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

Abstract

The object of the present invention is to provide a film with less surface defects, which can prevent light fog caused by the developer, less cracking of the unexposed film, high resolution, high masking film strength and good peelability after pattern formation, which can form A pattern forming material for a higher-definition pattern, a pattern forming device including the pattern forming material, and a pattern forming method using the pattern forming material. To this end, a pattern forming material is provided, wherein the photosensitive layer contains a binder, a polymerizable compound, a photopolymerization initiator, a heterocondensed ring compound, a polymerization inhibitor, a color developer and an organic solvent, and the binder The acid value is 50 to 400 mgKOH/g, and the mass average molecular weight is 10,000 to 100,000. The polymerizable compound contains at least one of a compound having a urethane group and a compound having an aryl group. The organic solvent is selected from ketones and alcohols. and at least one selected from ethers, and the content is 0.5% by mass or less.

Description

Pattern forming material, pattern forming device, and pattern forming method

technical field

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

Background technique

When forming a permanent pattern such as a wiring pattern, a pattern forming material that forms a photosensitive layer by applying and drying a photosensitive resin composition on a support is used. As a method of manufacturing the permanent pattern, for example, on a substrate such as a copper-clad laminated board on which the permanent pattern is formed, the pattern forming material is laminated to form a laminate, and the photosensitive layer in the laminate is exposed. , after this exposure, the photosensitive layer is developed to form a pattern, and then the permanent pattern is formed by performing an etching process or the like.

For the above-mentioned pattern forming material, there is a proposal of adding a compound having a phenolic hydroxyl group, an aromatic ring, a heterocycle, or an imino group to the photosensitive resin composition in order to improve storage stability or improve resolution. Polymerization inhibitor (see Patent Documents 1 to 4). However, even in this case, there is no disclosure or suggestion of a high-sensitivity dry film resist capable of suppressing a decrease in sensitivity by reducing the remaining amount of an organic solvent.

In addition, for DFR, in addition to improving the sensitivity, peelability after pattern formation and the like are also required.

Therefore, there has not yet been provided a method that has less surface defects, can prevent light fog caused by the developer, has less cracking of the unexposed film, has high resolution, has high masking film strength, and has good peelability after pattern formation, and can form a high-quality film. Further improvement and development are required for a fine pattern pattern forming material, a pattern forming device including the pattern forming material, and a pattern forming method using the pattern forming material.

Patent Document 1: JP-A-2000-268211

Patent Document 2: JP-A-2003-29399

Patent Document 3: JP-A-2004-4527

Patent Document 4: JP-A-2004-4528

Contents of the invention

The present invention has been made in view of the above-mentioned current situation, and aims to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention provides a film having less surface defects, preventing photofog caused by a developer, less cracking of an unexposed film, high resolution, high masking film strength, good peelability after pattern formation, and capable of forming a more transparent film. A pattern forming material for a high-definition pattern, a pattern forming device including the pattern forming material, and a pattern forming method using the pattern forming material.

As means for solving the above-mentioned problems, as follows, that is,

<1> A pattern forming material characterized in that,

It has a support and a photosensitive layer on the support, and the photosensitive layer contains (A) binder, (B) polymerizable compound, (C) photopolymerization initiator, (D) heterocondensed ring compound , (E) polymerization inhibitor, (F) developer and (G) organic solvent,

(A) The acid value of the binder is 50-400 mgKOH/g, and the mass-average molecular weight is 10,000-100,000,

(B) The polymerizable compound contains at least any one of (b1) a compound having a urethane group, (b2) a compound having an aryl group, and (b3) a compound having a polyalkylene oxide chain,

(G) The organic solvent is at least one selected from ketones, alcohols, and ethers, and the remaining amount is 0.5% by mass or less. In the pattern forming material described in <1>, by specifying the acid value and weight average molecular weight of the binder contained in the photosensitive layer, not only the compound contained in the polymerizable compound but also the compound contained in the organic solvent is specified. The compound and content can form less surface faults, prevent light fog caused by the developer, less cracking of the unexposed film, high resolution, high strength of the masking film and good peelability after pattern formation, higher fineness picture of.

<2> The pattern forming material according to <1>, wherein,

(A) The I/O value of the adhesive is 0.35 to 0.60.

<3> The pattern forming material according to <1> or <2>, wherein,

(B) The polymerizable compound contains a compound having a polyalkylene oxide chain having at least one of an ethylene group and a propyl group.

<4> The pattern forming material according to any one of <1> to <3>, wherein,

(D) The heterocondensed ring system compound includes at least one selected from heterocondensed ring system ketone compounds, quinoline compounds, and acridine compounds.

<5> The pattern forming material according to any one of <1> to <4>, wherein the (E) polymerization inhibitor is a compound having at least two or more phenolic hydroxyl groups, an aromatic At least one selected from a compound having a ring, a compound having a heterocyclic ring substituted with an imino group, and a hindered amine compound.

<6> The pattern forming material according to any one of <1> to <5>, further comprising a dye containing a compound having a triallylmethane skeleton, a reducing agent, and a hydrogen donor compound.

<7> The pattern forming material according to any one of <1> to <6>, wherein (G) the organic solvent is at least one of methyl ethyl ketone, cyclohexanone, methanol, methyl propylene glycol, and tetrahydrofuran any kind.

<8> The pattern forming material according to any one of <6> to <7>, wherein the dye containing a compound having a triallylmethane skeleton is an allylsulfonic acid compound.

<9> The pattern forming material according to any one of <6> to <8>, wherein the reducing agent is 1-phenyl-3-pyrazolidinone.

<10> The pattern forming material according to any one of <1> to <9>, wherein, for the photosensitive layer, when the photosensitive layer is exposed and developed, the thickness of the exposed portion of the photosensitive layer is set at the The minimum energy of light used for the exposure that does not change after exposure and development is 0.1 to 20 mJ/cm ² .

<11> The pattern forming material according to any one of <1> to <10>, wherein the binder shows swelling or solubility with respect to an aqueous alkaline solution.

<12> The pattern forming material according to any one of <1> to <11>, wherein the binder contains a copolymer having at least one of styrene and styrene derivatives. Structural units.

<13> The pattern forming material according to any one of <1> to <12>, wherein the binder has a glass transition temperature of 80° C. or higher.

<14> The pattern forming material according to any one of <1> to <13>, wherein the polymerization inhibitor is at least one selected from aromatic rings, heterocyclic rings, imino groups, and phenolic hydroxyl groups.

<15> The pattern forming material according to any one of <1> to <14>, wherein the polymerization inhibitor is selected from the group consisting of catechol, phenothiazine, phenoxazine, hindered amine and their at least one of the derivatives.

<16> The pattern forming method according to any one of <1> to <15>, wherein the content of the polymerization inhibitor is 0.005 to 0.5% by mass relative to the polymerizable compound.

<17> The pattern forming material according to any one of <1> to <16>, wherein the photopolymerization initiator contains a halogenated hydrocarbon derivative, phosphine oxide, hexaarylbidiimidazole, At least one selected from oxime derivatives, organic peroxides, thio compounds, ketone compounds, acylphosphine oxide compounds, aromatic onium salts, and ketoxime ethers.

<18> The pattern forming material according to any one of <1> to <17>, wherein the photopolymerization initiator contains hexaarylbidiimidazole.

<19> The pattern forming material according to any one of <1> to <18>, wherein the photosensitive layer has a thickness of 1 to 100 μm.

<20> The pattern forming material according to any one of <1> to <19>, wherein the support body is an elongated object.

<21> The pattern forming material according to any one of <1> to <20>, wherein the pattern forming material is an elongated object and is rolled into a roll shape.

<22> The pattern forming material according to any one of <1> to <21>, which has a protective film on the photosensitive layer in the pattern forming material.

<23> The pattern forming material according to any one of <1> to <22>, which has a protective film on the photosensitive layer, and the protective film contains a polypropylene resin, an ethylene-propylene copolymer resin, and a polyethylene glycol resin. At least one selected from ethylene glycol phthalate resins.

<24> A pattern forming device comprising the pattern forming material according to any one of <1> to <23>,

It includes at least: a light irradiation unit capable of irradiating light; and a light modulation unit for modulating the light from the light irradiation unit to expose the photosensitive layer in the pattern forming material. In the pattern forming apparatus described in <24>, the light irradiation means irradiates light to the light modulation means. The light modulation means modulates the light received from the light irradiation means. The modulated light is exposed to the photosensitive layer by the light modulation mechanism. For example, if the photosensitive layer is developed later, a high-definition pattern is formed.

<25> The pattern forming device according to the above <24>, wherein the light modulating means further includes a pattern signal generating means for generating a control signal based on the formed pattern information, and corresponds to the control generated by the pattern signal generating means. The signal modulates the light irradiated from the light irradiation mechanism. In the pattern forming device described in <25>, the light modulation means includes the pattern signal generation means, and the light irradiated from the light irradiation means is modulated in accordance with a control signal generated by the pattern signal generation means.

<26> The pattern forming device according to any one of the above <24> to <25>, wherein the light modulating mechanism has n drawing parts, which can correspond to the pattern information to be formed, and for the n drawing parts, Arbitrary less than n number of the drawing units arranged consecutively among the drawing units are controlled. In the pattern forming apparatus described in <26>, any number of less than n drawing units arranged consecutively from the n drawing units in the light modulation mechanism is controlled in accordance with the pattern information, whereby The light of the light irradiation mechanism is modulated at high speed.

<27> The pattern forming device according to any one of <24> to <26>, wherein the light modulation mechanism is a spatial light modulation element.

<28> The pattern forming device according to the above <27>, wherein the spatial light modulator is a digital micromirror device (DMD).

<29> The pattern forming device according to any one of <26> to <28>, wherein the drawing unit is a micromirror.

<30> The pattern forming apparatus according to any one of <24> to <29>, wherein the light irradiation means can compositely irradiate two or more kinds of light. In the pattern forming apparatus described in <30>, two or more types of light can be compositely irradiated by the light irradiation means, and exposure can be performed with exposure light having a deep focal depth. As a result, the pattern forming material can be exposed extremely finely. For example, if the photosensitive layer is developed afterwards, an extremely fine pattern can be formed.

<31> The pattern forming apparatus according to any one of the above <24> to <30>, wherein the light irradiation means has multiple types of lasers, a multimode optical fiber, and laser beams respectively irradiated from the multiple types of lasers. Concentrating light to be combined with the light concentrating optical system of the multimode optical fiber. In the pattern forming device described in <31>, the light irradiation mechanism can converge the laser light irradiated from the plurality of types of lasers by using the condensing optical system to be combined with the multimode optical fiber, and can Expose with exposure light with a deep depth of focus. As a result, the pattern forming material can be exposed extremely finely. For example, if the photosensitive layer is developed afterwards, an extremely fine pattern can be formed.

<32> A pattern forming method, comprising at least a step of exposing the photosensitive layer in the pattern forming material according to any one of <1> to <23>. In the pattern formation method described in this <32>, exposure is performed with respect to the said pattern formation material. For example, if the photosensitive layer is developed afterwards, a high-definition pattern can be formed.

<33> The pattern forming method according to <32>, wherein the pattern forming material is laminated and exposed while applying at least one of heating and pressure to the base.

<34> The pattern forming method according to any one of <32> to <33>, wherein the exposure is performed as a sample based on information on a pattern to be formed.

<35> The pattern forming method according to any one of <32> to <34>, wherein the exposure is performed using light modulated according to the control signal after generating a control signal based on the pattern information to be formed. In the patterning method described in <35>, a control signal is generated based on the formed patterning information, and light is modulated according to the control signal.

<36> The pattern forming method according to any one of <32> to <35>, wherein the exposure is performed using a light irradiation mechanism that irradiates light, and irradiating from the light irradiation mechanism based on pattern information to be formed. Light is modulated by a light modulation mechanism.

<37> The pattern forming method according to <36>, wherein the exposure is performed through a microlens array in which microlenses are arranged after the light is modulated by a light modulation mechanism, and the microlenses have a function capable of correcting the Aspherical surface with aberrations caused by deformation of the output surface of the drawing part in the light modulation mechanism. In the pattern forming method described in <37>, the light modulated by the light modulation mechanism passes through the aspherical surface in the microlens array, and the image caused by the deformation of the emission surface in the drawing part The difference is corrected. As a result, deformation of the image formed on the pattern forming material can be suppressed, and the exposure of the pattern forming material can be performed extremely finely. For example, if the photosensitive layer is developed afterwards, an extremely fine pattern can be formed.

<38> The pattern forming method according to <37>, wherein the aspherical surface is a toric surface. In the pattern forming method described in <38>, by making the aspheric surface a toric surface, the aberration caused by the deformation of the radiation surface in the drawing part can be effectively corrected, and the pattern forming material can be effectively suppressed. The deformation of the above image. As a result, exposure to the pattern forming material is performed extremely finely. For example, if the photosensitive layer is developed afterwards, an extremely fine pattern can be formed.

<39> The pattern forming method according to any one of <32> to <38>, wherein the exposure is performed through an aperture array. In the pattern forming method described in <39>, the extinction ratio can be increased by exposing through the aperture array. As a result, exposure can be performed extremely finely. For example, if the photosensitive layer is developed afterwards, extremely fine patterns can be formed.

<40> The pattern forming method according to any one of <32> to <39>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer. In the pattern forming method described in <40>, exposure can be performed at a high speed by performing exposure while moving the modulated light relative to the photosensitive layer. For example, if the photosensitive layer is developed afterwards, a high-definition pattern can be formed.

<41> The pattern forming method according to any one of <32> to <40>, wherein the exposure is performed on a part of the photosensitive layer.

<42> The pattern forming method according to any one of <32> to <41>, wherein the photosensitive layer is developed after exposure. In the pattern forming method described in <42>, a high-definition pattern can be formed by developing the photosensitive layer after the exposure.

<43> The pattern forming method according to <42>, wherein a permanent pattern is formed after performing development.

<44> The pattern forming method according to <43>, wherein the permanent pattern is a wiring pattern, and the permanent pattern is formed by at least one of etching and plating.

Utilizing the present invention, the conventional problems can be solved, the surface defect is less, the light fog caused by the developer can be prevented, the crack of the unexposed film is less, the resolution is high, the strength of the masking film is high, and the peelability after pattern formation is good. A pattern forming material capable of forming higher-definition patterns, a pattern forming device including the pattern forming material, and a pattern forming method using the pattern forming material.

Detailed ways

(pattern forming material)

The pattern forming material of the present invention has at least a support and a photosensitive layer on the support, and may also have a protective film and other layers selected as appropriate.

<photosensitive layer>

The photosensitive layer contains (A) binder, (B) polymerizable compound, (C) photopolymerization initiator, (D) heterocondensed ring compound, (E) polymerization inhibitor, (F) color developer And (G) an organic solvent contains other components selected suitably, such as a dye and a reducing agent, as needed. Here, the number of lamination of the photosensitive layer may be one layer, or may be two or more layers.

In addition, when exposing and developing the photosensitive layer, the minimum energy of light at which the thickness of the exposed portion of the photosensitive layer does not change before and after the development is preferably 0.1 to 20 mJ/cm ² , more preferably 0.5 to 10 mJ/cm ² , particularly preferably 1 to 8 mJ/cm ² .

If the minimum energy is less than 0.1 mJ/cm ² , fogging may occur in the processing step, and if it exceeds 20 mJ/cm ² , the time required for exposure may become longer and the processing speed may become slower.

Here, the "minimum energy of the light used in the exposure so that the thickness of the exposed portion of the photosensitive layer does not change after the exposure and development" refers to the so-called development sensitivity, which can be expressed, for example, from the A graph (sensitivity curve) of the relationship between the energy of light used in the exposure (exposure amount) when the photosensitive layer is exposed and the thickness of the cured layer produced by the development process subsequent to the exposure Get it.

The thickness of the cured layer increases as the exposure amount increases, and then becomes approximately the same as the thickness of the photosensitive layer before the exposure and is approximately constant. The development sensitivity is a value obtained by reading the minimum exposure amount at which the thickness of the cured layer becomes substantially constant.

When the difference between the thickness of the cured layer and the thickness of the photosensitive layer before the exposure is within ±1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.

The method for measuring the thickness of the cured layer and the photosensitive layer before the exposure is not particularly limited, and can be appropriately selected according to the purpose, for example, using a film thickness measuring device, a surface roughness measuring machine (such as a FUCOM 1400D, manufactured by Tokyo Seiki Co., Ltd.) and the like.

—(A) Adhesive—

The acid value of the binder is 50-400 mgKOH/g, preferably 75-300 mgKOH/g, more preferably 100-250 mgKOH/g.

If the acid value is less than 50 mgKOH/g, the developability is insufficient, or the resolution is poor, and patterns such as wiring patterns may not be obtained with high precision. If it exceeds 400 mgKOH/g, the developer resistance and adhesion of the pattern may be deteriorated. At least one of them deteriorates, and permanent patterns such as wiring patterns cannot be obtained with high precision.

The mass average molecular weight in the molecular weight of the said binder is 10,000-100,000, Preferably it is 30,000-80,000.

When the said mass average molecular weight is less than 10,000, the intensity|strength of a film will run short easily, and stable manufacture may become difficult, and when it exceeds 100,000, developability may fall.

The upper limit of the I/O value is, for example, preferably 0.60, and more preferably 0.58, from the viewpoint of further improving at least one of the resolution and hiding properties.

The lower limit of the I/O value is preferably 0.35, more preferably 0.40, for example, from the viewpoint of improving developability.

As a method of adjusting the I/O value of the adhesive, it can be adjusted to, for example, 0.35 by appropriately selecting at least one of the type of monomer constituting the copolymer and the polymerization ratio (content) when the monomer is polymerized. ~0.60 range.

The I/O value is a value that treats the polarity of various organic compounds called (inorganic value)/(organic value) from the perspective of the organic concept, and is a functional group assignment method that sets parameters in each functional group one. Specifically, the I/O value is described in Organic Concept Map (Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Items 1 to 16 (1954); Field of Chemistry, No. 11 Volume No. 10, Items 719-725 (1957); Aroma Magazine No. 34, Items 97-111 (1979); Aroma Magazine No. 50, Items 79-82 (1981) and others are described in detail.

The concept of the I/O value divides the properties of compounds into organic groups representing covalency and inorganic groups representing ionic bonding, and the positions of all organic compounds are determined on the axis named organic axis and inorganic axis Every 1 point on the orthogonal coordinates of .

The inorganicity value refers to a value obtained by numericalizing the influence of various substituents, bonds, etc., which an organic compound has on the boiling point, on the basis of a hydroxyl group, based on a hydroxyl group. Specifically, if the distance between the boiling point curve of a straight-chain alcohol with about 5 carbon atoms and the boiling point curve of a straight-chain paraffin is about 100°C, the influence of one hydroxyl group is set to 100 by numerical value, based on This numerical value is the value of the inorganicity of the substituents that the organic compound has by quantifying the influence of various substituents, various bonds, etc. on the boiling point. For example, the inorganicity value of the -COOH group is 150, and the inorganicity value of the double bond is 2. Therefore, the inorganicity value of a certain organic compound means the sum of the inorganicity values of various substituents, bonds, etc. that the compound has.

The organic value refers to a value determined based on the influence of a carbon atom representing the methylene group on the boiling point in units of methylene groups in the molecule. That is to say, the average value of the boiling point rise of straight-chain saturated hydrocarbon compounds with carbon number 5 to 10 is 20°C for every addition of 1 carbon. Therefore, based on this, the organic value of 1 carbon atom is set as 20. This is a standard, and the numerical value of the influence of various substituents, bonds, etc. on the boiling point is an organic value. For example, the organic value of nitro (—NO ₂ ) is 70.

The closer the I/O value is to 0, the more it indicates a non-polar (hydrophobic, highly organic) organic compound, and the larger it is, the more it indicates a polar (hydrophilic, highly inorganic) organic compound.

An example of the calculation method of the I/O value will be described below.

The I/O value of methacrylic acid/methyl methacrylate/styrene copolymer (copolymer composition (molar ratio): 2/5/3) is calculated by calculating the inorganic value and organic value of the copolymer by the following method It can be obtained by calculating the following formula (inorganic value of the copolymer)/(organic value of the copolymer) after calculating the property value.

The inorganic value of the copolymer was obtained by obtaining (the inorganic value of the methacrylic acid)×(the molar ratio of the methacrylic acid), (the inorganic value of the methyl methacrylate)×(the The molar ratio of the above methyl methacrylate), and the sum of (the inorganic value of the styrene)×(the molar ratio of the styrene).

The methacrylic acid has 1 carboxyl group, the methyl methacrylate has 1 ester group, and the styrene has 1 aromatic ring, so

The inorganic value of the methacrylic acid: 150 (the inorganic value of the carboxyl group) × 1 (the number of the carboxyl group) = 150,

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

The inorganic value of the styrene: 15 (the inorganic value of the aromatic ring) × 1 (the number of the aromatic ring) = 15,

Thus, the inorganicity value of the copolymer utilizes the following formula: 150 x 2 (molar ratio of methacrylic acid) + 60 x 5 (molar ratio of methyl methacrylate) + 15 x 3 (molar ratio of styrene) The calculation was calculated as 645.

The organic value of the copolymer is obtained by obtaining (the organic value of the methacrylic acid) × (the molar ratio of the methacrylic acid), (the organic value of the methyl methacrylate) × (the The molar ratio of methyl methacrylate) and the sum of (the organic value of styrene)×(the molar ratio of styrene) are calculated.

The methacrylic acid has 4 carbon atoms, the methyl methacrylate has 5 carbon atoms, and the styrene has 8 carbon atoms, so

The organic value of the methacrylic acid: 20 (organic value of carbon atoms) × 4 (number of carbon atoms) = 80,

The organic value of the methyl methacrylate: 20 (organic value of carbon atoms) × 5 (number of carbon atoms) = 100,

The organic value of the styrene: 20 (organic value of carbon atoms) x 8 (number of carbon atoms) = 160.

Thus, the organic value of the copolymer utilizes the following formula: 80×2 (the molar ratio of the methacrylic acid)+100×5 (the molar ratio of the methyl methacrylate)+160×3 (the The molar ratio of styrene) was calculated to be 1140.

Accordingly, the I/O value of the copolymer was judged to be 645 (inorganic value of the copolymer)/1140 (organic value of the copolymer)=0.566.

The binder is not particularly limited as long as the I/O value is within the numerical range, and may be appropriately selected according to the purpose, and may have, for example, an acidic group.

As the binder, the acid value and mass average molecular weight are not particularly limited as long as they are within the above ranges. For example, the binder is preferably swellable to an alkaline aqueous solution, and more preferably soluble to an alkaline aqueous solution. In addition, a polymerizable group may be contained in the binder.

As a binder which shows swelling property or solubility with respect to an alkaline aqueous solution, the binder which has an acidic group is mentioned preferably, for example.

The acidic group is not particularly limited and may be appropriately selected according to the purpose, for example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc., and a carboxyl group is preferable among them.

Examples of binders having carboxyl groups include vinyl copolymers having carboxyl groups, polyurethane resins, polyamic acid resins, and modified epoxy resins. From the viewpoints of solubility, synthesis suitability, ease of adjustment of film physical properties, etc., ethylene copolymers having carboxyl groups are preferred. In addition, from the viewpoint of developability, a copolymer of at least any one of styrene and a styrene derivative is also preferable.

The ethylene copolymer having a carboxyl group can be obtained by at least copolymerization of (1) vinyl monomers having a carboxyl group and (2) monomers copolymerizable with them. Specific examples of these monomers include compounds described in paragraphs [0164] to [0201] and [0203] to [0205] of JP-A-2005-258431.

The content of the binder in the photosensitive layer is not particularly limited and can be appropriately selected according to the purpose, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, particularly preferably 40 to 80% by mass.

If the content is less than 10% by mass, the alkali developability or the adhesion to the substrate for forming a printed wiring board (for example, a copper-clad laminate) will decrease, and if it exceeds 90% by mass, the stability relative to the development time will decrease. Or the strength of the cured film (masking film) may decrease. In addition, the said content may be the total content of the polymer binder used together with the said adhesive as needed.

When the binder is a substance having a glass transition temperature, the glass transition temperature is not particularly limited and can be appropriately selected according to the purpose, but it can be selected from the tack, edge fusion, etc. of the pattern forming material, for example. From the viewpoint of at least any one of the detachability of the support, it is preferably 80°C or higher, more preferably 100°C or higher, and particularly preferably 120°C or higher.

When the said glass transition temperature is less than 80 degreeC, the viscosity of the said pattern forming material may increase and the detachability of the said support body may worsen.

—(B) Polymeric compound—

As the polymerizable compound, at least one of (b1) a compound having a urethane group and (b2) a compound having an aryl group is contained, and if necessary, a compound having a polyalkylene oxide compound and other polymerizable compounds are included. become. In addition, they preferably have two or more kinds of polymerizable groups.

Examples of the polymerizable group include ethylenically unsaturated bonds (such as (meth)acryloyl, (meth)acrylamide, styryl, vinyl such as vinyl ester or vinyl ether, allyl ether or Allyl groups such as allyl esters, etc.), polymerizable cyclic ether groups (such as epoxy groups, oxetanyl groups, etc.), among them, ethylenically unsaturated bonds are preferred.

——(b1) Monomers with urethane groups——

The monomer having a urethane group is not particularly limited as long as it has a urethane group, and can be appropriately selected according to the purpose. compound etc.

The content of the compound having the urethane group in the polymerizable compound is preferably 70% by mass or less, more preferably 20 to 60% by mass, and still more preferably 30 to 50% by mass. When the content exceeds 70% by mass, resolution, adhesiveness, and the like may deteriorate.

——(b2) A monomer having an aryl group——

The compound having an aryl group is not particularly limited as long as it has an aryl group, and can be appropriately selected according to the purpose. Esters or amides of unsaturated carboxylic acids, etc.

Specifically, compounds described in paragraph numbers [0264] to [0271] of JP-A-2005-258431 and the like are exemplified.

The content of the compound having an aryl group in the polymerizable compound is preferably 70% by mass or less, more preferably 20 to 60% by mass, and still more preferably 30 to 50% by mass. When the content exceeds 70% by mass, resolution, adhesiveness, hiding properties, and the like may deteriorate.

——compounds having polyalkylene oxide chains—

A compound having a polyalkylene oxide chain may also be contained in the pattern forming material of the present invention.

The compound having a polyalkylene oxide chain is not particularly limited, and may be a monofunctional monomer or a polyfunctional monomer.

As said monofunctional monomer, the compound represented by following structural formula (i) is mentioned preferably, for example.

[chemical 1]

结构式(i)

Structural formula (i)

In the structural formula (i), R ¹ represents a hydrogen atom or a methyl group.

X represents an alkylene group having 2 to 6 carbon atoms, and preferably has a chain structure rather than a ring structure. A chain alkylene group may also have a branch. As this alkylene group, an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group etc. are mentioned, for example, Among these, an ethylene group and a propylene group are preferable.

n is an integer of 1 to 30. When n is 2 or more, a plurality of (-X-O-) are the same or different from each other. When (-X-O-) is different from each other, for example, ethylene and propylene are preferably used. base combination etc.

Examples of R ² include alkyl groups, aryl groups, and aralkyl groups, and these groups may be further substituted with substituents.

As the alkyl group, examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, hexyl, cyclohexyl, 2-ethylhexyl, dodecyl, hexadecane base, octadecyl, etc. This alkyl group may have a substituent, and may have a branched chain or ring structure.

As said aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned, for example. This aralkyl group may also have a substituent.

Examples of the aryl group include phenyl, naphthyl, tolyl, xylyl, ethylphenyl, methoxyphenyl, propylphenyl, butylphenyl, tert-butylphenyl, Octylphenyl, nonylphenyl, chlorophenyl, cyanophenyl, dibromophenyl, tribromophenyl, biphenyl, benzylphenyl, α-dimethyl-benzylphenyl, etc. This aryl group may also have a substituent.

As a substituent in the said alkyl group, an aralkyl group, and an aryl group, a halogen atom, an aryl group, an alkenyl group, an alkoxy group, a cyano group etc. are mentioned, for example.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and the like.

The aryl group preferably has 6-20 total carbon atoms, more preferably 6-14. Examples of the aryl group include phenyl, naphthyl, anthracenyl, methoxyphenyl and the like.

The alkenyl group preferably has 2-10 total carbon atoms, more preferably 2-6. As this alkenyl group, an ethynyl group, a propenyl group, a butyryl group etc. are mentioned, for example.

The alkoxy group may be branched, and preferably has 1-10 total carbon atoms, more preferably 1-5. Examples of the alkoxy group include methoxy, ethoxy, propoxy, 2-methylpropoxy, butoxy and the like.

As a compound represented by the said structural formula (i), specifically, the compound etc. which are represented by the following structural formula are mentioned. However, in the following formulae, R represents a hydrogen atom or a methyl group. n represents an integer of 1-30, m and L represent an integer of 1 or more, and m+L represents an integer of 1-30. Me represents a methyl group, and Bu represents a butyl group.

[Chem 2]

[Chem 3]

In addition, among the compounds having a polyalkylene oxide chain, as a compound having at least any one of ethylene and propylene groups, polyalkylene oxides having 10 to 30 ethylene or propylene groups are also preferably used. Ethylene glycol, polypropylene glycol.

The compound which has the said polyalkylene oxide chain may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate having 2 to 30 ethylene groups (such as diethylene glycol di(meth)acrylate) (Meth)acrylate, Triethylene glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, Macrogol #400 Dimethacrylate, Polyethylene Glycol #600 Dimethacrylate acrylate, polyethylene glycol #1000 dimethacrylate, etc.), propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate with 2 to 18 acrylic groups (such as dipropylene glycol di(meth)acrylate) Meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, dodecapropylene glycol di(meth)acrylate, etc.), each having at least 1 ethylene glycol chain/propylene glycol Di(meth)acrylates of alkylene glycol chains (for example, compounds described in International Publication No. 01/98832), polytetramethylene glycol di(meth)acrylates, and the like.

Among them, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and alkylene diacrylate having at least one ethylene glycol chain/propylene glycol chain are preferable from the viewpoint of the ease of acquisition. Alcohol chain di(meth)acrylate, etc.

The content of the compound having the polyalkylene oxide chain in the polymerizable compound is preferably 40% by mass or less, more preferably 1 to 30% by mass, and still more preferably 1 to 25% by mass. If the content is less than 0.1% by mass, the effect of improving peelability or development range may become insufficient, and if it exceeds 40% by mass, resolution, adhesiveness, hiding properties, etc. may deteriorate.

——Other polymeric compounds——

The pattern formation material of this invention can also use the polymeric compound other than the said polymeric compound. For example, esters of unsaturated carboxylic acids (such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and aliphatic polyhydric alcohol compounds, unsaturated carboxylic acids and polyamine compounds amides etc.

Specifically, compounds described in paragraph numbers [0273] to [0283] of JP-A-2005-258431 and the like are exemplified.

The content of the polymerizable compound in the photosensitive layer is, for example, preferably 5 to 90% by mass, more preferably 15 to 60% by mass, particularly preferably 20 to 50% by mass.

If the content is 5% by mass, the strength of the masking film may decrease, and if it exceeds 90% by mass, edge fusion during storage (bleeding failure from the roll end) may deteriorate.

—(C) Photopolymerization Initiator—

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. The active photopolymerization initiator can be a heterocondensed ring compound excited by light or an activator that interacts with a sensitizer to generate active free radicals, or it can be an initiator that initiates cationic polymerization according to the type of monomer .

In addition, the photopolymerization initiator preferably contains at least one component having a molecular absorption coefficient of at least about 50 in the range of about 300 to 800 nm. The wavelength is more preferably 330 to 500 nm.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (such as derivatives having a triazine skeleton, derivatives having an oxadiazole skeleton, etc.), phosphine oxide, hexaarylbiimidazole, and oxime derivatives. substances, organic peroxides, thio compounds, ketone compounds, acyl phosphine oxides, aromatic onium salts, ketoxime ethers, etc. Specific examples of photopolymerization initiators other than the oxime derivatives include those described in paragraphs [0288] to [0299] and paragraphs [0305] to [0309] of JP-A-2005-258431 compounds, etc.

Examples of the oxime derivatives include 3-benzoyloxyiminobutan-2-one, 3-acetyliminobutan-2-one, 3-propionyloxyiminobutane -2-ketone, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-benzene ylpropan-1-one, 3-(4-tosyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, etc.

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

—(D) Heterocondensed ring compound—

As the heterocondensed ring compound, in order to adjust the exposure sensitivity or the photosensitive wavelength when exposing the photosensitive layer to be described later, or to increase the thickness of the exposed part of the photosensitive layer at the time of exposing and developing the photosensitive layer It is added from the viewpoint of the minimum energy (sensitivity) of the light that does not change before and after development. By using the heterocondensed ring compound in combination, the minimum energy (sensitivity) of the photosensitive layer can be adjusted very easily to 0.1 to 20 mJ/cm ² , for example.

The heterocondensed ring compound is preferably an appropriate compound corresponding to a visible ray, an ultraviolet laser, a visible laser, or the like as a light irradiation mechanism described later.

The heterocondensed ring system compound becomes an excited state under the action of active energy rays, and can generate free radicals by interacting with other substances (such as free radical generators, acid generators, etc.) (such as energy movement, electron movement, etc.) Or useful bases such as acids.

In addition, the heterocondensed ring compound not only improves the sensitivity of the photosensitive layer but also functions as a photopolymerization initiator for initiating polymerization of monomers under light excitation.

The heterocondensed ring system compound refers to a polycyclic compound having a heteroelement in the ring, and preferably contains a nitrogen atom in the ring.

As the heterocondensed ring compound, for example, it is preferable to contain at least one selected from a heterocondensed ring compound, a quinoline compound, and an acridine compound.

Specific examples of the heterocondensed ring compound include acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone Acridone compounds such as ketones; 3-(2-benzofuroyl)-7-diethylaminocoumarin, 3-(2-benzofuryl)-7-(1-pyrrolidinyl) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3-(2-methoxybenzoyl)-7-diethylaminocoumarin, 3-(4-dimethyl Aminobenzoyl)-7-diethylaminocoumarin, 3,3'-carbonylbis(5,7-di-n-propoxycoumarin), 3,3'-carbonylbis-(7 -diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3-(2-furoyl)-7-diethylaminocoumarin, 3-(4- Diethylaminocinnamoyl)-7-diethylaminocoumarin, 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzoyl-5,7-dipropoxy Base coumarin, 7-benzotriazol-2-yl coumarin, 7-diethylamino-4-methyl coumarin, in addition there are JP 5-19475 bulletin, JP 7-271028 2002-363206, 2002-363207, 2002-363208, 2002-363209, and the like.

Specific examples of the quinoline compound include quinoline, 9-hydroxy-1,2-dihydroquinolin-2-one, 9-ethoxy-1,2-dihydroquinoline- 2-keto, 9-dibutylamino-1,2-dihydroquinolin-2-one, 8-hydroxyquinoline, 8-mercaptoquinoline, quinoline-2-carbonic acid, etc.

Specific examples of the acridine compound include 9-phenylacridine, 1,7-bis(9,9'-acridyl)heptane, and the like.

In the heterocondensed ring system compound, it is more preferable to contain a nitrogen element in the ring. Preferable examples of the compound containing a nitrogen element in the ring include the above-mentioned acridine compound, amino-substituted coumarin compound, acridone compound, and the like. Among them, acridone compounds are particularly preferable.

As the heterocondensed ring compound, the acridone, amino-substituted coumarin, 9-phenylacridine, etc. are more preferable, and among them, the acridone is particularly preferable.

As a combination of the photopolymerization initiator and the heterocondensed ring compound, for example, the electron transfer type initiator system described in JP-A-2001-305734 [(1) Electron-donating initiator and sensitizing dye , (2) electron-accepting initiator and sensitizing dye, (3) electron-donating initiator, sensitizing dye and electron-accepting initiator (ternary initiating system)] and other combinations.

The content of the heterocondensed ring compound in the photosensitive layer is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, particularly preferably 0.2 to 10% by mass. If the content is less than 0.05% by mass, the sensitivity to active energy rays may decrease, the exposure process may take time, and productivity may decrease. If the content exceeds 30% by mass, the heterocondensed ring compound may be precipitated from the photosensitive layer during storage. .

In addition to the heterocondensed ring compound, other sensitizers may be added as needed.

—(E) Inhibitor—

The polymerization inhibitor is not particularly limited and can be appropriately selected according to the purpose.

The polymerization inhibitor performs hydrogen donation (or hydrogen acceptance), energy supply (or energy acceptance), and electron donation (or electron acceptance) to the polymerization initiation radical component generated from the above photopolymerization initiator under the action of the above exposure. etc., to inactivate the polymerization-initiating free radicals and inhibit the polymerization initiation.

As the above-mentioned polymerization inhibitors, there may be mentioned compounds with lone electron pairs (such as compounds with oxygen, nitrogen, sulfur, metals, etc.), compounds with π electrons (such as aromatic compounds), etc., and specifically, compounds with phenolic Compounds with neutral hydroxyl groups, compounds with imino groups, compounds with nitro groups, compounds with nitroso groups, compounds with aromatic rings, compounds with heterocycles, compounds with metal atoms (including coordination compounds with organic compounds )wait. Among them, compounds having a phenolic hydroxyl group, compounds having an imino group, compounds having an aromatic ring, and compounds having a heterocycle are preferred.

The compound having a phenolic hydroxyl group is not particularly limited and may be appropriately selected according to the purpose, for example, a compound having at least two phenolic hydroxyl groups is preferable. In the compound having at least two phenolic hydroxyl groups, at least two phenolic hydroxyl groups may be substituted on the same aromatic ring, or may be substituted on different aromatic rings in the same molecule.

The above-mentioned compound having at least two phenolic hydroxyl groups is, for example, more preferably a compound represented by the following structural formula.

[chemical 4]

In the above structural formula, Z represents a substituent, and m represents an integer of 2 or more. n represents an integer of 0 or more. The m and n are preferably integers and m+n=6. Moreover, when n is an integer of 2 or more, said Z may mutually be same or different.

In addition, if the aforementioned m is less than 2, the resolution may deteriorate.

Examples of the substituent include carboxyl, sulfo, cyano, halogen (such as fluorine, chlorine, bromine), hydroxyl, and alkoxycarbonyl having 30 or less carbon atoms (such as methoxycarbonyl, ethyl oxycarbonyl, benzyloxycarbonyl), aryloxycarbonyl with 30 or less carbon atoms (such as phenoxycarbonyl), alkylsulfonylaminocarbonyl with 30 or less carbon atoms (such as methylsulfonylaminocarbonyl, octylsulfonyl aminocarbonyl), arylsulfonylaminocarbonyl (such as tosylaminocarbonyl), amidosulfonyl groups with 30 or less carbon atoms (such as benzamidosulfonyl, acetamidosulfonyl, trimethylacetamidosulfonyl acyl group), alkoxy group with 30 or less carbon atoms (such as methoxy, ethoxy, benzyloxy, phenoxyethoxy, phenethoxy), arylthio group with 30 or less carbon atoms, alkyl Thio (such as phenylthio, methylthio, ethylthio, dodecylthio, etc.), aryloxy with 30 or less carbon atoms (such as phenoxy, p-tolyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), nitro, alkyl groups with 30 or less carbon atoms, alkoxycarbonyloxy groups (such as methoxycarbonyloxy, stearyloxycarbonyloxy, phenoxyethoxycarbonyloxy ), aryloxycarbonyloxy (such as phenoxycarbonyloxy, chlorophenoxycarbonyloxy), acyloxy groups with less than 30 carbon atoms (such as acetyloxy, propionyloxy, etc.), carbon atoms Acyl groups below 30 (such as acetyl, propionyl, benzoyl), carbamoyl (such as carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbonyl, piperidylcarbonyl, etc.), ammonia Sulfonyl (such as sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl, piperidinylsulfonyl, etc.), alkylsulfonyl with 30 or less carbon atoms (such as methylsulfonyl, tri Fluoromethylsulfonyl, ethylsulfonyl, butylsulfonyl, dodecylsulfonyl), arylsulfonyl (such as benzenesulfonyl, toluenesulfonyl, naphthalenesulfonyl, pyridinesulfonyl, quinolinesulfonyl ), aryl groups with less than 30 carbon atoms (such as phenyl, dichlorophenyl, toluoyl, methoxyphenyl, diethylaminophenyl, acetylaminophenyl, methoxycarbonylphenyl, hydroxyphenyl tert-octylphenyl, naphthyl, etc.), substituted amino (such as amino, alkylamino, dialkylamino, arylamino, diarylamino, acylamino, etc.), substituted phosphono (such as Phosphate, diethylphosphate, diphenylphosphate), heterocyclic groups (such as pyridyl, quinolinyl, furyl, thienyl, tetrahydrofurfuryl, pyrazolyl, isoxazolyl, isothiazole base, imidazolyl, oxazolyl, thiazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazolyl, tetrazolyl, benzoxazolyl, benzimidazole, isoquinolyl, thiadiazole morpholino, piperidinyl, piperazinyl, indolyl, isoindolyl, thiomorpholino), ureido (e.g. methylureido, dimethylureido, phenylurea group, etc.), sulfamoylamino group (such as dipropylsulfamoylamino group, etc.), alkoxycarbonylamino group (such as ethoxycarbonylamino group, etc.), aryloxycarbonylamino group (such as phenoxycarbonylamino group, etc.), alkyl Sulfinyl (such as methylsulfinyl, etc.), Arylsulfinyl (such as phenylsulfinyl, etc.), silyl (such as trimethoxysilyl, triethoxysilyl, etc.), silyloxy (such as trimethylsilyloxy etc.

Examples of compounds represented by the above structural formula include alkyl catechols (such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, etc.) Teaphenol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol , 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl Catechol, 4-tert-butyl catechol, 3,5-di-tert-butyl catechol, etc.), alkyl resorcinols (such as 2-methylresorcinol, 4-methylresorcinol Diphenol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4 - n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, etc.), alkylhydroquinones (such as methylhydroquinone, ethylhydroquinone diphenol, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, etc.), pyrogallol, phloroglucinol, etc.

In addition, the compound having the above-mentioned phenolic hydroxyl group is also preferably a compound in which aromatic rings having at least one of the above-mentioned phenolic hydroxyl groups are linked by a divalent linking group, for example.

Examples of the divalent linking group include groups having 1 to 30 carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, SO, SO ₂ and the like. The aforementioned sulfur atom, oxygen atom, SO and SO ₂ may also be directly bonded.

The above-mentioned carbon atom and oxygen atom may have a substituent, and examples of the substituent include Z in the above-mentioned structural formula.

In addition, the above-mentioned aromatic ring may have a substituent, and examples of the substituent include Z in the above-mentioned structural formula.

Specific examples of the compound having a phenolic hydroxyl group include bisphenol A, bisphenol S, bisphenol M, and known bisphenol compounds used as color developers in thermal paper, JP-A-2003-305945 Bisphenol compounds described in the gazette, hindered phenol compounds used as antioxidants, and the like. In addition, 4-methoxyphenol, 4-methoxy-2-hydroxybenzophenone, β-naphthol, 2,6-di-tert-butyl-4-methylphenol, methyl salicylate Monohydric phenolic compounds with substituents such as esters, hydroxydiethylaniline, etc.

As a commercial item of the compound which has the said phenolic hydroxyl group, the bisphenol compound by Honshu Chemical Co., Ltd. is mentioned.

The compound having an imino group is not particularly limited and may be appropriately selected according to the purpose. For example, a compound having a molecular weight of 50 or more is preferable, and a compound having a molecular weight of 70 or more is more preferable.

The above compound having an imino group preferably has a cyclic structure substituted with an imino group. The cyclic structure is preferably a condensed product of at least one of an aromatic ring and a heterocyclic ring, more preferably a condensed product of an aromatic ring. In addition, the above ring structure may have an oxygen atom, a nitrogen atom, or a sulfur atom.

Specific examples of the compound having an imino group include phenothiazine, phenoxazine, dihydrophenazine, hydroquinone, and compounds in which Z in the above-mentioned structural formula (37) is substituted for these compounds.

As the compound having a cyclic structure substituted with an imino group, a hindered amine derivative having a hindered amine (Hinder-Damine) in part is preferable.

As said hindered amine, the hindered amine described in Unexamined-Japanese-Patent No. 2003-246138 is mentioned, for example.

The compound having a nitro group or the compound having a nitroso group is not particularly limited and may be appropriately selected according to the purpose. For example, a compound having a molecular weight of 50 or more is preferable, and a compound having a molecular weight of 70 or more is more preferable.

Specific examples of the compound having a nitro group or the compound having a nitroso group include nitrobenzene, a chelate compound of a nitroso compound and aluminum, and the like.

The above-mentioned compound having an aromatic ring is not particularly limited and may be appropriately selected according to the purpose. For example, a compound in which the above-mentioned aromatic ring is substituted with a substituent having a lone electron pair (for example, a substituent having an oxygen atom, a nitrogen atom, a sulfur atom, etc.) is preferable. .

Specific examples of the compound having the above-mentioned aromatic ring include the above-mentioned compound having a phenolic hydroxyl group, the above-mentioned compound having an imino group, and some compounds having an aniline skeleton (eg, methylene blue, crystal violet, etc.).

The compound having a heterocyclic ring is not particularly limited and may be appropriately selected according to the purpose. For example, a compound having an atom in which the heterocyclic ring has a lone pair of electrons such as nitrogen, oxygen, and sulfur is preferable.

Specific examples of the compound having a heterocyclic ring are not particularly limited, and pyridine, quinoline, and the like can be mentioned.

The compound having a metal atom is not particularly limited and can be appropriately selected according to the purpose.

The metal atom is not particularly limited as long as it has an affinity with the radical generated from the polymerization initiator, and can be appropriately selected according to the purpose. Examples thereof include copper, aluminum, titanium, and the like.

Among the above-mentioned polymerization inhibitors, compounds having at least two phenolic hydroxyl groups, compounds having an aromatic ring substituted by an imino group, and compounds having a heterocyclic ring substituted by an imino group are preferable, and it is particularly preferable that the imino group constitutes a part of a ring structure. compounds, hindered amine compounds. Specifically, catechol, phenothiazine, phenoxazine, hindered amine, or derivatives thereof are preferred.

The above-mentioned polymerization inhibitor is usually contained in a small amount in commercially available polymerizable compounds, but in the present invention, from the viewpoint of improving the resolution, a polymerization inhibitor different from that contained in the above-mentioned commercially available polymerizable compounds is contained. Polymerization inhibitor. Therefore, it is preferable that the said polymerization inhibitor is a compound other than the monohydric phenol compound, such as 4-methoxyphenol contained in the said polymeric compound marketed in order to provide stability.

Moreover, in the manufacturing process of a pattern forming material, you may add the said polymerization inhibitor previously to a photosensitive resin composition solution.

The content of the polymerization inhibitor is preferably 0.005 to 0.5% by mass, more preferably 0.01 to 0.4% by mass, particularly preferably 0.02 to 0.2% by mass relative to the polymerizable compound in the photosensitive layer. If the said content is less than 0.005 mass %, resolution may fall, and when it exceeds 0.5 mass %, the sensitivity to active energy rays may fall.

In addition, content of the said polymerization inhibitor shows the content except the monohydric phenol type compound, such as 4-methoxyphenol contained in the said polymeric compound marketed in order to provide stability.

—(F) Chromogenic agent—

The color developer may be added in order to impart a visible image (printing function) to the exposed photosensitive layer.

Examples of the color developer include compounds described in paragraphs [0320] to [0321] of JP-A-2005-258431 and the like.

The content of the color developer in the photosensitive layer 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. Moreover, as content of the said halogen compound in the said photosensitive layer, it is preferable that it is 0.001-5 mass %, and it is more preferable that it is 0.005-1 mass %.

—(G) Organic solvents—

The organic solvent is added to prepare a coating solution for forming a photosensitive layer.

The remaining amount of the organic solvent in the photosensitive layer is 0.5% by mass or less, preferably 0.45% by mass or less, more preferably 0.4% by mass or less, particularly preferably 0.35% by mass or less. If the remaining amount exceeds 0.5% by mass, peelability will decrease, and the strength of the masking film will also become weak.

The organic solvent is at least one selected from ketones, alcohols, and ethers.

Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone and the like.

Examples of the alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol, methylpropanediol, 1-methoxy-2-propanol and the like.

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

Among the above-mentioned organic solvents, methyl ethyl ketone, cyclohexanone, methanol, tetrahydrofuran, and propylene glycol monomethyl ether are preferable because the remaining amounts thereof are reduced when the photosensitive layer is formed.

In addition, these organic solvents may be used individually by 1 type, and may use 2 or more types together. In addition, known surfactants may also be added.

—Other Ingredients—

Examples of the other components include dyes, reducing agents, hydrogen donors, sensitizers, plasticizers, colorants, etc., and furthermore, adhesion promoters and other auxiliary agents (such as pigments) to the surface of the substrate may be used in combination. , conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension regulators, chain transfer agents, etc.). By appropriately containing these components, properties such as stability, photographic properties, printing properties, and film physical properties of the desired pattern forming material can be adjusted.

-dye-

The dye is added to improve operability such as visibility when inspecting the coated surface, and is preferably a dye that does not lower the coated surface and exposure sensitivity of the photosensitive layer.

As the dye, a dye that has a large difference between the absorption wavelength and the absorption wavelength after color development with a color developer and does not absorb with respect to the exposure wavelength is preferable.

In addition, as the absorption wavelength of the dye, the photosensitive layer has excellent visibility during inspection and exhibits a green color that does not irritate the operator's vision. Therefore, it is preferable to have a maximum absorption wavelength at 500 to 650 nm.

The dye is not particularly limited as long as the dye has a filtration pressure of 0.3 MPa or less in a 0.5% by mass solution of methyl ethyl ketone in a filter with a pore size of 0.45 μm, and can be appropriately selected according to the purpose. It is a compound having a triallylmethane skeleton. In addition, the dye is preferably an ionic dye, and the counter anion (counter anion) of the ionic dye preferably has, for example, an aromatic acid, carbonic acid, phosphoric acid, or the like.

Examples of the aromatic acid include naphthalenesulfonic acid, phenylsulfonic acid, and the like, and among them, naphthalenesulfonic acid is preferably used from the viewpoint of solubility.

As the compound having a triallylmethane skeleton, it has excellent solubility in organic solvents, excellent operability such as visibility when inspecting the coated surface of the photosensitive layer, and does not make the coating of the photosensitive layer difficult. From the viewpoint of surface and reduction in exposure sensitivity, an allylsulfonic acid compound is preferably used, and a naphthalenesulfonic acid compound is particularly preferable.

As said naphthalenesulfonic acid compound, Victoria pure blue NAPS is mentioned preferably, for example.

"Solubility in Relative Organic Solvents"

The dye preferably has a filtration pressure of 0.5 mass % methyl ethyl ketone solution in a filter with a pore size of 0.45 μm of 0.3 MPa or less. This filtration pressure can be measured as follows. However, the measurement of the filtration pressure is carried out under the conditions of room temperature and atmospheric pressure.

(1) The dye was dissolved in a methyl ethyl ketone solution at 0.5% by mass.

(2) Connect a filter (manufactured by ADVANTEC, DISMIC; 25HP045AN) with a pore size of 0.45 μm to a syringe (manufactured by Terumo Co., Ltd., SS-20ESZ; diameter 1.5 cm, length 9.5 cm), and filter and fill the syringe through the filter. 0.5 mass % methyl ethyl ketone solution of the coloring dye in it. The filtration rate at this time was 50 cc/min.

(3) During the above filtration, the pressure acting on the syringe was measured with a pressure gauge, and it was used as the filtration pressure of the 0.5% by mass methyl ethyl ketone solution of the coloring dye.

When the filtration pressure is 0.3 MPa or less, the solubility of the coloring dye in an organic solvent is excellent, the surface of the photosensitive layer or the exposure sensitivity are not lowered, and residues of undissolved substances are less likely to be generated. If the filtration pressure exceeds 0.3 MPa, the solubility will be poor, and undissolved matter may cause surface failure of the photosensitive layer, decrease in exposure sensitivity, and residues of coloring dyes may easily occur.

The content of the dye is preferably 0.001 to 20% by mass, more preferably 0.03 to 3% by mass, particularly preferably 0.05 to 0.1% by mass, based on the total components of the photosensitive layer. If the said content is less than 0.001 mass %, color development property will fall and the visibility at the time of a surface inspection will become poor, and if it exceeds 20 mass %, the color development by a color developer may not be confirmed.

——Reducing Agents and Hydrogen Donor Compounds——

The reducing agent is not particularly limited as long as it is capable of reacting with radicals and suppressing the color development of the color developing agent, and can be appropriately selected according to the purpose. For example, p-methoxyphenol, Hydroquinone, alkyl-substituted hydroquinone, catechol, alkyl-substituted catechol, phenothiazine, pyrogallol, and 1-phenyl-3-pyrazolidinone, etc. Among them, 1-phenyl-3-pyrazolidinone is preferable.

The hydrogen donor compound is not particularly limited, and examples include compounds having a -SH group, compounds having a -CH ₂ X-(X=R) group (R represents any one of O, N, and S) Substituents) compounds, etc.

Examples of the compound having the -SH group include compounds represented by the following structural formula.

[chemical 5]

Examples of the compound having the -CH ₂ X-(X=R) group include N-phenylglycine, dimethylaminocinnamic acid, dimethylaminobenzaldehyde and the like.

Among these hydrogen donor compounds, N-phenylglycine is preferable from the same viewpoint as the reducing agent.

——Sensitizer——

The said sensitizer can be suitably selected according to the visible ray, ultraviolet-visible laser, etc. which are the light irradiation means mentioned later.

The above-mentioned sensitizer becomes an excited state under the action of active energy rays, and can generate free radicals or acids by interacting with other substances (such as free radical generators, acid generators, etc.) (such as energy transfer, electron transfer, etc.) Useful basis.

The above-mentioned sensitizer is not particularly limited, and may be appropriately selected from known sensitizers according to the purpose, for example, compounds described in paragraph numbers [0313] to [0314] of JP-A-2005-258431, etc. .

The content of the sensitizer in the photosensitive layer is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, particularly preferably 0.2 to 10% by mass.

If the content is less than 0.05% by mass, the sensitivity to active energy rays may decrease, the exposure process may take time, and productivity may decrease, and if it exceeds 30% by mass, it may precipitate from the photosensitive layer during storage.

—Plasticizer—

In order to control the film physical properties (flexibility) of the photosensitive layer, the plasticizer may also be added.

As said plasticizer, the compound etc. which are described in the paragraph number [0318] of Unexamined-Japanese-Patent No. 2005-258431 are mentioned, for example.

The content of the plasticizer in the photosensitive layer is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, particularly preferably 1 to 30% by mass.

-Colorant-

The coloring agent is not particularly limited and may be appropriately selected according to the purpose. For example, known pigments or dyes such as red, green, blue, yellow, purple, magenta, cyan, and black can be mentioned. Specifically, Examples include Victoria Pure Blue BO (C.I.42595), (Basic) Sophora Yellow (C.I.41000), Fat Black HB (C.I.26150), Monoright Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red 146), Advertising Paint Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11) , Fastel Pink B Supra (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monoright Fast Black B (C.I. Pigment Black 1), Carbon Black .

In addition, as the coloring agent preferable for producing a color filter, for example, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, C.I. Pigment Yellow 139, C.I. Pigment Yellow 83, C.I. Pigment Violet 23, colorants described in (0138) to (0141) of JP-A-2002-162752, and the like. The average particle size of the colorant is not particularly limited and may be appropriately selected according to the purpose, for example, it is preferably 5 μm or less, more preferably 1 μm or less. In addition, when producing a color filter, the average particle diameter is preferably 0.5 μm or less.

——Adhesion Promoter——

In order to improve the adhesion between the layers or the adhesion between the pattern forming material and the substrate, a known so-called adhesion promoter can be used in each layer.

Examples of the adhesion promoter include compounds described in paragraph [0326] of JP-A-2005-258431 and the like.

The content of the adhesion promoter in the photosensitive layer is preferably 0.001% by mass to 20% by mass, more preferably 0.01% to 10% by mass, particularly preferably 0.1% by mass to 5% by mass.

The photosensitive layer may also contain, for example, organic sulfur compounds, peroxides, redox compounds, azo or diazo compounds, light Reductive pigments, organic halogen compounds, etc.

Specifically, for example, compounds described in paragraph numbers [0329] to [0333] of JP-A-2005-258431 and the like can be mentioned.

--Surfactant--

In order to improve the surface unevenness which arises at the time of manufacture of the said pattern forming material of this invention, a well-known surfactant can be used together.

As the surfactant, for example, it can be appropriately selected from anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, fluorine-containing surfactants and the like.

As content of the said surfactant in the said photosensitive layer, 0.001-10 mass % is preferable. If the said content is less than 0.001 mass %, the effect of surface improvement may not be acquired, and if it exceeds 10 mass %. Then, the adhesiveness may be lowered.

The thickness of the photosensitive layer is not particularly limited, and can be appropriately selected according to the purpose, for example, preferably 1-100 μm, more preferably 2-50 μm, particularly preferably 4-30 μm.

<Support and protective film>

The support is not particularly limited, and may be appropriately selected according to the purpose. A support that can peel the photosensitive layer and has good light permeability is preferable, and more preferably, the surface smoothness is good.

Specifically, for example, the forms described in paragraph numbers [0342] to [0348] of JP-A-2005-258431 and the like are exemplified.

<other layers>

The other layer is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include layers such as a buffer layer, a barrier layer, a release layer, an adhesive layer, a light-absorbing layer, and a surface protection layer. The pattern forming material may have one of these layers alone, may have two or more layers, and may have two or more layers of the same type.

The photosensitive layer in the pattern forming material of the present invention is preferably exposed to light as described below, that is, by using a light modulation mechanism having n drawing parts that receive and emit light from the light irradiation mechanism, the light from the light irradiation mechanism is modulated. After the light from the light irradiation mechanism passes through a microlens array in which aspherical microlenses capable of correcting aberrations caused by deformation of the output surface in the drawing unit are arranged. Details of the light irradiation unit, the drawing unit, the light modulation unit, the aspheric surface, the microlens, and the microlens array will be described later.

[Manufacturing method of pattern forming material]

The pattern forming material can be produced, for example, as follows.

First, a coating liquid is prepared by dissolving, emulsifying or dispersing materials contained in the photosensitive layer and other layers in water or an organic solvent.

However, as the organic solvent, it is as described in the description of the pattern forming material of the present invention.

Next, the coating liquid can be applied on the support and dried to form each layer to produce a pattern forming material. For example, a photosensitive resin composition solution obtained by dissolving, emulsifying or dispersing the components of the photosensitive layer is applied and dried on a support to form a photosensitive layer, and a protective film is formed thereon to produce a pattern forming material.

The coating method of the coating liquid is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include spray coating, roll coating, spin coating, slot coating, extrusion coating, and curtain coating. , die coating method, gravure printing coating method, wire drawing bar coating method, air knife coating method and other known coating methods.

The drying conditions vary depending on the components, the type of solvent, the ratio of use, and the like, but are usually at a temperature of 60 to 110° C. for about 30 seconds to 15 minutes.

Since the pattern forming material of the present invention has less surface defects, can prevent light fog caused by the developer, has less cracks in the unexposed film, has high resolution, high masking film strength, and good peelability after pattern formation, it can It is preferably used for forming various patterns, for forming permanent patterns such as wiring patterns, for manufacturing liquid crystal structural members such as color filters, pillars, ribs, spacers, and partitions, for holography, micromotors, printing samples, etc. For pattern formation, etc., especially, it can be preferably used for the formation of high-definition wiring patterns. In addition, it can also be preferably used in the pattern forming method and the pattern forming apparatus of the present invention.

(Pattern forming device and pattern forming method)

The pattern forming device 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 further includes other steps selected as appropriate.

In addition, the pattern forming apparatus of the present invention will be clarified through the description of the pattern forming method of the present invention.

[Exposure process]

The said exposure process is a process of exposing the photosensitive layer in the pattern forming material of this invention. The pattern forming material of the present invention is as described above.

The object of exposure is not particularly limited as long as it is the photosensitive layer in the pattern forming material, and can be appropriately selected according to the purpose. For example, it is preferably performed on a laminate formed by forming the pattern forming material on a substrate.

The substrate is not particularly limited, and can be appropriately selected from known materials, from substrates with high surface smoothness to substrates with uneven surfaces, preferably plate-shaped substrates (substrates), and specifically, Examples include known substrates for forming printed wiring boards (for example, copper-clad laminates), glass plates (for example, soda-lime glass plates, etc.), synthetic resin films, paper, metal plates, and the like. Among them, copper-containing The above-mentioned copper-clad film laminated board is preferable in terms of excellent adhesion of materials. .

The method for forming the laminate is not particularly limited and may be appropriately selected depending on the purpose, but it is preferable to laminate the pattern forming material on the substrate while applying at least one of heating and pressure.

The heating temperature is not particularly limited and can be appropriately selected according to the purpose, but for example, it is preferably 15 to 180°C, and more preferably 60 to 140°C.

The pressurized pressure is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.1 to 1.0 MPa, and more preferably 0.2 to 0.8 MPa, for example.

The device for performing at least one of the heating and pressurization is not particularly limited and may be appropriately selected according to the purpose, for example, a laminator (for example, VP-II manufactured by Taisei Laminator Co., Ltd.) and the like are preferably used.

The exposure is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include digital exposure, analog exposure, and the like, and among them, digital exposure is preferable.

Digital exposure is not particularly limited, and can be appropriately selected according to the purpose. For example, it is preferable to generate a control signal based on patterning information to be formed, and perform using light modulated according to the control signal.

The digital exposure mechanism is not particularly limited and can be appropriately selected according to the purpose, for example, a light irradiation mechanism that irradiates light, and a light modulation mechanism that modulates light irradiated from the light irradiation mechanism based on pattern information to be formed wait.

—Light Modulation Mechanism—

The light modulation means is not particularly limited as long as it can modulate light, and can be appropriately selected according to the purpose. For example, it is preferable to have n drawing units.

The light modulation mechanism having the n drawing units is not particularly limited and may be appropriately selected according to the purpose, for example, a spatial light modulation element is preferable.

As the spatial light modulation element, for example, digital micromirror device (DMD), MEMS (Micro Electro Mechanical Systems (Micro Electro Mechanical Systems)) type spatial light modulation element (SLM; spatial light modulator (Space Light Modulator) Light Modulator)), an optical element (PLZT element) that modulates transmitted light by electro-optical effects, a liquid crystal light switch (FLC), etc. Among them, DMD is preferably used.

In addition, the light modulating means preferably has a pattern signal generating means for generating a control signal based on pattern information to be formed. In this case, the light modulation means modulates light in response to the control signal generated by the pattern signal generation means.

The control signal is not particularly limited and may be appropriately selected according to the purpose, and for example, a digital signal is preferably used.

Examples of the light modulation mechanism and the pattern forming device including the light modulation mechanism include those described in paragraphs [0016] to [0047] of JP-A-2005-258431.

<Light irradiation mechanism>

The light irradiation means is not particularly limited, and can be appropriately selected according to the purpose, for example, (ultra) high pressure mercury lamp, xenon lamp, carbon rod arc lamp, halogen lamp, fluorescent tube for copying machine, LED, semiconductor laser, etc. A light source or a mechanism capable of compositely irradiating two or more types of light is known, and among them, a mechanism capable of compositely emitting two or more types of light is preferable.

As the light irradiated from the light irradiation means, for example, in the case of light irradiation via a support, electromagnetic waves that pass through the support and activate the photopolymerization initiator or sensitizer used, from ultraviolet to Visible light rays, electron beams, X-rays, laser light, etc. Among them, laser light is preferable, and laser light combining two or more kinds of light (hereinafter sometimes referred to as "combined laser light") is more preferable. In addition, when light irradiation is performed after peeling off a support body, the same light can also be used.

The wavelength of the ultraviolet to visible light is, for example, preferably 300 to 1,500 nm, more preferably 320 to 800 nm, particularly preferably 330 nm to 650 nm.

The wavelength of the laser light is, for example, preferably 200 to 1,500 nm, more preferably 300 to 800 nm, still more preferably 330 to 500 nm, particularly preferably 400 to 450 nm.

As a mechanism capable of irradiating the multiplexed laser light, for example, a plurality of lasers, a multimode fiber, and a condensing optic that condenses the laser light irradiated from the plurality of lasers and couples them to the multimode fiber are preferable. system of institutions.

The following means (fiber array light source) capable of irradiating multiplexed laser light includes, for example, methods described in paragraph numbers "0130" to "0177" of JP-A-2005-316431.

<Microlens Array>

The exposure is preferably performed by passing the modulated light through a microlens array, and may also be performed through an aperture array, an imaging optical system, and the like.

The microlens array is not particularly limited, and can be appropriately selected according to the purpose. For example, it is preferably an array of microlenses having aspheric surfaces that can correct aberrations caused by deformation of the output surface in the drawing section. microlens array.

The aspheric surface is not particularly limited and may be appropriately selected according to the purpose, for example, a toric surface is preferable.

In addition, examples of the microlens array, the aperture array, and the imaging optical system include, for example, paragraph numbers [0051] to [0063], paragraph number [0065], Organizations, etc. described in paragraph numbers [0070] to [0073] and paragraph numbers [0083] to [0088].

<Other Optical Systems>

In the pattern forming method of the present invention, another optical system appropriately selected from known optical systems may be used in combination, for example, a light quantity distribution correction optical system composed of a pair of combined lenses, and the like.

The light quantity distribution correction optical system changes the beam width of each exit position so that the ratio of the beam width of the peripheral portion to the beam width of the central portion close to the optical axis is smaller on the exit side than on the incident side. When the parallel beam of the mechanism is irradiated, the light distribution on the irradiated surface is corrected to be approximately uniform.

Specific examples of the optical system for correcting light quantity distribution include mechanisms described in paragraphs [0090] to [0105] of JP-A-2005-258431, and the like.

[Other processes]

It does not specifically limit as said other process, The process selected suitably from the process in well-known pattern formation is mentioned, For example, a developing process, an etching process, a plating process etc. are mentioned. These may be used individually by 1 type, and may use 2 or more types together.

The developing step is a step of forming a pattern by exposing the photosensitive layer in the pattern forming material in the exposing step and curing the exposed regions of the photosensitive layer, followed by developing to remove uncured regions.

The developing step can be preferably performed using a developing mechanism, for example.

As the developing mechanism, a developing solution can be used for developing, and it is not particularly limited, and can be appropriately selected according to the purpose. institutions, etc. These can be used individually by 1 type or in combination of 2 or more types.

In addition, the developing mechanism may include a developer exchange mechanism for exchanging the developer, a developer supply mechanism for supplying the developer, and the like.

The developing solution is not particularly limited, and may be appropriately selected according to the purpose. Examples thereof include alkaline solutions, aqueous developing solutions, organic solvents, and the like. Among them, weakly alkaline aqueous solutions are preferred. Examples of the alkali component of the weak alkaline solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, Potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, borax, etc.

The pH of the weakly alkaline aqueous solution is, for example, preferably about 8-12, and more preferably about 9-11. As said weakly basic aqueous solution, 0.1-5 mass % sodium carbonate aqueous solution, potassium carbonate aqueous solution, etc. are mentioned, for example.

The temperature of the developing solution can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25°C to 40°C, for example.

Described developing solution also can be mixed with surfactant, defoamer, organic base (for example ethylenediamine, ethanolamine, tetramethylammonium hydroxide, triethylenetriamine, triethylenepentamine, morpholine, triethanolamine etc. ) or organic solvents (such as alcohols, ketones, esters, ethers, amides, lactones, etc.) used to promote development, etc. In addition, the developer may be an aqueous developer mixed with water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

As the etching step, it can be performed by a method appropriately selected from known etching treatment methods.

The etchant used in the etching process is not particularly limited, and can be appropriately selected according to the purpose. For example, in the case of forming the metal layer from copper, copper chloride solution, ferric chloride solution, and alkali etching solution can be mentioned. , hydrogen peroxide-based etchant, etc. Among them, ferric chloride solution is preferable from the viewpoint of etching factor.

A permanent pattern can be formed on the surface of the base by removing the pattern after the etching process by the etching process.

The permanent pattern is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include wiring patterns and the like.

As the plating step, it can be performed by a method appropriately selected from known plating treatments.

Examples of the plating treatment 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, hard (hard) gold plating, soft gold plating and other gold plating.

A permanent pattern can be formed on the surface of the substrate by removing the pattern after the plating treatment in the plating step, and further removing unnecessary portions by etching or the like as necessary.

[Manufacturing method of printed wiring board and color filter]

The pattern forming method of the present invention can be suitably used in the manufacture of printed wiring boards, especially in the manufacture of printed wiring boards having holes such as through-holes and through-holes, and in the manufacture of color filters. An example of a method of manufacturing a printed wiring board and a method of manufacturing a color filter using the pattern forming method of the present invention will be described below.

—Manufacturing method of printed circuit board—

In particular, as a method for manufacturing a printed wiring board having a hole such as a through hole or a through hole, the photosensitive layer can be formed by (1) forming the printed wiring board as the base on a substrate for forming a printed wiring board having a hole. The positional relationship on the side of the substrate is to layer the pattern forming material to form a laminate, (2) to irradiate a desired region with light from the side of the laminate opposite to the substrate to cure the photosensitive layer, (3) to cure the photosensitive layer from the The support, buffer layer and barrier layer in the pattern forming material are removed from the laminate, and (4) the photosensitive layer in the laminate is developed to remove uncured parts in the laminate to form a pattern.

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

Then, in order to obtain a printed wiring board, it is only necessary to utilize the method of etching or plating the substrate for forming a printed wiring board (for example, a known subtractive method or an additive method ( For example, half-additive (semiadditive) method, full-additive (full additive) method)) can be processed. Among them, the subtraction method is preferable in order to form a printed wiring board by an industrially advantageous tenting process. The cured resin remaining on the substrate for forming a printed wiring board after the treatment is peeled off, and in the case of the semi-additive method, a desired printed wiring board can be produced by further etching the copper thin film portion after the peeling. Moreover, a multilayer printed wiring board can also be manufactured similarly to the manufacturing method of the said printed wiring board.

Next, a method of manufacturing a printed wiring board having through holes using the pattern forming material will be further described.

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

Next, in the case where the pattern forming material has a protective film, the protective film is peeled off, and the photosensitive layer in the pattern forming material is brought into contact with the surface of the substrate for forming a printed wiring board by using a pressure roller. (Lamination process). In this way, a laminated body having the substrate for forming a printed wiring board and the laminated body in this order can be obtained.

The lamination temperature of the pattern forming material is not particularly limited, and examples thereof include room temperature (15 to 30°C) or heating (30 to 180°C), among which heating (60 to 140°C) is preferable.

The rolling pressure of the pressure-contacting roll is not particularly limited, but is preferably 0.1 to 1 MPa, for example.

The pressure-bonding speed is not particularly limited, but is preferably 1 to 3 m/min.

In addition, the substrate for forming a printed wiring board may be preheated or laminated under reduced pressure.

The laminate may be formed by laminating the pattern forming material on the printed wiring board forming substrate, or by directly applying and drying the pattern forming material on the surface of the printed wiring board forming substrate. A photosensitive resin composition solution or the like is used, and a photosensitive layer, a barrier layer, a buffer layer, and a support are laminated on the substrate for forming a printed wiring board.

Next, light is irradiated from the surface of the laminate opposite to the base to cure the photosensitive layer. In addition, at this time, exposure may be performed after peeling off the said support body, a buffer layer, and a barrier layer as needed (for example, when the light transmission property of a support body is insufficient, etc.).

At this point, when the support body, buffer layer, and barrier layer have not been peeled off, the support body, buffer layer, and barrier layer are peeled off from the laminate (peeling step).

Next, the uncured region of the photosensitive layer on the substrate for forming a printed wiring board is dissolved and removed with an appropriate developer, and a cured layer for forming a wiring pattern and a pattern of a cured layer for protecting a metal layer of a through hole are formed. The metal layer is exposed on the surface of the substrate for forming a printed wiring board (development process).

Moreover, after development, you may further perform the process of promoting the curing reaction of a hardened part by post-heating process or post-exposure process as needed. Image development may be the wet image development method mentioned above, and may be dry image image development method.

Next, the metal layer exposed on the surface of the substrate for forming a printed wiring board is removed by dissolving with an etchant (etching step). The opening of the through hole is covered with the cured resin composition (mask film), so the etching solution does not enter the through hole and corrode the metal plating in the through hole, and the metal plating in the through hole remains in a predetermined shape. In this way, a wiring pattern is formed on the substrate for forming a printed wiring board.

The etchant is not particularly limited and can be appropriately selected according to the purpose. For example, when the metal layer is formed of copper, copper chloride solution, ferric chloride solution, alkali etching solution, hydrogen peroxide-based Etching solution etc. Among them, ferric chloride solution is preferable from the viewpoint of etching factors.

Next, using a strong alkali aqueous solution or the like, the cured layer is removed from the printed wiring board forming substrate as a release sheet (cured product removal step).

The alkali component in the strong alkali aqueous solution is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, and the like.

The pH of the strong alkali aqueous solution is, for example, preferably about 12-14, and more preferably about 13-14.

It does not specifically limit as said strong alkali aqueous solution, For example, 1-10 mass % sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. are mentioned.

In addition, the printed wiring board may also be a printed wiring board with a multilayer structure.

In addition, the pattern forming material may be used not only in the etching process but also in the 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, gold plating such as hard (hard) gold plating, soft gold plating, etc.

—Manufacturing method of color filter—

When the photosensitive layer in the pattern forming material of the present invention is attached to a substrate such as a glass substrate, and the support, buffer layer, and barrier layer are peeled off from the pattern forming material, the charged support (film) ) and the human body may receive uncomfortable electric shocks, or there may be problems such as dust adhering to the charged support. Therefore, it is preferable to provide a conductive layer on the support, or to perform a treatment for imparting conductivity to the support itself. In addition, when the conductive layer is provided on the support on the side opposite to the buffer layer, it is preferable to provide a hydrophobic polymer layer in order to improve damage resistance.

Next, a pattern forming material having a red photosensitive layer, a pattern forming material having a green photosensitive layer, a pattern forming material having a blue photosensitive layer, and a pattern forming material having a black photosensitive layer, in which the photosensitive layers are colored red, green, blue, and black, respectively, are manufactured. layer of patterning material. Using the pattern forming material having the red photosensitive layer for red pixels, after laminating the red photosensitive layer on the surface of the substrate to form a laminate, an image sample is exposed and developed to form red pixels. After the red pixels were formed, the laminate was heated to cure the uncured portion. The same procedure is performed for green and blue pixels to form each pixel.

The laminate can be formed by laminating the pattern forming material on the glass substrate, or by directly coating and drying the photosensitive resin composition for producing the pattern forming material on the surface of the glass substrate. solution, etc., thereby laminating a photosensitive layer, a barrier layer, a buffer layer, and a support on the glass substrate. In addition, in the case of arranging three types of pixels of red, green, and blue, an arrangement such as a mosaic type, a triangular type, or a four-pixel arrangement type is also possible.

Laminating the pattern forming material with the black photosensitive layer on the surface on which the pixels are formed, performing back exposure and development on the side where the pixels are not formed, to form a black matrix. A color filter can be manufactured by heating the laminated body which formed this black matrix, and hardening an uncured part.

The pattern forming method of the present invention uses the pattern forming material of the present invention, so it can be preferably used for forming various patterns, forming permanent patterns such as wiring patterns, color filters, pillars, ribs, and spacers. It is especially suitable for the manufacture of liquid crystal structural members such as partition walls, holograms, micro motors, and prints, especially for the formation of high-definition wiring patterns. Since the pattern forming device of the present invention includes the pattern forming material of the present invention, it can be suitably used for forming various patterns, forming permanent patterns such as wiring patterns, color filters, pillars, ribs, spacers, partition walls, etc. The manufacture of structural members such as liquid crystals, the manufacture of holograms, micro motors, prints, etc., can be particularly preferably used for the formation of high-definition wiring patterns.

Example

Hereinafter, the present invention will be described in further detail using examples, but the present invention is not limited thereto.

(Example 1)

As the support, a photosensitive composition solution composed of the following composition was applied to a polyethylene terephthalate film (manufactured by Toray Co., Ltd., 16FB50) with a thickness of 16 μm and dried to form a photosensitive film with a thickness of 18 μm. layer, making the patterning material.

[Composition of Photosensitive Resin Composition Solution]

Methyl methacrylate/styrene/methacrylic acid copolymer (copolymer composition (mass%): 19/52/29, mass average molecular weight: 60,000, acid value 189 mgKOH/g, I/O value: 0.55): 139.6 parts by mass

- A polymeric compound represented by the following structural formula (1) (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., GX8702c): 44.33 parts by mass

- A polymeric compound represented by the following structural formula (2) (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., BPEM-10F): 44.33 parts by mass

- A polymeric compound represented by the following structural formula (3) (Aronix M270, manufactured by Toagosei Co., Ltd.): 6.37 parts by mass

・Polyethylene glycol #1000 dimethacrylate (New Nakamura Chemical, NK Ester 23G): 16.75 parts by mass

2,2-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole as a photopolymerization initiator: 18.5 parts by mass

・N-butylchloroacridone as a heterocondensed ring compound: 0.99 parts by mass

Phenoxazine as a polymerization inhibitor: 0.032 parts by mass

· Colorless crystal violet as a developer: 1.10 parts by mass

- Methyl ethyl ketone as an organic solvent for ketones: 327.4 parts by mass

・Propylene glycol monomethyl ether as an organic solvent of ethers: 304.9 parts by mass

- Cyclohexanone as an organic solvent for ketones: 58.1 parts by mass

・Methanol as an organic solvent for alcohols: 36.3 parts by mass

Naphthalenesulfonate of Victoria Pure Blue: 0.186 parts by mass

· 1-phenyl-3-pyrazolidinone: 0.022 parts by mass

· N-phenylglycine as a hydrogen donor compound: 0.370 parts by mass

· Fluorinated surfactant (manufactured by Dainippon Ink Co., Ltd., F780F): 0.78 parts by mass

However, the remaining amount of the organic solvent in the obtained photosensitive layer was 0.30% by mass.

[chemical 6]

结构式(1)

Structural formula (1)

Wherein, in the structural formula (1), m+n represents 20. Among them, the compound represented by the structural formula (1) is an example of a polymerizable compound having a urethane group.

[chemical 7]

结构式(2)

Structural formula (2)

Wherein, in the structural formula (2), m+n represents 10. Among them, the compound represented by the structural formula (2) is an example of a polymerizable compound having an aryl group.

[chemical 8]

结构式(3)

Structural formula (3)

Wherein, in the structural formula (3), n represents 12. However, the compound represented by the said structural formula (3) is an example of the compound which has a polyalkylene oxide chain.

<Evaluation of Surface Failure>

The coated surface of the obtained photosensitive layer was observed under a yellow light, and the surface failure of the coated surface was evaluated. As the evaluation method of the surface defect, the number of surface defects less than 40 μm and the number of surface defects of 40 μm or more per 1 m ² of the surface of the photosensitive layer were counted. Based on this number, surface defectivity was evaluated by the following evaluation criteria. The results are shown in Table 1.

-evaluation standard-

○... less than 20 surface defects of less than 40 μm, and less than 3 surface defects of 40 μm or more, showing an excellent coated surface.

△... There were 20 or more and less than 50 surface defects of less than 40 μm, and 3 or more and less than 30 surface defects of 40 μm or more. The coated surface was slightly poor and did not pose a practical problem.

×... There were 50 or more surface defects of less than 40 μm or 30 or more surface defects of 40 μm or more, and the coated surface was extremely poor.

<Evaluation of Fogging of Color Developer>

With respect to the photosensitive layer of the pattern forming material in the laminated body, the extinction degree (OD) at 550 nm is measured with a spectrophotometer (manufactured by Shimadzu Corporation, MPS-200), and if the extinction degree is 0.4 or less, then it is ○ , if it exceeds 0.4, then it is ×, and the fogging of the developer is evaluated. The results are shown in Table 1.

On the photosensitive layer of the pattern forming material, a polyethylene film (manufactured by Tambori Co., Ltd., GF-1) having a thickness of 25 μm was laminated as the protective film. Then, as the substrate, the surface was ground and washed with water, and the dried copper-plated laminated board (30 holes each with a diameter of 1, 2, 3, 4, 5 and 6 mm, a total of 180 openings, and a copper thickness of 12 μm) ) on the surface of the pattern forming material, while peeling off the protective film of the pattern forming material, using a laminator (MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.) The copper-plated laminates are in contact with each other, and a laminate in which the copper-plated laminate, the photosensitive layer, and the polyethylene terephthalate film (support) are sequentially laminated is prepared.

The crimping conditions were a crimping roll temperature of 105° C., a crimping roll pressure of 0.3 MPa, and a lamination speed of 1 m/min.

<Evaluation of Unexposed Film Crack>

Next, except that the photosensitive layer was laminated on both sides of the copper-plated laminated board in the laminated body under the pressure-bonding conditions described above, it was carried out in the same manner as the laminated body described above, and a film in which the unexposed film was broken was prepared. The laminated body for evaluation was stored at room temperature (25° C., 50% RH) for 5 days. From the laminated body after storage, the support was peeled off, and the number of cracks after peeling off the photosensitive layer in the hole portion was counted to evaluate cracks in the unexposed film. Among the holes with a diameter of 1 to 6 mm, the diameter of the largest hole among the 30 holes that were not cracked at all was the value at which the unexposed film cracked. The results are listed in Table 1.

—Development process—

Peel off the polyethylene terephthalate film (support) from the laminate, and spray 1 mass of 30° C. on the entire surface of the photosensitive layer on the copper-plated laminate with a pressure of 0.15 MPa. % sodium carbonate solution in water to remove uncured areas. Then, it is washed and dried to form a permanent pattern.

Among them, the time required for dissolving and removing the photosensitive layer on the copper-plated laminated board was measured from the start of spraying the sodium carbonate aqueous solution, and it was taken as the shortest developing time. The shorter the shortest developing time, the more excellent the developability.

A heat treatment at 160° C. for 30 minutes was performed on the entire surface of the laminate on which the permanent pattern was formed to cure the surface of the permanent pattern and increase the film strength. As a result of visual observation of the permanent pattern, no air bubbles were observed on the surface of the permanent pattern.

In addition, with respect to the printed wiring board on which the permanent pattern has been formed, gold plating is performed according to a conventional method, and then water-soluble flux treatment is performed. Next, immersion in a solder bath set at 260° C. for 5 seconds was repeated three times, and the flux was removed by washing with water.

<resolution>

(1) Determination of sensitivity

To the photosensitive layer of the pattern forming material in the laminate, from the polyethylene terephthalate film (support) side, a pattern forming device having a laser light source of 405 nm as the light irradiation mechanism was used to Light of different light energies of 0.1 mJ/cm ² to 100 mJ/cm ² is irradiated at intervals of 2 ^1/2 times to cure a part of the photosensitive layer. Let stand at room temperature for 10 minutes, then peel off the polyethylene terephthalate film (support body) from the laminate, and spray the entire surface of the photosensitive layer on the copper-plated laminate with a spray pressure of 0.15 MPa. For the aqueous sodium carbonate solution (30° C., 1% by mass), the spraying time was twice the shortest developing time obtained in the above-mentioned developing step. The uncured area was removed by dissolution, and the thickness of the remaining cured area was measured. Next, the relationship between the amount of light irradiation and the thickness of the cured layer was plotted as a graph to obtain a sensitivity curve. From the sensitivity curve obtained in this way, it can be seen that the light energy when the thickness of the cured region becomes 15 μm is regarded as the light energy necessary for curing the photosensitive layer. The results are shown in Table 1.

(2) Determination of resolution

The laminate was left to stand at room temperature (23° C., 55% RH) for 10 minutes. From the polyethylene terephthalate film (support) of the obtained laminate, using the pattern forming device, with line (line)/space (space) = 1/1, from line (line) width From 5 μm to 20 μm, the exposure was performed for each line width of 1 μm, and for the line width of 20 μm to 50 μm, the exposure was performed for each line width of 5 μm. The exposure amount at this time is the light energy necessary for curing the photosensitive layer of the pattern forming material measured in (1) above. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the laminate. Spray an aqueous solution of sodium carbonate (30° C., 1% by mass) as the developing solution to the entire surface of the photosensitive layer on the copper-plated film laminate with a spray pressure of 0.15 MPa, and the spray time is the shortest developing time obtained in the method. Twice the time, dissolve to remove uncured areas. The surface of the thus-obtained copper-clad laminate with a cured resin pattern was observed with an optical microscope, and the minimum line width without abnormalities such as clogging and wrinkles in the lines of the cured resin pattern was measured, and this was defined as the resolution. The smaller the numerical value of the resolution, the better. The results are shown in Table 1.

<coverage>

Except that the copper-plated laminated board in the laminated body for evaluation of unexposed film cracking was replaced with a copper-plated laminated board having 200 through-holes with a diameter of 2 mm, the same procedure as the laminated body was carried out. A laminate for hiding evaluation was prepared and left to stand for 10 minutes at room temperature (23° C., relative humidity 55%). Next, from the polyethylene terephthalate film (support body) of the laminated body produced above, the whole surface of the photosensitive layer in this laminated body was exposed using the said pattern forming apparatus. The exposure amount at this time is the light energy required for hardening the photosensitive layer of the said pattern forming material measured in the evaluation of said resolution (2). After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the laminate. Spray an aqueous solution of sodium carbonate (30° C., 1% by mass) as the developing solution to the entire surface of the photosensitive layer on the copper-plated film laminate with a spray pressure of 0.15 MPa, and the spray time is during the development process. Twice the shortest developing time obtained. The presence or absence of defects such as peeling or breakage of the cured layer (mask film) formed on the opening of the through-hole in the copper-clad laminate obtained in this way was observed with a microscope, and the occurrence rate of defects was counted. The results are shown in Table 1.

<Measurement of peeling time>

The said laminated body was produced on the same method and conditions as evaluation of the said developability, and it left still at room temperature (23 degreeC, 55 %RH) for 10 minutes. From the polyethylene terephthalate film (support body) of the obtained laminated body, surface exposure was performed using the said pattern forming apparatus. The exposure amount at this time is the light energy necessary for curing the photosensitive layer of the pattern forming material measured above. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the laminate. Spray an aqueous solution of sodium carbonate (30°C, 1% by mass) as the developing solution to the entire surface of the photosensitive layer on the copper-plated film laminate with a spraying pressure of 0.15 MPa, and the spraying time is obtained in the developing process. 2 times the shortest developing time. After drying, the substrate was vertically dipped in a 3% by mass sodium hydroxide aqueous solution, and the time until the film was completely peeled off was measured. The shorter the time, the better. The results are shown in Table 1.

(Example 2)

In Example 1, except having used tetrahydrofuran which is an ether organic solvent instead of cyclohexanone which is an organic solvent of ethers, it carried out similarly to Example 1, and manufactured the pattern forming material and laminated body. However, the remaining amount of the organic solvent in the photosensitive layer was obtained to be 0.30% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(Example 3)

In Example 1, the binder was changed to methyl methacrylate/styrene/methacrylic acid copolymer (copolymer composition (mass%): 46/31/23, mass average molecular weight: 60,000, acid value 150mgKOH /g, I/O value: 0.63), except that, it carried out similarly to Example 1, and manufactured the pattern forming material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 0.30% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(Example 4)

In Example 1, except having changed the composition of the organic solvent as follows, it carried out similarly to Example 1, and manufactured the pattern formation material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 0.40% by mass.

- Methyl ethyl ketone as an organic solvent for ketones: 227.4 parts by mass

・Propylene glycol monomethyl ether as an organic solvent of ethers: 327.4 parts by mass

· Cyclohexanone as an organic solvent of ketones: 79.0 parts by mass

・Methanol as an organic solvent for alcohols: 58.1 parts by mass

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(Example 5)

In Example 1, the polymeric compound represented by the structural formula (40) and polyethylene glycol #1000 dimethacrylate were not contained, and the polymeric compound represented by the structural formula (38) and the polymeric compound represented by the structural formula (39) were not contained. Except having contained 55.89 mass parts of polymeric compounds in total, it carried out similarly to Example 1, and manufactured the pattern forming material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 0.30% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(Example 6)

In Example 1, except that the support was changed to a polyethylene terephthalate film (manufactured by Toray Co., Ltd., 16QS52) with a thickness of 16 μm, it was carried out in the same manner as in Example 1 to produce a pattern forming material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 0.30% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(Example 7)

In Example 1, except having changed the support body into the polyester film (Mitsubishi Chemical Corporation make, R-340G) of thickness 16 micrometers, it carried out similarly to Example 1, and manufactured the pattern forming material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 0.30% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(Embodiment 8)

In Example 1, except having changed the protective film into a 12-micrometer-thick polypropylene film (manufactured by Oji Special Paper Co., Ltd., E-501), it carried out similarly to Example 1, and manufactured the pattern forming material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 0.30% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(Example 9)

In Example 6, except having changed the protective film into a 20-micrometer-thick polypropylene film (manufactured by Oji Special Paper Co., Ltd., E-200), it carried out similarly to Example 6, and manufactured the pattern forming material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 0.30% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 6, and evaluated surface defect, fog of a color developer, crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(comparative example 1)

In Example 1, except having changed the composition of the organic solvent as follows, it carried out similarly to Example 1, and manufactured the pattern formation material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 1% by mass.

- Methyl ethyl ketone as an organic solvent for ketones: 127.4 parts by mass

・Propylene glycol monomethyl ether as an organic solvent of ethers: 404.9 parts by mass

· Cyclohexanone as an organic solvent of ketones: 158.1 parts by mass

・Methanol as an organic solvent for alcohols: 36.3 parts by mass

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(comparative example 2)

In the comparative example 1, except having changed the composition of the organic solvent as follows, it carried out similarly to the comparative example 1, and manufactured the pattern forming material and a laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 0.80% by mass.

・Propylene glycol monomethyl ether as an organic solvent of ethers: 350 parts by mass

· Cyclohexanone as an organic solvent for ketones: 100 parts by mass

・Methanol as an organic solvent for alcohols: 149.3 parts by mass

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, fog of a color developer, crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(comparative example 3)

In Example 1, except having changed the composition of the organic solvent as follows, it carried out similarly to Example 1, and manufactured the pattern formation material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 1% by mass.

[Composition of organic solvent]

- Methyl ethyl ketone as an organic solvent for ketones: 227.4 parts by mass

・Propylene glycol monomethyl ether as an organic solvent of ethers: 404.9 parts by mass

· Cyclohexanone as an organic solvent for ketones: 94.4 parts by mass

・Methanol as an organic solvent for alcohols: Not added

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(comparative example 4)

In Comparative Example 1, the binder was changed to methyl methacrylate/styrene/methacrylic acid copolymer (copolymer composition (mass%): 46/31/23, mass average molecular weight: 60,000, acid value 150 mgKOH /g, I/O value: 0.63): 139.58 parts by mass, except that, it carried out similarly to the comparative example 1, and manufactured the pattern forming material and a laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 1% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(comparative example 5)

In Comparative Example 1, the polymerizable compound was changed to only 111.78 parts by mass of the polymerizable compound represented by the following structural formula (39) (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., BPEM-10F), and the same procedure as Comparative Example 1 was performed except that It proceeds, and manufactures a pattern forming material and a laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 1% by mass.

[chemical 9]

结构式(39)

Structural formula (39)

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(comparative example 6)

In Comparative Example 1, except that 1-phenyl-3-pyrazolidinone as a reducing agent was not added, it carried out similarly to Comparative Example 1, and produced the pattern forming material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 1% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(comparative example 7)

In the comparative example 1, except having not added the phenoxazine which is a polymerization inhibitor, it carried out similarly to the comparative example 1, and manufactured the pattern forming material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 1% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(comparative example 8)

In Comparative Example 1, except that N-butylchloroacridone, which is a heterocondensed ring compound, was changed to diethylaminobenzophenone, the pattern forming material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 1% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, the fog of a color developer, the crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(comparative example 9)

In the comparative example 1, except having changed the naphthalene sulfonate of Victoria pure blue into malachite green, it carried out similarly to the comparative example 1, and manufactured the pattern forming material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 1% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, fog of a color developer, crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

(comparative example 10)

In Comparative Example 1, except that N-phenylglycine was not added, it carried out similarly to Comparative Example 1, and manufactured the pattern forming material and laminated body. However, the remaining amount of the organic solvent in the obtained photosensitive layer was 1% by mass.

<Evaluation>

Using the obtained pattern forming material, it carried out similarly to Example 1, and evaluated surface defect, fog of a color developer, crack of an unexposed film, sensitivity, resolution, hiding property, and peeling time. The results are shown in Table 1.

[Table 1]

Organic solvent content (mass%) surface failure Fog of developer Breakage of unexposed film (mm) Sensitivity(mJ/cm ² ) Resolution (μm) Concealment Stripping time (seconds) Example 1 0.30 ○ ○ 6 8 15 0% twenty one Example 2 0.30 ○ ○ 6 8 15 0% twenty one Example 3 0.30 ○ ○ 5 8 18 1% twenty three Example 4 0.40 ○ ○ 3 10 15 1% 25 Example 5 0.30 ○ ○ 5 10 15 3% 25 Example 6 0.30 ○ ○ 6 8 15 0% twenty one Example 7 0.30 ○ ○ 6 8 15 0% twenty one Example 8 0.30 ○ ○ 6 8 15 0% twenty one Example 9 0.30 ○ ○ 6 8 15 0% twenty one Comparative example 1 1 ○ ○ 1 15 18 2% 28 Comparative example 2 0.80 ○ ○ 2 13 17 2% 26 Comparative example 3 1 ○ ○ 1 15 17 1% 28 Comparative example 4 1 ○ ○ 1 15 25 2% 26 Comparative Example 5 1 ○ ○ 1 15 15 35% 28 Comparative example 6 1 ○ × 1 10 17 3% 28 Comparative example 7 1 ○ × 1 10 30 2% 28 Comparative example 8 1 ○ ○ 1 20 20 2% 28 Comparative example 9 1 × ○ 1 20 17 1% 28 Comparative Example 10 1 ○ ○ 1 twenty two 18 2% 28

It can be judged from the results in Table 1 that in the pattern forming materials of Examples 1 to 9, at least one organic solvent selected from ketones, alcohols and ethers is contained in the photosensitive layer, and its residual amount is 0.5 wt. % or less, so there are few surface defects, it is possible to prevent light fog caused by the developer, there is less cracking of the unexposed film, the resolution is high, the strength of the masking film is high, and the peelability after pattern formation is good, and a higher fineness can be formed. pattern. In particular, Examples 1, 2 and 6 to 9 in which the remaining amount of the organic solvent is 0.35% by mass or less, the I/O value of the binder is 0.35 to 0.60, and a compound having a polyalkylene oxide chain is contained as a polymerizable compound. Among the pattern forming materials, it is judged that there are very few surface defects, the light fog caused by the developer can be prevented, the cracking of the unexposed film is small, the resolution is high, the strength of the masking film is strong, and the peelability after pattern formation is good. form a finer pattern. On the other hand, the pattern forming materials of Comparative Examples 1 to 10 were judged to have at least a lot of cracks in the unexposed film, the strength of the masking film was weak, and the peelability after pattern formation was poor, and even in other evaluation items, they were often inferior to Examples. A high-definition pattern cannot be formed.

Industrial availability

The pattern forming material of the present invention has less surface defects, can prevent light fog caused by the developer, has less cracks in the unexposed film, has high resolution, has high masking film strength, and has good peelability after pattern formation, and can form more A pattern forming material of a high-definition pattern. Therefore, it can be preferably used in the formation of various patterns, the formation of permanent patterns such as wiring patterns, the manufacture of liquid crystal structural members such as color filters, pillars, ribs, spacers, and partitions, holography, micromotors, and printing. Manufacturing etc., especially, it can be suitably used for formation of a high-definition wiring pattern.

In addition, since the pattern forming device of the present invention includes the pattern forming material of the present invention, it can be preferably used in the formation of various patterns, the formation of permanent patterns such as wiring patterns, color filters, pillars, ribs, spacers, Production of liquid crystal structural members such as barrier ribs, production of holograms, micromotors, prints, etc., can be particularly preferably used for the formation of high-definition wiring patterns.

Since the pattern forming method of the present invention includes the pattern forming material of the present invention, it can be preferably used in the formation of various patterns, the formation of permanent patterns such as wiring patterns, color filters, pillars, ribs, spacers, and partition walls. The manufacture of structural members such as liquid crystals, the manufacture of holograms, micro motors, prints, etc., can be particularly preferably used for the formation of high-definition wiring patterns.

Claims (20)

1. A pattern forming material, characterized in that, It has a support and a photosensitive layer on the support, and the photosensitive layer contains (A) 40 to 80% by mass of a binder, (B) a polymerizable compound, (C) a photopolymerization initiator, (D) a heterocondensed ring series compound, (E) polymerization inhibitor, (F) color developer, N-phenylglycine and (G) organic solvent, (A) The acid value of the binder is 50-400 mgKOH/g, and the mass-average molecular weight is 10,000-100,000, (B) The polymerizable compound contains at least one of (b1) a compound having a urethane group and (b2) a compound having an aryl group, (D) The heterocondensed ring system compound includes at least one selected from heterocondensed ring system ketone compounds, quinoline compounds and acridine compounds, and the content of the heterocondensed ring system compound in the photosensitive layer is 0.05- 30% by mass, (G) The organic solvent is at least one selected from ketones, alcohols, and ethers, and the remaining amount is 0.5% by mass or less. 2. The pattern forming material according to claim 1, wherein, (A) The I/O value of the adhesive is 0.35 to 0.60. 3. The pattern forming material according to claim 1, wherein, (B) The polymeric compound contains the compound which has a polyalkylene oxide chain which has at least 1 sort(s) of an ethylene group and a propylene group. 4. The pattern forming material according to claim 1, wherein, (C) The photopolymerization initiator contains halogenated hydrocarbon derivatives, phosphine oxides, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, acyl phosphine oxide compounds, aromatic onium salts And at least one selected from ketoxime ether. 5. The pattern forming material according to claim 1, wherein, (E) The polymerization inhibitor is at least one selected from a compound having at least two phenolic hydroxyl groups, a compound having an aromatic ring substituted by an imino group, a compound having a heterocyclic ring substituted by an imino group, and a hindered amine compound . 6. The pattern forming material according to claim 1, wherein, Further, dyes and reducing agents containing compounds having a triallylmethane skeleton are included. 7. The pattern forming material according to claim 1, wherein, (G) The organic solvent is at least one of methyl ethyl ketone, cyclohexanone, methanol, methyl propylene glycol, and tetrahydrofuran. 8. The pattern forming material according to claim 6, wherein, The dye containing a compound having a triallylmethane skeleton is an allylsulfonic acid compound. 9. The pattern forming material according to claim 6, wherein, The reducing agent is 1-phenyl-3-pyrazolidinone. 10. The pattern forming material according to claim 1, wherein, For the photosensitive layer, when the photosensitive layer is exposed and developed, the minimum energy of the light used in the exposure so that the thickness of the exposed portion of the photosensitive layer does not change after the exposure and development is 0.1 ~20mJ/cm ² . 11. The pattern forming material according to claim 2, wherein, The binder exhibits swelling or solubility with respect to an aqueous alkaline solution. 12. The pattern forming material according to claim 11, wherein, The binder includes a copolymer having a structural unit derived from at least one of styrene and styrene derivatives. 13. The pattern forming material according to claim 11, wherein, The glass transition temperature of the adhesive is above 80°C. 14. A pattern forming device, characterized in that, Having the pattern forming material described in claim 1, It includes at least: a light irradiation unit capable of irradiating light; and a light modulation unit for modulating the light from the light irradiation unit to expose the photosensitive layer in the pattern forming material. 15. A pattern forming method, characterized in that, At least including the step of exposing the photosensitive layer in the pattern forming material according to claim 1 . 16. The pattern forming method according to claim 15, wherein, Exposure is performed using light modulated according to the control signal after generating a control signal based on the pattern information to be formed. 17. The pattern forming method according to claim 15, wherein, Exposure is performed through a microlens array in which microlenses having aberrations capable of correcting deformation of an exit surface of a drawing section in the light modulation mechanism are corrected after light is modulated by a light modulation mechanism. Aspherical. 18. The pattern forming method according to claim 17, wherein, Aspheric surfaces are toric surfaces. 19. The pattern forming method according to claim 15, wherein, After exposure, development of the photosensitive layer is performed. 20. The pattern forming method according to claim 19, wherein, After development is performed, permanent pattern formation is performed.