JP2008058636A - Pattern forming material and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming material having high sensitivity and high resolution, excellent in adhesion and temporal stability of sensitivity, and capable of forming a high-definition pattern with less residue on development, and a pattern forming method using the pattern forming material. <P>SOLUTION: The pattern forming material has on a support a photosensitive layer formed of a photosensitive composition comprising at least a binder, a polymerizable compound and a photopolymerization initiator, wherein the binder comprises a polymer having an I/O value of 0.300-0.650 and the photopolymerization initiator comprises a hexaarylbiimidazole compound having a hydrophilic group. The pattern forming method using the pattern forming material is also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a pattern forming material suitable for a dry film resist (DFR) and a pattern forming method using the pattern forming material.

In the field of printed wiring boards, usually, a copper wiring pattern is first formed on a copper clad laminate using DFR. At this time, a pattern forming material made of a photosensitive composition containing a binder, a polymerizable compound, a photopolymerization initiator, and the like is used (see Patent Documents 1 and 2).
In general, the pattern forming material is exposed using a mask. However, in recent years, a digital micromirror device (DMD) or the like is used from the viewpoint of productivity and resolution. A maskless exposure apparatus using a conventional laser beam has been actively studied.

In the pattern forming material, for the purpose of reducing development residue, a pattern forming material using a hexaarylbiimidazole having a hydrophilic group as a photopolymerization initiator in a photosensitive composition has been proposed (Patent Document 3). reference).
However, as the hexaarylbiimidazole compound having a hydrophilic group, a compound further having a chlorine atom is preferably used from the viewpoint of achieving high sensitivity, but even in such a case, when digital exposure is performed sensitivity because not necessarily high beyond 20 mJ / cm ^2, there is a problem that even the resolution and adhesion in the resulting pattern is deteriorated.

  On the other hand, when hexaarylbiimidazole having a hydrophilic group is used, if a coating solution containing a photosensitive composition using a hydrophilic polymer as a binder is left for about 7 days, leuco crystal violet or the like can be obtained. The color former gradually developed color, resulting in a problem that the sensitivity of the pattern forming material was lowered and the stability over time of the sensitivity was poor. Further, hexaarylbiimidazole having a chlorine atom has high crystallinity, and in a coating solution containing a photosensitive composition using the same, crystals are precipitated by low-temperature storage, and this also causes a problem that sensitivity is lowered.

  Therefore, a pattern forming material capable of forming a high-definition pattern with high sensitivity and high resolution, excellent adhesion and sensitivity over time, little development residue, and a pattern forming method using the pattern forming material are still available. It is not provided and the current situation is that further improvement and development is desired.

International Publication No. 01/071428 Pamphlet JP 2004-252421 A Special table 2002-507004 gazette

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention provides a pattern forming material capable of forming a high-definition pattern with high sensitivity and high resolution, excellent adhesion and sensitivity over time, little development residue, and pattern using the pattern forming material. An object is to provide a forming method.

Means for solving the problems are as follows. That is,
<1> A photosensitive layer comprising a photosensitive composition containing at least a binder, a polymerizable compound, and a photopolymerization initiator is provided on a support,
The binder includes a polymer having an I / O value of 0.300 to 0.650, and the photopolymerization initiator includes a hexaarylbiimidazole compound having a hydrophilic group. .
<2> The pattern forming material according to <1>, wherein the hydrophilic group of the hexaarylbiimidazole compound is an alkoxy group.
<3> The pattern forming material according to <2>, wherein the alkoxy group is a methoxy group.
<4> The pattern forming material according to any one of <1> to <3>, wherein the glass transition temperature (Tg) of the polymer having an I / O value of 0.300 to 0.650 is 80 ° C. or higher. .
<5> A polymer having an I / O value of 0.300 to 0.650 includes a copolymer, and the copolymer is a structural unit derived from at least one of styrene, a styrene derivative, and benzyl (meth) acrylate. The pattern forming material according to any one of <1> to <4>.
<6> The pattern forming material according to any one of <1> to <5>, wherein the polymer having an I / O value of 0.300 to 0.650 is alkali-soluble or swellable.

<7> The pattern forming material according to any one of <1> to <6>, wherein the polymerizable compound includes a monomer having at least one of a urethane group and an aryl group.
<8> The pattern forming material according to any one of <1> to <7>, wherein the polymerizable compound includes a monomer having a propylene oxide group.
<9> The pattern forming material according to any one of <1> to <8>, including a sensitizer.
<10> The pattern forming material according to <9>, wherein the sensitizer is a hetero-fused ketone compound.
<11> The pattern forming material according to any one of <1> to <10>, including a compound having an NH group.
<12> The pattern forming material according to any one of <1> to <11>, containing 10 to 90% by mass of a binder and 5 to 90% by mass of a polymerizable compound.

<13> The pattern forming material according to any one of <1> to <12>, wherein the support includes a synthetic resin and is transparent.
<14> The pattern forming material according to any one of <1> to <13>, wherein the support is elongated.
<15> The pattern forming material according to any one of <1> to <14>, which is long and wound in a roll shape.
<16> The pattern forming material according to any one of <1> to <15>, having a protective film on the photosensitive layer.
<17> The pattern forming material according to any one of <1> to <16>, wherein the photosensitive layer has a thickness of 1 to 100 μm.

<18> A pattern forming method comprising at least exposing the photosensitive layer in the pattern forming material according to any one of <1> to <17>.
<19> The pattern forming method according to <18>, wherein the exposure is performed without using a photomask.
<20> The pattern forming method according to any one of <18> to <19>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
<21> Exposure is emitted from the light irradiation unit to the photosensitive layer while moving at least one of the exposure head including at least a light irradiation unit and a light modulation unit, and the photosensitive layer. The pattern forming method according to any one of <19> to <20>, wherein the light is irradiated from the exposure head while modulating light according to pattern information by the light modulation unit.
<22> The light modulation unit according to <21>, wherein the light modulation unit is capable of controlling any less than n pixel elements arranged continuously from n pixel elements in accordance with pattern information. This is a pattern forming method.
<23> The pattern forming method according to any one of <21> to <22>, wherein the light modulation unit is a spatial light modulation element.
<24> The pattern forming method according to <23>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<25> The pattern forming method according to any one of <21> to <24>, wherein the exposure is performed through an aperture array.
<26> The pattern forming method according to any one of <21> to <25>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
<27> The light irradiation unit includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects and couples the laser beams irradiated from the plurality of lasers to the multimode optical fiber. <21> to the pattern forming method according to any one of <26>.
<28> The pattern forming method according to <27>, wherein the wavelength of the laser beam is 350 to 420 nm.

<29> The method for forming a permanent pattern according to any one of <18> to <28>, wherein the photosensitive layer is developed after the exposure.
<30> The pattern forming method according to <29>, wherein after the development, at least one of an etching process and a plating process is performed.

  <31> A pattern formed by the pattern forming method according to any one of <18> to <30>.

  The pattern forming material of the present invention has a photosensitive layer comprising a photosensitive composition containing at least a binder, a polymerizable compound, and a photopolymerization initiator on a support, and the binder has an I / O value of 0. .300 to 0.650 polymer, and the photopolymerization initiator includes at least one hexaarylbiimidazole compound having a hydrophilic group. As a result, it is possible to form a high-definition pattern with high sensitivity and high resolution, excellent adhesion and sensitivity over time, little development residue.

  Since the pattern forming method of the present invention uses the pattern forming material of the present invention, it is possible to form a high-definition pattern with high sensitivity and high resolution, excellent adhesion and sensitivity over time, little development residue. In particular, a pattern can be formed with high production by performing direct patterning without using a photomask.

  According to the present invention, a pattern forming material that can solve conventional problems, has high sensitivity and high resolution, is excellent in adhesion and sensitivity over time, has little development residue, and can form a high-definition pattern; And a pattern forming method using the pattern forming material.

(Pattern forming material)
The pattern forming material of the present invention has a photosensitive layer made of a photosensitive composition containing a predetermined component on a support, and is laminated with other appropriately selected layers such as a cushion layer according to the purpose. Do it.

<Photosensitive layer>
The photosensitive layer includes at least a binder, a polymerizable compound, and a photopolymerization initiator, preferably includes at least one of a sensitizer and a compound having an NH group, and other components appropriately selected as necessary. It consists of a photosensitive composition containing.

-Photopolymerization initiator-
The photopolymerization initiator includes at least one hexaarylbiimidazole compound having a hydrophilic group.

  The hexaarylbiimidazole compound is usually 2,4,5-triphenylimidazolyl dimer and is well known as a photopolymerization initiator. Photosensitive compositions using the same include, for example, Chambers US Pat. No. 3,479,185, Chang et al. US Pat. No. 3,549,367, Cescon US Pat. No. 3,684,557. Dessauer U.S. Pat. Nos. 4,252,887 and 4,311,783; Chambers et al. U.S. Pat. No. 4,264,708; Wada et al. U.S. Pat. No. 4,410. 621, Tanaka et al., US Pat. No. 4,459,349, and Sheets US Pat. No. 4,622,286.

In the present invention, a hexaarylbiimidazole compound having a hydrophilic group is used from the viewpoint of reducing development residues. Here, the hydrophilic group means a group that can easily associate with water.
The hydrophilic group in the hexaarylbiimidazole compound having a hydrophilic group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a hydroxy group, a dialkylamino group such as diethylamino and dipropylamino, Carboxylic acid groups and alkyl esters thereof, alkoxy groups such as methoxy and ethoxy, amides and salts, and the like can be mentioned. Among these, alkoxy groups are preferable and methoxy groups are particularly preferable from the viewpoint of high sensitivity. Moreover, the hexaaryl biimidazole compound which has these hydrophilic groups may be used individually by 1 type, and may use 2 or more types together.

  The hexaarylbiimidazole compound having a hydrophilic group preferably has at least one chlorine atom, and more preferably has two chlorine atoms, from the viewpoint of increasing sensitivity.

  Examples of the hexaarylbiimidazole compound having a hydrophilic group include 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenyl- Biimidazole, 2,2 ', 4,4'-tetra- (o-chlorophenyl) -5,5'-bis- (3,4-dimethoxyphenyl) -biimidazole, 2,2'-bis- (o- Chlorophenyl) -4,4 ′, 5,5′-tetra- (m-methoxyphenyl) -1,2-biimidazole, 2,2′-bis (2-ethoxyphenyl) -4,4 ′, 5,5 Preferred examples include '-tetraphenyl-1,1'-biimidazole. Among these, 2,2 ', 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4', 5'-diphenyl-biimidazole is particularly preferable.

  The hexaarylbiimidazole compound having a hydrophilic group is usually prepared by oxidative coupling of substituted triphenylimidazole. The preparation of substituted triphenylimidazoles is disclosed in US Pat. No. 3,784,557 to Cescon and US Pat. No. 4,311,783 to Dessauer. For oxidative coupling, Hayashi et al., Bull. Chem. Soc. Japan 33, 565 (1960), Zimmerman et al., Angew. Chem. 73, 808 (1961). For the preparation of 2,2 ', 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4', 5'-diphenyl-biimidazole, see Sheets U.S. Pat. No. 4,622. No. 286.

  The hexaarylbiimidazole compound having a hydrophilic group may be used without completely separating and purifying a reaction mixture containing one or more of them. Such reaction mixtures include 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4) as described in Sheets US Pat. No. 4,622,286. -Dimethoxyphenyl) -4 ', 5'-diphenyl-biimidazole-containing mixtures, in particular 2- (o-chlorophenyl) -4,5-diphenylimidazole and 2,4-bis- (o-chlorophenyl) -5 It is an oxidative coupling product of [3,4-dimethoxyphenyl] -imidazole, and the reaction product is 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 A mixture of 2,4,5-triphenylimidazolyl dimer, which is', 5'-diphenyl-biimidazole, can be used.

  In the hexaarylbiimidazole compound having a hydrophilic group, a hydrogen donor compound may be used together. Examples of the hydrogen donor include organic thiols such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, tertiary amine, N-phenylglycine, 1,1-dimethyl-3,5- Examples thereof include compounds containing at least one of diketocyclohexane, ether, ester, alcohol, allyl hydrogen, benzyl hydrogen, acetal, aldehyde, amide, and the like. Such hydrogen donors are discussed in US Pat. No. 3,390,996 to MacLachlan.

  The photopolymerization initiator may further include, for example, compounds described in “0288” to “0309” of JP-A-2005-258431.

  The content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 15% by mass in the photosensitive composition.

-Binder-
The binder is a polymer having an I / O value of 0.300 to 0.650. In the present invention, “(meth) acryl” means either “acryl” or “methacryl”.

The polymer having an I / O value of 0.300 to 0.650 is not particularly limited as long as it is 0.300 to 0.650, and can be appropriately selected according to the purpose. When the I / O value exceeds 0.650, there is a problem that the adhesiveness is lowered or the edge roughness is increased.
For example, the upper limit value of the I / O value is more preferably 0.630 and particularly preferably 0.600 from the viewpoint of further improving at least one of resolution and tent property.
For example, the lower limit value of the I / O value is more preferably 0.350 and particularly preferably 0.400 from the viewpoint of improving developability.
As a method for adjusting the I / O value of the binder, by appropriately selecting at least one of the type of monomer constituting the copolymer and the polymerization ratio (content) when the monomer is polymerized, for example, , 0.300 to 0.650 can be adjusted.

The I / O value is a value that organically handles the polarity of various organic compounds, also called (inorganic value) / (organic value), and is a functional group contribution method that sets parameters for each functional group. One. The I / O values are specifically shown in an organic conceptual diagram (Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, No. 1-16 (1954); No. 10, No. 719-725 (1957); Fragrance Journal No. 34, No. 97-111 (1979); Fragrance Journal No. 50, No. 79-82 (1981); It is explained in detail in the literature.
The concept of the I / O value is that the properties of a compound are divided into an organic group exhibiting a covalent bond and an inorganic group exhibiting an ionic bond, and all organic compounds are named as an organic axis and an inorganic axis. Each point on the coordinates is shown.
The inorganic value is obtained by quantifying the magnitude of the influence on the boiling point of various substituents and bonds of an organic compound, based on the hydroxyl group. Specifically, when the distance between the boiling point curve of a linear alcohol and the boiling point curve of a linear paraffin is about 100 ° C., the influence of one hydroxyl group is set to 100 as a numerical value. Based on this numerical value, the value obtained by quantifying the influence on the boiling point of various substituents or various bonds is the inorganic value of the substituent that the organic compound has. For example, the inorganic value of the —COOH group is 150, and the inorganic value of the double bond is 2. Therefore, the inorganic value of a certain organic compound means the sum of inorganic values such as various substituents and bonds of the compound.
The organic value is determined based on the influence of the methylene group in the molecule as a unit and the boiling point of the carbon atom representing the methylene group. That is, since the average value of the boiling point increase due to addition of one carbon in the vicinity of 5 to 10 carbon atoms of the linear saturated hydrocarbon compound is 20 ° C., the organic value of one carbon atom is set to 20 on the basis of this. Based on this, the value obtained by quantifying the influence on the boiling point of various substituents and bonds is the organic value. For example, the organic value of a nitro group (—NO 2) is 70.
The closer the I / O value is to 0, the more non-polar (hydrophobic and organic) organic compounds are, and the larger the I / O value is, the more polar (hydrophilic and inorganic) organic compounds are. Show.
Hereinafter, an example of a method for calculating the I / O value will be described.

  The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (molar ratio): 2/5/3) is determined by the following method. And calculated by the following formula: (inorganic value of the copolymer) / (organic value of the copolymer).

  The inorganic value of the copolymer is the inorganic value of the methacrylic acid x the molar ratio of the methacrylic acid, the inorganic value of the methyl methacrylate x the molar ratio of the methyl methacrylate, and the inorganic value of the styrene. X Calculated by calculating the sum of the styrene molar ratio.

The methacrylic acid has one carboxyl group, the methyl methacrylate has one ester group, and the styrene has one aromatic ring.
The inorganic value of the methacrylic acid is 150 (inorganic value of carboxyl group) × 1 (number of carboxyl groups) = 150,
The inorganic value of methyl methacrylate is 60 (inorganic value of ester group) × 1 (number of ester groups) = 60,
The inorganic value of styrene is 15 (inorganic value of aromatic ring) × 1 (number of aromatic rings) = 15.
Therefore, the inorganic value of the copolymer is calculated as follows: 150 × 2 (molar ratio of methacrylic acid) + 60 × 5 (molar ratio of methyl methacrylate) + 15 × 3 (molar ratio of styrene) Is calculated to be 645.

  The organic value of the copolymer is the organic value of the methacrylic acid x the molar ratio of the methacrylic acid, the organic value of the methyl methacrylate x the molar ratio of the methyl methacrylate, and the organic value of the styrene. X Calculated by calculating the sum of the styrene molar ratio.

The methacrylic acid has 4 carbon atoms, the methyl methacrylate has 5 carbon atoms, and the styrene has 8 carbon atoms,
The organic value of the methacrylic acid is 20 (organic value of carbon atoms) × 4 (number of carbon atoms) = 80,
The organic value of the methyl methacrylate is 20 (organic value of carbon atoms) × 5 (number of carbon atoms) = 100,
The organic value of styrene is 20 (organic value of carbon atoms) × 8 (number of carbon atoms) = 160.
Therefore, the organic value of the copolymer has the following formula: 80 × 2 (molar ratio of the methacrylic acid) + 100 × 5 (molar ratio of the methyl methacrylate) + 160 × 3 (molar ratio of the styrene) By calculating, it is calculated to be 1,140.

  Therefore, it can be seen that the I / O value of the copolymer is 645 (inorganic value of the copolymer) / 1,140 (organic value of the copolymer) = 0.666.

When the binder is a substance having a glass transition temperature, the glass transition temperature is not particularly limited as long as it is 80 ° C. or higher, and can be appropriately selected according to the purpose, but is preferably 100 ° C. or higher. 115 ° C. or higher is more preferable.
When the glass transition temperature is less than 80 ° C., the tack of the formed photosensitive layer may increase, or the peelability between the photosensitive layer and the support may deteriorate when a pattern forming material is produced. In addition, when the exposure amount is changed, fluctuations in resolution and the like may increase.

The binder having an I / O value of 0.300 to 0.650 preferably includes, for example, a copolymer, and the copolymer has a structural unit derived from at least one of styrene and a styrene derivative. . In addition to the structural unit derived from at least one of the styrene and the styrene derivative, examples of the combination of components to be copolymerized include, for example, a combination containing at least (meth) acrylic acid and an alkyl (meth) acrylate, (meth) A combination including acrylic acid, alkyl (meth) acrylate and benzyl (meth) acrylate, a combination including (meth) acrylic acid and benzyl (meth) acrylate, and the like are more preferable.
The alkyl group of the alkyl (meth) acrylate is particularly preferably a methyl group or an ethyl group.

Examples of the binder having an I / O value of 0.300 to 0.650 and a glass transition temperature of 80 ° C. or higher include a methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer (copolymer). Polymer composition (mass ratio): 25/8/30/37), methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 23/8/15/54) methacrylic acid / Methyl methacrylate / styrene / benzyl methacrylate copolymer (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 / Tyl acrylate 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 / cyclohexyl methacrylate / 2-ethylhexyl methacrylate copolymer (copolymer composition (mass ratio): 25/70/5), methacrylic acid / cyclohexyl methacrylate / 2-ethylhexyl methacrylate 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 (copolymer composition (mass ratio): 29/61/10), methacrylic acid / styrene / ethyl acrylate copolymer (copolymer composition (mass ratio): 23/60/17) , 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 composition ratio (mass ratio): 28/72), methacryl Acid / styrene copolymer (copolymerization composition ratio (mass ratio): 32/68), methacrylic acid / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25) / 65/10), methacrylic acid / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 30/61/9), methacrylic acid / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization) Composition ratio (mass ratio): 29/60/11), methacrylic acid / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/47/24), methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/22/40/13), methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio) ): 29/15/47/9), methacrylic acid / methyl methacrylate / styrene / 2 Ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/18/50/3), methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25 / 15/40/20), methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/15/35/25), methacrylic acid / styrene / cyclohexyl methacrylate Polymer (copolymerization composition ratio (mass ratio): 31/64/5), methacrylic acid / styrene / cyclohexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/15/60), methacrylic acid / methyl Methacrylate / styrene / butyl methacrylate copolymer (copolymerization composition ratio (quality 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), 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 (Copolymerization composition ratio (mass ratio): 25/29/46), methacrylic acid / methyl methacrylate / su Tylene 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 / 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 / methyl Tacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 20/56/24), methacrylic acid / styrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 30/15/55), Methacrylic acid / styrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 30/25/45), and methacrylic acid / methylstyrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 30 / 15/55).
Among these, methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 25/8/30/37), methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer (copolymer) Polymer composition (mass ratio): 29/16/35/20), methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer (copolymer composition (mass ratio): 25/25/39/11), methacryl 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 (co-polymer) Body 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 (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 / 2-ethylhexyl methacrylate copolymer (copolymerization composition) Ratio (mass ratio): 25/65/10), methacrylic acid / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 30/61/9), methacrylate Acid / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/60/11), methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass Ratio): 25/22/40/13), methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/15/47/9), methacrylic acid / methyl Methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/18/50/3), methacrylic acid / styrene / cyclohexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 31/64/5), methacrylic acid / styrene / cyclohexyl methacrylate Copolymer (copolymerization composition ratio (mass ratio): 25/15/60), methacrylic acid / methyl methacrylate / styrene / butyl 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), methacrylic acid / 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 / Chill 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 / 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 / benzyl methacrylate copolymer (copolymer composition (mass ratio): 30/15/55), methacrylic acid / styrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 30 / 25/45) and methacrylic acid / methylstyrene / benzyl methacrylate copolymers (copolymer composition (mass ratio): 30/15/55) are preferred.
Further, methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 29/16/35/20), methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer (copolymer) Combined composition (mass ratio): 25/25/45/5), methacrylic acid / styrene / methyl 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): 32/68), methacrylic acid / styrene / 2-ethylhexyl Methacrylate copolymer (copolymerization composition ratio (mass ratio): 30/61/9), methacrylic acid / styrene / 2-ethylhexyl Tacrylate copolymer (copolymerization composition ratio (mass ratio): 29/60/11), methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/15 / 47/9), methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/18/50/3), methacrylic acid / styrene / cyclohexyl methacrylate copolymer ( Copolymerization composition ratio (mass ratio): 31/64/5), methacrylic acid / methyl methacrylate / styrene / butyl 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 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 / methyl methacrylate / Styrene copolymer (copolymerization composition ratio (mass ratio): 32/8/60), methacrylic acid / methyl methacrylate / styrene copolymer (copolymer Polymerization composition ratio (mass ratio): 29/31/40), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 25/41/34), methacrylic acid / styrene / benzyl methacrylate Polymer (copolymer composition (mass ratio): 30/15/55), methacrylic acid / styrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 30/25/45), and methacrylic acid / A methylstyrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 30/15/55) is particularly preferred.

The binder is not particularly limited as long as the I / O value and the glass transition temperature are within the above numerical ranges, and can be appropriately selected according to the purpose. It is preferable that it is soluble in an alkaline liquid.
As the binder exhibiting swellability or solubility with respect to the alkaline liquid, for example, those having an acidic group are preferably mentioned.
The acid value of the binder is not particularly limited as long as the I / O value is within the above numerical range, and can be appropriately selected according to the purpose. For example, the acid value of the binder is 100 to 250 mgKOH / What is g is preferable, 120-220 mgKOH / g is more preferable, 150-220 mgKOH / g is especially preferable.
When the acid value is less than 100 mgKOH / g, developability may be insufficient or resolution may be inferior, and a high-definition pattern may not be obtained. At least one of the liquidity and the adhesiveness may deteriorate, and a high-definition pattern may not be obtained.

There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, Among these, a carboxyl group is preferable.
Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, and a modified epoxy resin. Among these, the solubility in a coating solvent, the solubility in an alkali developer, and the like. A vinyl copolymer having a carboxyl group is preferable from the viewpoint of solubility, suitability for synthesis, ease of adjustment of film properties, and the like. From the viewpoint of developability, a copolymer of at least one of styrene and a styrene derivative is also preferable.

The vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.
Examples of the vinyl copolymer include compounds described in “0164” to “0205” of JP-A-2005-258431.

There is no restriction | limiting in particular in content of the said binder in the said photosensitive composition, Although it can select suitably according to the objective, For example, 10-90 mass% is preferable, 20-80 mass% is more preferable, 40 ˜80 mass% is particularly preferred.
When the content is less than 10% by mass, alkali developability and adhesion with a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. The stability of the film and the strength of the cured film (tent film) may decrease. The content may be the total content of the binder and the polymer binder used in combination as necessary.

  The content ratio of the at least one hexaarylbiimidazole compound having a hydrophilic group and a polymer having an I / O value of 0.300 to 0.650 is, for example, mass ratio, preferably 1:10 to 1: 1. 1:30 to 1: 2 is more preferable, and 1:20 to 1: 4 is particularly preferable.

-Polymerizable compound-
The polymerizable compound in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a monomer or oligomer having at least one of a urethane group and an aryl group is preferable. It is done. Moreover, it is preferable that these have 2 or more types of polymeric groups.

  Examples of the polymerizable group include an ethylenically unsaturated bond (for example, (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester). Etc.) and a polymerizable cyclic ether group (for example, epoxy group, oxetane group, etc.) and the like. Among these, an ethylenically unsaturated bond is preferable.

--Monomer having urethane group--
As long as it has a urethane group, there is no restriction | limiting in particular as a monomer which has the said urethane group, According to the objective, it can select suitably, For example, it describes in "0210"-"0262" of Unexamined-Japanese-Patent No. 2005-258431. And the like.

--Monomer having aryl group--
The monomer having an aryl group is not particularly limited as long as it has an aryl group, and can be appropriately selected depending on the purpose. Examples thereof include esters or amides of at least one of alcohol compounds and an unsaturated carboxylic acid.
Specifically, for example, compounds described in “0264” to “0271” of JP-A-2005-258431 can be mentioned.

-Other polymerizable monomers-
In the photosensitive composition, a polymerizable monomer other than the monomer containing the urethane group and the monomer having an aryl group is used in a range that does not deteriorate the characteristics of the photosensitive layer formed using the photosensitive composition. May be.

Examples of the polymerizable monomer other than the monomer containing a urethane group and the monomer containing an aromatic ring include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) And an ester of an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and a polyvalent amine compound.
Specific examples thereof include compounds described in “0273” to “0284” of JP-A-2005-258431.

  As mentioned above, it is preferable that the exemplified polymerizable compound also contains at least a monomer having a propylene oxide group from the viewpoint of effectively functioning as an antifoaming agent and capable of forming a higher definition pattern.

The content of the polymerizable compound in the photosensitive composition is, for example, preferably 5 to 90% by mass, more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass.
When the content is less than 5% by mass, the strength of the tent film may be reduced. When the content exceeds 90% by mass, edge fusion during storage of the pattern forming material (a bleed-out failure from the end of the roll) May get worse.
Further, the content of the polyfunctional monomer having two or more polymerizable groups in the polymerizable compound in the photosensitive layer is preferably 5 to 100% by mass, more preferably 20 to 100% by mass, and 40 to 100% by mass. Is particularly preferred.

-Sensitizer-
In order to adjust the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer, it is possible to add a sensitizer in addition to the photopolymerization initiator.
The sensitizer can be appropriately selected by a visible light, an ultraviolet laser, a visible light laser, or the like as a light irradiation means described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

  Examples of the combination of the photopolymerization initiator and the sensitizer include, for example, an electron transfer start system described in JP-A-2001-305734 [(1) an electron donating initiator and a sensitizing dye, (2) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye and an electron-accepting initiator (ternary initiation system)], and the like.

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, Methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin, acriflavine, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane), anthraquinones (eg anthraquinone), squalium (Eg, squalium), acridones (eg, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone (eg, 2-chloro-10-butylacridone) Etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- ( 2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3 ′ -Carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxyc Phosphorus, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5 7-dipropoxycoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc. And the like, and thioxanthone compounds (thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, Quantacure QTX, etc.), among these, aromatic rings And the heterocycle is condensed The compound (condensed ring compound) and an amine compound substituted with at least two aromatic hydrocarbon rings or aromatic heterocyclic rings are preferred.

  Among the condensed ring compounds, hetero-fused ketone compounds (acridone compounds, thioxanthone compounds, coumarin compounds, etc.) and acridine compounds are more preferable. Among the hetero-fused ketone compounds, an acridone compound and a thioxanthone compound are particularly preferable.

  The amine compound substituted with any one of the at least two aromatic hydrocarbon rings and the aromatic heterocyclic ring is preferably a sensitizer having an absorption maximum with respect to light in a wavelength region of 330 to 450 nm, For example, a disubstituted aminobenzophenone compound, a disubstituted amino-benzene compound having a heterocyclic group as a substituent at a carbon atom at the para position relative to an amino group on the benzene ring, Disubstituted amino-benzene compounds having a substituent containing a sulfonylimino group at the carbon atom at the position, disubstituted amino-benzene compounds having a carbostyryl skeleton, and at least two aromatic rings on the nitrogen atom Examples thereof include compounds having a disubstituted amino-benzene as a partial structure, such as a compound having a bonded structure.

The said sensitizer may be used individually by 1 type and may use 2 or more types together.
The content of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, and particularly preferably 0.05 to 1% by mass with respect to all components of the photosensitive composition. .
When the content is less than 0.01% by mass, the sensitivity may decrease, and when it exceeds 4% by mass, the shape of the pattern may be deteriorated.

-Compound having NH group-
For the purpose of improving the tent property in the formed pattern and reducing the development residue, it is possible to add a compound having an NH group.
The compound having an NH group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include NH-containing heterocyclic compounds and NH-containing sulfonamide compounds. Among these, a benzotriazole skeleton-containing compound, a benzimidazole skeleton-containing compound, and a benzenesulfonamide skeleton-containing compound are preferable.
Specific examples include benzotriazole, carboxybenzotriazole, dibutylaminomethylbenzotriazole, dibutyaminomethylcarboxybenzotriazole, benzimidazole, benzenesulfonamide, toluenesulfonamide, and butylbenzenesulfonamide. Moreover, you may add the thing of NH containing among the below-mentioned thermal polymerization inhibitors.
As the compound having an NH group, one kind may be used alone, or two or more kinds may be used in combination. Toluenesulfonamide is preferable from the viewpoint of improving tent properties, and viewpoints of reducing development residue. Are preferably benzotriazole-based compounds such as carboxybenzotriazole.

  The content of the NH group-containing compound in the photosensitive composition is, for example, preferably 0.001 to 5% by mass, and more preferably 0.002 to 3% by mass.

-Other ingredients-
Examples of other components in the photosensitive composition include known thermal polymerization inhibitors, surfactants, plasticizers, color formers, colorants, and the like, and further adhesion promoters to the substrate surface and other assistants. Combined use of agents (for example, pigments, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, chain transfer agents, etc.) May be. By appropriately containing these components, it is possible to adjust properties such as stability, photographic properties, print-out properties, and film physical properties of the intended photosensitive layer (the pattern forming material).

--- Thermal polymerization inhibitor ---
The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound in the photosensitive layer made of the photosensitive composition.
Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine. , Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

The content of the thermal polymerization inhibitor is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and particularly preferably 0.01 to 1% by mass with respect to the polymerizable compound.
When the content is less than 0.001% by mass, stability during storage may be reduced, and when it exceeds 5% by mass, sensitivity to active energy rays may be reduced.

--Plasticizer--
The plasticizer may be added to control film physical properties (flexibility) of the photosensitive layer made of the photosensitive composition.
Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, and the like. Phthalic acid esters: Triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters of tricresyl phosphate, triphenyl phosphate, etc. Acid esters; Amides such as 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl Aliphatic dibasic acid esters such as sepacate, dioctyl azelate, dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid Examples include glycols such as dioctyl acid, polyethylene glycol, and polypropylene glycol.

  The content of the plasticizer is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass with respect to all components of the photosensitive composition.

--Coloring agent--
The color former may be added to give a visible image (printing function) to the photosensitive layer after exposure.
Examples of the color former include tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, tris (4- Diethylamino-2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolylmethane, tris (4-di Aminotriarylmethanes such as propylaminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine, etc. Aminoxanthines; 3,6-bis (diethyl Aminothioxanthenes such as mino) -9- (2-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9- Amino-9,10-dihydroacridine such as phenylacridine, 3,6-bis (benzylamino) -9,10-dividro-9-methylacridine; aminophenoxazine such as 3,7-bis (diethylamino) phenoxazine Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (4-dimethylamino) Aminophenylmethanes such as phenyl) anilinomethane; 4-amino-4 ′ Aminohydrocinnamic acids such as dimethylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis ( Ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; phenethylanilines such as N, N-diethyl-4-phenethylaniline; 10-acetyl-3,7-bis (dimethylamino) ) An acyl derivative of a leuco dye containing basic NH such as phenothiazine; a leuco-like compound that does not have oxidizable hydrogen such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmentane, but can be oxidized to a coloring compound; Id dyes; U.S. Pat. Nos. 3,042,515 and 3,042 Organic amines that can be oxidized to a colored form as described in No. 517 (eg, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediamine triphenylamine, N-vinylcarbazole), and among these, triarylmethane compounds such as leuco crystal violet are preferable.

Furthermore, it is generally known that the color former is combined with a halogen compound for the purpose of coloring the leuco body.
Examples of the halogen compound include halogenated hydrocarbons (for example, carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, Diphenylmethyl bromide, hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3 tribromopropane, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, 1,1,1-trichloro-2,2-bis (4- Chlorophenyl) ethane); halogenated alcohol compounds (eg, 2,2,2-trichloroethanol, Bromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribromo-t-butyl alcohol, 2,2,3-trichlorobutane 1,4-diol, etc .; halogenated carbonyl compounds (for example, 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1 , 1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc.); halogenated ether compounds (eg 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether) Di (2-bromoethyl) ether, 1,2- Chloroethyl ethyl ether, etc.); halogenated ester compounds (eg, bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, α, β Halogenated amide compounds (for example, chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2- Trichloropropionamide, N-chlorosuccinimide, N-bromosuccinimide, etc.); a compound having sulfur or phosphorus (for example, tribromomethylphenylsulfone, 4-nitro) Phenyl tribromomethyl sulfone, 4-chlorophenyl tribromomethyl sulfone, tris (2,3-dibromopropyl) phosphate, etc.), e.g., 2,4-bis (trichloromethyl) 6- phenyltriazole and the like. As the organic halogen compound, a halogen compound having two or more halogen atoms bonded to the same carbon atom is preferable, and a halogen compound having three halogen atoms per carbon atom is more preferable. The said organic halogen compound may be used individually by 1 type, and may use 2 or more types together. Among these, tribromomethylphenyl sulfone and 2,4-bis (trichloromethyl) -6-phenyltriazole are preferable.

  The content of the color former is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 5% by mass with respect to all components of the photosensitive composition. . Moreover, 0.001-5 mass% is preferable with respect to all the components of the said photosensitive composition, and, as for content of the said halogen compound, 0.005-1 mass% is more preferable.

--Colorant--
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, known pigments or dyes such as red, green, blue, yellow, purple, magenta, cyan, and black may be used. Specifically, Victoria Pure Blue BO (C.I. 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146) ), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (C.I. Pigment black 1) and carbon black.

--- Dye--
In the photosensitive composition, a dye can be used for the purpose of improving handleability or imparting storage stability.
Examples of the dye include brilliant green (for example, sulfate thereof), eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein. , Methyl violet 2B, quinaldine red, rose bengal, metanil-yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenyltylocarbazone, 2,7-dichlorofluorescein, paramethyl red, congo red, benzo Purpurin 4B, α-naphthyl-red, Nile blue A, phenacetalin, methyl violet, malachite green, parafuchsin, oil blue # 603 (Orien Chemical Co., Ltd.), Rhodamine B, Rhodamine 6G, etc. Victoria Pure Blue BOH can be cited, among these cationic dyes (e.g., Malachite Green oxalate, malachite green sulfates) are preferable. The counter anion of the cationic dye may be a residue of an organic acid or an inorganic acid, for example, a residue such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid, toluenesulfonic acid ( Anion) and the like.

  0.001-10 mass% is preferable with respect to all the components of the said photosensitive composition, as for content of the said dye, 0.01-5 mass% is more preferable, 0.1-2 mass% is especially preferable.

-Adhesion promoter-
The photosensitive composition improves the adhesion of a photosensitive layer formed using the photosensitive composition (adhesion with other layers when used as the pattern forming material, or adhesion with a substrate). Therefore, a known so-called adhesion promoter can be used for each layer.

  Suitable examples of the adhesion promoter include adhesion promoters described in JP-A Nos. 5-11439, 5-341532, and 6-43638.

  0.001 mass%-20 mass% are preferable with respect to all the components of the said photosensitive composition, as for content of the said adhesion promoter, 0.01-10 mass% is more preferable, 0.1 mass%-5 Mass% is particularly preferred.

  The photosensitive composition is, for example, J.P. It may contain organic sulfur compounds, peroxides, redox compounds, azo or diazo compounds, photoreducible dyes, organic halogen compounds, etc. as described in Chapter 5 of “Light Sensitive Systems” Good.

  Examples of the organic sulfur compound include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethane sulfenate, and 2-mercaptobenzimidazole. Is mentioned.

  Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.

  The redox compound is a combination of a peroxide and a reducing agent, and examples thereof include ferrous ions and persulfate ions, ferric ions and peroxides.

  Examples of the azo and diazo compounds include α, α'-azobisiributyronitrile, 2-azobis-2-methylbutyronitrile, and diazonium such as 4-aminodiphenylamine.

  Examples of the photoreducible dye include rose bengal, erythrosine, eosin, acriflavine, lipoflavin, and thionine.

--Surfactant--
A known surfactant can be added to the photosensitive composition in order to improve planar unevenness that occurs when the photosensitive layer is formed.
The surfactant can be appropriately selected from, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a fluorine-containing surfactant.

As for content of the said surfactant, 0.001-10 mass% is preferable with respect to solid content of the said photosensitive composition.
When the content is less than 0.001% by mass, the effect of improving the surface shape may not be obtained, and when it exceeds 10% by mass, the adhesion may be deteriorated.

  As the surfactant, in addition to the above-mentioned surfactant, as a fluorine-based surfactant, it contains 40% by mass or more of fluorine atoms in a carbon chain of 3 to 20, and at least 3 counted from the non-bonding terminal A polymer surfactant having, as a copolymerization component, an acrylate or methacrylate having a fluoroaliphatic group in which a hydrogen atom bonded to a carbon atom is fluorine-substituted is also preferred.

There is no restriction | limiting in particular in the location provided in the said pattern formation material of the said photosensitive layer, According to the objective, it can select suitably, Usually, it laminates | stacks on the said support body. The photosensitive layer may be a single layer or a plurality of layers.
There is no restriction | limiting in particular in the thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 1-100 micrometers is preferable, 2-50 micrometers is more preferable, and 4-30 micrometers is especially preferable.

<Support>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.

-Haze value-
The haze value of the support is preferably 5.0% or less, more preferably 3.0% or less, and particularly preferably 1.0% or less, with respect to 405 nm light. When the haze value exceeds 5.0%, the amount of light scattering in the photosensitive layer increases, resulting in a decrease in resolution when obtaining a fine pitch, a decrease in adhesion, and an increase in edge roughness. Detrimental effects may occur.

  Moreover, it is preferable that the total light transmittance with respect to 405 nm light of the said support body is 86% or more, and it is more preferable that it is 87% or more.

There is no restriction | limiting in particular as a measuring method of the said haze value and total light transmittance, Although it can select suitably according to the objective, For example, the method demonstrated below is mentioned.
First, (1) the total light transmittance is measured. The method for measuring the total light transmittance is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an integrating sphere and a spectrophotometer capable of irradiating 405 nm light (for example, Shimadzu Corporation) And UV-2400). (2) In the total light transmittance measurement method, the parallel light transmittance is measured in the same manner as the total light transmittance measurement method except that the integrating sphere is not used. Next, the diffuse light transmittance calculated from (3) the following calculation formula, the total light transmittance-the parallel light transmittance, is calculated, and (4) the following calculation formula, the diffuse light transmittance / the total light transmission. The haze value can be determined from the ratio × 100.
In addition, the thickness of the measurement sample at the time of calculating | requiring the said total light transmittance and the said haze value is 16 micrometers.

  The support may be coated with inert fine particles on at least one side. The inert fine particles are preferably applied on the surface opposite to the surface on which the photosensitive layer is formed.

  Examples of the inert fine particles include crosslinked polymer particles, inorganic particles (for example, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, etc. ), Organic particles (for example, hexamethylene bisbehenamide, hexamethylene bisstearyl amide, N, N′-distearyl terephthalamide, silicone, calcium oxalate, etc.), precipitated particles generated during polyester polymerization, and the like. Of these, silica, calcium carbonate, and hexamethylene bisbehenamide are preferable.

  The precipitated particles are, for example, particles precipitated in a reaction system by polymerizing a system using an alkali metal or alkaline earth metal compound as a transesterification catalyst by a conventional method, and during the transesterification reaction or polycondensation reaction It may be precipitated by adding terephthalic acid. In the transesterification or polycondensation reaction, phosphoric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, acidic ethyl phosphate, phosphorous acid, trimethyl phosphite, triethyl phosphite, tributyl phosphite, etc. One or more of the phosphorus compounds may be present.

The average particle diameter of the inert fine particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Particularly preferred.
When the average particle diameter of the inert fine particles is less than 0.01 μm, the transportability of the pattern forming material may be deteriorated. The haze value of the support may increase. On the other hand, if the average particle diameter of the inert fine particles exceeds 2.0 μm, the resolution may decrease due to scattering of exposure light.

  There is no restriction | limiting in particular as a coating method of the said inert fine particle, According to the objective, it can select suitably. For example, a method of applying a coating solution containing the inert fine particles by a known method after the production of the synthetic resin film as the support is mentioned. Alternatively, the synthetic resin containing the inert fine particles may be melted and discharged from a die to be formed on a synthetic resin film serving as the support. Furthermore, you may form by the method as described in Unexamined-Japanese-Patent No. 2000-221688.

  The thickness of the coating layer containing the inert fine particles in the support is preferably 0.02 to 3.0 μm, more preferably 0.03 to 2.0 μm, and particularly preferably 0.04 to 1.0 μm.

  The synthetic resin film used as the support is preferably transparent. For example, a polyester resin film is preferable, and a biaxially stretched polyester film is particularly preferable.

  Examples of the polyester resin include polyethylene terephthalate, polyethylene naphthalate, poly (meth) acrylic acid ester copolymer, poly (meth) acrylic acid alkyl ester, polyethylene-2,6-naphthalate, polytetramethylene terephthalate, and polytetramethylene. And methylene-2,6-naphthalate. These may be used alone or in combination of two or more.

  Examples of the resin other than the polyester resin include polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride, Examples include vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose resin, and nylon resin. These may be used alone or in combination of two or more.

  The synthetic resin film may be composed of one layer or may be composed of two or more layers. In the case of two or more layers, the inert fine particles are preferably contained in the layer farthest from the photosensitive layer.

The synthetic resin film is preferably a biaxially stretched polyester film from the viewpoint of mechanical strength characteristics and optical characteristics.
There is no restriction | limiting in particular in the biaxial orientation method of the said biaxially stretched polyester film, According to the objective, it can select suitably. For example, the polyester resin is melt-extruded into a sheet and rapidly cooled to form an unstretched film. When the unstretched film is biaxially stretched, the stretching temperature is 85 to 145 ° C., and the stretching ratio in the longitudinal and transverse directions is 2. It can be prepared by heat-fixing the film after biaxial stretching as necessary at a temperature of 150 to 210 ° C.
The biaxial stretching may be a sequential biaxial stretching method in which an unstretched film is stretched in the longitudinal direction or the transverse direction to form a uniaxially stretched film, and then the uniaxially stretched film is stretched in the transverse direction or the longitudinal direction. A simultaneous biaxial stretching method in which the unstretched film is stretched simultaneously in the machine direction and the transverse direction may be used. In addition, the biaxially stretched film can be further stretched in at least one of the longitudinal direction and the transverse direction as necessary.

  There is no restriction | limiting in particular in the thickness of the said support body, Although it can select suitably according to the objective, For example, 2-150 micrometers is preferable, 5-100 micrometers is more preferable, and 8-50 micrometers is especially preferable.

  There is no restriction | limiting in particular in the shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular in the length of the said elongate support body, For example, the thing of 10-20,000m length is mentioned.

<Other layers>
The other layers in the pattern forming material are not particularly limited, and can be appropriately selected depending on the purpose. Examples thereof include a cushion layer, an oxygen barrier layer (PC layer), a release layer, an adhesive layer, and a light absorption layer. You may have layers, such as a layer and a surface protective layer. These layers may be used alone or in combination of two or more. Moreover, you may have a protective film on the said photosensitive layer.

−Cushion layer−
There is no restriction | limiting in particular as said cushion layer, According to the objective, it can select suitably, Swelling thru | or soluble with respect to alkaline liquid may be sufficient, and it may be insoluble.

  When the cushion layer is swellable or soluble in an alkaline liquid, examples of the thermoplastic resin include a saponified product of ethylene and an acrylate ester copolymer, a copolymer of styrene and a (meth) acrylate ester Saponification of coalescence, saponification of vinyltoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer such as (meth) acrylic acid butyl and vinyl acetate And a copolymer of (meth) acrylic acid ester and (meth) acrylic acid, a copolymer of styrene, (meth) acrylic acid ester and (meth) acrylic acid, and the like.

The softening point (Vicat) of the thermoplastic resin in this case is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 80 ° C. or lower.
As the thermoplastic resin having a softening point of 80 ° C. or lower, in addition to the above-mentioned thermoplastic resin, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, October 1968) Among those organic polymers having a softening point of about 80 ° C. or less, which are soluble in an alkaline solution. In addition, even in an organic polymer material having a softening point of 80 ° C. or higher, various plasticizers compatible with the organic polymer material are added to the organic polymer material so that the substantial softening point is 80 ° C. or lower. It is also possible to lower it.

  In addition, when the cushion layer is swellable or soluble in an alkaline liquid, the interlayer adhesive force of the pattern forming material is not particularly limited and can be appropriately selected according to the purpose. Of the interlayer adhesive strength of each layer, it is preferable that the interlayer adhesive strength between the support and the cushion layer is the smallest. With such an interlayer adhesive strength, only the support is peeled off from the laminate, the photosensitive layer is exposed through the cushion layer, and then the photosensitive layer is developed using an alkaline developer. be able to. Further, after exposing the photosensitive layer while leaving the support, only the support is peeled off from the laminate, and the photosensitive layer can be developed using an alkaline developer.

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected according to the purpose. For example, a known polymer, supercooling substance, adhesion improver, surfactant in the thermoplastic resin, The method of adding a mold release agent etc. is mentioned.

  The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate Examples thereof include alcohols and esters such as phosphate and biphenyldiphenyl phosphate; amides such as toluenesulfonamide.

When the cushion layer is insoluble in an alkaline liquid, examples of the thermoplastic resin include a copolymer whose main component is ethylene as an essential copolymer component.
The copolymer having ethylene as an essential copolymer component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer A polymer (EEA) etc. are mentioned.

  When the cushion layer is insoluble in the alkaline liquid, the interlayer adhesion of the pattern forming material is not particularly limited and can be appropriately selected depending on the purpose. Of the adhesive strength, it is preferable that the adhesive force between the photosensitive layer and the cushion layer is the smallest. By setting such an interlayer adhesive strength, the support and the cushion layer are peeled from the laminate, and the photosensitive layer is exposed, and then the photosensitive layer can be developed using an alkaline developer. Further, after exposing the photosensitive layer while leaving the support, the support and the cushion layer can be peeled from the laminate, and the photosensitive layer can be developed using an alkaline developer.

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected depending on the purpose. For example, various polymers, supercooling substances, adhesion improvers, surfactants in the thermoplastic resin, Examples thereof include a method of adding a release agent and the like, and a method of adjusting an ethylene copolymerization ratio described below.

The ethylene copolymerization ratio in the copolymer containing ethylene as an essential copolymerization component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 60 to 90% by mass is preferable, and 60 to 80 % By mass is more preferable, and 65 to 80% by mass is particularly preferable.
When the ethylene copolymerization ratio is less than 60% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. When the amount exceeds 90% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer becomes too small, so that the cushion layer and the photosensitive layer are very easily peeled off, including the cushion layer. It may be difficult to manufacture the pattern forming material.

There is no restriction | limiting in particular in the thickness of the said cushion layer, Although it can select suitably according to the objective, For example, 5-50 micrometers is preferable, 10-50 micrometers is more preferable, and 15-40 micrometers is especially preferable.
If the thickness is less than 5 μm, unevenness on the surface of the substrate and unevenness followability to bubbles and the like may be reduced, and a high-definition permanent pattern may not be formed. Such a problem may occur.

-Oxygen barrier layer (PC layer)-
The oxygen barrier layer is preferably formed usually with polyvinyl alcohol as a main component, and is preferably a film having a thickness of about 0.5 to 5 μm.

-Protective film-
The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular in the location provided in the said pattern formation material of the said protective film, According to the objective, it can select suitably, Usually, it provides on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, and among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular in the thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

  The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C. for 1 to 30 minutes. The drying temperature is particularly preferably 50 to 120 ° C.

[Method for producing pattern forming material]
The pattern forming material can be manufactured, for example, as follows.
First, the material contained in the photosensitive layer is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive resin composition solution for a pattern forming material.

  There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  Next, the photosensitive composition solution is applied onto the support and dried to form a photosensitive layer, whereby a pattern forming material can be produced.

The method for applying the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a spray method, a roll coating method, a spin coating method, a slit coating method, an extrusion coating method, Examples of the coating method include a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

(Photosensitive laminate)
The photosensitive laminate is formed by laminating at least the photosensitive layer of the invention on a substrate and other layers appropriately selected according to the purpose.

-Substrate-
The substrate is a substrate to be processed on which a photosensitive layer is formed or a transfer target to which at least the photosensitive layer of the pattern forming material of the present invention is transferred, and is not particularly limited, and is appropriately selected according to the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include a substrate for producing a known printed wiring board, a glass plate (such as a soda glass plate), a synthetic resin film, paper, and a metal plate.

[Method for producing photosensitive laminate]
Examples of the method for producing the photosensitive laminate include, as a first aspect, a method in which the photosensitive resin composition solution is applied to the surface of the substrate and then dried, and as a second aspect, the photosensitive film of the present invention. And a method of transferring and laminating at least one of the photosensitive layer while performing at least one of heating and pressing.

In the method for producing a photosensitive laminate of the first aspect, a photosensitive layer is formed by applying and drying the photosensitive resin composition solution on the substrate.
The method for applying and drying is not particularly limited and may be appropriately selected depending on the purpose. For example, the material contained in the photosensitive layer is dissolved, emulsified or dissolved in water or a solvent on the surface of the substrate. A method of laminating by preparing a photosensitive composition solution by dispersing, directly applying the solution, and drying the solution may be mentioned.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, The same solvent as what was used for the said photosensitive film is mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  There is no restriction | limiting in particular as said coating method and drying conditions, According to the objective, it can select suitably, It carries out by the same method and conditions as what was used for the said photosensitive film.

In the method for producing a photosensitive laminate of the second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular in the said heating temperature, Although it can select suitably according to the objective, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular in the pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, Although it can select suitably according to the objective, For example, a laminator (for example, MODEL8B-720-PH, Taisei Laminator Co., Ltd. product) etc. Preferably mentioned.

  Since the pattern forming material of the present invention and the photosensitive laminate have high sensitivity and high resolution, excellent adhesion and sensitivity over time, little development residue, and high-definition patterns can be formed. Can be suitably used for the production of liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, and the like. Can be suitably used.

(Pattern forming apparatus and pattern forming method)
The pattern forming apparatus of the present invention includes the pattern forming material of the present invention, and has at least light irradiation means and light modulation means.

The pattern forming method of the present invention includes at least an exposure step, and includes other steps such as an appropriately selected development step.
In addition, the said pattern formation apparatus of this invention is clarified through description of the said pattern formation method of this invention.

[Exposure process]
The said exposure process is a process of exposing with respect to the photosensitive layer of this invention. The photosensitive layer and substrate material of the present invention are as described above.

  The exposure target is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose. For example, as described above, the pattern forming material is heated and pressurized on the substrate. It is preferably performed on the photosensitive layer in the photosensitive laminate formed by laminating at least one of them.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned, Among these, digital exposure is preferable.

  The analog exposure is not particularly limited and can be appropriately selected depending on the purpose. For example, exposure with a (super) high pressure mercury lamp, xenon lamp, halogen lamp, etc. through a photomask having a predetermined pattern. The method of performing is mentioned.

  The digital exposure is not particularly limited as long as it is performed without using the photomask, and can be appropriately selected according to the purpose. For example, an exposure head including at least a light irradiation unit and a light modulation unit; The exposure head irradiates the photosensitive layer with light emitted from the light irradiation means while modulating at least one of the photosensitive layers according to pattern information by the light modulation means. It is preferable.

  The light source used in the digital exposure is not particularly limited as long as it is a light source that emits ultraviolet to near infrared rays, and can be appropriately selected according to the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp , Fluorescent lamps for use in halogen lamps and copying machines, or known light sources such as laser light are used. Among these, (ultra) high pressure mercury lamps and laser light are preferable, and laser light is more preferable.

  The (super) high pressure mercury lamp is a discharge lamp in which mercury is enclosed in a quartz glass tube or the like, and has a higher vapor pressure to increase luminous efficiency. Among the emission line spectra, an emission line spectrum of only one wavelength may be used using an ND filter or the like, or a light beam having a plurality of emission line spectra may be used.

The “laser” of the laser light is an acronym for Light Amplification by Stimulated Emission of Radiation. As an apparatus for emitting the laser light, an oscillator and an amplifier that generate monochromatic light having a higher coherence and directivity by amplification and oscillation of light waves using a phenomenon of stimulated emission that occurs in a material having an inversion distribution is preferably used. Can be mentioned.
Examples of the laser light excitation medium include crystals, glass, liquid, pigment, gas, and the like, and known lasers such as a solid laser, a liquid laser, a gas laser, and a semiconductor laser can be used.
Specifically, Ar ion lasers (364 nm, 351 nm), Kr ion lasers (356 nm, 351 nm), and He—Cd lasers (325 nm) can be cited as gas lasers, and YAG lasers, YVO ₄ lasers (1, 1, 064 nm), YAG laser or YVO ₄ laser, second harmonic (532 nm), third harmonic (355 nm), fourth harmonic (266 nm), a combination of a waveguide wavelength conversion element and an AlGaAs or InGaAs semiconductor (380 to 400 nm) ), A combination of a waveguide type wavelength conversion element and an AlGaInP or AlGaAs semiconductor t (300 to 350 nm), AlGaInN (350 to 470 nm), and the like. Among these, suitable laser light includes an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 375 nm or 405 nm) in terms of cost, and a 355 nm laser having a high output in terms of productivity.

  The wavelength of the laser beam is, for example, preferably 200 to 1,500 nm, more preferably 300 to 800 nm, still more preferably 330 to 500 nm, and particularly preferably 350 to 420 nm.

-Light modulation means-
As the light modulation means, a typical method is a method having n pixel parts and controlling the pixel parts according to the pattern information. Specifically, a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), an optical element (PLZT element) that modulates transmitted light by an electro-optic effect. And liquid crystal light shutter (FLC). Among these, DMD is preferable.

When the DMD is used, light from a light source is irradiated onto the DMD by an appropriate optical system, and reflected light from each mirror arranged two-dimensionally on the DMD is exposed to light through another optical system. An image of light spots arranged in two dimensions is formed on the layer. In this state, the light spot is not exposed between the light spots. However, if the image of the light spots arranged in two dimensions is moved in a direction slightly inclined with respect to the two-dimensional arrangement direction, the light spots in the first row are used. The light spot in the rear row exposes between the light spot and the light spot, so that the entire surface of the photosensitive layer can be exposed. The DMD can form an image pattern by controlling the angle of each mirror and controlling the light spot on and off. By aligning and using such exposure heads having the DMD, it is possible to deal with substrates of various widths.
In the DMD, the brightness of the light spot has only two gradations, ON or OFF, but exposure with 256 gradations can be performed using a mirror gradation type spatial modulation element.

Moreover, it is preferable that the said light modulation means has a pattern signal generation means which produces | generates a control signal based on the pattern information to form. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned suitably.

  On the other hand, another typical method of the light modulation means is a method using a polygon mirror. Here, the polygon mirror is a rotating member having a series of plane reflecting surfaces around it. The polygon mirror reflects and irradiates light from the light source onto the photosensitive layer, and the light spot of the reflected light is scanned by the rotation of the plane mirror. By moving the substrate at right angles to the scanning direction, the entire surface of the photosensitive layer on the substrate can be exposed. Then, an image pattern can be formed by controlling the intensity of light from the light source to ON-OFF or halftone by an appropriate method. At this time, the scanning time can be shortened by using a plurality of lights from the light source.

  As the light modulation means of the present invention, in addition, an example of drawing using a polygon mirror described in JP-A-5-150175, as described in JP-T-2004-523101 (International Publication No. 2002/039793 pamphlet). An example in which a part of the image of the lower layer is visually acquired, and exposure is performed by aligning the position of the upper layer with the position of the lower layer with an apparatus using a polygon mirror, and exposure with the DMD described in JP-A-2004-56080 For example, an exposure apparatus provided with a polygon mirror described in JP-T-2002-523905, an exposure apparatus provided with a polygon mirror described in JP-A-2001-255661, DMD, LD, and multiple exposure described in JP-A-2003-50469 An example of a combination of an exposure method in which the exposure amount is changed depending on the part of the substrate described in Japanese Patent Application Laid-Open No. 2003-156853 , Etc. Examples of an exposure method for performing a positional deviation adjustment described in JP 2005-43576 Publication and the like.

-Light irradiation means-
There is no restriction | limiting in particular as said light irradiation means, ie, the light irradiation method, Although the above-mentioned exposure light source can be suitably selected according to the objective, Two or more light from these light sources is synthesize | combined and irradiated. It is particularly preferable to irradiate a laser beam (combined laser beam) obtained by combining two or more lights.

  There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this several laser light source A method of composing and irradiating a combined laser beam with a collective optical system that collects light and couples it to the multimode optical fiber is preferable.

The beam diameter of the laser light is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of the resolution of the dark color separation partition wall, the Gaussian beam 1 / e ² value is preferably 5 to 30 μm, 7-20 micrometers is more preferable.
In the present invention, it is preferable to spatially modulate laser light according to image data. Therefore, it is preferable to use the DMD which is a spatial light modulator for this purpose.

  Examples of the exposure apparatus having the light modulating unit and the light irradiating unit are described in JP-A-2005-222039, JP-A-2005-258431, JP-A-2006-30966, and the like. However, the exposure apparatus in the present invention is not limited to this.

[Other processes]
There is no restriction | limiting in particular as said other process, It can select suitably from the processes in well-known pattern formation, For example, a image development process, an etching process, a plating process, a hardening process process etc. are mentioned.

-Development process-
The developing step can be preferably performed by, for example, developing means.
The developing means is not particularly limited as long as it can be developed using a developer, and can be appropriately selected according to the purpose. For example, means for spraying the developer, means for applying the developer And means for immersing in the developer. These may be used alone or in combination of two or more.
In addition, the developing unit may include a developer replacing unit that replaces the developer, a developer supplying unit that supplies the developer, and the like.

  There is no restriction | limiting in particular as said developing solution, According to the objective, it can select suitably, For example, an alkaline solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline liquid include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

The pH of the weak alkaline aqueous solution is, for example, preferably about 8 to 12, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include a 0.1 to 5% by mass aqueous sodium carbonate solution or an aqueous potassium carbonate solution.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

-Etching process-
The etching step can be performed by a method appropriately selected from known etching methods.
There is no restriction | limiting in particular as an etching liquid used for the said etching process, According to the objective, it can select suitably, For example, when the said metal layer is formed with copper, a cupric chloride solution, chloride. A ferric solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, and the like can be mentioned. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor. Moreover, a well-known sandblasting method can be used.
A wiring pattern (circuit) can be formed on the surface of the substrate by removing the pattern after performing the etching process in the etching step.

-Plating process-
The plating step can be performed by an appropriately selected method selected from known plating processes.
Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. And gold plating such as soft gold plating.
A metal wiring pattern (circuit) is formed on the surface of the substrate by removing the pattern after plating by the plating process and further removing unnecessary portions by a resist stripping process or the like as necessary. Can do.

[Method of manufacturing printed wiring board]
The said pattern formation method of this invention can be used suitably for manufacture of a printed wiring board, especially the manufacture of a printed wiring board which has hole parts, such as a through hole or a via hole. Hereinafter, an example of the manufacturing method of the printed wiring board using the pattern formation method of this invention is demonstrated.

  As a method of manufacturing a printed wiring board having a hole portion such as a through hole or a via hole, (1) the pattern forming material is formed on a printed wiring board forming substrate having a hole portion as the substrate, and the photosensitive layer is the substrate. (2) The photosensitive layer is cured by irradiating a desired region from the opposite side of the laminate to the base, and (3) the laminate. A pattern can be formed by removing the support in the pattern forming material from the body, (4) developing the photosensitive layer in the laminate, and removing the uncured portion in the laminate.

  The removal of the support in (3) may be performed between (1) and (2) instead of between (2) and (4).

  Thereafter, in order to obtain a printed wiring board, a method of etching or plating the printed wiring board forming substrate using the formed pattern (for example, a known subtractive method or additive method (for example, a semi-additive method) And the full additive method)). Among these, in order to form a printed wiring board by industrially advantageous tenting, the subtractive method is preferable. After the treatment, the cured resin remaining on the printed wiring board forming substrate is peeled off. In the case of the semi-additive method, a desired printed wiring board can be manufactured by further etching the copper thin film portion after peeling. it can. A multilayer printed wiring board can also be manufactured in the same manner as the printed wiring board manufacturing method.

  Next, the manufacturing method of the printed wiring board which has a through hole using the said pattern formation material is further demonstrated.

  First, a printed wiring board forming substrate having through holes and having a surface covered with a metal plating layer is prepared. As the printed wiring board forming substrate, for example, a copper-clad laminate substrate and a substrate in which a copper plating layer is formed on an insulating substrate such as glass-epoxy, or an interlayer insulating film is laminated on these substrates to form a copper plating layer A substrate (laminated substrate) can be used.

Next, when the protective film is provided on the pattern forming material, the protective film is peeled off so that the photosensitive layer in the pattern forming material is in contact with the surface of the printed wiring board forming substrate. Is used for pressure bonding (lamination process). Thereby, the laminated body which has the said board | substrate for printed wiring board formation and the said laminated body in this order is obtained.
There is no restriction | limiting in particular as lamination | stacking temperature of the said pattern formation material, For example, room temperature (15-30 degreeC) or under heating (30-180 degreeC) is mentioned, Among these, under heating (60-140 degreeC) Is preferred.
There is no restriction | limiting in particular as roll pressure of the said crimping | compression-bonding roll, For example, 0.1-1 Mpa is preferable.
There is no restriction | limiting in particular as the speed | rate of the said crimping | compression-bonding, and 1-3 m / min is preferable. The printed wiring board forming substrate may be preheated or laminated under reduced pressure.

  In the formation of the laminate, the pattern forming material may be laminated on the printed wiring board forming substrate, and a photosensitive composition solution or the like for manufacturing the pattern forming material is used as the printed wiring board forming substrate. The photosensitive layer and the support may be laminated on the printed wiring board forming substrate by directly applying to the surface and drying.

  Next, the photosensitive layer is cured by irradiating light from the surface of the laminate opposite to the substrate. At this time, exposure may be performed after peeling off the support as necessary (for example, when the light transmittance of the support is insufficient).

  At this time, when the support is not yet peeled off, the support is peeled from the laminate (peeling step).

  Next, the uncured region of the photosensitive layer on the printed wiring board forming substrate is dissolved and removed with an appropriate developer to form a pattern of the cured layer for forming the wiring pattern and the cured layer for protecting the metal layer of the through hole. And a metal layer is exposed on the surface of the printed wiring board forming substrate (developing step).

  Moreover, you may perform the process which further accelerates | stimulates the hardening reaction of a hardening part by post-heat processing or post-exposure processing as needed after image development. The development may be a wet development method as described above or a dry development method.

  Next, the metal layer exposed on the surface of the printed wiring board forming substrate is dissolved and removed with an etching solution (etching step). Since the opening of the through hole is covered with a cured resin composition (tent film), the metal plating of the through hole is predetermined without etching liquid entering the through hole and corroding the metal plating in the through hole. It will remain in the shape. Thus, a wiring pattern is formed on the printed wiring board forming substrate.

  There is no restriction | limiting in particular as said etching liquid, According to the objective, it can select suitably, For example, when the said metal layer is formed with copper, a cupric chloride solution, a ferric chloride solution, Examples include alkaline etching solutions and hydrogen peroxide-based etching solutions. Among these, ferric chloride solutions are preferable from the viewpoint of etching factors.

Next, it removes from the said board | substrate for printed wiring board formation by making the said hardening layer into a peeling piece with strong alkaline aqueous solution etc. (hardened | cured material removal process).
There is no restriction | limiting in particular as a base component in the said strong alkali aqueous solution, For example, sodium hydroxide, potassium hydroxide, etc. are mentioned.
As pH of the said strong alkali aqueous solution, about 12-14 are preferable, for example, and about 13-14 are more preferable.
There is no restriction | limiting in particular as said strong alkali aqueous solution, For example, 1-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution etc. are mentioned.

  The printed wiring board may be a multilayer printed wiring board. The pattern forming material may be used not only for the above etching process but also for a plating process. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. And gold plating such as soft gold plating.

  Since the pattern forming apparatus and the pattern forming method of the present invention use the pattern forming material of the present invention, formation of various patterns, production of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, It can be suitably used for the production of holograms, micromachines, and proofs.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

(Example 1)
-Manufacture of pattern forming materials-
A photosensitive composition solution having the following composition was applied to a PET (polyethylene terephthalate) film (Toray Industries, 16FB50) having a thickness of 16 μm as the support and dried to form a photosensitive layer having a thickness of 30 μm. On the photosensitive layer, a 25 μm thick polyethylene film was laminated as a protective film to produce the pattern forming material.

ただし、前記式Ｍ−１中、ＥＯは、エチレンオキサイド基を表し、ＰＯは、プロピレンオキサイド基を表し、ＰＯは下記構造式（ｉ）及び（ii）のいずれであってもよく、ｒ＋ｓの平均値は１０であり、ｐ＋ｑの平均値は４である。

[Composition of photosensitive composition solution]
Methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 25/8/30/37, mass average molecular weight: 68,800, Tg: 105 ° C.) 5 parts by mass-polymerizable monomer represented by the following formula M-1 6.0 parts by mass-1 / 2 molar ratio adduct of decamethylene diisocyanate and tetraethylene oxide monomethacrylate 6.0 parts by mass Trimethylolpropane propylene oxide modified triacrylate (Toagosei Co., Ltd., Aronix M-310) 2.0 parts by mass Sensitizer represented by the following formula S-1 0.09 parts by mass 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenyl-biimidazole (photopolymerization initiator, 2 Compounds prepared by oxidative coupling of (o-chlorophenyl) -4,5-diphenylimidazole and 2,4-bis- (o-chlorophenyl) -5- [3,4-dimethoxyphenyl] -imidazole (Special Table 2002) No. 507004))) 2.2 parts by mass, toluenesulfonamide ... 1.0 parts by mass, carboxybenzotriazole ... 0.01 parts by mass, malachite green oxalate ... 0.02 Part by mass / leuco crystal violet ... 0.29 part by mass / F780F (Dainippon Ink Co., Ltd.) 30% by mass concentration product (methyl ethyl ketone solution) ... 0.05 part by mass / methyl ethyl ketone ... 40 mass Parts 1-methoxy-2-propanol 20 parts by mass The methacrylic acid / methyl methacrylate / s Len / benzyl methacrylate copolymer (copolymer composition (mass ratio): 25/8/30/37) I / O value of was 0.554 as calculated as described above.

However, in said formula M-1, EO represents an ethylene oxide group, PO represents a propylene oxide group, PO may be any of the following structural formulas (i) and (ii), and the average of r + s The value is 10, and the average value of p + q is 4.

-Preparation of photosensitive layer laminate-
As the substrate, the pattern-forming material photosensitive layer is peeled off from the surface of a copper-clad laminate (no through-hole, copper thickness 12 μm) polished, washed with water and dried. A laminator (MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.) so as to be in contact with the tension laminate, and the copper clad laminate, the photosensitive layer, the polyethylene terephthalate film (support), A photosensitive laminate was prepared in which were laminated in this order.
The pressure bonding conditions were a pressure roll temperature of 105 ° C., a pressure roll pressure of 0.3 MPa, and a laminating speed of 1 m / min.
These photosensitive compositions, pattern forming materials, and photosensitive laminates were evaluated for the shortest development time, sensitivity, resolution, adhesion, storage stability, presence / absence of development residues, and tent properties by the following methods. The results other than the shortest development time are shown in Table 1.

<Minimum development time>
The polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. The time required from the start of spraying of the aqueous sodium solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time.
As a result, the shortest development time was 19 seconds (the same applies to the following examples).

<Sensitivity>
The pattern described in JP-A-2006-30966 having a 405 nm laser light source as the light irradiation unit from the polyethylene terephthalate film (support) side to the photosensitive layer of the pattern forming material in the photosensitive laminate. It is using forming apparatus, and the exposure by irradiating with light energy of different light from 0.1 mJ / cm ² to 100 mJ / cm ² in ^{2 1/6} interval to cure the part of the area of the photosensitive layer It was. After standing at room temperature for 15 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate, and an aqueous sodium carbonate solution (30 ° C., 1% by mass) was formed on the entire surface of the photosensitive layer on the copper clad laminate. ) Was sprayed at a spray pressure of 0.15 MPa for twice the minimum development time to dissolve and remove uncured regions, and the thickness of the remaining cured regions was measured.
Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve thus obtained, the amount of light energy when the thickness of the cured region was the same as that before exposure was determined as the amount of light energy necessary for curing the photosensitive layer. Table 1 shows the amount of light energy (sensitivity) necessary for curing the photosensitive layer thus obtained.
The pattern forming apparatus has a light modulation unit made of the DMD.

<Resolution>
The said photosensitive laminated body was created by the method similar to the above, and it left still for 10 minutes at room temperature (23 degreeC, 55% RH). From the obtained polyethylene terephthalate film (support) of the photosensitive laminate, exposure of each line width is performed in increments of 1 μm from 5 μm to 50 μm with a line / space = 1/1 by using the pattern forming apparatus. It was. The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the pattern forming material determined by the sensitivity measurement. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate. Spray the entire surface of the photosensitive layer on the copper-clad laminate with a sodium carbonate aqueous solution (30 ° C., 1% by mass) as the developer at a spray pressure of 0.15 MPa for twice the shortest development time determined by the above method. Then, the uncured region was dissolved and removed. The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twisting was measured on the cured resin pattern line. did. The smaller the numerical value, the better the resolution.

<Adhesion>
Except for exposing a pattern with line / space = 1/5 and line width 10 to 100 μm using the pattern forming apparatus and spraying it for 6 times the shortest development time, the same operation as the resolution evaluation method is performed. The minimum line width without any abnormality such as peeling or twisting was measured on the cured resin pattern line and evaluated as being in close contact. Therefore, the smaller the value, the better the adhesion.

<Storage stability>
-Color development over time-
When the prepared photosensitive composition solution was allowed to stand for 7 days at 40 ° C. and a relative humidity of 70%, the color development with time (fogging with time) by leuco crystal violet was visually evaluated according to the following criteria.
○ ... No color development △ ... Slight color development is observed × ... Color development is remarkable

-Presence or absence of crystal precipitation-
The presence or absence of crystal precipitation of the photopolymerization initiator when the prepared photosensitive composition solution was allowed to stand at 0 ° C. for 7 days was visually evaluated according to the following criteria.
○: No crystal precipitation Δ: Some crystal precipitation is observed ×: Crystal precipitation is remarkably recognized

-Stable sensitivity over time-
The pattern forming material was prepared and a photosensitive laminate was prepared using the photosensitive composition solution in which the presence or absence of crystal precipitation was observed, and the sensitivity was measured by the above method.

-Edge fusion-
The pattern forming material was wound with a winder to produce a pattern forming material roll.
The obtained pattern forming material roll is slit with a coaxial slitter and wound up to a cylindrical core made of ABS resin having a length of 300 mm and an inner diameter of 76 mm by a width of 200 m to produce a photosensitive pattern forming material roll. did.
The pattern forming material roll thus obtained was wrapped in a black polyethylene cylindrical bag (film thickness: 80 μm, water vapor transmission rate: 25 g / m ² · 24 hr or less), and a polypropylene bush was pushed into both ends of the winding core. .
A roll-like sample whose both ends were closed with the bush was stored at 25 ° C. and 55% RH for 30 days, and then the presence or absence of end face fusion was observed and evaluated according to the following criteria.
〔Evaluation criteria〕
○: End face fusion is not confirmed, and it can be used satisfactorily △: Part of the end face is glossy, and a little amount of end face fusion occurs (use limit)
×: The state where the entire end surface is glossy and a large amount of end surface fusion occurs

<Presence of development residue>
The photosensitive layered product is exposed and developed by the same method as in the resolution evaluation using the pattern forming apparatus after 14 days in the dark (light-shielded) in the dark state (light-shielded). Using this, the surface of the exposed copper-clad laminate in the laminate is sprayed with an iron chloride etchant (ferric chloride-containing etching solution, 40 ° Baume, liquid temperature 40 ° C.) at 0.25 MPa for 36 seconds. Then, the etching process was performed by dissolving and removing the exposed copper layer not covered with the hardened layer.
The copper residue (development residue) in the non-pixel part of the unexposed part after the etching treatment was visually evaluated according to the following evaluation criteria.
-Evaluation criteria-
○ ・ ・ ・ No copper residue △ ・ ・ ・ There is some copper residue, but there is no problem in use.

<Tent characteristics>
A photosensitive laminate for tent property evaluation was prepared in the same manner as the photosensitive laminate, except that the copper-clad laminate in the photosensitive laminate was replaced with a copper-clad laminate having 200 through-holes with a diameter of 4 mm. Prepared and allowed to stand at room temperature (23 ° C., relative humidity 55%) for 10 minutes.
Next, the entire surface of the photosensitive layer in the photosensitive laminate was exposed from the polyethylene terephthalate film (support) of the prepared photosensitive laminate using the pattern forming apparatus.
The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the pattern forming material. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate. An aqueous solution of sodium carbonate (30 ° C., 1% by mass) as the developer was sprayed over the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa for twice the shortest development time.
The presence or absence of defects such as peeling or tearing of the hardened layer (tent film) formed on the through-hole opening in the copper-clad laminate thus obtained was observed with a microscope, and the incidence of defects was counted. .

(Example 2)
In Example 1, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenyl-biimidazole was converted to 2,2 ′, 4, 4-tetra- (o-chlorophenyl) -5,5 '-(3,4-dimethoxyphenyl) -biimidazole The sensitivity, resolution, and adhesion were the same as in Example 1 except that the amount was changed to 2.2 parts by mass. Property, storage stability, presence of development residue, and tent property were evaluated. The results are shown in Table 1.

(Example 3)
In Example 1, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenyl-biimidazole was converted to 2,2′-bis- (O-chlorophenyl) -4,4 ′, 5,5′-tetra- (m-methoxyphenyl) -1,2-biimidazole, 2,2′-bis (2-ethoxyphenyl) -4,4 ′, Except for changing to 2.6 parts by mass of 5,5′-tetraphenyl-1,1′-biimidazole, in the same manner as in Example 1, sensitivity, resolution, adhesion, storage stability, presence or absence of development residue, And the tent property was evaluated. The results are shown in Table 1.

Example 4
In Example 1, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenyl-biimidazole was converted to 2,2 ′, 5- Sensitivity and resolution were the same as in Example 1 except that 3 parts by mass of tris- (o-chlorophenyl) -4- (3,4-diethoxyphenyl) -4 ′, 5′-diphenyl-biimidazole was used. , Adhesion, storage stability, presence of development residue, and tent properties were evaluated. The results are shown in Table 1.

(Example 5)
In Example 1, a methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer was converted into a methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymer composition (mass ratio): 25/15/40. / 20, mass average molecular weight: 130,000, Tg: 93 ° C.) In the same manner as in Example 1, the sensitivity, resolution, adhesion, storage stability, presence / absence of development residue, and tent property were determined. evaluated. The results are shown in Table 1.
The I / O value of the methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymer composition (mass ratio): 25/15/40/20) is 0 as calculated above. .520.

(Example 6)
In Example 1, a methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer was converted into a methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 25/29/46, mass average molecular weight: 43,000, Tg: 127 ° C.) In the same manner as in Example 1, sensitivity, resolution, adhesion, storage stability, presence / absence of development residue, and tent property were evaluated. The results are shown in Table 1.
The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 25/29/46) was 0.550 when calculated as described above.

(Example 7)
In Example 1, a methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer was converted into a methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 20/56/24, mass average molecular weight: 75,000, Tg: 123 ° C.) In the same manner as in Example 1, sensitivity, resolution, adhesion, storage stability, presence / absence of development residue, and tent property were evaluated. The results are shown in Table 1.
The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 20/56/24) was 0.645 when calculated as described above.

(Example 8)
In Example 1, a methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer was converted into a methacrylic acid / styrene copolymer (copolymer composition (mass ratio): 28/72, mass average molecular weight: 53,100, Tg). Except for changing to 129 ° C.), the sensitivity, resolution, adhesion, storage stability, presence / absence of development residue, and tent property were evaluated in the same manner as in Example 1. The results are shown in Table 1.
The I / O value of the methacrylic acid / styrene copolymer (copolymer composition (mass ratio): 28/72) was 0.433 when calculated as described above.

Example 9
In Example 1, a methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer was changed to a methacrylic acid / styrene copolymer (copolymer composition (mass ratio): 20/80, mass average molecular weight: 43,700, Tg). : 120 ° C.) The sensitivity, resolution, adhesion, storage stability, presence or absence of development residue, and tent properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.
The I / O value of the methacrylic acid / styrene copolymer (copolymer composition (mass ratio): 20/80) was 0.328 when calculated as described above.

(Example 10)
In Example 1, a methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer was converted into a methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymer composition (mass ratio): 25/22/40. / 13, mass average molecular weight: 55,000, Tg: 105 ° C.) In the same manner as in Example 1, the sensitivity, resolution, adhesion, storage stability, presence / absence of development residue, and tent property were determined. evaluated. The results are shown in Table 1.
The I / O value of the methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymer composition (mass ratio): 25/22/40/13) is 0 as calculated above. .543.

(Example 11)
In Example 1, a methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer was converted into a methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 29/19/52, mass average molecular weight: 49, 900, Tg: 131 ° C.) In the same manner as in Example 1, sensitivity, resolution, adhesion, storage stability, presence / absence of development residue, and tent property were evaluated. The results are shown in Table 1.
The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 29/19/52) was 0.552 when calculated as described above.

Example 12
In Example 1, a methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer was converted into a methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 29/31/40, mass average molecular weight: 60,500, Tg: 132 ° C.) In the same manner as in Example 1, sensitivity, resolution, adhesion, storage stability, presence / absence of development residue, and tent property were evaluated. The results are shown in Table 1.
The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 29/31/40) was 0.627 when calculated as described above.

(Example 13)
In Example 1, a methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer was converted into a methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 25/41/34, mass average molecular weight: 58, 500, Tg: 128 ° C.) The sensitivity, resolution, adhesion, storage stability, presence or absence of development residue, and tent properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.
The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 25/41/34) was 0.627 when calculated as described above.

(Example 14)
In Example 1, except that toluenesulfonamide was not added, the sensitivity, resolution, adhesion, storage stability, presence / absence of development residue, and tent property were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 15)
In Example 1, except that carboxybenzotriazole was not added, the sensitivity, resolution, adhesion, storage stability, presence / absence of development residue, and tent property were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 16)
In Example 1, except that toluenesulfonamide and carboxybenzotriazole were not added, the sensitivity, resolution, adhesion, storage stability, presence of development residue, and tent property were evaluated in the same manner as in Example 1. . The results are shown in Table 1.

(Comparative Example 1)
In Example 1, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenyl-biimidazole was converted to 2,2′-bis ( o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole The sensitivity, resolution, adhesion, storage stability, development were the same as in Example 1 except that the amount was changed to 2.2 parts by mass. The presence or absence of residue and the tent property were evaluated. The results are shown in Table 1.

(Comparative Example 2)
In Example 1, a methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer was converted into an n-butyl acrylate / ethyl acrylate / methyl methacrylate / methacrylic acid copolymer (copolymer composition (mass ratio): 20/13 / 42/25, mass average molecular weight: 50,000) In the same manner as in Example 1, sensitivity, resolution, adhesion, storage stability, presence of development residue, and tent property were evaluated. The results are shown in Table 1.
The I / O value of the n-butyl acrylate / ethyl acrylate / methyl methacrylate / methacrylic acid copolymer (copolymer composition (mass ratio): 20/13/42/25) is calculated as described above. It was over 0.650.

表１の結果から、バインダーが、Ｉ／Ｏ値が０．３００〜０．６５０のポリマーを含み、前記光重合開始剤が、親水性基を有するヘキサアリールビイミダゾール化合物を含む実施例１〜１６では、感度、解像度、密着性、保存安定性、及びテント性が良好であり、現像残渣が少ないことが判った。特に、メトキシ基を有するヘキサアリールベンゾイミダゾール化合物を用いた実施例１〜３及び実施例５〜１６では、高感度であることが判った。また、トルエンスルホンアミド及びカルボキシベンゾトリアゾールを含む実施例１〜１３では、現像残渣がなく、かつテント性に優れることが判った。

From the result of Table 1, Examples 1-16 in which a binder contains the polymer of I / O value 0.300-0.650, and the said photoinitiator contains the hexaaryl biimidazole compound which has a hydrophilic group. Thus, it was found that the sensitivity, resolution, adhesion, storage stability, and tent property were good, and the development residue was small. In particular, Examples 1 to 3 and Examples 5 to 16 using a hexaarylbenzimidazole compound having a methoxy group were found to have high sensitivity. Moreover, in Examples 1-13 containing toluenesulfonamide and carboxybenzotriazole, it was found that there was no development residue and excellent tent properties.

The pattern forming material of the present invention has high sensitivity and high resolution, excellent adhesion and sensitivity over time, little development residue, and can form patterns such as wiring patterns with high definition. It can be suitably used for the production of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, etc., holograms, micromachines, and proofs.
Since the pattern forming apparatus and the pattern forming method of the present invention use the pattern forming material of the present invention, the formation of various patterns, the manufacture of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, It can be suitably used for the production of holograms, micromachines, and proofs.

Claims (10)

Having a photosensitive layer comprising a photosensitive composition containing at least a binder, a polymerizable compound, and a photopolymerization initiator on a support;
The pattern forming material, wherein the binder includes a polymer having an I / O value of 0.300 to 0.650, and the photopolymerization initiator includes a hexaarylbiimidazole compound having a hydrophilic group.   The pattern forming material according to claim 1, wherein the hydrophilic group of the hexaarylbiimidazole compound is an alkoxy group.   The pattern forming material according to claim 2, wherein the alkoxy group is a methoxy group.   The pattern forming material according to any one of claims 1 to 3, wherein a glass transition temperature (Tg) of a polymer having an I / O value of 0.300 to 0.650 is 80 ° C or higher.   A polymer having an I / O value of 0.300 to 0.650 includes a copolymer, and the copolymer has a structural unit derived from at least one of styrene, a styrene derivative, and benzyl (meth) acrylate. The pattern forming material according to any one of claims 1 to 4, which is alkali-soluble or swellable.   The pattern forming material according to claim 1, wherein the polymerizable compound contains a monomer having a propylene oxide group.   The pattern formation material in any one of Claim 1 to 6 containing a sensitizer.   The pattern formation material in any one of Claim 1 to 7 containing the compound which has NH group.   The pattern formation method characterized by including exposing at least the photosensitive layer in the pattern formation material in any one of Claims 1-8. The pattern forming method according to claim 9, wherein the exposure is performed without using a photomask.