipolymer is formed (mass ratio): it is 0.554 that I/O value 25/8/30/37) is calculated as stated to said methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer.

[changing 1]

M-1

Wherein, in said formula M-1, EO representative ring oxidative ethane, PO representative ring Ethylene Oxide, PO also can be for following structural formula (i) reach (ii) any one, and the mean value of r+s is 10, and the mean value of p+q is 4.

[changing 2]

Structural formula (i) structural formula (ii)

[changing 3]

The preparation of-photographic layer duplexer-

As said matrix; (there is not reach through hole the surface having been carried out grinding, washing, dry copper-clad laminates; The thick 12 μ m of copper) on the surface; Peel off the protective film that said pattern becomes material, use laminating machine (MODEL8B-720-PH, great achievement laminating machine (strain) system) to press sticking this pattern to become the photographic layer of material simultaneously; It is contacted with said copper-clad laminates, make the duplexer that has stacked gradually said copper-clad laminates, said photographic layer, said pet film (supporter).

Pressing stick spare is 105 ℃ of extrusion coater temperature, extrusion coater pressure 0.3MPa, range upon range of speed 1m/ minute.

These photosensitive composites, pattern are become material and photosensitive laminate, utilize following method, carry out the evaluation of the covering property that has that it's too late of the shortest development time, sensitivity, exploring degree, adhesiveness, storage stability, development residue.Result beyond the shortest development time is as shown in table 1.

< the shortest development time >

Peel off polyethylene terephthalate (supporter) from said photosensitive laminate; 1 quality % aqueous sodium carbonate with 30 ℃ of comprehensive injections of the said photographic layer of pressure on copper-clad laminates of 0.15MPa; Mensuration is removed the needed time of photographic layer on the copper-clad laminates from beginning to spray aqueous sodium carbonate to dissolving, with it as the shortest development time.

As a result, the shortest said development time is 19 seconds (following example is also identical).

< sensitivity >

The said pattern of said photosensitive laminate is become the photographic layer of material; From pet film (supporter) side; Use is opened the pattern apparatus for converting of putting down in writing in the 2006-30966 communique as the spy of the LASER Light Source with 405nm of said light irradiating means, and irradiation is with 2 ^1/6Doubly at interval, from 0.1mJ/cm ²To 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 15 minutes; Peel off pet film (supporter) from said photosensitive laminate then; With comprehensive injection aqueous sodium carbonate (30 ℃, 1 quality %) of spray pressing the said photographic layer of 0.15MPa on copper-clad laminates, injecting time is 2 times of said the shortest development time; Uncured zone is removed in dissolving, measures the thickness of residual consolidation zone.

Then, the curve map of the relation between the exposure of drafting light and the thickness of cured layer obtains sensitivity curve.Can know from the sensitivity curve that obtains like this, consolidation zone thick become with exposure before luminous energy during same thickness, solidify necessary luminous energy for making photographic layer.The luminous energy (sensitivity) essential for the said photographic layer of trying to achieve is like this solidified is as shown in table 1.

In addition, said pattern apparatus for converting has the optical modulator body that is made up of said DMD.

< exploring degree >

Use with said identical method and make said photosensitive laminate, at room temperature (23 ℃ 55%RH) leave standstill 10 minutes.From the pet film (supporter) of the said photosensitive laminate that obtains; Use said pattern apparatus for converting, with line (line)/space (space)=1/1, from the wide 5 μ m of line (line)～100 μ m; With per 1 μ m, carry out the exposure of each live width.The exposure of this moment is the necessary luminous energy of photographic layer that the said pattern that is solidificated in said sensitivity determination becomes material.After at room temperature leaving standstill 10 minutes, peel off pet film (supporter) from said photosensitive laminate.With comprehensive injection of spray pressing the said photographic layer of 0.15MPa on copper-clad laminates 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-clad laminates 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.

< adhesiveness >

Use said pattern apparatus for converting; With line (line)/space (space)=1/5; Pattern to the wide 10 μ m of line (line)～100 μ m makes public, and except injecting time is 6 times of said the shortest development time, carries out the evaluation method identical operations with said exploring degree; In the line of solidified resin pattern, measure unusual minimum feature such as the crust that do not wrinkle, its adhesion is estimated.Thereby the more little adhesiveness of numerical value is good more.

< storage stability >

-through time colour developing-

Under 40 ℃, the condition of relative humidity 70%, when the photosensitive composite solution of having prepared is placed 7 days, with criterion, the visual valuation LCV through the time colour rendering (through the time spreadability).

Zero ... Not colour developing fully

△ ... Some visible colour developings

* ... Colour developing significantly

-crystallization is separated out has or not-

When the photosensitive composite solution that 0 ℃ condition held was prepared in 7 days, with criterion, what the crystallization of visual valuation Photoepolymerizationinitiater initiater was separated out has or not.

Zero ... There is not separating out of crystallization fully

△ ... Separating out of some visible crystallizations

* ... Separating out of significantly visible crystallization

The ageing stability of-sensitivity-

Utilize and observed the photosensitive composite solution that has or not that said crystallization is separated out, make said pattern and become material and preparation photosensitive laminate, utilize said method to measure sensitivity.

The fusion of-edge-

Become material with the up-coiler said pattern of reeling, make pattern and form the reels of material paper bowl.

The said pattern that obtains with coaxial cutting machine (slitter) cutting (slit) becomes the material platen roller, on the ABS resin rounding tubular volume core of, internal diameter 76mm long at 300mm, with the wide coiling 200m of 250mm, makes the photonasty pattern material roller of becoming a useful person.

Become the tube-shape bag (thickness: 80 μ m, moisture-vapor transmission: 25g/m of parcel black polyethylene system on the material in the said pattern that obtains like this ²Below the 24hr), clamp-on polypropylene system sleeve (bush, Block Star シ ユ) at the two ends of axle core.

The sample retention of roller shape that to fill in two ends with said sleeve under 25 ℃, 55%RH 30 days is observed having or not of end face fusion, estimates with criterion.

-evaluation criterion-

Zero: do not confirm the end face fusion, be the state that can use well

△: a part of glossy at end face is in the state (operating limit) of the end face fusion that some amounts take place

*: in that all end face is glossy, be in the state of a large amount of generation end face fusions

< having or not of development residue >

Under the state before said photosensitive laminate is made public, in the dark (shading) use said pattern apparatus for converting through after 14 days; Utilize in the evaluation with said exploring degree identical method to make public and develop, the product after the use is through the surface of the copper-clad laminates that in this duplexer, exposes; With 0.25MPa; Spray 36 seconds iron chloride mordant (etchant) (etching solution that contains ferric trichloride, 40 ° of Baumes, 40 ℃ of liquid temperature); The copper layer that the zone of exposing that is covered by cured layer is removed not in dissolving carries out etch processes.

With criterion, the copper residual (development residue) of unexposed the non-pixel portions of visual valuation after said etch processes.

-evaluation criterion-

Zero ... There is not copper residual

△ ... There are some copper residual, but do not influence use

* ... There is copper residual

< covering property >

Copper-clad laminates in the said photosensitive laminate is replaced the copper-clad laminates for the reach through hole with 200 diameter 4mm; In addition; Likewise make the photosensitive laminate of covering property evaluation usefulness with said photosensitive laminate; The condition held of room temperature (23 ℃, relative humidity 55%) 10 minutes.

Then, from the pet film (supporter) of the photosensitive laminate of said making, use said pattern apparatus for converting, comprehensively the making public of the photographic layer in this photosensitive laminate.

The exposure of this moment is to make said pattern 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 photosensitive laminate.With the aqueous sodium carbonate (30 ℃, 1 quality %) of comprehensive injection of spray pressing the said photographic layer of 0.15MPa on said copper-clad laminates as said developer solution, injecting time is 2 times of said the shortest development time.

The cured layer that on the reach through hole peristome, forms (masked film) in the said copper-clad laminates that obtains like this with microscopic examination peel off or defective such as breakage have or not the incidence of counting defective.

(embodiment 2)

In embodiment 1, with 2,2 ', 5-three-(Chloro-O-Phenyl)-4-(3; The 4-Dimethoxyphenyl)-4 ', it is 2,2 ' that 5 '-diphenyl-di-imidazoles replaces; 4,4 '-four-(Chloro-O-Phenyl)-5,5 '-(3; The 4-Dimethoxyphenyl)-and di-imidazoles 2.2 mass parts, in addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

(embodiment 3)

In embodiment 1, with 2,2 ', 5-three-(Chloro-O-Phenyl)-4-(3; The 4-Dimethoxyphenyl)-4 ', it is 2,2 '-two-(Chloro-O-Phenyl)-4 that 5 '-diphenyl-di-imidazoles replaces, 4 '; 5,5 '-four-(m-methoxyphenyl)-1,2-di-imidazoles, 2,2 '-two (2-ethoxyl phenenyl)-4; 4 ', 5,5 '-tetraphenyl-1; 1 '-di-imidazoles, 2.6 mass parts in addition, are likewise carried out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

(embodiment 4)

In embodiment 1, with 2,2 '; 5-three-(Chloro-O-Phenyl)-4-(3, the 4-Dimethoxyphenyl)-4 ', it is 2 that 5 '-diphenyl-di-imidazoles replaces; 2 ', 5-three-(Chloro-O-Phenyl)-4-(3, the 4-Dimethoxyphenyl)-4 '; 5 '-diphenyl-di-imidazoles 3 mass parts in addition, likewise carries out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

(embodiment 5)

In embodiment 1; Methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer is replaced being methacrylic acid/methyl methacrylate/styrene/methacrylic acid 2-ethylhexyl ester copolymer (multipolymer composition (mass ratio): 25/15/40/20; The matter average molecular weight: 130,000, Tg:93 ℃); In addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

Wherein, (multipolymer is formed (mass ratio): it is 0.520 that I/O value 25/15/40/20) is calculated as stated to said methacrylic acid/methyl methacrylate/styrene/methacrylic acid 2-ethylhexyl ester copolymer.

(embodiment 6)

In embodiment 1; Methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer is replaced being methacrylic acid/methyl methacrylate/styrol copolymer (multipolymer composition (mass ratio): 25/29/46; The matter average molecular weight: 43,000, Tg:127 ℃); In addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

Wherein, (multipolymer is formed (mass ratio): it is 0.550 that I/O value 25/29/46) is calculated as stated to said methacrylic acid/methyl methacrylate/styrol copolymer.

(embodiment 7)

In embodiment 1; Methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer is replaced being methacrylic acid/methyl methacrylate/styrol copolymer (multipolymer composition (mass ratio): 20/56/24; The matter average molecular weight: 75,000, Tg:123 ℃); In addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

Wherein, (multipolymer is formed (mass ratio): it is 0.645 that I/O value 20/56/24) is calculated as stated to said methacrylic acid/methyl methacrylate/styrol copolymer.

(embodiment 8)

In embodiment 1; Methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer is replaced being methacrylic acid/styrol copolymer (multipolymer composition (mass ratio): 28/72; The matter average molecular weight: 53,100, Tg:129 ℃); In addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

Wherein, (multipolymer is formed (mass ratio): it is 0.433 that I/O value 28/72) is calculated as stated to said methacrylic acid/styrol copolymer.

(embodiment 9)

In embodiment 1; Methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer is replaced being methacrylic acid/styrol copolymer (multipolymer composition (mass ratio): 20/80; The matter average molecular weight: 43,700, Tg:120 ℃); In addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

Wherein, (multipolymer is formed (mass ratio): it is 0.328 that I/O value 20/80) is calculated as stated to said methacrylic acid/styrol copolymer.

(embodiment 10)

In embodiment 1; Methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer is replaced being methacrylic acid/methyl methacrylate/styrene/methacrylic acid 2-ethylhexyl ester copolymer (multipolymer composition (mass ratio): 25/22/40/13; The matter average molecular weight: 55,000, Tg:105 ℃); In addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

Wherein, (multipolymer is formed (mass ratio): it is 0.543 that I/O value 25/22/40/13) is calculated as stated to said methacrylic acid/methyl methacrylate/styrene/methacrylic acid 2-ethylhexyl ester copolymer.

(embodiment 11)

In embodiment 1; Methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer is replaced being methacrylic acid/methyl methacrylate/styrol copolymer (multipolymer composition (mass ratio): 29/19/52; The matter average molecular weight: 49,900, Tg:131 ℃); In addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

Wherein, (multipolymer is formed (mass ratio): it is 0.552 that I/O value 29/19/52) is calculated as stated to said methacrylic acid/methyl methacrylate/styrol copolymer.

(embodiment 12)

In embodiment 1; Methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer is replaced being methacrylic acid/methyl methacrylate/styrol copolymer (multipolymer composition (mass ratio): 29/31/40; The matter average molecular weight: 60,500, Tg:132 ℃); In addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

Wherein, (multipolymer is formed (mass ratio): it is 0.627 that I/O value 29/31/40) is calculated as stated to said methacrylic acid/methyl methacrylate/styrol copolymer.

(embodiment 13)

In embodiment 1; Methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer is replaced being methacrylic acid/methyl methacrylate/styrol copolymer (multipolymer composition (mass ratio): 25/41/34; The matter average molecular weight: 58,500, Tg:128 ℃); In addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

Wherein, (multipolymer is formed (mass ratio): it is 0.627 that I/O value 25/41/34) is calculated as stated to said methacrylic acid/methyl methacrylate/styrol copolymer.

(embodiment 14)

In embodiment 1, do not add toluenesulfonamide, in addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

(embodiment 15)

In embodiment 1, do not add carboxyl benzotriazole, in addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

(embodiment 16)

In embodiment 1, do not add toluenesulfonamide and carboxyl benzotriazole, in addition, likewise carry out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

(comparative example 1)

In embodiment 1, with 2,2 '; 5-three-(Chloro-O-Phenyl)-4-(3, the 4-Dimethoxyphenyl)-4 ', it is 2 that 5 '-diphenyl-di-imidazoles replaces; 2 '-two (Chloro-O-Phenyl)-4,4 ', 5; 5 '-tetraphenyl di-imidazoles, 2.2 mass parts in addition, are likewise carried out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

(comparative example 2)

In embodiment 1; Methacrylic acid/methyl methacrylate/styrene/methacrylic acid benzyl ester multipolymer is replaced being n-butyl acrylate/ethyl acrylate/methyl methacrylate/methacrylic acid copolymer (multipolymer composition (mass ratio): 20/13/42/25; Matter average molecular weight: 50; 000), in addition, likewise carries out the evaluation of the covering property that has that it's too late of sensitivity, exploring degree, adhesiveness, storage stability, development residue with embodiment 1.The result is as shown in table 1.

Wherein, said n-butyl acrylate/ethyl acrylate/methyl methacrylate/methacrylic acid copolymer (multipolymer is formed (mass ratio): calculate as stated to surpassing 0.650 by I/O value 20/13/42/25).

Can judge from the result of table 1; Containing the I/O value at bonding agent contains among the embodiment 1～16 of six aryl di-imidazolium compoundss of possess hydrophilic property base at 0.300～0.650 polymkeric substance, said Photoepolymerizationinitiater initiater; Sensitivity, exploring degree, adhesiveness, storage stability and covering property are good, and the development residue is few.Particularly have among the embodiment 1～3 and embodiment 5～16 of six aryl benzimidazole compounds of methoxyl, be judged as high sensitivity in use.In addition, in the embodiment that contains toluenesulfonamide and carboxyl benzotriazole 1～13, do not develop residue and covering property are outstanding.

Utilize the present invention; Can solve problem in the past, can provide a kind of pattern that can form the pattern that ageing stability is outstanding, the development residue is few, height is meticulous of high sensitivity and high-resolution, adhesiveness and sensitivity to become material and use this pattern to become the pattern formation method of material.

Pattern of the present invention becomes material owing to can high form the patterns such as wiring pattern that ageing stability is outstanding, the development residue is few of high sensitivity and high-resolution, adhesiveness and sensitivity meticulously; 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 various patterns, the manufacturing of pull etc.

Pattern apparatus for converting of the present invention and pattern formation method become 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 various patterns; Holographic photography, micromachine, the manufacturing of pull etc. etc.

Claims (8)

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

On supporter, have the photographic layer that constitutes by the photosensitive composite that contains bonding agent, polymerizable compound and Photoepolymerizationinitiater initiater at least and form,

It is 0.300～0.650 polymkeric substance that said bonding agent contains the I/O value, and said Photoepolymerizationinitiater initiater contains six aryl di-imidazolium compoundss of possess hydrophilic property base,

Said six aryl di-imidazolium compoundss are selected from 2, and 2 ', 5-three-(Chloro-O-Phenyl)-4-(3, the 4-Dimethoxyphenyl)-4 ', 5 '-diphenyl-di-imidazoles, 2; 2 ', 4,4 '-four-(Chloro-O-Phenyl)-5,5 '-two-(3, the 4-Dimethoxyphenyl)-di-imidazoles, 2; 2 '-two-(Chloro-O-Phenyl)-4,4 ', 5,5 '-four-(m-methoxyphenyl)-1,2-di-imidazoles and 2; 2 '-two (2-ethoxyl phenenyl)-4,4 ', 5,5 '-tetraphenyl-1,1 '-di-imidazoles.

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

The I/O value is that the glass temperature (Tg) of 0.300～0.650 polymkeric substance is more than 80 ℃.

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

The I/O value is that 0.300～0.650 polymkeric substance contains multipolymer, this multipolymer have derive from styrene, styrene derivative and (methyl) acrylic acid benzyl ester at least any one structural unit and also be alkali-soluble or swellability.

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

Polymerizable compound contains the monomer with epoxypropane base.

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

Contain sensitizer.

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

Contain compound with NH base.

7. a pattern formation method is characterized in that,

At least comprise and become the photographic layer in the material to carry out step of exposing the described pattern of claim 1.

8. pattern formation method according to claim 7, wherein,

Exposure does not use photomask to carry out.