TWI411880B - Pattern forming material, pattern forming device and pattern forming method - Google Patents

Abstract

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

Description

Pattern forming material, pattern forming device and pattern forming method

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

When a permanent pattern such as a circuit pattern is formed, a photosensitive resin composition is coated on a support, and a pattern forming material which is dried to form a photosensitive layer is used. The permanent pattern is formed by, for example, laminating a pattern forming material on a substrate such as a copper area laminate forming the permanent pattern to form a layered body, exposing the photosensitive layer to the layered body, and developing the photosensitive layer after the exposing The pattern is then subjected to an etching treatment or the like to form the above permanent pattern.

The pattern forming material is a proposal for adding a polymerization inhibitor of a compound having a phenolic hydroxyl group, an aromatic ring, a heterocyclic ring or an imine group to the photosensitive resin composition for the purpose of improving storage stability and improving resolution (refer to For example, Patent Documents 1 to 4). However, there is no disclosure at this time, and the disclosure or suggestion of a high-sensitivity dry film photoresist film capable of suppressing a decrease in sensitivity can be suppressed by reducing the amount of organic solvent remaining.

In addition to the improvement in sensitivity of DFR, there is a demand for peelability after pattern formation.

Therefore, the current situation is that the surface failure is small, the light leakage caused by the color developer is prevented, the crack of the unexposed film is small, the resolution is high, the strength of the mask film is large, and the peeling property after pattern formation is good, and a highly fine pattern can be formed. A pattern forming material, a pattern forming apparatus including the pattern forming material, and a pattern forming method using the pattern forming material have not been provided, and further improvement development is expected.

Japanese Unexamined Patent Publication No. Publication No. JP-A No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No.

The present invention has been made in view of the above circumstances, and the object of the present invention is to solve the above problems. That is, the object of the present invention is to provide a surface failure, to prevent light leakage caused by a color developer, to have less cracking of an unexposed film, to have high resolution, to have a high strength of a mask film, and to have good peelability after pattern formation. A pattern forming material for forming a more highly detailed pattern, a pattern forming device including the pattern forming material, and a pattern forming method using the pattern forming material.

The means for solving the above problems are as follows. That is, <1> has a support and a photosensitive layer on the support, and the photosensitive layer contains (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a hybrid ring. a compound, (E) a polymerization inhibitor, (F) a color developer, and (G) an organic solvent, wherein the (A) binder has an acid value of 50 to 400 mgKOH/g and a mass average molecular weight of 10,000 to 100,000, (B) The polymerizable compound contains at least one of (b1) a compound having a urethane group, (b2) a compound having an aryl group, and (b3) a compound having a polyoxyalkylene chain, (G) an organic solvent selected A pattern forming material characterized by at least one of a ketone, an alcohol, and an ether, and having a residual amount of 0.5% by mass or less. The pattern forming material according to the above <1>, wherein the acid value and the weight average molecular weight of the binder contained in the photosensitive layer are defined, and not only the compound contained in the polymerizable compound but also the compound and the content of the organic solvent are specified, that is, It can form less surface failure, can prevent light leakage caused by coloring agent, has less cracking of unexposed film, has high resolution, high strength of covering film, and good peeling property after pattern formation, and a more highly detailed pattern.

<2> The pattern forming material according to <1> above, wherein the (A) binder has an I/O value of from 0.35 to 0.60.

<3> The pattern forming material according to the above <1> or <2>, wherein the (B) polymerizable compound contains a compound having a polyoxyalkylene chain having at least an ethyl group and a stretching propyl group. Either.

The pattern forming material according to any one of <1> to <3> wherein the (D) heterocyclic ring compound contains at least one selected from the group consisting of a heterocyclic ketone compound, a quinoline compound, and an acridine compound. .

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

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

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

<8> A pattern forming material according to the above <6> or <7>, which comprises a dye-based arylsulfonic acid compound having a compound having a triarylmethane skeleton.

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

<10> The pattern forming material according to any one of <1> to <9> wherein, when the photosensitive layer is exposed to the photosensitive layer, the thickness of the exposed portion of the photosensitive layer is unchanged after the exposure and development. The minimum energy used for the above exposure is 0.1 to 20 mJ/cm ² .

<11> The pattern forming material according to any one of <1> to <10> wherein the binder is swellable or soluble in an aqueous alkaline solution.

The pattern forming material according to any one of <1> to <11> wherein the binder contains a copolymer having a structural unit derived from at least one of styrene and a styrene derivative.

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

The pattern forming material according to any one of <1> to <13> wherein the polymerization inhibitor has at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, an imido group, and a phenolic hydroxyl group.

<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 and thiophene ,coffee At least one of hindered phenol and derivatives thereof.

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

The pattern forming material according to any one of <1> to <16> wherein the photopolymerization initiator is selected from the group consisting of a halogenated hydrocarbon derivative, a phosphine oxide, a hexaarylbiimidazole, an anthracene derivative, and an organic peroxide. At least one of a sulfur compound, a ketone compound, a mercaptophosphine oxide compound, an aromatic onium salt, and a ketoxime.

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

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

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

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

<22> The pattern forming material according to any one of <1> to <21> wherein a protective film is provided on the photosensitive layer.

<23> The pattern forming material according to any one of <1> to <22> wherein a protective film is provided on the photosensitive layer, the protective film comprising a polypropylene resin, an ethylene-propylene copolymer resin, and a polyethylene terephthalate. At least one of the ester resins.

<24> A pattern forming apparatus comprising the pattern forming material according to any one of the above <1> to <23>, characterized in that at least the illuminating mechanism is provided, and light from the illuminating means is modulated, and the pattern is formed A light modulating mechanism for exposing the photosensitive layer of the material. In the pattern forming apparatus according to <24>, the illumination unit is illuminated toward the light modulation unit. The light modulation mechanism modulates light from the illumination unit. The light modulated by the light modulating mechanism exposes the photosensitive layer. For example, the above photosensitive layer is then developed, that is, a highly fine pattern is formed. <25> The pattern forming apparatus according to the above <24>, wherein the light modulating means further has a pattern signal generating means for generating a control signal based on the formed pattern information, and modulating the irradiation of the self-illuminating means according to the control signal generated by the pattern signal generating means Light. In the pattern forming apparatus according to the above aspect, the light modulating means is configured to have the pattern signal generating means, and the light irradiated from the illuminating means is modulated by the control signal generated by the pattern signal generating means.

<26> The pattern forming apparatus according to <24> or <25>, wherein the light modulating mechanism has n pixel portions, and any of the n pixel portions that are consecutively arranged in the n pixel portions can be formed according to the pattern Information is controlled. In the pattern forming apparatus according to the above aspect, the pixel portion of the n pixel portions of the light modulating mechanism that is continuously disposed in any of the n pixels is controlled by the pattern information, and the light from the illumination unit can be used. High speed modulation.

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

<28> The pattern forming device of <27>, wherein the spatial light modulation element coefficient bit micromirror device (DMD).

<29> The pattern forming device of any one of <26> to <28> wherein the pixel portion is a micromirror.

<30> The pattern forming apparatus according to any one of <24> to <29> wherein the illuminating means combines two or more lights to illuminate. In the pattern forming apparatus according to the <30>, the illuminating means can illuminate by combining two or more lights, and the exposure is performed by exposure light having a large depth of focus. As a result, the exposure of the pattern forming material described above can be performed extremely finely. For example, after the above photosensitive layer is developed, a highly highly detailed pattern can be formed.

<31> The pattern forming apparatus of any one of <24> to <30> wherein the illumination mechanism has a plurality of lasers, a multimode optical fiber, and condensing the laser light irradiated by each of the plurality of lasers into the plurality of A collection optical system of mode fibers. In the pattern forming apparatus according to the <31>, the illumination unit condenses the laser light irradiated by each of the plurality of lasers by the collection optical system, and combines the multi-mode optical fibers to expose the exposure to a large depth of focus. Light is carried out. As a result, the exposure of the pattern forming material described above can be performed extremely finely. For example, after the above photosensitive layer is developed, a highly highly detailed pattern can be formed.

<32> A pattern forming method, characterized in that at least the photosensitive layer of the pattern forming material of any one of <1> to <23> is exposed. In the pattern forming method of <32>, the exposure system is performed on the pattern forming material. For example, after the above photosensitive layer is developed, a highly fine pattern can be formed.

<33> The pattern forming method according to <32>, wherein the pattern forming material is laminated on the substrate while exposing at least one of heating and pressurization.

<34> A pattern forming method according to <32> or <33>, wherein the exposure is performed based on the formed pattern information.

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

<36> The pattern forming method according to any one of <32> to <35> wherein the exposure system is performed using an illumination mechanism that illuminates with light, and a light modulation mechanism that modulates light that is irradiated from the illumination unit based on the formed pattern information.

<37> The pattern forming method according to <36>, wherein the exposure system modulates light by a light modulation mechanism, and passes through an aspherical microlens having aberrations correctable by deformation of an exit surface of the pixel portion of the light modulation mechanism. Performed by arranging the microlens arrays. In the pattern forming method of <37>, the light modulated by the light modulating means is corrected by the distortion of the exit surface of the pixel portion by the aspherical surface of the microlens array. As a result, the deformation of the image formed on the pattern forming material is suppressed, and the exposure pole of the pattern forming material is highly finely performed. For example, after the above photosensitive layer is developed, a highly fine pattern can be formed.

<38> A pattern forming method according to <37>, wherein the aspherical surface is a toric surface. In the pattern forming method of <38>, the aberration due to the deformation of the radiating surface of the pixel portion can be effectively corrected by the aspherical toric surface, and the deformation of the image formed on the pattern forming material is effectively suppressed. As a result, the exposure electrode of the pattern forming material described above is highly finely performed. For example, after the above photosensitive layer is developed, a highly fine pattern can be formed.

<39> A pattern forming method according to any one of <32> to <38> wherein the exposure system is performed through an aperture array. In the pattern forming method of <39>, since the exposure system is performed through the aperture array, the extinction ratio is improved. As a result, the exposure is extremely fine. For example, after the above photosensitive layer is developed, a highly highly detailed pattern can be formed.

<40> The pattern forming method according to any one of <32> to <39> wherein the exposure is performed while the exposure light and the photosensitive layer are relatively moved. In the pattern forming method of <40>, exposure is performed while moving the modulated light relative to the photosensitive layer, and exposure can be performed at high speed. For example, after the above photosensitive layer is developed, a highly fine pattern can be formed.

<41> The pattern forming method of any one of <32> to <40>, wherein the exposure is performed in a partial region of the photosensitive layer.

<42> The pattern forming method according to any one of <32> to <41> wherein the exposure of the photosensitive layer is performed after the exposure. In the pattern forming method of <42>, the photosensitive layer is developed after the exposure, and a highly fine pattern can be formed.

<43> A pattern forming method according to <42>, wherein the formation of the permanent pattern is performed after development.

<44> The pattern forming method according to <43>, wherein the permanent pattern is a circuit pattern, and the formation of the permanent pattern is performed by at least one of an etching treatment and a plating treatment.

According to the present invention, the conventional problem can be solved, and the surface failure can be provided, the light leakage caused by the color developer can be prevented, the crack of the unexposed film is small, the resolution is high, the strength of the mask film is large, and the pattern is peeled off after the formation. A pattern forming material capable of forming a more highly detailed pattern, a pattern forming apparatus provided with the pattern forming material, and a pattern forming method using the pattern forming material.

(patterning material)

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

<Photosensitive layer>

The photosensitive layer contains (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator, (D) a heterocyclic ring compound, (E) a polymerization inhibitor, (F) a color developer, and (G) An organic solvent, if necessary, a dye, a reducing agent, or the like, which is appropriately selected. The number of layers of the photosensitive layer may be one layer or two or more layers.

When the photosensitive layer is exposed and developed, the minimum energy of the light which does not change the thickness of the exposed portion of the photosensitive layer before and after the development is preferably 0.1 to 20 mJ/cm ^{2 , more} preferably 0.5 to 10 mJ/cm ² . 1~8mJ/cm ^{2 is} especially good.

It said minimum energy less than 0.1mJ / cm ² of light leakage may occur in the processing step, than 20mJ / cm ^2, the exposure time consuming, the process slows down.

Here, the above-mentioned "minimum energy for the light for the exposure which does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development" means a so-called development sensitivity, which can be used, for example, when exposing the photosensitive layer The energy (exposure amount) of the light to be exposed is obtained from a relationship (sensitivity curve) of the thickness of the hardened layer which is formed by the development process of the exposure described above.

The thickness of the hardened layer increases as the amount of exposure increases, and is then approximately equal to the thickness of the photosensitive layer before exposure and is approximately constant. The development sensitivity is a value obtained by reading the minimum exposure amount when the thickness of the hardened layer is approximately constant.

When the thickness of the hardened layer is less than +/- 1 μm from the thickness of the photosensitive layer before the exposure, the thickness of the hardened layer may be regarded as not to be changed by exposure and development.

The method for measuring the thickness of the hardened layer and the photosensitive layer before the exposure is not particularly limited, and may be appropriately selected according to the purpose, and for example, a film thickness measuring device or a surface roughness measuring device (for example, SURFCOM1400D, manufactured by Tokyo Precision Co., Ltd.) may be used. The method of measurement.

- (A) binder -

The above-mentioned binder has an acid value of 50 to 400 mgKOH/g, preferably 75 to 300 mgKOH/g, more preferably 100 to 250 mgKOH/g.

When the acid value is less than 50 mgKOH/g, the development is insufficient, the resolution is poor, and a permanent pattern such as a circuit pattern of a high degree of precision is not required. When the value exceeds 400 mgKOH/g, at least the liquid resistance and the adhesion of the pattern deteriorate. A permanent pattern such as a highly detailed circuit pattern shall not be used.

The molecular weight of the above binder is preferably 10,000 to 100,000 by mass average molecular weight, more preferably 30,000 to 80,000.

When the mass average molecular weight is less than 10,000, the strength of the film tends to be insufficient, and it is difficult to manufacture, and if it exceeds 100,000, the developability is lowered.

The upper limit of the I/O value is preferably 0.60, and more preferably 0.58, from the viewpoint of at least one of improving the resolution and the covering property.

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

The method of adjusting the binding agent I/O value is appropriately selected from at least one of the monomer type constituting the copolymer and the polymerization ratio (content) at the time of polymerizing the monomer, and can be adjusted, for example, to 0.35 to 0.60.

The above-mentioned I/O value is also called (inorganic value) / (organic value), which is an organic concept for treating the polarity of various organic compounds, and is one of the functional group contribution methods for setting parameters of each functional group. In detail, the above I/O values have been detailed in the organic concept map (Jia Tian Shansheng, San Gong Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, No. 1~16 (1954); Chemistry, No. Volume 11, No. 10, 719-725 (1957); FRAGRANCE JOURNAL, No. 34, No. 97-111 (1979); FRAGRANCE JOURNAL, No. 50, No. 79-82 (1981), etc. literature.

The concept of the above I/O value is to divide the properties of the compound into organic groups representing covalent bonds, and inorganic groups representing ionic bonds, and all organic compounds are referred to as orthogonal coordinates of the organic and inorganic axes. The 1 point is indicated.

The inorganic value is a numerical value which affects the boiling point of various substituents, bonds, and the like of the organic compound, and is quantified based on the hydroxyl group. Specifically, the distance between the boiling point curve of the linear alcohol and the boiling point curve of the linear paraffin is about 100 ° C in the vicinity of the carbon number of 5, and the influence of one hydroxyl group is set to a value of 100. Based on the value, various substituents are used. Or the value of the numerical value of the influence of various bonds and the like on the boiling point, that is, the inorganic value of the substituent of the organic compound. For example, the -COOH group has an inorganic value of 150 and the double bond has an inorganic value of 2. Therefore, the inorganic value of an organic compound means the sum of inorganic values of various substituents, bonds, and the like of the compound.

The above organic value is determined by the influence of the boiling point of the carbon atom represented by the methylene group based on the methylene group in the molecule. That is, the average value of the boiling point rise due to the addition of one carbon atom to the linear saturated hydrocarbon compound in the vicinity of 5 to 10 carbon atoms is 20 ° C, based on which the organic value of one carbon atom is determined. 20. The numerical value of the influence of various substituents, bonding, and the like on the boiling point based on this 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 the non-polar (hydrophobic, organic) organic compound, and the larger the organic compound, the more polar (hydrophilic, inorganic).

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

The I/O value of methacrylic acid/methyl methacrylate/styrene copolymer (copolymer composition (mole ratio): 2/5/3), the inorganic value of the copolymer and the organic value were calculated by the following method The property value was calculated from the following formula (the inorganic value of the above copolymer) / (the organic value of the above copolymer).

The inorganic value of the copolymer is determined by (the inorganic value of methacrylic acid) × (the molar ratio of the above methacrylic acid), (the inorganic value of the methyl methacrylate) × (the above methyl group) Calculated by the total of the molar ratio of methyl acrylate and (the inorganic value of styrene described above) × (the molar ratio of styrene described above).

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

The organic value of the above copolymer is determined by (the organic value of methacrylic acid) × (the molar ratio of the above methacrylic acid), (the organic value of the above methyl methacrylate) × (the above methyl group) Calculated by the total of the molar ratio of methyl acrylate and (the organic value of styrene described above) × (the molar ratio of styrene described above).

The methacrylic acid has 4 carbon atoms, the methyl methacrylate has 5 carbon atoms, and the styrene has 8 carbon atoms. Therefore, the organic value of the methacrylic acid is 20 (the organic value of carbon atoms). ×4 (number of carbon atoms) = 80, and the organic value of the above methyl methacrylate is 20 (organic value of carbon atom) × 5 (number of carbon atoms) = 100, and the organic value of the above styrene is 20 ( The organic value of carbon atoms) × 8 (number of carbon atoms) = 160, and the organic value of the above copolymer is from the formula 80 × 2 (the above molar ratio of methacrylic acid) + 100 × 5 (the above methacrylic acid The molar ratio of the ester to +160 x 3 (the molar ratio of the above styrene) was calculated to be 1140.

Therefore, the I/O value of the above copolymer was 645 (inorganic value of the above copolymer) / 1140 (organic value of the above copolymer), 0.566.

The above-mentioned binder is only required to have the above I/O value within the above numerical range, and is not particularly limited, and may be appropriately selected depending on the purpose, and may have, for example, an acidic group.

The above-mentioned binder is not particularly limited as long as the acid value and the mass average molecular weight are in the above range, and it is preferably, for example, those having a swelling property in an alkaline aqueous solution and being more soluble in an alkaline aqueous solution. It is also preferred that the binder contains a polymerizable group.

It is swellable or soluble in an aqueous alkaline solution, and is preferably an acidic group, for example.

The above acidic group is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like, and among them, a carboxyl group is preferred.

The carboxyl group-bonding agent is, for example, an ethyl group copolymer having a carboxyl group, a polyurethane resin, a polyamide resin, a modified epoxy resin, or the like, wherein solubility in a coating solvent, solubility in an alkaline aqueous solution, synthesis From the viewpoints of suitability and ease of adjustment of the physical properties of the membrane, it is preferred to use an ethyl group copolymer having a carboxyl group. From the viewpoint of development, a copolymer of at least any of styrene and a styrene derivative is preferred.

The above-mentioned carboxyl group-extended ethyl copolymer may be obtained by copolymerization of at least (1) a ethyl group having a carboxyl group and (2) a monomer copolymerizable with these. Specific examples of such a monomer include, for example, the compounds described in paragraphs [0164] to [0201] and [0203] to [0205] of JP-A-2005-258431.

The content of the above-mentioned binder in the photosensitive layer is not particularly limited and may be appropriately selected depending on the purpose, and is preferably, for example, 10 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 40 to 80% by mass.

When the content is less than 10% by mass, the adhesion between the alkali developability and the substrate for forming a printed circuit board (for example, a copper-area laminate) is lowered, and when it exceeds 90% by mass, the stability of the development time and the cured film (for the development time) The cover film has low strength. The above content may also be the total content of the above-mentioned binder and, if necessary, the polymer binder.

When the above-mentioned binder is a material having a glass transition temperature, the glass transition temperature is not particularly limited and may be appropriately selected depending on the purpose, for example, at least one of viscosity of the pattern forming material, edge fusion, and peelability of the support. The viewpoint is preferably 80 ° C or more, more preferably 100 ° C or more, and particularly preferably 120 ° C or more.

When the glass transition temperature is less than 80 ° C, the viscosity of the pattern forming material is increased, and the peelability of the support is deteriorated.

- (B) Polymeric Compound -

The polymerizable compound contains at least one of (b1) a compound having urethane group and (b2) a compound having an aryl group, and more preferably a compound having a polyoxyalkylene group or another polymerizable compound. These polymerizable groups are preferably two or more.

The above polymerizable group is, for example, an ethylenically unsaturated bond (for example, (meth) acrylonitrile, (meth) acrylamide, phenylethyl, vinyl, vinyl ether, etc. ethyl, allyl ether, alkene An aryl group such as a propyl ester or the like, a polymerizable cyclic ether group (e.g., an epoxy group, an oxetane group, etc.), and the like, wherein an ethylenically unsaturated bond is preferred.

--(b1) compounds with urethane--

The compound having the urethane group is not particularly limited as long as it has an urethane group, and may be appropriately selected according to the purpose, and examples thereof include a compound described in paragraphs [0210] to [0262] of JP-A-2005-258431.

The content of the urethane group-containing compound 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 is more than 70% by mass, the resolution, the adhesion, and the like may be deteriorated.

--(b2) monomer with aryl group --

The aryl group-containing compound is not particularly limited as long as it has an aryl group, and may be appropriately selected according to the purpose, and may be, for example, an ester of an aryl group-containing polyol compound, a polyamine compound, and a polyamine alcohol compound, and an ester of an unsaturated carboxylic acid. Or guanamine and the like.

Specific examples thereof include the compounds described in paragraphs [0264] to [0271] of JP-A-2005-258431.

The content of the above-mentioned aryl group-containing compound in the above polymerizable compound is preferably 70% by mass or less, more preferably 20 to 60% by mass, still more preferably 30 to 50% by mass. When the content is more than 70% by mass, the resolution, the adhesion, the covering property, and the like may be deteriorated.

-- compounds with polyoxyalkylene chain --

The pattern forming material of the present invention may also contain a compound of a polyoxyalkylene chain. The above compound having a polyoxyalkylene chain is not particularly limited and may be a monofunctional monomer or a polyfunctional monomer.

The above monofunctional monomer is, for example, a compound of the following structural formula (i).

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

The X-sheet has an alkyl group having 2 to 6 carbon atoms, and the ring structure is superior to the chain structure. Chain alkyl groups may have branches. The alkylene group has, for example, an ethyl group, a propyl group, a tetramethylene group, a pentamethylene group, a hexamethylene group or the like, and an ethyl group and a propyl group are preferred.

n is an integer of 1 to 30, and when n is 2 or more, the plural (-X-O-) may be the same or different, and (-X-O-) is different from each other, for example, an ethyl group and a propyl group. Combination, etc.

R ₂ is, for example, an alkyl group, an aryl group, an arylalkyl group or the like, and these groups may be substituted with a substituent.

The alkyl group is an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group, and an octadecyl group. The alkyl group may have a substituent or a branched or cyclic structure.

The above aralkyl group is, for example, a benzyl group or a phenethyl group. The aralkyl group may also have a substituent.

The above aryl group is, for example, phenyl, naphthyl, tolyl, xylyl, ethylphenyl, methoxyphenyl, propylphenyl, butylphenyl, tert-butylphenyl, octylphenyl, phenylphenyl, chloro Phenyl, cyanophenyl, dibromophenyl, tribromophenyl, biphenyl, phenyltolyl, α-xylene tolyl, and the like. The aryl group may also have a substituent.

The substituent of the above alkyl group, aralkyl group and aryl group is, for example, a halogen atom, an aryl group, an aliphatic alkenyl group, an alkoxy group, a cyano group or the like.

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and the like.

The above aryl group is preferably 6 to 20 in total carbon atoms, and more preferably 6 to 14 carbon atoms. The aryl group is, for example, a phenyl group, a naphthyl group, an anthranyl group, a methoxyphenyl group or the like

The above alkenyl group is preferably 2 to 10 in total carbon atoms, and more preferably 2 to 6 carbon atoms. The alkenyl group is, for example, an ethynyl group, a propyl group, a butyl group or the like.

The above alkoxy group may have a branch, and the total number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 5. The alkoxy group is, for example, a methoxy group, an ethoxy group, a propoxy group, a 2-methylpropoxy group or the like.

The compound of the above structural formula (i) specifically includes a compound of the following structural formula and the like. In the following formula, R represents a hydrogen atom or a methyl group. n The integers of Tables 1 to 30, m and L are integers of Table 1 or higher, and m + L are integers of Tables 1 to 30. Me is methyl, Bu is butyl.

Among the compounds having a polyoxyalkylene chain, a suitable compound having at least one of a stretched ethyl group and a stretched propyl group is a polyethylene glycol or a polypropylene glycol having a stretched ethyl group or a stretched propyl group of 10 to 30.

The compound having a polyoxyalkylene chain may be used singly or in combination of two or more.

The above polyfunctional monomer is, for example, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate having an ethyl group number of 2 to 30 (for example, diethylene glycol di(methyl)). Acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol #400 dimethacrylate, polyethylene glycol #600 dimethacrylate, poly Glycol #1000 dimethacrylate, etc.), propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate having a number of propyl groups of 2 to 18 (for example, dipropylene glycol di(methyl)) Acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, etc.), ethylene glycol chain/propylene glycol chain have at least one extension A di(meth)acrylate of an alkanediol chain (for example, a compound described in the pamphlet of International Publication No. 01/98832), polytetramethylene glycol di(meth)acrylate, or the like.

Among them, from the viewpoint of easy availability, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol chain/propylene glycol chain have at least one of the alkylene glycol chains (A) Acrylate is preferred.

The content of the compound having a polyoxyalkylene chain in the above polymerizable compound is preferably 40% by mass or less, more preferably 1 to 30% by mass, particularly preferably 1 to 25% by mass. When the content is less than 0.1% by mass, the effect of improving the peeling property and the development width may be insufficient. When the content is more than 40% by mass, the analysis, the adhesion, the covering property, and the like may be deteriorated.

--Other polymeric compounds --

In the pattern forming material of the present invention, other polymerizable compounds may be used in addition to the above polymerizable compound. For example, esters of unsaturated carboxylic acids (such as acrylic acid, methacrylic acid, isaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyol compounds, unsaturated carboxylic acids and polyamine compounds Amidoxime and the like.

Specifically, there are, for example, the compounds described in paragraphs [0273] to [0283] of JP-A-2005-258431.

The content of the polymerizable compound in the photosensitive layer is preferably, for example, 5 to 90% by mass, more preferably 15 to 60% by mass, still more preferably 20 to 50% by mass. When the content is 5% by mass, the strength of the coating film is lowered. When the content is more than 90% by mass, the edge fusion (deterioration of the bleeding from the end portion) is deteriorated during storage.

-(C) Photopolymerization Initiator -

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the above polymerizable compound, and may be appropriately selected from conventional photopolymerization initiators, and is preferably one which is photosensitive to ultraviolet light to a visible range, for example, to generate photoexcited impurities. The action of the condensed ring system or the sensitizer, the active agent which generates the active radical is also good, and the initiator which initiates the cationic polymerization depending on the monomer type.

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

The above photopolymerization initiator is, for example, a halogenated hydrocarbon derivative (for example, having three Skeleton A bisazole skeleton or the like), a phosphine oxide, a hexaarylbiimidazole, an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, a mercaptophosphine oxide compound, an aromatic onium salt, a ketoxime or the like. Specific examples of the photopolymerization initiator other than the above-described anthracene derivative include the compounds described in paragraphs [0288] to [0299] and paragraphs [0305] to [0309] of JP-A-2005-258431.

The above anthracene derivatives are, for example, 3-benzylideneoxyiminebutan-2-one, 3-acetoxyiminebutan-2-one, 3-propionoxime-4-butan-2-one, 2-acetamidine Oxyimine butan-3-one, 2-acetoxyimine-1-phenylpropan-1-one, 2-benzylideneimine-1-phenylpropan-1-one, 3-(4-toluene Sulfomethoxy)iminobutan-2-one, 2-ethoxycarbonyloxyimine-1-phenylpropan-1-one, and the like.

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

-(D) a heterocyclic ring compound -

The above-mentioned hybrid ring-based compound adjusts the exposure sensitivity and the photosensitive wavelength during exposure of the photosensitive layer described later, or enhances the development of the photosensitive layer without causing the thickness of the exposed portion of the photosensitive layer to change before and after the development. Add the minimum energy of the light. The minimum energy (sensitivity) of the photosensitive layer can be adjusted extremely easily by using the above-mentioned hybrid ring-based compound at 0.1 to 20 mJ/cm ² .

The above-mentioned hybrid ring-based compound is preferably selected from a light-receiving mechanism, a visible light, an ultraviolet laser, and a visible light laser.

The above heterocyclic ring compound is in an excited state due to an active energy ray, and interacts with other substances (for example, a radical generator, an acid generator, etc.) (for example, energy transfer, electron transfer, etc.) to generate a useful group of a radical, an acid, or the like. .

The heterocyclic ring compound not only enhances the sensitivity of the photosensitive layer, but also functions as a photopolymerization initiator for initiating polymerization of the monomer by photoexcitation.

The above heterocyclic ring compound refers to a polycyclic compound having a hetero element in the ring, and a nitrogen atom is preferred among the above rings.

The heterocyclic ring compound is preferably, for example, at least one selected from the group consisting of a heterocyclic ketone compound, a quinoline compound, and an acridine compound.

The above heterocyclic ring compound may specifically be an acridone compound such as acridone, chloroacridone, N-methylacridone, N-butylacridone or N-butylchloroacridone; (2-benzofurancarbenyl)-7-diethylamine coumarin, 3-(2-benzofuranylmethyl)-7-(1-pyrrolidinyl)coumarin, 3-phenyl醯-7-diethylamine coumarin, 3-(2-methoxybenzhydryl)-7-diethylamine coumarin, 3-(4-dimethylamidobenzylidene)-7-di Ethyl coumarin, 3,3'-carbonyl bis(5,7-di-n-propoxycoumarin), 3,3'-carbonyl bis(7-diethylamine coumarin), 3-benzamide -7-methoxycoumarin, 3-(2-furanyl)-7-diethylamine coumarin, 3-(4-diethylamine cinnamate)-7-diethylamine coumarin , 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzylformamide-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, 7 -Ethylamine-4-methylcoumarin, and Japanese Laid-Open Patent Publication No. Hei. No. 5-19475, Japanese Patent Laid-Open No. Hei 7-271028, JP-A-2002-363206, JP-A-2002-363207, and JP-A-2002-363208 Bulletin Laid-Open coumarin compound of the Publication No. 2002-363209 and the like.

The above quinoline compound is specifically, for example, quinoline, 9-hydroxy-1,2-dihydroquinolin-2-one, 9-ethoxy-1,2-dihydroquinolin-2-one, 9-dibutyl Amine-1,2-dihydroquinolin-2-one, 8-hydroxyquinoline, 8-quinoxaline, quinoline-2-carboxylic acid, and the like.

Specific examples of the acridine compound include 9-benzopyridinium, 1,7-bis(9,9-acridinyl)heptane and the like.

Among the above heterocyclic ring compounds, those containing a nitrogen element in the ring are preferred. The nitrogen element in the ring may be the acridine compound, the coumarin compound substituted with an amine group, or an acridone compound. Among them, an acridone compound is particularly preferred.

The above heterocyclic ring compound is more preferably the above acridone, an amino group-substituted coumarin, 9-benzo acridine or the like, and an acridone is preferred.

The combination of the photopolymerization initiator and the above-mentioned heterocyclic ring compound is, for example, an electron transfer type initiator described in JP-A-2001-305734 [(1) Electron-donating initiator and sensitizing dye, and (2) electron accepting. A combination of a type initiator and a sensitizing dye, (3) an electron donating initiator, a sensitizing dye, and an electron accepting initiator (ternary initiator).

The content of the above-mentioned hybrid ring-based compound in the photosensitive layer is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and particularly preferably 0.2 to 10% by mass. When the content is less than 0.05% by mass, the sensitivity to the active energy ray is low, the exposure process takes time, and the productivity is lowered. When the content exceeds 30% by mass, the above-mentioned hybrid ring-based compound is chromatographed from the above.

In addition to the above heterocyclic ring compound, other sensitizers may be added as necessary.

- (E) polymerization inhibitor -

The above polymerization inhibitor is not particularly limited and may be appropriately selected depending on the purpose.

The polymerization inhibitor is used to impart hydrogen (or receive hydrogen) to a photopolymerization-initiating radical component generated by exposure from the photopolymerization initiator, to impart energy (or receive energy), to give electrons (or to accept electrons), and the like. Photopolymerization initiates the deactivation of free radicals and inhibits polymerization initiation.

The polymerization inhibitor includes a compound having an isolated electron pair (for example, a compound having oxygen, nitrogen, sulfur, a metal, or the like), a compound having a π electron (for example, an aromatic compound), and the like, and specifically a compound having a phenolic hydroxyl group, and having a compound An amine group compound, a compound having a nitro group, a compound having a nitroso group, a compound having an aromatic ring, a compound having a hetero ring, a compound having a metal atom (containing a complex compound with an organic compound), and the like. Among these, a compound having a phenolic hydroxyl group, a compound having an imine group, a compound having an aromatic ring, and a compound having a hetero ring are preferred.

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

The above compound having at least two phenolic hydroxyl groups is more preferably a compound of the following structural formula.

In the above structural formula, the Z table is substituted, and m is an integer of 2 or more. n Table 0 or more integers. Preferably, m and n are selected to be m+n=6. When n is 2 or more, the above Z may be the same or different.

If the above m is less than 2, the resolution will deteriorate.

The above substituent may, for example, be a carboxyl group, a sulfonic acid group, a cyano group, a halogen atom (e.g., a fluorine atom, a chlorine atom or a bromine atom), a hydroxyl group or an alkoxycarbonyl group having a carbon number of 30 or less (e.g., methoxycarbonyl, ethoxycarbonyl, benzene). a methoxycarbonyl group, an aryloxycarbonyl group having 30 or less carbon atoms (for example, toluyloxycarbonyl group), an alkylguanamine carbonyl group having 30 or less carbon atoms (for example, a decylamine carbonyl group or a decylamine carbonyl group), or an arylamine carbonyl group (for example, Tolylamine carbonyl), amidoxime group having 30 or less carbon atoms (for example, benzoguanamine oxime group, acetamimidoxime group, trimethylacetamido fluorenyl group), alkoxy group having 30 or less carbon atoms (e.g., methoxy, ethoxy, benzyloxy, phenoxyethoxy, ethylphenoxy, etc.), an arylthio group having 30 or less carbon atoms, an alkylthio group (e.g., phenylthio, methylthio) , ethylthio group, dodecyl group), aryloxy group having 30 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, 1-naphthyloxy group, 2-naphthyloxy group), nitro group, carbon atom number An alkyl group of 30 or less, an alkoxycarbonyloxy group (e.g., methoxycarbonyloxy group, stearyloxycarbonyloxy group, phenoxyethoxycarbonyloxy group), an aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group, chlorobenzene) a carbonyloxy group), a decyloxy group having 30 or less carbon atoms (for example, an ethoxylated group or a propyloxy group), and a fluorenyl group having 30 or less carbon atoms (for example, an ethyl group, a propyl group, a benzyl group) ), an amine methyl sulfhydryl group (eg, an amine methyl sulfhydryl group, an N,N-dimethylamine carbhydryl group, Alkyl carbonyl, piperidine carboxy, etc., an amine sulfhydryl group (eg N,N-dimethylamine thiol, a fluorenyl group, a piperidinyl group, etc., an alkyl group having a carbon number of 30 or less (for example, a fluorenyl group, a trifluoromethyl fluorenyl group, an ethyl fluorenyl group, a butyl fluorenyl group, a fluorenyl group), an aryl fluorenyl group (for example, benzene) An aryl group having a carbon number of 30 or less (for example, a phenyl group, a dichlorophenyl group, a tolyl group, a methoxyphenyl group, a diethylamine group), an aryl group having a carbon number of 30 or less or a fluorenyl group, a pyridinium group, a naphthyl group, a pyridinium group, or a quinolinyl group. Phenyl, acetaminophen phenyl, methoxycarbonylphenyl, hydroxyphenyl, trioctylphenyl, naphthyl, etc.), substituted amines (eg, amine, alkylamino, dialkylamino, arylamino) , a diarylamine group, a guanamine group, etc.), a substituted phosphonium group (for example, a phosphorous group, a diethylphosphonyl group, a diphenylphosphonyl group), a heterocyclic group (for example, a pyridyl group, a quinolyl group, a furyl group, Thienyl, tetrahydroindenyl, pyrazolyl, iso Azyl, isothiazolyl, imidazolyl, Azyl, thiazolyl, anthracene Base, pyrimidinyl, pyridyl Base, triazolyl, tetrazolyl, benzo Azyl, benzopyrazole, isoquinolyl, thiadiazolyl, Lolinyl, piperidinyl, piperidine Base, sulfhydryl, isodecyl, sulfur Alkyl), a ureido group (e.g., a methylureido group, a dimethylureido group, a phenylureido group, etc.), an amine sulfonamide group (e.g., a dipropylamine sulfonyl group, etc.), an alkoxycarbonylamine group (e.g., an ethoxycarbonylamine group) And the like, an aryloxycarbonylamino group (for example, phenoxycarbonylamino group), an alkylphosphino group (for example, a methylphosphino group, etc.), an arylphosphino group (for example, a phenylphosphino group, etc.), a decyl group (for example, a trimethoxyalkyl group, a triethyl group) An oxonyl group or the like, a decyloxy group (for example, a trimethyldecyloxy group), or the like.

The compound of the above formula is, for example, an alkylcatechol (for example, catechol, resorcin, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol). , 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propanol, 3-propychol, 4-propychol, 2-n-butylcatechol , 3-n-butyl catechol, 4-n-butyl catechol, 2-third catechin, 3-third catechol, 4-third catechol, 3,5-di ( Third, catechol, etc.), alkyl resorcinol (eg 2-methyl resorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propyl resorcinol, 4-propenyl resorcinol, 2-n-butyl resorcinol, 4-n-butyl resorcinol, 2-third butyl resorcinol, 4-third dibutyl Hydroquinone, etc.), alkylhydroquinone (such as indomethacin, ethylhydroquinone, propylhydroquinone, tributylhydroquinone, 2,5-di(tributyl)hydroquinone, etc.), gallicol, root bark Trisphenol and the like.

The compound having a phenolic hydroxyl group is preferably a compound in which at least one of the phenolic hydroxyl groups is bonded to each other by a divalent linking group.

The divalent linking group may have, for example, a group having 1 to 30 carbon atoms, an oxygen atom, a nitrogen atom, a sulfur atom, SO, SO ₂ or the like. The above sulfur atom, SO and SO ₂ may be directly bonded.

The above carbon atom and oxygen atom may have a substituent, and the substituent may have, for example, Z in the above structural formula.

The above aromatic ring may have a substituent such as Z in the above structural formula.

Specific examples of the above phenolic hydroxyl group-containing compound include bisphenol A, bisphenol S, bisphenol M, a conventional bisphenol compound used as a color developing agent in a heat sensitive paper, and a bisphenol described in JP-A-2003-305945. A compound, a hindered phenol compound used as an antioxidant, and the like. Also having 4-methoxyphenol, 4-methoxy-2-hydroxydiphenyl ketone, β-naphthol, 2,6-di(t-butyl)-4-cresol, methyl salicylate, two a monophenolic compound such as a substituent such as diethylamine or the like.

A commercially available product of the above phenolic hydroxyl group-containing compound is a bisphenol compound manufactured by Honshu Chemical Co., Ltd.

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

The compound having an imido group is preferably a cyclic structure substituted with an imine group, and the cyclic structure preferably contains at least one of an aromatic ring and a hetero ring, and an aromatic ring condensate is more preferable. The above cyclic structure may have an oxygen atom, a nitrogen atom or a sulfur atom.

A specific example of the above compound having an imine group is thiophene ,coffee Dihydromorphine And hydroquinone, or a compound in which these compounds are substituted by Z in the above structural formula (37).

The above-mentioned compound having a cyclic structure substituted with an imine group is preferably a hindered amine derivative partially hindered with an amine.

The hindered amine is, for example, a hindered amine described in JP-A-2003-246138.

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

Specific examples of the above nitro group-containing compound or the above nitroso group-containing compound include a benzene benzene, a nitroso compound, and a chelate compound of aluminum.

The above compound having an aromatic ring is not particularly limited and may be appropriately selected depending on the purpose, and for example, it is preferred that the above aromatic ring is substituted with a substituent having an isolated electron pair (for example, a substituent having an oxygen atom, a nitrogen atom or a sulfur atom).

Specific examples of the compound having an aromatic ring include the compound having a phenolic hydroxyl group, the compound having an imine group, and a compound having an aniline skeleton (for example, methylene blue or crystal violet).

The above heterocyclic compound is not particularly limited and may be appropriately selected depending on the purpose, and it is preferred that the heterocyclic ring has an atom having an isolated electron pair such as nitrogen, oxygen or sulfur.

Specific examples of the above heterocyclic compound include pyridine, quinoline and the like.

The above compound having a metal atom is not particularly limited and may be appropriately selected depending on the purpose.

The metal atom is not particularly limited as long as it has affinity with a radical generated from the polymerization initiator, and may be appropriately selected depending on the purpose, and examples thereof include copper, aluminum, and titanium.

Among the above polymerization inhibitors, a compound having at least two phenolic hydroxyl groups, a compound having an aromatic ring substituted with an imine group, and a compound having a heterocyclic ring substituted with an imido group are preferred, and the imine group constitutes a cyclic group. It is especially preferred to construct a compound or a hindered amine compound. Specifically, catechol, thiophene ,coffee A hindered amine or a derivative thereof is preferred.

In general, the polymerization inhibitor is contained in the commercially available polymerizable compound. In the present invention, in order to improve the resolution, a polymerization inhibitor other than the polymerization inhibitor contained in the commercially available polymerizable compound is contained. Therefore, the polymerization inhibitor is preferably a compound other than a monophenol compound such as 4-methoxyphenol which is contained in the above-mentioned polymerizable compound which is commercially available.

Further, the polymerization inhibitor may be previously added to the photosensitive resin composition solution in the process of patterning the material.

The content of the polymerization inhibitor is preferably 0.005 to 0.5% by mass, more preferably 0.01 to 0.4% by mass, even more preferably 0.02 to 0.2% by mass, based on the polymerizable compound of the photosensitive layer. When the content is less than 0.005% by mass, the resolution is lowered, and when it exceeds 0.5% by mass, the sensitivity to the active energy ray is lowered.

The content list of the above-mentioned polymerization inhibitor is a content excluding a monophenolic compound such as 4-methoxyphenol contained in the above-mentioned polymerizable compound which is imparted with stability.

-(F) developer -

The coloring agent is added after the exposure to give a visible image (printing function) to the photosensitive layer.

The above-mentioned color developing agent is, for example, a compound described in paragraphs [0320] and [0321] of JP-A-2005-258431.

The content of the coloring agent 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. The content of the halogen compound in the photosensitive layer is preferably 0.001 to 5% by mass, more preferably 0.005 to 1% by mass.

-(G) organic solvent -

The organic solvent is added to prepare a coating liquid when the photosensitive layer is formed.

The remaining amount of the organic solvent in the photosensitive layer is preferably 0.5% by mass or less, more preferably 0.45% by mass or less, more preferably 0.4% by mass or less, and particularly preferably 0.35% by mass or less. When the remaining amount is more than 0.5% by mass, the peeling property is poor and the strength of the coating film is low.

The organic solvent is at least one selected from the group consisting of ketones, alcohols, and ethers.

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

The above alcohols are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, n-hexanol, methylpropanediol, 1-methoxy-2-propanol and the like.

The above ethers are tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and the like.

Among the above organic solvents, methyl ethyl ketone, methanol, tetrahydrofuran, and propylene glycol monomethyl ether are preferred because they have a small remaining amount when the photosensitive layer is formed.

These organic solvents may be used alone or in combination of two or more. A conventional surfactant can be added.

-Other ingredients -

The other components include, for example, a dye, a reducing agent, a hydrogen donor, a sensitizer, a plasticizer, a colorant, etc., and may be used in combination with a adhesion promoter on the surface of the substrate and other auxiliary agents (for example, pigments, conductive particles, Fillers, defoamers, flame retardants, flattening agents, antioxidants, perfumes, thermal crosslinkers, surface tension modifiers, chain transfer agents, etc.). These components suitably contain properties such as stability, reproducibility, printability, and film properties of the pattern forming material of the target.

--dye--

The dye is added for improving the visibility such as visibility during the inspection of the coated surface, and it is preferable that the coating surface of the photosensitive layer and the exposure sensitivity are not lowered.

The dye is preferably a difference in absorption wavelength between the absorption wavelength and the color development agent, and is preferably absorptive to the exposure wavelength.

The absorption wavelength of the dye is such that the photosensitive layer is excellent in visibility at the time of inspection, and is preferably green which does not irritate the operator's vision. Therefore, it is preferable to have a maximum absorption at 500 to 650 nm.

The dye is not particularly limited as long as the filtration pressure of the methyl ketone solution of 0.5% by mass of the dye in the pore size of 0.45 μm is 0.3 MPa or less, and may be appropriately selected depending on the purpose, and a compound having a triarylmethane skeleton is preferred. The above dye is preferably an ionic dye, and the counter anion of the ionic dye is preferably, for example, an aromatic acid, a carboxylic acid, a phosphoric acid or the like.

The aromatic acid is, for example, naphthalenesulfonic acid or benzenesulfonic acid, and among them, naphthalenesulfonic acid is suitable from the viewpoint of solubility.

The above compound having a triarylmethane skeleton is dissolved in an organic solvent The photosensitive layer is excellent in visibility and the like when applied to the surface inspection, and the aryl sulfonic acid is preferably used, and the naphthalenesulfonic acid compound is preferable from the viewpoint that the photosensitive layer is coated in a planar shape and the exposure sensitivity is lowered. .

The above naphthalenesulfonic acid compound is, for example, Victoria Pure Blue NAPS.

<<Solubility in organic solvents>>

The dye is preferably a methyl ethyl ketone solution having a 0.5% by mass of the dye and a filtration pressure of 0.3 MPa or less in a pore size of 0.45 μm. This filtration pressure can be determined as follows. The filtration pressure is measured at room temperature under atmospheric pressure.

(1) A dye was dissolved in methyl ethyl ketone to form a 0.5% by mass solution.

(2) A syringe (SS-5ESZ, manufactured by TERUMO Co., Ltd.; 1.5 cm in diameter, 9.5 cm in length) was connected to a filter material having a pore size of 0.45 μm (DISMIC; 25HP045AN, manufactured by ADVANTEC Co., Ltd.), and the filter material was used to filter the coloring dye filled in the syringe. 0.5% by mass of a methyl ethyl ketone solution. The filtration rate here is 50 cc/min.

(3) At the time of the above filtration, the pressure applied to the syringe was measured with a pressure gauge to obtain a filtration pressure of a 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, and the surface of the photosensitive layer is not coated and the sensitivity of exposure is lowered, and the residue of undissolved matter is less likely to be generated. When the filtration pressure exceeds 0.3 MPa, the solubility is poor, and the undissolved matter causes the photosensitive layer to be coated in a planar shape, resulting in a decrease in exposure sensitivity and easy generation of a residue of the coloring dye.

The content of the dye is preferably 0.001 to 20% by mass based on the total composition of the photosensitive layer, more preferably 0.03 to 3% by mass, and particularly preferably 0.05 to 0.1% by mass. When the content is less than 0.001% by mass, the color rendering property is low, and the visibility is lacking in the surface inspection, and if it exceeds 20% by mass, the color development of the color developing agent cannot be confirmed.

-- reducing agent and hydrogen donor compound --

If the reducing agent can react with a radical, the color development of the coloring agent can be suppressed without any particular limitation, and can be appropriately selected according to the purpose, such as p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, Alkyl substituted catechol, morphine , gallic phenol and 1-phenyl-3-pyrazolone. Among them, 1-phenyl-3-pyrazolone is preferred.

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

The above compound having a -SH group is, for example, a compound of the following structural formula.

The above compound having a -CH ₂ X-(X=R) group is, for example, N-phenylamine acetic acid, dimethylamine cinnamic acid, dimethylamine benzaldehyde or the like.

Among these hydrogen donor compounds, N-phenylaminoacetic acid is preferred from the viewpoint of the above-mentioned reducing agent.

--sensitizer --

The above sensitizer can be used as the visible light and ultraviolet light of the illumination mechanism. The visible light laser or the like is appropriately selected.

The sensitizer is activated by an active energy ray and interacts with other substances (for example, a radical generator or an acid generator) (for example, energy transfer, electron transfer, etc.) to generate a useful group such as a radical or an acid.

The sensitizer is not particularly limited, and may be appropriately selected from conventional sensitizers, and examples thereof include compounds described in paragraphs [0313] and [0314] of JP-A-2005-258431.

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, and particularly preferably 0.2 to 10% by mass.

When the content is less than 0.05% by mass, the sensitivity to the active energy ray is low, and the exposure process takes time, the productivity is lowered, and when it exceeds 30% by mass, it is eluted from the above-mentioned photosensitive layer during storage.

--Plasticizer--

The plasticizer may be added to control the film properties (flexibility) of the photosensitive layer.

The plasticizing agent is, for example, a compound described in paragraph [0318] of JP-A-2005-258431.

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

--Colorant--

The coloring agent is not particularly limited and may be appropriately selected according to the purpose, and there are conventional pigments or dyes such as red, green, blue, yellow, purple, magenta, cyan, black, etc., specifically Victoria Pure Blue BO (CI42595), Olamine (CI41000), Ping Black HB (CI26150), Mono Wright Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), permanent Magenta FBB (CI Pigment Red 146), Christboom Red ESB (CI Pigment Violet 19), Permanent Ruby Red FBH (CI Pigment Red 11), Fastel Pink B Spira (CI Pigment Red 81), Monastral Strong Blue (CI Pigment Blue 15), Mono Wright Strong Black B (CI Pigment Black 1), carbon black.

The above colorants suitable for producing color filters are, for example, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red. 215, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, CI Pigment Yellow 139, CI Pigment Yellow 83, CI Pigment Violet 23, and JP-A-2002-162752 (0138) to (0141). The average particle diameter of the above coloring agent is not particularly limited and may be appropriately selected depending on the purpose, and is preferably, for example, 5 μm or less, more preferably 1 μm or less. When the color filter is produced, the above average particle diameter is preferably 0.5 μm or less.

-- adhesion promoter --

In order to improve the adhesion between the layers or the adhesion of the pattern forming material to the substrate, a conventional so-called adhesion promoter may be used for each layer.

The adhesion promoter is, for example, a compound described in paragraph [0326] of JP-A-2005-258431.

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

The photosensitive layer may also contain, for example, an organic sulfur compound, a peroxide, a redox compound, an azo or a heavy gas compound, a photoreducible pigment, or an organic halogen described in Chapter 5 of "Light Sensitive System" by J. Kosa. Compounds, etc.

Specifically, for example, the compound described in paragraphs [0329] to [0333] of JP-A-2005-258431.

--Interactive surfactant --

In order to improve the unevenness of the surface which occurs in the production of the pattern forming material of the present invention, a conventional surfactant may be used in combination. The surfactant may be appropriately selected, for example, from an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a fluorine-containing surfactant, or the like.

The content of the surfactant in the photosensitive layer is preferably 0.001 to 10% by mass, and if the content is less than 0.001% by mass, the surface-improving effect is not obtained, and when it exceeds 10% by mass, the adhesion is lowered.

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

<Support and Protective Film>

The support is not particularly limited, and may be appropriately selected depending on the purpose, so that the photosensitive layer can be peeled off, and the light transmittance is good, and the surface smoothness is better.

Specifically, for example, the aspect described in paragraphs [0342] to [0348] of JP-A-2005-258431.

<Other layers>

The other layers described above are not particularly limited and may be appropriately selected depending on the purpose, such as a buffer layer, a barrier layer, a release layer, an adhesive layer, a light absorbing layer, a surface protective layer, and the like. The pattern forming material may be one type of these layers, or two or more of these layers, and may have two or more layers of the same layer.

Preferably, the photosensitive layer of the pattern forming material of the present invention is exposed to light by a microlens array arranged by a microlens having an aspherical surface, the aspherical surface being calibratable, and having n light receiving light from the illumination mechanism The light modulating means of the emitted pixel portion modulates the aberration caused by the deformation of the emitting surface of the pixel portion after the light from the illuminating means is modulated. The details of the illumination unit, the pixel portion, the light modulation mechanism, the aspheric surface, the microlens, and the microlens array will be described later.

[Method of making pattern forming material]

The above pattern forming material can be produced as follows.

First, the material contained in the photosensitive layer and other layers is dissolved, emulsified or dispersed in water or an organic solvent to prepare a coating liquid.

The above organic solvent is as described in the description of the pattern forming material of the present invention.

Next, the coating liquid is applied onto the support and dried to form each layer, whereby a pattern forming material can be produced. For example, a component of the photosensitive layer is dissolved, emulsified or dispersed to form a photosensitive resin composition solution, which is applied onto a support, dried to form a photosensitive layer, and a protective film is formed thereon to form a pattern forming material.

The coating method of the above coating liquid is not particularly limited and may be appropriately selected depending on the purpose, such as a spray method, a roll coating method, a spin coating method, a gap coating method, an extrusion coating method, a curtain coating method, a die coating method, and a concave roller coating method. Various methods such as method, wire bar coating, and knife coating.

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

The pattern forming material of the present invention has less surface loss, prevents light leakage caused by the color developing agent, has less cracking of the unexposed film, has high resolution, has high strength of the covering film, and has good peelability after pattern formation, and is suitable for various types. Formation of patterns, formation of permanent patterns such as circuit patterns, manufacture of liquid crystal members such as color filters, pillars, ribs, spacers, and partition walls, pattern formation of full-phase diagrams, micromachines, electroscopes, etc. Suitable for the formation of highly detailed circuit patterns. It is also applicable to the pattern forming method and pattern forming apparatus of the present invention.

(pattern forming device and pattern forming method)

The pattern forming apparatus of the present invention is provided with the pattern forming material of the present invention, and has at least an illumination mechanism and a light modulation mechanism.

The pattern forming method of the present invention contains at least an exposure step and contains other steps as appropriate.

The above-described pattern forming apparatus of the present invention can be known from the description of the above-described pattern forming method of the present invention.

[Exposure step]

The above exposure step is a step of exposing the photosensitive layer of the pattern forming material of the present invention. The above pattern forming material of the present invention is as described above.

The object to be exposed is not particularly limited as long as it is a photosensitive layer of the pattern forming material, and may be appropriately selected depending on the purpose, and for example, a laminate having the pattern forming material formed on the substrate is preferably used.

The substrate is not particularly limited, and may be appropriately selected from those having a high surface smoothness in a known material to a concave-convex surface, preferably a plate-shaped substrate (substrate), specifically a substrate for forming a printed circuit board (for example, a copper-area layer). A plate, a glass plate (for example, a soda glass plate), a synthetic resin film, paper, a metal plate, or the like, and the copper layer is preferably used because of its excellent adhesion to the copper-containing material.

The method for forming the laminate is not particularly limited, and may be appropriately selected depending on the purpose, and at least one of heating and pressurization of the pattern forming material may be performed on the substrate.

The above heating temperature is not particularly limited and may be appropriately selected depending on the purpose, and is preferably, for example, 15 to 180 ° C, more preferably 60 to 140 ° C.

The pressure of the above pressurization is not particularly limited and may be appropriately selected depending on the purpose, and is preferably, for example, 0.1 to 1.0 MPa, more preferably 0.2 to 0.8 MPa.

The apparatus for performing at least one of the above-described heating and pressurization is not particularly limited, and may be appropriately selected depending on the purpose, and may be, for example, a laminating machine (for example, VP-II manufactured by Dai Seiki Co., Ltd.).

The above exposure is not limited, and may be appropriately selected according to the purpose, such as digital exposure, analog exposure, etc., preferably with digital exposure.

The above-described digital exposure is not particularly limited, and may be appropriately selected depending on the purpose, for example, based on the formed pattern forming information generation control signal, and it is preferable to use light modulated according to the control signal.

The above-described digital exposure mechanism is not particularly limited, and may be appropriately selected depending on the purpose, such as an illumination mechanism such as illumination, a light modulation mechanism that illuminates light modulated from the illumination mechanism based on the formed pattern formation information.

<Light Modulation Mechanism>

The light modulating means is not particularly limited as long as it can modulate light, and may be appropriately selected depending on the purpose, and for example, it is preferable to have n pixel portions.

The light modulating mechanism having n pixel portions described above is not particularly limited and may be appropriately selected depending on the purpose, and is preferably a spatial light modulating element, for example.

The spatial light modulation element includes, for example, a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (SLM: Space Light Modulator), an optical element (PLZT element) that modulates transmitted light by a photoelectric effect, and a liquid crystal. Grating (FLC), etc., where DMD is suitable.

The light modulating mechanism is preferably configured to have a pattern signal having a pattern forming information generation control signal based on the formed pattern. In this case, the light modulating means modulates the light by the control signal generated by the pattern signal generation configuration.

The above control signal is not particularly limited and may be appropriately selected depending on the purpose, such as a digital signal.

The light modulating mechanism and the pattern forming apparatus including the light modulating mechanism include, for example, the mechanism described in paragraphs [0016] to [0047] of JP-A-2005-258431.

<Lighting mechanism>

The above-mentioned illumination mechanism is not particularly limited and may be appropriately selected according to the purpose, and may be a conventional light source such as a (ultra) high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a photocopier, or the like, or a semiconductor light source or the like. The above-mentioned light combined illumination means, wherein a mechanism capable of combining two or more lights is preferred.

The light irradiated from the above-mentioned illuminating means is, for example, an electromagnetic wave that transmits the photopolymerization initiator, the sensitizer, and the ultraviolet ray to visible light, electron beam, X-ray, and thunder when the support is irradiated through the support. In the case of light, etc., it is preferable to use laser light, and a laser combining two or more lights (hereinafter referred to as "combined laser") is preferable. The same light can be used when the support is peeled off and the illumination is performed.

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

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

The above-described mechanism capable of illuminating the combined laser beam is preferably a mechanism having, for example, a plurality of laser beams, a multimode optical fiber, and concentrating laser light irradiated from the complex laser light into the collective optical system of the multimode optical fiber.

The above-described mechanism for illuminating the combined laser beam (fiber array light source) is, for example, described in paragraphs [0130] to [0177] of JP-A-2005-316431.

<Microlens array>

The exposure is preferably performed by passing the modulated light through the microlens array, or by an aperture array, an imaging optical system, or the like.

The microlens array is not particularly limited, and may be appropriately selected depending on the purpose, and may be, for example, an aspherical microlens array having an aberration that corrects aberration of the exit surface of the pixel portion.

The above aspherical surface is not particularly limited and may be appropriately selected depending on the purpose, and for example, a toric surface is preferred.

The microlens array, the aperture array, the imaging optical system, and the like, for example, paragraphs [0051] to [0063], paragraph [0065], paragraphs [0070] to [0073], and paragraph [0083] of JP-A-2005-258431 ~[0088] The mechanism described above.

<Other optical systems>

The pattern forming method of the present invention may be used in combination with other optical systems suitably selected from conventional optical systems, such as a light quantity distribution correcting optical system composed of a pair of combined lenses, and the like.

The light amount distribution correction optical system changes the beam width at each of the emission positions so that the ratio of the beam width of the peripheral portion to the beam width near the central portion of the optical axis is smaller than the incident side on the emission side, and the self-illumination mechanism illuminates the DMD with the parallel beam to correct So that the light quantity distribution of the illuminated surface is approximately uniform.

The light amount distribution correction optical system is specifically a mechanism described in, for example, paragraphs [0090] to [0105] of JP-A-2005-258431.

[other steps]

The other steps described above are not particularly limited, and may be appropriately selected from conventional pattern forming steps such as a developing step, an etching step, a plating step, and the like. These may be used alone or in combination of two or more.

The developing step is a step of exposing the photosensitive layer of the pattern forming material by the exposure step, curing the exposed region of the photosensitive layer, and removing the uncured region to develop a pattern.

The above development step can be suitably carried out, for example, with a developing mechanism.

The developing mechanism may be appropriately selected depending on the purpose as long as it can be developed by using a developing liquid, and may be, for example, a mechanism for spraying the developing liquid, a mechanism for applying the developing liquid, and soaking the developing liquid. Institutions, etc. These may be used alone or in combination of two or more.

The developing mechanism may include a developing liquid replacing mechanism for replacing the developing liquid, a developing liquid supply mechanism for supplying the developing liquid, and the like.

The above-mentioned developing liquid is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include an alkaline liquid, a water-based developing liquid, and an organic solvent. Among them, a weakly alkaline aqueous solution is preferred. The alkali component of the weakly alkaline liquid is, for example, lithium hydroxide, sodium hydroxide, lithium carbonate, potassium hydrogencarbonate, sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, borax or the like.

The pH of the above weakly alkaline aqueous solution is preferably, for example, about 8 to 12, more preferably about 9 to 11. The weakly alkaline aqueous solution is, for example, a 0.1 to 5% by mass aqueous solution of sodium carbonate or an aqueous solution of potassium carbonate.

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

The above developing solution can be combined with a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, An organic solvent (for example, an alcohol, a ketone, an ester, an ether, a guanamine, a lactone) or the like for promoting development is used in combination. The above developing solution may be a mixed water-based developing solution of water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

The above etching step can be appropriately selected from a conventional etching treatment method. The etching liquid used for the above etching treatment is not particularly limited, and may be appropriately selected depending on the purpose, such as a copper chloride solution, a ferric chloride solution, an alkali etching solution, a hydrogen peroxide-based etching liquid, etc. when the metal layer is formed of copper. Among them, a ferric chloride solution is preferred based on the etching factor.

After the etching process is performed by the etching step to remove the pattern, a permanent pattern can be formed on the surface of the substrate.

The above permanent pattern is not particularly limited and may be appropriately selected depending on the purpose, such as a circuit pattern or the like.

The above plating step can appropriately select a conventional plating treatment method.

The plating treatment includes, for example, copper plating such as copper sulfate plating or copper pyrophosphate plating, solder plating such as high-flow solder plating, Watt bath (nickel sulfate-nickel chloride) plating, nickel such as nickel sulfonate. Plating, hard gold plating, soft gold plating, etc.

After the plating process is performed by the plating step, the pattern is removed, and if necessary, etching is performed to remove unnecessary portions, and a permanent pattern can be formed on the surface of the substrate.

[Manufacturing method of printed circuit board and color filter]

The above pattern forming method of the present invention is suitable for the manufacture of printed circuit boards, particularly the manufacture of printed circuit boards having holes such as vias or via holes, and the manufacture of color filters. Hereinafter, an example of a method of producing a printed circuit board and a method of producing a color filter using the pattern forming method of the present invention will be described.

-Manufacturing of printed circuit boards -

In particular, a printed circuit board having a hole portion such as a through hole or a via hole is formed by (1) applying the pattern forming material to the photosensitive layer on the substrate for forming a printed circuit board having the hole portion of the substrate. (1) curing the photosensitive layer from the opposite side of the substrate on the substrate side, and (3) removing the pattern forming material from the laminated body. The body, the buffer layer and the barrier layer, (4) developing the photosensitive layer of the laminate, and removing the uncured portion of the laminate to form a pattern.

The removal of the support in the above (3) may be carried out between the above (2) and (4), or between (1) and (2) above.

Then, in order to obtain a printed circuit board, the pattern formed as described above may be used as an etching treatment or a plating treatment for the substrate for forming a printed circuit board (for example, a conventional subtractive method or an additive method (for example, a semi-additive method or a full additive method). ). Among them, the above subtraction method is preferable for forming a printed circuit board by industrially advantageous covering. After the above treatment, the cured resin remaining on the substrate for forming a printed circuit board is peeled off, and after the half-addition method is peeled off, the copper thin film portion is further etched to produce a desired printed circuit board. The multilayer printed circuit board can also be fabricated by a method similar to the above-described printed circuit board.

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

First, a substrate for forming a printed circuit board having a through hole and having a surface coated with a metal plating layer is prepared. The substrate for forming a printed circuit board can be formed by, for example, a copper-area laminate and a substrate on which a copper plating layer is formed on an insulating substrate such as a glass epoxy resin, or an interlayer insulating film is laminated between the substrates to form a copper plating layer. Substrate (multilayer substrate).

When the protective film is formed on the pattern forming material, the protective film is peeled off, and the photosensitive layer of the pattern forming material is brought into contact with the surface of the printed circuit board forming substrate, and pressed by a pressure roller (layering step). In this way, the laminated body for forming the printed circuit board and the laminated body of the laminated body described above are sequentially provided.

The layering temperature of the pattern forming material is not particularly limited, and is, for example, room temperature (15 to 30 ° C) or heating (30 to 180 ° C), and heating (60 to 140 ° C) is preferred.

The roll pressure of the above-mentioned pressure roller is not particularly limited, and is preferably, for example, 0.1 to 1 MPa.

The speed of the above pressing is not particularly limited, and is preferably 1 to 3 m/min.

The substrate for forming a printed circuit board can be preheated and laminated under reduced pressure.

The layered body may be formed by depositing a solution of a photosensitive resin composition on the substrate for forming a printed circuit board, or applying a solution of a photosensitive resin composition for producing the pattern forming material to the printed circuit board. The surface of the substrate for formation is dried and a photosensitive layer, a barrier layer, a buffer layer, and a support are laminated on the substrate for forming a printed circuit board.

Next, the photosensitive layer is hardened by backlighting from the substrate of the above laminated body. When necessary (for example, when the light transmittance of the support is insufficient), the support, the buffer layer, and the barrier layer may be peeled off and exposed.

At this time, when the support, the buffer layer, and the barrier layer are not peeled off, the support, the buffer layer, and the 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 circuit board is dissolved and removed by a suitable developing solution to form a pattern of a hardened layer for forming a circuit pattern and a hardened layer for protecting a metal layer of a via hole, thereby making a metal The surface of the substrate for forming a printed circuit board is exposed (developing step).

After the development, if necessary, post-heat treatment and post-exposure treatment may be performed to further promote the hardening reaction of the hardened portion. The development may be a wet development as above, or a dry development.

Next, the metal layer on the surface of the substrate for forming a printed circuit board is exposed and dissolved by an etching solution (etching step). The opening of the through hole is covered with a hardened resin composition (covering film), and the etching liquid enters the through hole and is not corroded by metal plating in the through hole, and the metal plating of the through hole is retained in a specific shape. Thereby, a circuit pattern is formed on the substrate for forming a printed circuit board.

The etching liquid is not particularly limited and may be appropriately selected depending on the purpose. For example, when the metal layer is formed of copper, there are a copper chloride solution, a ferric chloride solution, an alkali etching solution, a hydrogen peroxide etching solution, and the like. The etch factor is preferably a ferric chloride solution.

Next, the hardened layer is a release sheet by a strong alkali aqueous solution, and is removed from the substrate for forming a printed circuit board (cured material removal step).

The alkali component of the above aqueous alkali solution is not particularly limited, and examples thereof include sodium hydroxide and potassium hydroxide.

The pH of the above aqueous alkali solution is not particularly limited and may be appropriately selected depending on the purpose, and is preferably, for example, about 12 to 14, more preferably about 13 to 14.

The strong alkali aqueous solution is not particularly limited, and may be, for example, 1 to 10% by mass of an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution.

The printed circuit board can be a multilayer printed circuit board.

The pattern forming material described above may be used not only in the above etching process but also in a plating process. The plating method includes, for example, copper plating such as copper sulfate plating or copper pyrophosphate plating, solder plating such as high-flow solder plating, watt's bath (nickel sulfate-nickel chloride) plating, and amine sulfonate. Nickel plating such as nickel acid, hard gold plating, soft gold plating, etc.

-The method of producing color filters -

The photosensitive layer of the pattern forming material of the present invention is bonded to a substrate such as a glass substrate. When the support material, the buffer layer and the barrier layer are peeled off from the pattern forming material, the support (film) charged with the human body and the human body are shocked. Not fast, or the charged support has the problem of dust adhesion. Therefore, it is preferable to provide a conductive layer on the support and to apply a conductivity imparting treatment to the support itself. When the conductive layer is provided on the support on the opposite side of the buffer layer, it is preferred to provide a hydrophobic polymer layer for improving the scratch 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 black photosensitive layer are prepared by coloring each of the photosensitive layers into red, green, blue, and black. Pattern forming material. The pattern forming material of the red photosensitive layer for red pixels is used, and a red photosensitive layer is laminated on the surface of the substrate to form a laminated body, and then exposed to form a red pixel. After the red pixel is formed, the laminated body is heated to harden the uncured portion. The green and blue pixels are also performed to form each pixel.

The layered body may be formed by laminating the pattern forming material on the glass substrate, or directly applying a photosensitive resin composition solution for producing the pattern forming material to the surface of the glass substrate, and drying the layer on the glass substrate. A photosensitive layer, a barrier layer, a buffer layer, and a support. When configuring three types of red, green, and blue pixels, it can be configured as a mosaic type, a triangle type, or a four-pixel configuration type.

The pattern forming material having the black photosensitive layer is laminated on the surface on which the pixel is formed, and is back-exposed from the side where no pixel is formed, and developed to form a black matrix. The layered body of the black matrix is heated to harden the uncured portion, and a color filter can be produced.

The pattern forming method of the present invention is suitable for formation of various patterns, formation of permanent patterns such as circuit patterns, liquid crystal members such as color filters, pillars, ribs, spacers, and partition walls by using the above-described pattern forming material of the present invention. The manufacture, the fabrication of full phase diagrams, micromachines, electroscopes, etc., is particularly suitable for the formation of highly detailed circuit patterns. The pattern forming device of the present invention is suitable for the formation of various patterns, the formation of permanent patterns such as circuit patterns, and liquid crystal members such as color filters, pillars, ribs, spacers, and partition walls, by the above-described pattern forming material of the present invention. The manufacture, the fabrication of full phase diagrams, micromachines, electroscopes, etc., is particularly suitable for the formation of highly detailed circuit patterns.

Example

The invention is more specifically illustrated by the following examples, but the invention is not limited thereto.

(Example 1)

A solution of a photosensitive resin composition having the following composition was applied to a polyethylene terephthalate film (16 FB50, manufactured by Toray Co., Ltd.) having a thickness of 16 μm as the support, and dried to form a photosensitive layer having a thickness of 18 μm. The above pattern forming material.

[Composition of photosensitive resin composition solution]

. Methacrylate/styrene/methacrylic acid copolymer (copolymer composition (% by mass): 19/52/29, mass average molecular weight: 60,000, acid value 189 mgKOH/g, I/O value: 0.55): 139.6 mass Share. The polymerizable compound of the following structural formula (1) (manufactured by Daiichi Kogyo Co., Ltd., GX8702c): 44.33 parts by mass. The polymerizable compound of the following structural formula (2) (manufactured by Dai-Il Pharmaceutical Co., Ltd., BPEM-10F): 44.33 parts by mass. The polymerizable compound of the following structural formula (3) (ARONIX M270, manufactured by Toagosei Co., Ltd.): 6.37 parts by mass. Polyvinyl alcohol #1000 dimethacrylate (Xinzhongcun Chemical, NKESTER23G): 16.75 parts by mass. Photopolymerization initiator 2,2-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole: 18.5 parts by mass. The heterocyclic ring compound N-butylchloroacridone: 0.99 parts by mass. Polymerization inhibitor : 0.032 parts by mass. Color developer colorless crystal violet: 1.10 parts by mass. Ketone organic solvent methyl ethyl ketone: 327.4 parts by mass. Ether organic solvent propylene glycol monomethyl ether: 304.9 parts by mass. Ketone organic solvent cyclohexanone: 58.1 parts by mass. Alcohol organic solvent methanol: 36.3 parts by mass. Victoria pure blue naphthalene sulfonate: 0.186 parts by mass. 1-Benz-3-pyrazolone: 0.022 parts by mass. Hydrogen donor compound N-phenylamine acetic acid: 0.370 parts by mass. Fluorine-based surfactant (manufactured by Dainippon Ink Co., Ltd., F780F): 0.78 parts by mass

The residual amount of the organic solvent of the obtained photosensitive layer was 0.30% by mass.

m+n in the above structural formula (1) is 20. The compound of the above structural formula (1) is an example of a polymerizable compound having urethane group.

In the above structural formula (2), m+n is 10. The compound of the above structural formula (2) is an example of a polymerizable compound having an aryl group.

n in the above structural formula (3) is 12. The compound of the above structural formula (3) is an example of a compound having a polyoxyalkylene chain.

<Evaluation of facial loss>

The coating surface of the photosensitive layer obtained above was visually observed under a yellow light to evaluate the absence of the surface. The evaluation method of the above-mentioned planar deletion is to count the number of planar deletions of less than 40 μm per 1 m ^{2 of the} surface of the photosensitive layer and the number of 40 μm missing in the upper shape. The planar loss was evaluated based on the number based on the following criteria. The results are shown in Table 1.

- Evaluation benchmark -

○. . . Less than 20 facets of less than 40 μm, and less than 3 facets of 40 μm or more, are excellently coated.

△. . . The surface loss of less than 40 μm is less than 50, and 50 or more of 40 μm or more are missing, and less than 30, and the coating surface is slightly poor, which is not a problem in practical use.

×. . . There are 50 or more facets missing below 40 μm, or more than 30 facets missing from 40 μm or more, and the coating surface is extremely poor.

<Evaluation of light leakage of developer>

The absorbance (OD) at 550 nm of a photosensitive layer of the pattern forming material of the above-mentioned laminated body was measured by a spectrophotometer (MPS-200, manufactured by Shimadzu Corporation), and the absorbance was 0.4 or less and was more than 0.4, and the color developing agent was evaluated. Light leaks. The results are shown in Table 1.

On the photosensitive layer of the pattern forming material, a polyethylene film (GF-1 manufactured by TAMAPOLY Co., Ltd., GF-1) having a thickness of 25 μm was laminated as the protective film. Next, on the surface of the copper-area laminate (the diameter of each of the holes 1, 2, 3, 4, 5, and 6 mm, 30 holes, and the thickness of the copper is 12 μm) which are ground, washed, and dried as the surface of the substrate. The protective film of the pattern forming material is peeled off, and the photosensitive layer of the pattern forming material is brought into contact with the copper area laminate, and is laminated by a laminator (MODEL 8B-720-PH, manufactured by a large laminator). The layered body of the copper area laminate, the photosensitive layer, and the polyethylene terephthalate film (support) is laminated in this order.

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

<Evaluation of unexposure film rupture>

Next, the laminate of the copper-area laminate of the above-mentioned laminate was laminated on the both sides of the photosensitive layer in the same manner as the laminated body to prepare the laminate for evaluation of the unexposed film cracking, and the obtained laminate was at room temperature (25 ° C, 50). %RH) Save for 5 days. The deposited body after the storage was peeled off from the support, and the number of peeling and rupture of the photosensitive layer in the hole portion was counted to evaluate the crack of the unexposed film. In each of the hole portions having a diameter of 1 to 6 mm, the diameter of the largest one of the 30-hole not-broken portions is the unexposed film fracture value. The results are shown in Table 1.

- Imaging step -

The polyethylene terephthalate film (support) is peeled off from the laminate, and the photosensitive layer on the copper area layer is sprayed with a 1% by mass aqueous solution of sodium carbonate at 30 ° C at a pressure of 0.15 MPa to dissolve and remove. Hardened area. It is then washed with water and dried to form a permanent pattern.

The time required for the dissolution of the photosensitive layer on the copper area layer from the start of the spraying of the aqueous sodium carbonate solution was measured, which was the shortest development time. The shorter the shortest development time, the better the imaging performance.

The laminated body on which the above permanent pattern was formed was subjected to heat treatment at 160 ° C for 30 minutes to harden the surface of the permanent pattern to increase the film strength. Visually observing the permanent pattern, the surface of the permanent pattern is free of bubbles.

The printed circuit board on which the above permanent pattern is formed is subjected to an aqueous flux treatment by gold plating according to a usual method. Next, it was placed in a solder bath set at 260 ° C for 5 seconds, soaked 3 times, and washed with water to remove the flux.

<resolution> (1) Determination of sensitivity

For the photosensitive layer of the pattern forming material of the above laminated body, a pattern forming device having a 405 nm laser light source is used as the above-mentioned illumination mechanism from the side of the polyethylene terephthalate film (support), from 0.1 mJ/cm ^{2 to} 100 mJ/cm ² was exposed to light at a different light energy interval of 2 ^{1 / 2} times to harden a part of the photosensitive layer. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the laminate, and the photosensitive layer on the copper area layer was completely subjected to an aqueous solution of sodium carbonate (30 ° C, 1% by mass). The spray was applied at a spray pressure of 0.15 MPa twice as long as the shortest development time determined by the above development step, and the unhardened region was dissolved and removed, and the thickness of the remaining hardened region was measured. Next, the relationship between the amount of light irradiation and the thickness of the hardened layer is plotted as a sensitivity curve. From the sensitivity curve thus obtained, the light energy at a thickness of 15 μm in the hardened region is the energy required for the hardening of 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 obtained polyethylene terephthalate film (support) of the laminated body, the line forming device is used, and the line width/interval is 1/1, and the line width is 5 to 20 μm, and each line width is 1 μm. The exposure is performed at a line width of 20 to 50 μm and a difference of 5 μm for each line width. The amount of exposure at this time is the light energy required to harden the photosensitive layer of the pattern forming material measured in the above (1). After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the above laminate. On the copper area layer, the photosensitive layer is completely sprayed with a solution of sodium carbonate (30 ° C, 1% by mass) at a pressure of 0.15 MPa twice the shortest development time determined by the above-mentioned development step, and dissolved and removed. Hardened area. The surface of the copper-area laminate to which the hardened resin pattern was attached was observed by an optical microscope, and the minimum line width of the line of the hardened resin pattern without abnormality such as shrinkage or twist was measured, which was the resolution. The smaller the resolution value, the better. The results are shown in Table 1.

<coverage>

The copper-area laminate of the laminate for the evaluation of the unexposed film fracture was changed to a copper-area laminate having 200 through-holes having a diameter of 2 mm, and the laminate for evaluation of the covering property was prepared at room temperature as in the above-mentioned laminate. Leave at 23 ° C, 55% RH) for 10 minutes. Next, the above-mentioned pattern forming apparatus was used on the polyethylene terephthalate film (support) of the laminate prepared as described above, and the photosensitive layer of the laminate was entirely exposed. The amount of exposure at this time is the light energy required to harden the photosensitive layer of the pattern forming material measured in the above-described resolution evaluation (2). After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the above laminate. The photosensitive layer on the copper area layer plate is completely sprayed, and the developing solution sodium carbonate aqueous solution (30° C., 1% by mass) is sprayed at a spray pressure of 0.15 MPa twice as long as the shortest development time obtained by the above-mentioned developing step. . The hardened layer (masking film) formed on the opening of the through-hole of the copper-area layer thus obtained was observed by a microscope under the presence of a defect such as peeling or cracking, and the occurrence rate of the missing was counted. The results are shown in Table 1.

<Measurement of peeling time>

The laminate was produced in the same manner as in the evaluation of the above-mentioned developability, and allowed to stand at room temperature (23 ° C, 55% RH) for 10 minutes. From the polyethylene terephthalate film (support) of the obtained laminate, the above pattern forming apparatus was used for overall exposure. The amount of exposure at this time is the light energy required to harden the photosensitive layer of the pattern forming material as described above. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the above laminate. The photosensitive layer on the copper-area layer was completely sprayed, and the above-mentioned developing solution of sodium carbonate (30 ° C, 1% by mass) was sprayed at a spray pressure of 0.15 MPa twice as long as the shortest development time obtained by the above-mentioned development step. After drying, the substrate was immersed in a 3 mass% aqueous sodium hydroxide 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 that the ketone organic solvent cyclohexanone was changed to an ether organic solvent tetrahydrofuran, a pattern forming material and a laminate were produced as in Example 1. The residual amount of the organic solvent of the obtained photosensitive layer was 0.30% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Example 3)

The binder in Example 1 was changed to methyl methacrylate/styrene/methacrylic acid copolymer (copolymer composition (% by mass): 46/31/23, mass average molecular weight: 60,000, acid value 150 mgKOH/g, I A pattern forming material and a laminate were produced as in Example 1 except that the value of /O: 0.63). The residual amount of the organic solvent of the obtained photosensitive layer was 0.30% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Example 4)

The pattern forming material and the laminate were produced as in Example 1 except that the composition of the organic solvent in Example 1 was changed as follows. The residual amount of the organic solvent of the obtained photosensitive layer was 0.40% by mass.

. Ketone organic solvent methyl ethyl ketone: 227.4 parts by mass. Ether organic solvent propylene glycol monomethyl ether: 327.4 parts by mass. Ketone organic solvent cyclohexanone: 79.0 parts by mass. Ether organic solvent tetrahydrofuran: 58.1 parts by mass

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Example 5)

In the first embodiment, the polymerizable compound of the above structural formula (40) and polyvinyl alcohol #1000 dimethacrylate are not contained, and the polymerizable compound of the above structural formula (38) and the polymerizable compound of the structural formula (39) are contained. A pattern forming material and a laminate were produced as in Example 1 except for a total of 55.89 parts by mass. The residual amount of the organic solvent of the obtained photosensitive layer was 0.30% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Example 6)

In the same manner as in Example 1, except that the support was changed to a polyethylene terephthalate film (manufactured by Toray Co., Ltd., 16QS52) having a thickness of 16 μm, a pattern forming material and a laminate were produced as in Example 1. The residual amount of the organic solvent of the obtained photosensitive layer was 0.30% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Example 7)

In the same manner as in Example 1, except that the support was changed to a polyester film having a thickness of 16 μm (R-340G, manufactured by Mitsubishi Chemical Corporation), a pattern forming material and a laminate were produced as in Example 1. The residual amount of the organic solvent of the obtained photosensitive layer was 0.30% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Example 8)

In the same manner as in Example 1, except that the protective film of the first embodiment was changed to a polypropylene film (E-501, manufactured by Oji Paper Co., Ltd.) having a thickness of 12 μm, a pattern forming material and a laminate were produced as in Example 1. The residual amount of the organic solvent of the obtained photosensitive layer was 0.30% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Example 9)

In the same manner as in Example 6, except that the protective film was changed to a polypropylene film (E-200, manufactured by Oji Paper Co., Ltd.) having a thickness of 20 μm, a pattern forming material and a laminate were produced as in Example 6. The residual amount of the organic solvent of the obtained photosensitive layer was 0.30% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 6, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Comparative Example 1)

The pattern forming material and the laminate were produced as in Example 1 except that the composition of the organic solvent in Example 1 was changed as follows. The residual amount of the organic solvent of the obtained photosensitive layer was 1% by mass.

. Ketone organic solvent methyl ethyl ketone: 127.4 parts by mass. Ether organic solvent propylene glycol monomethyl ether: 404.9 parts by mass. Ketone organic solvent cyclohexanone: 158.1 parts by mass. Alcohol organic solvent methanol: 36.3 parts by mass

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Comparative Example 2)

The pattern forming material and the laminate were produced as in Example 1 except that the composition of the organic solvent in Example 1 was changed as follows. The residual amount of the organic solvent of the obtained photosensitive layer was 0.8% by mass.

. Ether organic solvent propylene glycol monomethyl ether: 350 parts by mass. Ketone organic solvent cyclohexanone: 100 parts by mass. Alcohol organic solvent methanol: 149.3 parts by mass

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Comparative Example 3)

The pattern forming material and the laminate were produced as in Example 1 except that the composition of the organic solvent in Example 1 was changed as follows. The residual amount of the organic solvent of the obtained photosensitive layer was 1% by mass.

[Composition of organic solvents]

. Ketone organic solvent methyl ethyl ketone: 227.4 parts by mass. Ether organic solvent propylene glycol monomethyl ether: 404.9 parts by mass. Ketone organic solvent cyclohexanone: 94.4 parts by mass. Alcohol organic solvent methanol: no added

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Comparative Example 4)

The binder in Example 1 was changed to methyl methacrylate/styrene/methacrylic acid copolymer (copolymer composition (% by mass): 46/31/23, mass average molecular weight: 60,000, acid value 150 mgKOH/g, I /O value: 0.63): A pattern forming material and a laminate were produced as in Example 1 except for 139.58 parts by mass. The residual amount of the organic solvent of the obtained photosensitive layer was 1% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Comparative Example 5)

In the comparative example 1, the polymerizable compound was changed to 111.78 parts by mass of the polymerizable compound of the following structural formula (39) (BPEM-10F, manufactured by Dai-ichi Kogyo Co., Ltd.), and a pattern forming material and a laminate were produced as in Comparative Example 1. The residual amount of the organic solvent of the obtained photosensitive layer was 1% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Comparative Example 6)

In Comparative Example 1, a pattern forming material and a laminate were produced as in Comparative Example 1, except that the reducing agent 1-phenyl-3-pyrazolone was not added. The residual amount of the organic solvent of the obtained photosensitive layer was 1% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Comparative Example 7)

No polymerization inhibitor thiophene was added in Comparative Example 1. A pattern forming material and a laminate were produced as in Comparative Example 1. The residual amount of the organic solvent of the obtained photosensitive layer was 1% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Comparative Example 8)

In Comparative Example 1, except that the heterocyclic ring compound N-butylchloroacridone was changed to diethylamine diphenyl ketone, a pattern forming material and a laminate were produced as in Comparative Example 1. The residual amount of the organic solvent of the obtained photosensitive layer was 1% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Comparative Example 9)

In Comparative Example 1, except that the Victoria Pure Blue Naphthylsulfonate was changed to Malachite Green, a pattern forming material and a laminate were produced as in Comparative Example 1. The residual amount of the organic solvent of the obtained photosensitive layer was 1% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

(Comparative Example 10)

In Comparative Example 1, a pattern forming material and a laminate were produced as in Comparative Example 1, except that N-phenylamineacetic acid was not added. The residual amount of the organic solvent of the obtained photosensitive layer was 1% by mass.

<evaluation>

Using the obtained pattern forming material, as in Example 1, the surface loss, the light leakage of the developer, the cracking of the unexposed film, the sensitivity, the resolution, the hiding property, and the peeling time were evaluated. The results are shown in Table 1.

As a result of the results of Table 1, the pattern forming materials of Examples 1 to 9 contain at least one organic solvent selected from the group consisting of ketones, alcohols, and ethers, and the remaining amount is 0.5% by mass or less. The loss is small, the light leakage caused by the color developer is prevented, the crack of the unexposed film is small, the resolution is high, the strength of the mask film is large, and the peelability after pattern formation is good, and a more highly detailed pattern can be formed. In particular, the residual amount of the organic solvent is 0.35 mass% or less, the I/O value of the binder is 0.35 to 0.60, and the polymerizable compound is a compound containing a polyoxyalkylene chain, and examples 1, 2, and 6 to 9 The pattern forming material is extremely thin, has little surface loss, prevents light leakage caused by the color developing agent, has less cracking of the unexposed film, has high resolution, has high strength of the covering film, and has good peelability after pattern formation, and can be formed more. Highly detailed pattern. On the other hand, in the pattern forming materials of Comparative Examples 1 to 10, at least the unexposed film was cracked, the thickness of the mask film was low, and the peeling property after pattern formation was poor, and other evaluation items were often inferior to the examples, and a fine pattern could not be formed.

Industrial use possibility

The pattern forming material of the present invention has less surface loss, can prevent light leakage caused by the color developing agent, has less cracking of the unexposed film, has high resolution, high strength of the covering film, and good peelability after pattern formation, and can form a higher height. Fine pattern. Therefore, it is suitable for the formation of various patterns, the formation of permanent patterns such as circuit patterns, the manufacture of liquid crystal members such as color filters, pillars, ribs, spacers, and partitions, and the production of full-phase diagrams, microlenses, and electroscopes. It is especially suitable for the formation of highly detailed circuit patterns.

The pattern forming device of the present invention is provided with the pattern forming material of the present invention, and is suitable for formation of various patterns, formation of permanent patterns such as circuit patterns, liquid crystal members such as color filters, pillars, ribs, spacers, and partition walls. Manufacturing, fabrication of full phase diagrams, microlenses, electroscopes, etc., is particularly suitable for the formation of highly detailed circuit patterns.

The pattern forming method of the present invention is suitable for formation of various patterns, formation of permanent patterns such as circuit patterns, and liquid crystal members such as color filters, pillars, ribs, spacers, and partition walls by using the above-described pattern forming material of the present invention. Manufacturing, fabrication of full phase diagrams, microlenses, electroscopes, etc., is particularly suitable for the formation of highly detailed circuit patterns.

Claims (19)

A pattern forming material having a support and a photosensitive layer on the support, the photosensitive layer comprising (A) a binder, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a toroidal ring a compound, (E) a polymerization inhibitor, (F) a color developer, and (G) an organic solvent, wherein the (A) binder has an acid value of 50 to 400 mgKOH/g and a mass average molecular weight of 10,000 to 100,000, (B) The polymerizable compound contains at least one of (b1) a compound having a urethane group and (b2) an aryl group-containing compound, and the (G) organic solvent is at least one selected from the group consisting of a ketone, an alcohol, and an ether. The residual amount is 0.5% by mass or less; and is characterized by a dye, a reducing agent, and a hydrogen donor compound further containing a compound having a triarylmethane skeleton. For example, in the pattern forming material of claim 1, wherein the (A) binder has an I/O value of 0.35 to 0.60. The pattern forming material according to claim 1, wherein the (B) polymerizable compound contains a compound having a polyoxyalkylene chain having at least one of an extended ethyl group and a stretched propyl group. The pattern forming material according to claim 1, wherein the (D) heterocyclic ring compound contains at least one selected from the group consisting of a heterocyclic ketone compound, a quinoline compound, and an acridine compound. For example, the pattern forming material of claim 1 of the patent scope, wherein (E) polymerization inhibits The preparation is selected from at least one selected from the group consisting of a compound having at least two phenolic hydroxyl groups, a compound having an aromatic ring substituted with an imine group, a compound having a heterocyclic ring substituted with an imine group, and a hindered amine compound. The pattern forming material according to claim 1, wherein the (G) organic solvent is at least one of methyl ethyl ketone, cyclohexanone, methanol, methyl propylene glycol, and tetrahydrofuran. A pattern forming material according to claim 1, which comprises a dye-based arylsulfonic acid compound having a compound of a triarylmethane skeleton. The pattern forming material of claim 1, wherein the reducing agent is 1-phen-3-pyrazolone. The pattern forming material of claim 1, wherein the photosensitive layer is exposed to the photosensitive layer, the thickness of the exposed portion of the photosensitive layer is unchanged after the exposure and development, and the minimum energy for the exposure is 0.1~20mJ/cm ² . The pattern forming material of claim 1, wherein the binder is swellable or soluble in an aqueous alkaline solution. The pattern forming material of claim 1, wherein the binder comprises a copolymer having a structural unit derived from at least one of styrene and a styrene derivative. The pattern forming material of claim 1, wherein the glass transition temperature of the bonding agent is above 80 °C. A pattern forming apparatus comprising the pattern forming material according to claim 1 which is characterized in that at least an illuminating light illuminating means is provided, and light from the illuminating means is modulated, and the photosensitive layer of the pattern forming material is exposed to light. Modulation mechanism. A pattern forming method characterized by comprising at least exposing the photosensitive layer to a pattern forming material according to claim 1 of the patent application. The pattern forming method of claim 14, wherein the exposure is based on the formed pattern information to generate a control signal, using light modulated according to the control signal. The pattern forming method of claim 14, wherein the exposure system modulates light by the light modulating mechanism, and passes through an aspherical microlens having aberrations that can correct deformation of the exit surface of the pixel portion of the light modulating mechanism. Performed by arranging the microlens arrays. The pattern forming method of claim 16, wherein the aspherical surface is a toric surface. The pattern forming method of claim 14, wherein the exposure of the photosensitive layer is performed after exposure. A pattern forming method according to claim 18, wherein the permanent pattern is formed after development.