TWI514076B - Pattern-forming material, pattern-forming device, and pattern-forming method - Google Patents

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) or the like, a pattern forming apparatus including the pattern forming material, and a pattern forming method using the pattern forming material.

Heretofore, when forming a permanent pattern such as a wiring pattern, a pattern forming material in which a photosensitive resin composition is applied onto a support and a photosensitive layer is formed by drying is used. As a method of producing the permanent pattern, for example, it is known that a pattern forming material is laminated on a substrate of a copper area laminate or the like on which the permanent pattern is formed to form a laminated body, and the photosensitive layer of the laminated body is exposed. After the exposure, the photosensitive layer is developed to form a pattern, and then an etching treatment or the like is performed to remove the hardened pattern to form the permanent pattern.

The photosensitive layer of the pattern forming material usually contains a binder, but focuses on the I/O value of the binder (inorganic/organic ratio of the organic concept map, refer to Non-Invention Patent Documents 1 to 5) and the acid value. When the I/O value and the acid value are combined in a certain numerical range, the resolution and the shielding property are excellent, the developing property is also excellent, and the point of the peeling property of the hardened pattern after etching is known.

Therefore, the current state of the art is that the I/O value and the glass transition temperature of the above-mentioned binder contained in the photosensitive layer are not within a certain numerical range, and the resolution and the shielding property are excellent, and the development property is also improved. A pattern forming material excellent in peelability of a hardened pattern after etching, a pattern forming apparatus including the pattern forming material, and a pattern forming method using the pattern forming material are desired, and further improvement development is desired.

Non-invention patent document 1 Organic concept map (Ada Satoshi, San Gong Publishing (1984))

Non-invention patent document 2 KUMAMOTO Pharmacopoeia, No. 1, pages 1 to 16 (1954)

Non-invention patent document 3 Field of Chemistry, Vol. 11, No. 10, pp. 719-725 (1957)

Non-invention patent document 4 FRAGRANCE Magazine, No. 34, pp. 97-111 (1979)

Non-invention patent document 5 FRAGRANCE magazine, No. 50, pages 79-82 (1981)

The present invention has been made in view of the above circumstances, and has been made to solve the above problems and achieve the following objects. That is, the object of the present invention is to provide an excellent resolution and shielding property by providing an I/O value and a glass transition temperature of the above-mentioned binder contained in the photosensitive layer in a certain numerical range, and excellent in development. And a pattern forming material having excellent releasability of the cured pattern after etching and a pattern having the pattern forming material A case forming device and a pattern forming method using the above-described pattern forming material.

The means to solve the above problems are as follows. which is,

<1> A pattern forming material characterized by having at least a photosensitive layer on a support, the photosensitive layer comprising a binder, a polymerizable compound, and a photopolymerization initiator, and the I/O value of the binder is 0.300 to 0.650, and The acid value is 130~250. In the pattern forming material according to the above aspect 1, the photosensitive layer contains the binder, the polymerizable compound, and the photopolymerization initiator, and the I/O value of the binder is 0.300 to 0.650, and the acid value is 130 to 250 (mgKOH/g), and at the same time, the resolution and the shielding property are improved, and the resolution, the shielding property, and the imaging property are coexisting in a high order, and the peeling property of the hardened pattern after etching is improved.

<2> The pattern forming material according to the above <1>, wherein the I/O value of the binder is 0.350 to 0.630.

<3> The pattern forming material according to the above <1>, wherein the acid value of the binder is 150 to 230 (mgKOH/g).

The pattern forming material according to the above <1>, wherein the binder contains a copolymer containing 30% by mass or more of a monomer constituting a homopolymer having an I/O value of 0.350 or less. In the pattern forming material according to the above <4>, the copolymer of the binder contains 30% by mass or more of a monomer constituting a homopolymer having an I/O value of 0.350 or less, so that a low I/O value is obtained. High acid prices coexist.

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

<6> The pattern forming material according to the above <1>, wherein the binder has an acidic group.

<7> The pattern forming material according to the above <1>, wherein the binder comprises a vinyl copolymer.

<8> The pattern forming material according to the above <1>, wherein the glass transition temperature of the binder is 80 ° C or higher.

The pattern forming material according to the above <1>, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group.

<10> The pattern forming material according to the above <1>, wherein the photopolymerization initiator comprises a halogenated hydrocarbon derivative, a hexaaryldiimidazole, an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, and an aromatic hydrazine. At least one selected from the group consisting of salts and metallocenes.

<11> The pattern forming material according to the above <1>, wherein the photosensitive layer has a thickness of 0.1 to 100 μm.

The pattern forming material according to the above <1>, wherein the photosensitive layer contains 30 to 90% by mass of a binder, 5 to 60% by mass of a polymerizable compound, and 0.1 to 30% by mass of a photopolymerization initiator.

<13> The pattern forming material according to the above <1>, wherein the support comprises a synthetic resin and is transparent.

<14> The pattern forming material according to the above <1>, wherein the support system has a long strip shape.

<15> The pattern forming material according to the above <1>, wherein the pattern forming material is elongated and rolled into a roll shape.

<16> The pattern forming material according to the above <1>, wherein the photosensitive layer of the pattern forming material has a protective film thereon.

<17> A pattern forming apparatus characterized by having at least a photosensitive layer on a support, the photosensitive layer comprising a binder, a polymerizable compound, and a photopolymerization initiator, and the I/O value of the binder is 0.300 to 0.650, and The acid value is 130 to 250 (mgKOH/g), and has at least a light irradiation mechanism that can illuminate light, and a light modulation that changes the light from the light irradiation means and exposes the photosensitive layer of the pattern forming material. mechanism. In the pattern forming apparatus according to <17>, the light irradiation means irradiates light toward the light modulation means. The light modulation mechanism adjusts light received from the light irradiation means. The light system modulated by the light modulation mechanism exposes the photosensitive layer. For example, when the photosensitive layer is then developed, a high-definition pattern can be formed.

<18> The pattern forming apparatus according to the above <17>, wherein the light modulation means further has a pattern signal generating means for generating a control signal based on the formed pattern information to correspond to the pattern signal generating means The control signal modulates the light irradiated by the light irradiation mechanism. In the pattern forming apparatus according to the above aspect of the invention, the light modulation means includes the pattern signal generating means, and the light emitted from the light irradiation means is associated with a control signal generated by the pattern signal generating means. Modulation.

<19> The pattern forming apparatus according to the above <17>, wherein the light modulation means has n pixel parts, and can control any less than n consecutively arranged in the n pixel parts in accordance with the pattern information. The above picture part. In the pattern forming apparatus according to the above <19>, the n pixel elements of the optical modulation mechanism are continuously arranged in accordance with the pattern information. Since there are less than n pixel parts, the light from the light irradiation means can be modulated at high speed.

<20> The pattern forming apparatus according to the above <17>, wherein the light modulation mechanism is a spatial light modulation element.

<21> The pattern forming apparatus according to <20> above, wherein the spatial light modulation element coefficient bit microlens device (DMD).

<22> The pattern forming apparatus according to the above <19>, wherein the pixel portion is a microlens.

<23> The pattern forming apparatus according to the above <17>, wherein the light irradiation means combines two or more lights to be irradiated. In the pattern forming apparatus according to the above <23>, since the light irradiation means combines two or more lights to be irradiated, the exposure is performed by exposure light having a deep depth of focus. As a result, exposure of the pattern forming material can be performed with extremely high precision. For example, when the photosensitive layer is then developed, an extremely fine pattern can be formed.

The pattern forming apparatus according to the item <17>, wherein the light-irradiating means includes a plurality of lasers, a multimode optical fiber, and a plurality of laser beams illuminating each of the plurality of lasers. A collection optical system of mode fibers. In the pattern forming apparatus according to the above <24>, the light irradiation means can condense the laser beam irradiated by each of the plurality of lasers by the collecting optical system to be coupled to the multimode optical fiber, thereby exposing This can be done by exposure light with a deep depth of focus. As a result, exposure of the pattern forming material can be performed with extremely high precision. For example, when the photosensitive layer is then developed, an extremely fine pattern can be formed.

<25> A pattern forming method comprising at least exposing a photosensitive layer of a pattern forming material, wherein the pattern forming material has at least a photosensitive layer on a support, the photosensitive layer comprising a binder, a polymerizable compound, and light The polymerization initiator has an I/O value of 0.300 to 0.650 and an acid value of 130 to 250 (mgKOH/g). In the pattern forming method according to <25>, the exposure system is performed on the pattern forming material. For example, when the photosensitive layer is then developed, a high-definition pattern can be formed.

<26> The pattern forming method according to <25>, wherein the photosensitive layer is provided with the light modulation mechanism having n pixel portions that receive and emit light from the light irradiation means. After the light of the mechanism is modulated, it is exposed by light having a microlens array in which aspherical microlenses capable of correcting aberrations due to distortion of the exit surface of the pixel portion are arranged. In the pattern forming method according to the <26>, the photosensitive layer is provided with the light modulation mechanism having n pixel portions that receive and emit light from the light irradiation means. After the light is modulated, the light is exposed by the light of the microlens array arranged to correct the aspherical microlenses due to the aberration caused by the distortion of the exit surface of the pixel portion, and the above figure can be corrected. Exposure is performed by suppressing aberration caused by distortion of the exit surface of the element portion and suppressing distortion of the image formed on the pattern forming material. As a result, the pattern forming material can be subjected to high-definition exposure, so that the photosensitive layer can be developed to form a high-definition pattern.

<27> The pattern forming method according to the above <25>, wherein the pattern forming material is laminated on the substrate and exposed.

<28> The pattern forming method according to the above <27>, wherein the base system prints the wiring forming substrate.

<29> The pattern forming method according to the above <27>, wherein at least one of heating and pressurizing the pattern forming material on the substrate is laminated.

<30> The pattern forming method according to the above <25>, wherein the exposure is performed based on the image pattern based on the formed pattern information.

<31> The pattern forming method according to the above <25>, wherein the exposure system generates a control signal based on the formed pattern information, and performs light modulation using the control signal. In the pattern forming method according to the <31>, a control signal is generated based on the formed pattern forming information, and the light is modulated in accordance with the control signal.

<32> The pattern forming method according to the above <25>, wherein the exposure system uses a light irradiation mechanism that irradiates light and a light modulation that modulates light irradiated from the light irradiation means based on the formed pattern information. Institutions to carry out.

<33> The pattern forming method according to the above <32>, wherein the exposure system is modulated by the light modulation mechanism, and then has distortion of the exit surface of the pixel portion that can be corrected by the light modulation mechanism. The resulting aspherical aspherical microlenses are arranged in a microlens array. In the pattern forming method according to the <33>, the light modulated by the optical modulation means is corrected by the distortion of the exit surface of the pixel portion by the aspherical surface of the microlens array. Aberration. As a result, distortion of the image formed on the pattern forming material can be suppressed, and the pattern forming material can be subjected to extremely high-definition exposure. For example, when the photosensitive layer is then developed, an extremely fine pattern can be formed.

<34> The pattern forming method according to the above <33>, wherein the aspherical surface is a toric surface. In the pattern forming method according to the above <34>, since the aspherical surface is a toric surface, the aberration due to the distortion of the radiation surface of the pixel portion can be efficiently corrected, and the image forming material can be efficiently suppressed. Distortion of the image. As a result, extremely fine exposure can be applied to the pattern forming material described above. For example, when the photosensitive layer is then developed, an extremely fine pattern can be formed.

<35> The pattern forming method according to the above <25>, wherein the exposure system is performed through an array of openings. In the pattern forming method according to <35>, since the exposure is performed through the opening array, the extinction ratio can be improved. As a result, exposure can be performed with extremely high precision. For example, when the photosensitive layer is then developed, an extremely fine pattern can be formed.

<36> The pattern forming method according to the above <25>, wherein the exposure is performed by moving the exposed light to the side of the photosensitive layer. In the pattern forming method according to the above <36>, since the modulated light is exposed while being moved relative to the photosensitive layer, exposure can be performed at a high speed. For example, when the photosensitive layer is then developed, a high-definition pattern can be formed.

<37> The pattern forming method according to the above <25>, wherein the exposure system is performed on a part of the photosensitive layer.

<38> The pattern forming method according to the above <25>, wherein the development of the photosensitive layer is performed after the exposure is performed. In the pattern forming method according to <38>, since the photosensitive layer is developed after the exposure is performed, a high-definition pattern can be formed.

<39> The pattern forming method according to the above <25>, wherein the permanent pattern is formed after the development is performed.

<40> The pattern forming method according to the above <39>, wherein the permanent pattern is a wiring 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 I/O value and the glass transition temperature of the adhesive contained in the photosensitive layer are all within a certain numerical range, thereby providing excellent resolution and shielding properties, and also exhibiting properties. A pattern forming material excellent in peelability of a hardened pattern after etching, a pattern forming apparatus including the pattern forming material, and a pattern forming method using the pattern forming material.

LD1~LD7‧‧‧GaN semiconductor laser

B1~B7‧‧‧Laser beam

10‧‧‧heating area

11~17‧‧‧ collimating lens

20‧‧‧ Concentrating lens

30~31‧‧‧Multimode fiber

30a‧‧ core

31a‧‧ core

40‧‧‧Encapsulation

41‧‧‧Enclosure cover

42‧‧‧Substrate

44‧‧‧ collimating lens holder

45‧‧‧Concentrating lens holder

46‧‧‧Fiber holder

47‧‧‧Wiring

3,50‧‧‧Digital Microlens Device (DMD)

51‧‧‧ imaging optical system

52‧‧‧Lens system

53‧‧‧Reflected light image (exposure beam)

4,54‧‧‧ lens system

55‧‧‧Microlens array

55a‧‧‧microlens

5,56‧‧‧Exposed surface (scanning surface)

57‧‧‧Lens system

6,58‧‧‧ lens system

59‧‧‧Open array

59a‧‧‧ openings

60‧‧‧SRAM unit

62‧‧‧Microlens

64‧‧‧Laser module

65‧‧‧Support board

1,66‧‧‧Fiber Array Light Source

2,67‧‧‧ lens system

68‧‧‧Laser exit department

69‧‧‧ lenses

70‧‧‧稜鏡

71‧‧‧ Concentrating lens

72‧‧‧ rod integrator

73‧‧‧稜鏡对

74‧‧‧ imaging lens

100‧‧‧heating area

110‧‧‧Multi-slot laser

110a‧‧‧Lighting point

111‧‧‧heating area

113‧‧‧ rod lens

114‧‧‧ lens array

120‧‧‧ Concentrating lens

130‧‧‧Multimode fiber

130a‧‧ core

140‧‧‧Laser array

144‧‧‧Lighting means

150‧‧‧ pattern forming materials

152‧‧‧ platform

154‧‧‧ feet

155a‧‧‧microlens

156‧‧‧Setting table

158‧‧‧Guide

160‧‧‧ brake

162‧‧‧Scanner

164‧‧‧ sensor

166‧‧‧Exposure head

168‧‧‧Exposure range

170‧‧‧Exposure completion area

180‧‧‧heating area

182‧‧‧heating area

184‧‧‧ collimating lens array

300‧‧‧All Control Department

301‧‧‧Modulation circuit

302‧‧‧ Controller

303‧‧‧LD drive circuit

304‧‧‧ platform driver

454‧‧‧Lens system

458‧‧‧ lens system

468‧‧‧Exposure range

472‧‧‧Microlens array

474‧‧‧Microlens

476‧‧‧Open array

478‧‧‧ openings

480‧‧‧Lens system

482‧‧‧Lens system

B‧‧‧Laser light

BS‧‧‧beam point

O, Z1‧‧‧ optical axis

H0‧‧‧full beam width

H1‧‧‧full beam width

H0, h1, h10, h11‧‧‧ beam width

Figure 1 is a partially enlarged illustration showing the construction of a digital microlens device (DMD).

Figure 2A is an illustration for illustrating the operation of the DMD.

Fig. 2B is an explanatory diagram for explaining the operation of the DMD in the same manner as Fig. 2A.

Fig. 3A shows an example of a plan view of the arrangement of the exposure light beams and the scanning lines when the DMD is not tilted and arranged in an inclined configuration.

In the same manner as in the third embodiment, FIG. 3B shows an example of a plan view of the arrangement of the exposure light beams and the scanning lines when the DMD is not tilted and arranged obliquely.

Fig. 4A is a diagram showing an example of a use area of the DMD.

Fig. 4B is a view showing an example of a use area of the DMD in the same manner as Fig. 4A.

Fig. 5 is a plan view showing an example of an exposure mode in which a photosensitive layer is exposed by scanning with a scanner once.

Fig. 6A is a plan view showing an example of an exposure mode in which a photosensitive layer is exposed by scanning a plurality of times by a scanner.

Fig. 6B is a plan view showing an example of an exposure mode in which the photosensitive layer is exposed by scanning a plurality of times in the same manner as in Fig. 6A.

Fig. 7 is a schematic perspective view showing an appearance of an example of a pattern forming apparatus.

Fig. 8 is a schematic perspective view showing a configuration of a scanner of a pattern forming apparatus.

Fig. 9A is a plan view showing an example of an exposure completion region formed in the photosensitive layer.

Fig. 9B is a diagram showing the arrangement of the exposure ranges of the respective exposure heads.

Fig. 10 is a perspective view showing an example of a schematic configuration of an exposure head including a light modulation mechanism.

Fig. 11 is a cross-sectional view showing the sub-scanning direction of the optical axis of the exposure head structure shown in Fig. 10.

Fig. 12 is an example of a controller that controls the DMD based on the pattern information.

Figure 13A is a cross-sectional view showing the optical axis along other exposure head configurations than the combined optical system.

Fig. 13B is a plan view example of an optical image projected on the surface to be exposed when no microlens array or the like is used.

Fig. 13C is a plan view showing an example of a plan of an optical image projected on an exposure surface when a microlens array or the like is used.

Fig. 14 is a diagram showing the distortion of the reflecting surface of the microlens constituting the DMD in a contour line.

Fig. 15A is a graph showing a distortion of the distortion of the reflecting surface of the lens for the two diagonal lines of the above microlens.

Fig. 15B is a graph showing a distortion of the reflection surface of the lens for the two diagonal lines of the microlens, similarly to Fig. 15A.

Fig. 16A is a front view of a microlens array used in the patterning device.

Fig. 16B is a side view showing a microlens array used in the patterning device.

Fig. 17A is a front view of a microlens constituting a microlens array.

Fig. 17B is a side view showing a microlens constituting a microlens array.

Fig. 18A is a schematic view showing a state of condensing light by a microlens in one section.

Fig. 18B is a schematic view showing a state of condensing light by a microlens in another cross section different from Fig. 18A.

Fig. 19A is a diagram showing a simulation result of the beam diameter in the vicinity of the condensing position of the microlens of the present invention.

Fig. 19B is a view showing a simulation result of simulation results at other positions as in the case of Fig. 19A.

Fig. 19C shows a legend of the simulation results at other positions as in the 19A and 19B drawings.

Fig. 19D shows a legend of the simulation results at other positions as in the 19th to 19thth views.

Fig. 20A is a diagram showing a simulation result of beam diameter in the vicinity of the condensing position of the microlens in the conventional pattern forming method.

Fig. 20B is a diagram showing a simulation result at another position as in Fig. 20A.

Fig. 20C shows a legend of the simulation result at another position as in the 20A and 20B drawings.

Fig. 20D shows a legend of the simulation result at another position as in the 20A to 20C.

Fig. 21 is a plan view showing another configuration of the composite wave laser light source.

Fig. 22A is a front view of a microlens constituting a microlens array.

Fig. 22B is a side view showing a microlens constituting a microlens array.

Fig. 23A is a schematic view showing an example of a condensed state of the microlens in Figs. 22A and 22B in one section.

Fig. 23B is a schematic view showing an example of a condensed state of the microlens of Figs. 22A and 22B in another cross section different from Fig. 23A.

Fig. 24A is an explanatory diagram showing the concept of correction by the light quantity distribution correcting optical system.

Fig. 24B is an explanatory diagram showing the concept of correction by the light amount distribution correction optical system in the same manner as Fig. 24A.

Fig. 24C is an explanatory diagram for explaining the concept of correction by the light amount distribution correcting optical system in the same manner as in Figs. 24A and 24B.

Fig. 25 is a diagram showing the light amount distribution when the light irradiation mechanism is Gaussian and the light amount distribution is not corrected.

Fig. 26 is a diagram showing the light amount distribution corrected by the light amount distribution correction system.

Fig. 27A(A) is a perspective view showing the structure of the fiber array light source, and Fig. 27A(B) is an example of a partially enlarged view of (A), and 27A(C) and (D) are the light emitting points of the laser exit portion. An example of arranging a plan.

Figure 27B is a front elevational view showing the arrangement of the light-emitting points of the laser exit portion of the fiber array light source.

Figure 28 is a diagram showing the construction of a multimode fiber.

Fig. 29 is a plan view showing a configuration of a composite wave laser light source.

Fig. 30 is a plan view showing an example of the configuration of the laser module.

Fig. 31 is a side view showing the configuration of the laser module shown in Fig. 30.

Figure 32 is a partial side elevational view showing the construction of the laser module as shown in Figure 30.

Fig. 33 is a perspective view showing an example of the configuration of the laser array.

Figure 34A is a perspective view showing a structure of a multi-slot laser.

Figure 34B is a perspective view showing an example of a multi-slot laser array in which the multi-slot lasers shown in Figure 34A are arranged.

Figure 35 is a plan view showing another configuration of a composite wave laser light source.

Fig. 36A is a plan view showing another configuration of a composite wave laser light source.

Figure 36B shows a cross-sectional illustration along the optical axis of Figure 36A.

Fig. 37A is a cross-sectional view showing the difference in the depth of focus of the conventional exposure apparatus and the depth of focus of the pattern forming method (pattern forming apparatus) of the present invention along the optical axis.

Fig. 37B is a cross-sectional view along the optical axis showing the difference between the depth of focus of the conventional exposure apparatus and the depth of focus of the pattern forming method (pattern forming apparatus) of the present invention, similarly to Fig. 37A.

[Best Mode for Carrying Out the Invention]

(patterning material)

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

<Photosensitive layer>

The photosensitive layer is not particularly limited as long as it contains a binder, a polymerizable compound, and a photopolymerization initiator, and may contain other components appropriately selected according to the purpose. Further, the number of layers of the photosensitive layer may be one layer or two or more layers.

-Adhesives -

The above-mentioned binder is not particularly limited as long as the I/O value is 0.300 to 0.650 and the acid value is 130 to 250, and can be appropriately selected according to the purpose.

Further, the above binder contains a copolymer, and the copolymer preferably contains a structural unit derived from at least one of styrene and a styrene derivative.

The upper limit of the I/O value is preferably 0.630, and particularly preferably 0.600, from the viewpoint of at least one of improving the resolution and the shielding property.

The lower limit of the I/O value is preferably 0.350, and particularly preferably 0.40, from the viewpoint of improving developability.

The above I/O value is a value called a (inorganic value)/(organic value) organic concept for operating the polarity of various organic compounds, and is one of the functional group imparting methods for setting parameters for each functional group. The above I/O values are in the organic concept map (Jia Tian Shansheng, San Gong Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, pp. 1~16 (1954); Chemical Fields, Volume 11, No. 10 , 719~725 (1957); FRAGRANCE Magazine, No. 34, pp. 97-111 (1979); FRAGRANCE Magazine, No. 50, pp. 79-82 (1981); details in the literature Description.

The above I/O value is a concept in which the properties of a compound are classified into an organic group indicating covalent bonding and an inorganic group indicating ionic bonding, and all organic compounds are made positive by the organic axis and the inorganic axis. Appropriate positions are given at every point on the coordinates.

The inorganic value is a numerical value which affects the boiling point of various substituents, bonds, and the like which are possessed by the organic compound, based on the hydroxyl group. Specifically, the boiling point curve of the linear alkanol is separated from the boiling point curve of the linear paraffin by taking about 100 ° C near the carbon number of 5, and the water acid group 1 is The influence of each is set to a value of 100, and the value of the influence of various substituents or various bonds on the boiling point is quantified as the inorganic value of all the substituents of the organic compound. For example, the inorganic value of the -COOH group is 150, and the inorganic value of the double bond is 2. Therefore, the inorganic value of an organic compound means the sum of the inorganic values of various substituents or bonds which the compound has.

The above organic value means that the methylene group in the molecule is used as a unit, and the influence of the carbon atom representing the methylene group on the boiling point is used as a reference. In other words, in the vicinity of the carbon number of the linear saturated hydrocarbon compound of 5 to 10, the average value of the boiling point rise is 20 ° C in the case of increasing the carbon number. Therefore, the organic value of one carbon atom is set to 20 based on this. On the basis of others, the value of the influence of various substituents or bonds on the boiling point is quantified as 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 (large hydrophobic, organic) organic compound is exhibited, and the larger the organic compound is, the more polar (large hydrophilic, inorganic) organic compound is.

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

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

Since the methacrylic acid has one carboxyl group, the methyl methacrylate has one ester group, and the styrene has one aromatic ring, the inorganic value of the methacrylic acid is 150 (inorganic value of a carboxyl group). ×1 (the number of carboxyl groups) = 150, and the inorganic value of the above methyl methacrylate is 60 (inorganic value of the ester group) × 1 (the number of ester groups) = 60, and the inorganic value of the above styrene Line 15 (inorganic value of aromatic ring) × 1 (number of aromatic rings) = 15. Therefore, the inorganic value of the above copolymer is obtained by the following formula: 150 × 2 (molar ratio of methacrylic acid) + 60 × 5 (mole ratio of methyl methacrylate) + 15 × 3 (more than styrene) Ear ratio) calculation, get 645.

The organic value of the copolymer is determined by (the organic value of methacrylic acid) × (the molar ratio of the above methacrylic acid), (the organic value of the methyl methacrylate) × (described above) The molar ratio of methyl methacrylate) (the organic value of styrene mentioned above) × (the molar ratio of the above styrene) was calculated.

Since the above methacrylic acid has 4 carbon atoms, the above methyl methacrylate has 5 carbon atoms, and the styrene has 8 carbon atoms, the organic value of the above methacrylic acid is 20 (organicity of carbon atoms) The value of x4 (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 (organic value of carbon atom) × 8 (number of carbon atoms) = 160. Therefore, the organic value of the above copolymer is obtained by the following formula: 80 × 2 (the above molar ratio of methacrylic acid) + 100 × 5 (the above molar ratio of methyl methacrylate) + 160 × 3 (the above benzene) The molar ratio of ethylene was calculated to give 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 acid value (the content of the acidic group) of the above-mentioned binder is not particularly limited as long as it is 130 to 250 (mgKOH/g), and may be appropriately selected according to the purpose, but is preferably 150 to 230 (mgKOH/g). ), particularly preferably 160~220 (mgKOH/g).

When the acid value is less than 130 (mgKOH/g), the developability is insufficient, the resolution is poor, and a permanent pattern such as a high-definition wiring pattern cannot be obtained. On the other hand, when it is more than 250 (mgKOH/g), at least one of the image-resistant liquid resistance and the adhesion of the pattern is deteriorated, and the resolution and the shielding property are deteriorated, and a permanent pattern such as a high-definition wiring pattern cannot be obtained.

In order to adjust the I/O value and the acid value of the above-mentioned binder so as to satisfy a certain numerical range, the monomer type constituting the copolymer contained in the binder and the polymerization ratio at the time of polymerizing the monomer can be appropriately selected. At least one of (content) is adjusted.

For example, the monomer constituting the copolymer contained in the above-mentioned binder is a monomer having a ratio of a monomer having the above acidic group of a mass% and a homopolymer having an I/O value of 0.35 or less. The ratio is b% by mass, and the ratio of the other monomer is c% by mass (here, a+b+c=100, and c is also 0), in order to improve the peeling property of the hardened pattern after etching. In the case where the value of the above a is increased, the I/O value of the binder tends to be high. Therefore, the above a, b, and c preferably satisfy the relationship of a < (b + c).

Specifically, the copolymer contained in the above-mentioned binder is preferably a monomer containing 25% by mass or more of a homopolymer having an I/O value of 0.35 or less, more preferably 30% by mass or more.

Examples of the monomer constituting the above homopolymer having an I/O value of 0.35 or less include styrene, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate.

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

The carboxyl group-containing binder is, for example, a carboxyl group-containing ethylene copolymer, a polyurethane resin, a polyaminic acid resin, a modified epoxy resin, etc., among these, solubility in a coating solvent. The vinyl copolymer having a carboxyl group is preferred for the solubility of the alkali developing solution, the suitability for synthesis, and the ease of adjustment of the film properties.

The above-mentioned carboxyl group-containing ethylene-based copolymer can be obtained by copolymerizing at least (1) a carboxyl group-containing vinyl monomer and (2) a monomer copolymerizable therewith.

The above vinyl monomer having a carboxyl group is, for example, (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimerization. Addition reaction of a monomer having a hydroxyl group (for example, 2-hydroxyethyl (meth)acrylate) to a cyclic acid anhydride (for example, maleic anhydride or fumaric anhydride, cyclohexane dicarboxylic anhydride), ω- Carboxy-polycaprolactone mono(meth)acrylate and the like. Among these, (meth)acrylic acid is more preferable in terms of copolymerizability, cost, solubility, and the like.

Further, a monomer having an acid anhydride such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as a precursor of a carboxyl group.

The other copolymerizable monomer is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include (meth)acrylates, crotonates, vinyl esters, and maleic acid diesters. Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes (eg styrene, styrene derivatives, etc.), (a) Acrylonitrile, vinyl substituted heterocyclic group (eg vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, etc.), N-vinylformamide, N-vinylacetamide, N -vinylimidazole, vinylcaprolactone, 2-propenylamine-2-methylpropanesulfonic acid, mono(2-propenyloxyethyl phosphate), mono(1-methyl-2-propenyl phosphate) Ethyl ethoxylate), a vinyl monomer having a functional group (for example, a urethane group, a ureido group, a sulfonamide group, a phenol group, or an imino group). Among these, from the viewpoint of reducing the above-described I/O value of the above-mentioned binder, forming a permanent pattern such as a wiring pattern in a high-definition manner, and from the viewpoint of improving the above-mentioned shielding property, the benzene is preferably used. Ethylene and styrene derivatives.

Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (methyl). N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butyl (meth)acrylate Cyclohexyl ester, 2-ethylhexyl (meth)acrylate, third octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, (methyl) Ethyloxyethyl acrylate, phenyl (meth) acrylate, (meth) acrylate 2-hydroxyethyl ester, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (methyl) Acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl Ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxy ethoxy acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, bicyclo Pentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoro Pento (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, phenoxyethyl (meth) acrylate or the like.

The above crotonate is, for example, butyl crotonate, hexyl crotonate or the like.

The vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, methoxyvinyl acetate, vinyl benzoate or the like.

The above maleic acid diesters are, for example, dimethyl maleate, diethyl maleate, dibutyl maleate and the like.

The above fumaric acid diester is, for example, dimethyl fumarate, diethyl fumarate or dibutyl fumarate.

The above-mentioned itaconic acid diester is, for example, dimethyl itaconate, diethyl itaconate or dibutyl itaconate.

The above (meth) acrylamides are, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (methyl) Acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl ( Methyl) acrylamide, N-(2-methoxyethyl)(methyl) acrylamide, N,N-dimethyl(meth) decylamine, N,N-diethyl (A Base) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) propylene decyl morpholine, diacetone acrylamide, and the like.

The styrenes are, for example, the above styrene, the above styrene derivatives (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, Hydroxystyrene, methoxystyrene, butoxystyrene, ethoxylated styrene, styrene chloride, styrene dichloride, styrene bromide, methyl styrene chloride, by acidity A substance (for example, t-Boc or the like) protected by a substance (for example, t-Boc or the like), hydroxystyrene, methyl benzoate, α-methylstyrene, etc.).

The vinyl ethers are, for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether or the like.

The method for synthesizing the vinyl monomer having the above functional group is, for example, an addition reaction of an isocyanato group with a hydroxyl group or an amine group, specifically, for example, a monomer having an isocyanate group, and a compound having one hydroxyl group or An addition reaction of a compound having one primary or secondary amine group, an addition reaction of a monomer having a hydroxyl group or a monomer having a primary or secondary amine group with a monoisocyanate.

The monomer having an isocyanate group is, for example, a compound represented by the following structural formulae (1) to (3).

In the above structural formulae (1) to (3), R ^' represents a hydrogen atom or a methyl group.

The above monoisocyanate is, for example, cyclohexyl isocyanate, n-butyl isocyanate, toluene isocyanate, benzyl isocyanate or phenyl isocyanate.

The monomer having a hydroxyl group is, for example, a compound represented by the following structural formulae (4) to (12).

[Chemical 4]

[Chemistry 9]

In the above structural formulae (4) to (12), R ^' represents a hydrogen atom or a methyl group, and n ₁ , n ₂ and n ₃ represent an integer of 1 or more.

The compound containing one of the above hydroxyl groups may be, for example, an alcohol (for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, n-hexanol, 2-ethyl). Hexanol, n-nonanol, n-dodecanol, n-octadecyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethanol, etc.), phenols (eg phenol, cresol, naphthol, etc.), Other substituents include, for example, fluoroethanol, trifluoroethanol, methoxyethanol, and benzene. Oxyethanol, chlorophenol, dichlorophenol, methoxyphenol, ethoxylated phenol, and the like.

The above monomer having a primary or secondary amine group is, for example, vinylbenzylamine or the like.

As the above compound containing one primary or secondary amine group, for example, it may be an alkylamine (methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, second butylamine, third butylamine, hexylamine, 2 -ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.) , an arylamine (benzylamine, phenethylamine, etc.), an aromatic amine (aniline, toluidine, xylene, naphthylamine, etc.), or a combination of these (N-methyl-N-benzylamine, etc.) And an amine (trifluoroethylamine, hexafluoroisopropylamine, methoxyaniline, methoxypropylamine, etc.) which further contains a substituent.

Further, as the other copolymerizable monomer other than the above, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, or benzyl (meth)acrylate may be used. , 2-ethylhexyl (meth)acrylate, styrene, chlorostyrene, bromostyrene, hydroxystyrene, and the like.

The other copolymerizable monomers may be used alone or in combination of two or more.

The above ethylene-based copolymer can be prepared by conventional copolymerization by a known method. For example, the monomer can be prepared by dissolving the above monomer in a suitable solvent by a method in which a radical polymerization initiator is added and polymerized in a solution (solution polymerization method). Further, it can be prepared by polymerization in a state in which the above monomers are dispersed in an aqueous solvent, that is, by emulsion polymerization or the like.

The suitable solvent to be used in the solution polymerization method is not particularly limited, and may be appropriately selected depending on the solubility of the monomer to be used and the copolymer to be produced, and the like, and may be, for example, methanol, ethanol, propanol or isopropanol. , 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxy propyl acetate, ethyl lactate, ethyl acetate, vinyl nitrile, tetrahydrofuran, dimethyl Formamide, chloroform, toluene, etc. These solvents may be used alone or in combination of two or more.

The radical polymerization initiator is not particularly limited, and may be, for example, 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis-(2,4'-di An azo compound such as methylvaleronitrile or a persulfate such as a peroxide such as benzammonium peroxide or potassium persulfate or ammonium persulfate.

In the ethylene-based copolymer, the content of the polymerizable compound having a carboxyl group is not particularly limited as long as the I/O value and the acid value are within the above numerical ranges, and may be appropriately selected depending on the purpose. For example, it is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, and particularly preferably 20 to 60 mol%.

When the content is less than 10 mol%, the developability to alkaline water is insufficient, and when it is more than 70 mol%, the development liquid resistance of the cured portion (image portion) is insufficient.

The molecular weight of the carboxyl group-containing binder is not particularly limited and may be appropriately selected depending on the purpose. For example, the mass average molecular weight is preferably 2,000 to 300,000, more preferably 4,000 to 150,000.

When the mass average molecular weight is less than 2,000, the strength of the film tends to be insufficient and it is difficult to manufacture stably, and when it is more than 300,000, the developability is lowered.

The above-mentioned carboxyl group-containing binder may be used alone or in combination of two or more. In the case of using two or more kinds of the above-mentioned binders, for example, a combination of two or more kinds of binders composed of different copolymerization components, two or more kinds of binders having different mass average molecular weights, and two or more kinds of binders having different degrees of dispersion .

In the above carboxyl group-containing binder, part or all of the carboxyl groups may be neutralized by a basic substance. Further, the above-mentioned binder may be used in combination with a resin having a different structure such as a polyester resin, a polyamide resin, a polyurethane resin, an epoxy resin, a polyvinyl alcohol or a gelatin.

Further, as the above-mentioned binder, a resin soluble in an alkaline aqueous solution described in Japanese Patent No. 2873889 or the like can be used. In the case where these resins are used in combination, the content of the above-mentioned binder may be appropriately selected depending on the purpose, for example, preferably 50% by mass or more, more preferably 70% by mass, based on the total amount of the binder contained in the photosensitive layer. The above is particularly preferably 90% by mass or more.

The above-mentioned binder having an I/O value of 0.300 to 0.650 and an acid value of 130 to 250 (mgKOH/g) is, for example, a methacrylic acid/methyl methacrylate/styrene/benzyl methacrylate copolymer (copolymer composition). (mass ratio): 25/8/30/37), methacrylic acid/methyl methacrylate/styrene/benzyl methacrylate copolymer (copolymer composition (mass ratio): 23/8/15/54 ) Methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 21/47/23/9), methacrylic acid / methyl methacrylate / benzene Ethylene/ethyl acrylate copolymer (copolymer composition (mass ratio): 23/30/30/17), methacrylic acid/methyl methacrylate/styrene/ethyl acrylate copolymer (copolymer composition (quality) Ratio: 25/25/45/5), methacrylic acid/methyl methacrylate/styrene/ethyl acrylate copolymer (copolymer composition (mass ratio): 25/34/33/8), methyl Acrylic/cyclohexyl methacrylate/2-ethylhexyl methacrylate copolymer (copolymer composition (mass ratio): 25/70/5), methacrylic acid/cyclohexyl methacrylate/methacrylic acid 2-ethylhexyl ester copolymer (copolymer composition (mass ratio): 23/70/7), methacrylic acid/styrene/methyl acrylate copolymer (copolymer composition (mass ratio): 22/58/20 ), methacrylic acid / styrene / methyl acrylate copolymer (copolymer composition (mass ratio): 25 / 38 / 37), methacrylic acid / styrene / methyl acrylate copolymer (copolymer composition (mass ratio) :29/61/10), methacrylic acid/styrene/ethyl acrylate copolymer (copolymer composition (mass ratio): 23/60/17), methacrylic acid/styrene/ethyl acrylate copolymer (copolymerization Composition (mass ratio): 29/61/10), methacrylic acid/styrene/ethyl acrylate copolymer (copolymer composition (mass ratio): 20/76/4), methacrylic acid/styrene copolymer (copolymerization composition ratio (mass ratio): 21/79 ), methacrylic acid/styrene copolymer (copolymerization composition ratio (mass ratio): 29/71), methacrylic acid/styrene copolymer (copolymerization composition ratio (mass ratio): 36/64), methyl group Acrylic/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 23/50/27), methacrylic acid/styrene/2-ethylhexyl methacrylate copolymerization (copolymerization composition ratio (mass ratio): 29/60/11), methacrylic acid/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 36/33/ 31), methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25 / 25 / 37 / 13), methacrylic acid / Methyl methacrylate/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio) ): 29/15/47/9), methacrylic acid/methyl methacrylate/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/18/50 /3), methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/15/40/20), methacrylic acid /Methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 36/5/45/14), methacrylic acid / styrene / methacrylic acid Cyclohexyl ester copolymer (copolymerization composition ratio (mass ratio): 31/64/5), methacrylic acid/styrene/cyclohexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/15 /60), methacrylic acid/methyl methacrylate/styrene/butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 23/37/30/10), methacrylic acid/methacrylic acid Methyl ester/styrene/butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 36/10/44/10), methacrylic acid/methyl methacrylate/styrene/butyl methacrylate Copolymer (copolymerization composition ratio (mass ratio): 25/27/36/12) , methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/13/38/20), methacrylic acid / methyl methacrylate / Styrene/butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 24/10/29/37), methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (quality) Ratio: 25/29/46), methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 20/53/27), methacrylic acid/methyl methacrylate /styrene copolymer (copolymerization composition ratio (mass ratio): 29/19/52), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 30/13 / 57), methacrylic acid / methyl methacrylate / styrene copolymer ( Copolymerization composition ratio (mass ratio): 31/5/64), methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 36/15/49), methacrylic acid /methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 29/31 / 40), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio ): 25/41/34), methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 36/5/59), and methacrylic acid/methyl methacrylate /styrene copolymer (copolymerization composition ratio (mass ratio): 24/46/30), etc., among them, methacrylic acid/methyl methacrylate/styrene/benzyl methacrylate is preferred. Copolymer (copolymer composition (mass ratio): 25/8/30/37), methacrylic acid/methyl methacrylate/styrene/benzyl methacrylate copolymer (copolymer composition (mass ratio): 23 /8/15/54), methacrylic acid/methyl methacrylate/styrene/ethyl acrylate copolymer (copolymer composition (mass ratio): 25/25/45/5), methacrylic acid/methyl Methyl acrylate / styrene / acrylic acid Ester copolymer (copolymer composition (mass ratio): 25/34/33/8), methacrylic acid/cyclohexyl methacrylate/2-ethylhexyl methacrylate copolymer (copolymer composition (mass ratio) ): 25/70/5), methacrylic acid/styrene/methyl acrylate copolymer (copolymer composition (mass ratio): 22/58/20), methacrylic acid/styrene/methyl acrylate copolymer ( Copolymer composition (mass ratio): 25/38/37), methacrylic acid/styrene/methyl acrylate copolymer (copolymer composition (mass ratio): 29/61/10), methacrylic acid/styrene/ Ethyl acrylate copolymer (copolymer composition (mass ratio): 23/60/17), methacrylic acid/styrene/ethyl acrylate copolymer (copolymer composition (mass ratio): 29/61/10), A Acrylic/styrene copolymer (copolymerization composition ratio (mass ratio): 29/71), methacrylic acid / Styrene copolymer (copolymerization composition ratio (mass ratio): 36/64), methacrylic acid/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 23/40 /27), methacrylic acid/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/60/11), methacrylic acid/methyl methacrylate/benzene Ethylene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/25/37/13), methacrylic acid/methyl methacrylate/styrene/methacrylic acid 2- Ethylhexyl ester copolymer (copolymerization composition ratio (mass ratio): 29/15/47/9), methacrylic acid/methyl methacrylate/styrene/2-ethylhexyl methacrylate copolymer ( Copolymerization composition ratio (mass ratio): 29/18/50/3), methacrylic acid/methyl methacrylate/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio) ): 25/15/40/20), methacrylic acid/methyl methacrylate/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 36/5/45 /14), methacrylic acid / styrene / cyclohexyl methacrylate (copolymerization composition ratio (mass ratio): 31/64/5), methacrylic acid/styrene/cyclohexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/15/60), Methacrylic acid/methyl methacrylate/styrene/butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 23/37/30/10), methacrylic acid/methyl methacrylate/benzene Ethylene/butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/27/36/12), methacrylic acid/methyl methacrylate/styrene/butyl methacrylate copolymer (total Polymerization composition ratio (mass ratio): 29/13/38/20), methacrylic acid/methyl methacrylate/styrene/butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 24/10 /29/37), methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (quality Ratio: 25/29/46), methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 29/19/52), methacrylic acid/methyl methacrylate /styrene copolymer (copolymerization composition ratio (mass ratio): 30/13/57), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 31/5 / 64), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 29/31 / 40), methacrylic acid / methyl methacrylate / styrene copolymer (total Polymer composition ratio (mass ratio): 25/41/34), and methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 36/5/59), particularly preferred Methyl acrylate/methyl methacrylate/styrene/benzyl methacrylate copolymer (copolymer composition (mass ratio): 25/8/30/37), methacrylic acid/methyl methacrylate/styrene /ethyl acrylate copolymer (copolymer composition (mass ratio): 25/25/45/5), methacrylic acid / styrene / methyl acrylate copolymer (copolymer composition (mass ratio): 29/61/10 ), methacrylic acid / styrene / acrylic acid Ethyl ester copolymer (copolymer composition (mass ratio): 29/61/10), methacrylic acid/styrene copolymer (copolymerization composition ratio (mass ratio): 29/71), methacrylic acid/styrene/ 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/60/11), methacrylic acid/methyl methacrylate/styrene/2-ethylhexyl methacrylate Copolymer (copolymerization composition ratio (mass ratio): 25/25/37/13), methacrylic acid/methyl methacrylate/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio) (mass ratio): 29/18/50/3), methacrylic acid/methyl methacrylate/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/ 15/40/20), methacrylic acid / styrene Alkene/cyclohexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 31/64/5), methacrylic acid/methyl methacrylate/styrene/butyl methacrylate copolymer (copolymerization) Composition ratio (mass ratio): 25/27/36/12), methacrylic acid/methyl methacrylate/styrene/butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 29/13/ 38/20), methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 25/29/46), methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 29/19/52), methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 30/13/57), methyl group Acrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 31/5/64), methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (quality) Ratio: 29/31/40), and methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 25/41/34).

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 according to the purpose, for example, from the above-mentioned pattern forming material, adhesion, edge melting, and peelability of the above support. At least one point of view is preferably 80 ° C or higher, more preferably 100 ° C or higher, and particularly preferably 115 ° C or higher.

When the glass transition temperature exceeds 80 ° C, the adhesiveness of the pattern forming material increases, and the peelability of the support is deteriorated.

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

When the content is less than 10% by mass, the alkali developability or the adhesion to the substrate for forming a printed wiring board (for example, a copper-area laminate) is lowered, and when it is more than 90% by mass, the stability to the development time or The strength of the cured film (masking film) is lowered. Further, the content may be a total amount of the above-mentioned binder and a polymer binder which are used in combination as needed.

- Polymeric compound -

The polymerizable compound is not particularly limited and may be appropriately selected according to the purpose. For example, a monomer or an oligomer having at least one of a urethane group and an aryl group is suitable. Moreover, it is preferable to have two or more types of polymerizable groups.

The polymerizable group may, for example, be an ethylenically unsaturated bond (for example, a vinyl group or an allyl ether such as a (meth) acrylonitrile group, a (meth) acryl amide group, a styryl group, a vinyl ester or a vinyl ether. Or an allyl group such as an allyl ester or the like, a polymerizable cyclic ether group (for example, an epoxy group or an oxetane), and the like, and among these, an ethylenically unsaturated bond is preferred.

-- Monomers with urethane groups --

The urethane group-containing monomer is not particularly limited as long as it has a urethane group, and can be appropriately selected according to the purpose, for example, JP-A-48-41708, JP-A-51-37193 A compound or the like described in JP-A No. 2001-356476, for example, a polyisocyanate compound having two or more isocyanate groups in a molecule, and the like. An adduct of a vinyl monomer having a hydroxyl group in a molecule or the like.

The polyisocyanate compound having two or more isocyanate groups in the molecule may be, for example, hexamethylene diisocyanate or the like. Methylhexamethylene diisocyanate, isophorone diisocyanate, benzodimethyl diisocyanate, toluene diisocyanate, phenyl diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane a diisocyanate such as diisocyanate or 3,3' dimethyl-4,4'-diphenyl diisocyanate; a polyaddition of the diisocyanate to a bifunctional alcohol (in this case, isocyanic acid at both ends) a terpolymer of a biuret or isocyanurate such as a diisocyanate; a polyfunctional alcohol such as a diisocyanate or a diisocyanate and trimethylolpropane, isopentaerythritol or glycerin; or An adduct of another functional alcohol obtainable by an ethylene oxide adduct or the like.

The vinyl monomer having a hydroxyl group in the molecule may be, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate. Ester, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, octaethylene glycol mono (meth) acrylate, Polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate Ester, polypropylene glycol mono (meth) acrylate, dibutyl diol mono (meth) acrylate, tributyl diol mono (meth) acrylate, tetrabutyl diol mono (meth) acrylate, octagonal Alcohol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and the like. Further, for example, it is a terminal (meth) acrylate of a diol having a different alkylene oxide moiety such as a copolymer of ethylene oxide and propylene oxide (random, block, etc.).

Further, as the monomer having a urethane group, for example, tris((meth)acryloyloxyethyl)isocyanurate, di(meth)acrylated isocyanurate, epoxy Ethane is a compound having an isocyanuric acid ring such as (meth) acrylate of isocyanuric acid. Among these, the compound represented by the following structural formula (13) or structural formula (14) is preferable, and from the viewpoint of shielding properties, it is particularly preferable to contain at least the above-mentioned structural formula (14). Compound. Further, these compounds may be used alone or in combination of two or more.

In the above-described structure of formula (13) and ^{(14), R '1 ~} R' 3 each represent a hydrogen atom or a methyl group. X ₁ to X _{3 are each} an epoxy group, and may be used alone or in combination of two or more.

The above epoxyalkyl group such as ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, a combination of these groups (random, any combination of blocks), etc. Among them, ethylene oxide, propylene oxide, butylene oxide, or a combination thereof is preferred, and ethylene oxide and propylene oxide are more preferred.

In the above structural formulas (13) and (14), m ₁ to m ₃ represent an integer of 1 to 60, preferably 2 to 30, more preferably 4 to 15.

In the above-described structure of formula (13) and (14), Y ¹ and Y ² represents a C 2 to 30. The divalent organic group such as alkylene, arylene group, alkenylene group, extending alkynyl group, a carbonyl group (- CO-), an oxygen atom (-O-), a sulfur atom (-S-), an imido group (-NH-), an imido group, a substituted imido group substituted with a monovalent hydrocarbon group, or a sulfonyl group ( -SO ₂ -) or a combination of such groups, etc., wherein the alkyl group, the aryl group, or a combination thereof is preferred.

The above alkylene group may have a branched structure or a cyclic structure, such as methylene, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neopentyl, Extending a hexyl group, stretching a trimethylhexyl group, stretching a cyclohexyl group, stretching a heptyl group, stretching an octyl group, a 2-ethylexene group, a hydrazine group, a hydrazine group, a dodecyl group, an octadecyl group, or the following Show any kind of basis.

The above aryl group may be substituted by a hydrocarbon group such as a phenyl group, a tolyl group, a diphenyl group, a naphthyl group, or a group represented by the following.

The above-mentioned combination of such groups is, for example, benzodimethyl group or the like.

The above alkyl group, aryl group, or a combination thereof may further have a substituent such as a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an aryl group, or an alkoxy group ( For example, methoxy, ethoxy, 2-ethoxyethoxy), aryloxy (eg phenoxy), fluorenyl (eg ethionyl, propyl), decyloxy (eg ethoxylated) A group, a butyloxy group, an alkoxycarbonyl group (e.g., a methoxycarbonyl group, an ethoxycarbonyl group), an aryloxycarbonyl group (e.g., a phenoxycarbonyl group), and the like.

In the above structural formulas (13) and (14), n ₄ represents an integer of 3 to 6, and it is preferable to use 3, 4 or 6 in order to supply raw materials in the case of synthesizing a polymerizable monomer.

In the above-described structure of formula (13) and (14), Z ₁ represents a divalent n ₄ (3 to 6. The) of the linking group, for example, any of the following as the group represented.

Wherein X ₄ represents an alkylene oxide group. m ₄ represents an integer from 1 to 20. n ₅ represents an integer from 3 to 6. A ₂ represents a divalent n ₅ (3 to 6. The) of the organic group.

The above A _{2 is,} for example, an n ₅ -valent aliphatic group, an n ₅ -valent aromatic group, or the like, an alkyl group, an extended aryl group, an extended alkenyl group, a carbonyl group, an oxygen atom, a sulfur atom, an imido group, or an imido group. The substituted imine group in which the hydrogen atom is substituted with a monovalent hydrocarbon group or the group in combination with the sulfonyl group is preferably an n ₅ valence (3 valence to 6 valence) aliphatic group and an n ₅ valence (3 valence to 6 valence). An aromatic group, or a combination of these groups with an alkyl group, an aryl group, and an oxygen atom, preferably an n ₅ valent aliphatic group, an n ₅ valence (trivalent to hexavalent) aliphatic group and an alkylene group, The combination of oxygen atoms is excellent.

The number of carbon atoms of the above A ₂ is, for example, preferably an integer of from 1 to 100, more preferably an integer of from 1 to 50, and particularly preferably an integer of from 3 to 30.

The n _5- valent (trivalent to hexavalent) aliphatic group may have a branched structure or a cyclic structure.

The number of carbon atoms of the above aliphatic group is, for example, preferably an integer of 1 to 30, more preferably an integer of 1 to 20, and particularly preferably an integer of 3 to 10.

The number of carbon atoms of the above aromatic group is preferably an integer of 6 to 100, more preferably an integer of 6 to 50, and particularly preferably an integer of 6 to 30.

The above-mentioned n ₅ valence (trivalent to hexavalent) aliphatic group or aromatic group may further have a substituent such as a hydroxyl group or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom). , aryl, alkoxy (eg methoxy, ethoxy, 2-ethoxyethoxy), aryloxy (eg phenoxy), fluorenyl (eg ethionyl, propyl), An alkoxy group (e.g., an ethoxycarbonyl group, a butoxy group), an alkoxycarbonyl group (e.g., a methoxycarbonyl group, an ethoxycarbonyl group), an aryloxycarbonyl group (e.g., a phenoxycarbonyl group), and the like.

The above alkylene group may have a branched structure or a cyclic structure.

The carbon number of the above alkyl group is, for example, preferably an integer of from 1 to 18, more preferably an integer of from 1 to 10.

The above aryl group may be further substituted by a hydrocarbon group.

The carbon number of the above aryl group is preferably an integer of 6 to 18, more preferably an integer of 6 to 10.

The carbon number of the monovalent hydrocarbon group of the substituted imido group is preferably an integer of from 1 to 18, particularly preferably an integer of from 1 to 10.

Preferred examples of the above A ₂ are as follows.

The compound represented by the above structural formulae (13) to (14) may, for example, be a compound represented by the following structural formulae (15) to (34).

In the above structural formulae (15) to (34), n ₆ , n ₇ , n ₈ and m ₅ mean 1 to 60, and l means 1 to 20, and R' represents a hydrogen atom or a methyl group.

--A monomer with an aryl group --

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

The above aryl group-containing polyol compound, polyamine compound or polyvalent amino alcohol compound, for example, polystyrene oxide, benzene dimethyl glycol, bis(β-hydroxyethoxy)benzene, 1,5-di Hydroxy-1,2,3,4-tetrahydronaphthalene, 2,2,-diphenyl-1,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1-phenyl-1,2- Ethylene glycol, 2,3,5,6-tetramethyl-p-xylene-α,α'-diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1 , 1,4,4-tetraphenyl-2-butyne-1,4-diol, 1,1'-di-2-naphthol, dihydroxynaphthalene, 1,1'-methylene-di- 2-naphthol, 1,2,4-benzenetriol, bisphenol, 2,2'-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, Bis(hydroxyphenyl)methane, catechol, 4-chlororesorcinol, hydroquinone, hydroxybenzyl alcohol, methylhydroquinone, methylene-2,4,6-trihydroxybenzoate, fluorine Glycidylphenol, pyrogallol, resorcinol, α-(1-aminoethyl)-p-hydroxybenzyl alcohol, α-(1-aminoethyl)-p-hydroxybenzyl alcohol, 3 -Amino-4-hydroxyphenylhydrazine and the like. Further, other examples are obtained by adding an α,β-unsaturated carboxylic acid to a glycidyl compound such as benzodimethylbis(meth)acrylamide, a novolak epoxy resin or bisphenol A diglycidyl ether. An esterified product of a compound, a citric acid or a trimellitic acid with a vinyl monomer having a hydroxyl group in a molecule, diallyl phthalate, triallyl trimellitate, diallyl benzenedisulfonate a cationically polymerizable divinyl ether (for example, bisphenol A divinyl ether) or an epoxy compound (for example, a novolac type epoxy resin, a double as a polymerizable monomer) Phenol A diglycidyl ether, etc.), vinyl esters (for example, divinyl phthalate, divinyl phthalate, divinyl benzene - 1,3-disulfonate, etc.), styrene compounds (for example) Divinylbenzene, p-allylstyrene, p-isopropenestyrene, etc.). Among these, a compound represented by the following structural formula (35) is preferred.

In the above structural formula (35), R ' 4, R ' 5 represents a hydrogen atom or an alkyl group.

In the above structural formula (35), X ₅ and X ₆ represent an alkylene oxide group, and they may be used alone or in combination of two or more. The epoxyalkyl group is, for example, ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, a combination of these groups (may be random, any combination of blocks), etc. Among these, ethylene oxide, propylene oxide, butylene oxide, or a combination thereof is preferred, and ethylene oxide and propylene oxide are more preferred.

In the above structural formula (35), m ₆ and m _{7 are} preferably an integer of from 1 to 60, more preferably an integer of from 2 to 30, particularly preferably an integer of from 4 to 15.

In the above structural formula (35), T represents a divalent linking group such as a methylene group, an exoethyl group, MeCMe, CF ₃ CCF ₃ , CO, SO ₂ or the like.

In the above structural formula (35), Ar ¹ and Ar ² represent a aryl group which may have a substituent, such as a phenylene group, a naphthyl group or the like. The above substituent is, for example, an alkyl group, an aryl group, an aralkyl group, a halogen group, an alkoxy group, or a combination thereof.

Specific examples of the above aryl group-containing monomer may be, for example, 2,2-bis[4-(3-(methyl)propenyloxy-2-hydroxypropoxy)phenyl]propane, 2,2- Bis[4-((meth)acryloxyethoxy)phenyl]propane, 2 phenolic OH group substituted 2,2-bis(4-(() Methyl)propenyloxypolyethoxy)phenyl)propane (eg 2,2-bis(4-((methyl)propenyloxydiethoxy)phenyl)propane, 2,2-double (4-((meth)acryloxytetraethoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxypentaethoxy)phenyl)propane, 2 , 2-bis(4-((meth)propenyloxylethoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxypentadecane)benzene The number of substituted ethoxy groups of 2,2-bis[4-((methyl)propenyloxypropoxy)phenyl]propane, 1 phenolic OH group is 2-20 2,2-bis(4-((meth)propenyloxypolypropoxy)phenyl)propane (eg 2,2-bis(4-((methyl)propenyloxydipropoxy)) Phenyl)propane, 2,2-bis(4-((meth)propenyloxytetrapropoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy-5) Propoxy)phenyl)propane, 2,2- (4-((meth)propenyloxydapoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxypentadecapropoxy)phenyl)propane, etc. Or a compound containing a polycyclohexane skeleton and a polypropylene oxide skeleton in the same molecule as a polyether moiety of such a compound (for example, a compound described in WO01/98832, or a commercial product of Shin-Nakamura) Chemical industry company, BPE-200, BPE-500, BPE-1000), a polymerizable compound having a bisphenol skeleton and a urethane group, and the like. Further, these may be a compound obtained by changing a portion derived from the bisphenol A skeleton into bisphenol F or bisphenol S.

As the above polymerizable compound having a bisphenol skeleton and a urethane group, for example, bisphenol and ethylene oxide or propylene oxide may be added. a compound having an isocyanato group and a polymerizable group in a compound having a hydroxyl group at a terminal obtained by a product or a polyaddition product (for example, 2-isocyanate ethyl (meth) acrylate, α, α-dimethyl-ethylene Benzomethyl isocyanate, etc.).

--Other polymerizable monomers --

In the pattern forming method of the present invention, a polymerizable monomer other than the above-described urethane group-containing monomer and aryl group-containing monomer may be used in combination.

The polymerizable monomer other than the urethane group-containing monomer and the aromatic ring-containing monomer may be, for example, an unsaturated carboxylic acid (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid). An ester of an aliphatic polyol compound, an unsaturated carboxylic acid, and a guanamine of a polyamine compound.

The monomer which is an ester of the unsaturated carboxylic acid and the aliphatic polyol compound may, for example, be ethylene glycol di(meth)acrylate of (meth)acrylate or polyethylene glycol having a vinyl number of 2-18. Di(meth)acrylate (eg diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nine ethylene glycol di (meth) acrylate, dodecaethylene glycol di(meth) acrylate, tetradecyl glycol di(meth) acrylate, etc.), propylene glycol di(meth) acrylate, propylene group number 2 to 18 Polypropylene glycol di(meth)acrylate (for example, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, dodecapropanediol di(methyl) Acrylate, etc., neopentyl alcohol di(meth)acrylate, ethylene oxide modified neopentyl alcohol di(meth)acrylate, propylene oxide modified neopentyl alcohol di(meth)acrylate, three Hydroxymethylpropane tri(meth)acrylate, trimethylolpropane II Methyl) acrylate, trimethylolpropane tris((meth) propylene methoxypropyl) ether, trimethylolethane tri(meth) acrylate, 1,3-propanediol di(methyl) Acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1.6-hexanediol di(meth)acrylate, tetramethyl glycol Di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, 1,5-pentanediol (A) Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, diisopentaerythritol penta (methyl) Acrylate, diisopentaerythritol hexa(meth) acrylate, sorbitol tri(meth) acrylate, sorbitol tetra(meth) acrylate, sorbitol penta (meth) acrylate, Sorbitol hexa(meth) acrylate, dimethylol dicyclopentane di(meth) acrylate, tricyclodecane di(meth) acrylate, neopentyl bis (meth) acrylate, Neopentyl alcohol modified trimethylolpropane di(meth)acrylate, having at least one ethylene glycol chain per a di(meth)acrylate of a diol chain (for example, a compound described in WO01/98832), and a tris(methyl group) of at least trimethylolpropane having any one of ethylene oxide and propylene oxide. Acrylate, polybutylene glycol di(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, xylenol di(meth)acrylate, and the like.

Among the above (meth) acrylates, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and propylene glycol di(a) are preferable from the viewpoint of availability. Acrylate, polypropylene glycol di(meth)acrylate, di(meth)acrylate having at least one aglycol chain of one ethylene glycol chain/propylene glycol chain, trimethylolpropane tris(methyl) ) acrylate, pentaerythritol tetra (meth) acrylate, isovalerol tri ( Methyl) acrylate, pentaerythritol di(meth) acrylate, diisopentaerythritol penta (meth) acrylate, diisopentaerythritol hexa (meth) acrylate, glycerol tris (a) Acrylate, diglycerol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, 1,4 -cyclohexanediol di(meth)acrylate, 1,5-pentanediol (meth)acrylate, neopentyl alcohol di(meth)acrylate, ethylene oxide addition trimethylolpropane (meth) acrylate and the like.

As the ester (ikonate) of the above-mentioned itaconic acid and the above aliphatic polyol compound, for example, ethylene glycol dicone ester, propylene glycol diconcanate, and 1,3-butylene glycol diacon An acid ester, 1,4-butanediol diconconate, tetramethylene glycol diconconate, isoprenol diconconate, and sorbitol tetraconcanate.

As the ester of the above-mentioned crotonic acid and the above aliphatic polyhydric alcohol compound (for example, crotonate), for example, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, Sorbitol tetracrotonate and the like.

As the ester of the above-mentioned isocrotonic acid and the above aliphatic polyol compound (for example, isocrotonate), for example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocroton may be used. Acid esters, etc.

As the ester of the above maleic acid and the above aliphatic polyol compound (for example, maleate), for example, ethylene glycol dimaleate, triethylene glycol dimaleate, and isopentaerythritol can be used. Ester, sorbitol tetramaleate, and the like.

The above-mentioned polyamine compound and the above-mentioned unsaturated carboxylic acid-derived guanamine may be, for example, methylene bis(meth) acrylamide, and Bis-(meth)acrylamide, 1,6-hexamethylenebis(meth)acrylamide, octamethylbis(meth)acrylamide, diamethylenetriamine (methyl) Acrylamide, diethylenetriamine bis(meth)acrylamide, and the like.

Further, in addition to the above, the polymerizable monomer is, for example, butanediol-1,4-diglycidyl ether, cyclohexane dimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl glycol. a glycidyl group-containing compound such as ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, isoprene tetraglycidyl ether, glycerol triglycidyl ether or the like A compound obtained by adding an α,β-unsaturated carboxylic acid, a polyester acrylate or a polyester (method) described in each of JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490 Acrylate oligomers, epoxy compounds (for example, butanediol-1,4-diglycidyl ether, cyclohexane dimethanol glycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether) Epoxy acrylate reacted with (meth)acrylic acid, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerol triglycidyl ether, etc. Multifunctional acrylate or methacrylate, etc., Japan Association of Associations vol.20 Photohardenable monomers and oligomers, allyl esters (for example, diallyl citrate, diallyl adipate, diallyl malonate), No. 7, 300-308 (1984) , diallylguanamine (for example, diallylacetamide, etc.), cationically polymerizable divinyl ether (for example, butanediol-1,4-divinyl ether, cyclohexane dimethanol divinyl ether, B) Glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerol trivinyl ether Ethylene compound (such as butanediol-1,4-diglycidyl ether, cyclohexane dimethanol glycidyl ether, ethylene glycol) Diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, isoprenol tetraglycidyl ether, C3 Alcohol triglycidyl ether, etc., oxetane (for example, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, etc.), epoxy compound Oxetane (for example, a compound described in WO01/22165), N-β-hydroxyethyl-β-(methacrylamide)ethyl acrylate, N,N-bis (β-) A compound having two or more different ethylenically unsaturated double bonds, such as methacryloxyethyl)acrylamide or allyl methacrylate.

The vinyl esters may be, for example, divinyl salicylate or divinyl adipate.

These polyfunctional monomers or oligomers may be used alone or in combination of two or more.

The polymerizable monomer may be used in combination with a polymerizable compound (monofunctional monomer) containing one polymerizable group in one molecule.

The monofunctional monomer can be, for example, the compound exemplified as the binder raw material, and the monovalent mono((meth) propylene oxyalkyl ester) monovalent (halogenated hydroxyl group) described in JP-A-6-236031. Monofunctional monomer such as alkyl ester) (for example, γ-chloro-β-hydroxypropyl-β'-methacryloxyethyl-o-phthalate), Japanese Patent No. 2744643, WO00 A compound described in Japanese Laid-Open Patent Publication No. 25,480,916, and the like.

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

When the content is 5% by mass, the strength of the masking film is lowered, and when it is more than 90% by mass, the edge melting condition (a failure due to bleeding from the end portion of the roller) during storage is deteriorated.

Further, in the polymerizable compound, the content of the polyfunctional monomer having two polymerizable groups is preferably from 5 to 100% by mass, more preferably from 20 to 100% by mass, particularly preferably from 40 to 100% by mass.

-Photopolymerization initiator -

The photopolymerization initiator is not particularly limited as long as it has the ability to start polymerization of the polymerizable compound, and can be appropriately selected from conventional photopolymerization initiators, for example, those having photosensitivity from the ultraviolet range to the visible light. Preferably, it may be an active agent which generates any action with a photoexcited sensitizer to form a living radical, or an initiator which initiates cationic polymerization depending on the kind of the monomer.

Further, the photopolymerization initiator preferably contains at least one component having a molecular light coefficient of at least about 50 in a range of from about 300 to 800 nm, preferably from 330 to 500 nm.

The above photopolymerization initiator is, for example, a halogenated hydrocarbon derivative (for example, having three A skeleton, a oxadiazole skeleton, etc., a hexaaryldiimidazole, an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a metallocene derivative or the like. Among these, the sensitivity and storage stability of the photosensitive layer, and the adhesion between the photosensitive layer and the substrate for forming a printed wiring board are three The halogenated hydrocarbon, the anthracene derivative, the ketone compound, and the hexaaryldiimidazole-based compound of the skeleton are preferred.

The above hexaaryldiimidazole is, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-chlorobenzene) Base)-4,4',5,5'- Tetraphenyldiimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorobenzene -4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(3-methoxy Phenyl)diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-methoxyphenyl)diimidazole, 2,2'-bis ( 4-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5 '-Tetraphenyldiimidazole, 2,2'-bis(2-nitrophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-methyl Phenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-trifluoromethylphenyl)-4,4',5,5'-tetraphenyl Diimidazole, a compound described in WO00/52529, and the like.

The above diimidazoles can be easily synthesized, for example, by the method disclosed in Bull. Chem. Soc. Japan, 33, 565 (1960) and J. Org. Chem, 36 (16) 2262 (1971).

As having three on The halogenated hydrocarbon compound of the structure is, for example, a compound described in Bull. Chem. Soc. Japan, 42, 2924 (1969), and a compound described in the specification of the British Patent No. 1,388,492, and JP-A-53-133428. The compound described in the specification of the German Patent No. 3337024, the compound described in J. Org. Chem.; 29, 1527 (1964) of FC Schaefer et al., and the compound described in JP-A-62-58241, JP-A No. 5-281728 The compound described in the publication, the compound described in JP-A-H05-34920, and the compound described in the specification of U.S. Patent No. 4,212,976.

The compound described in Bull. Chem. Soc. Japan, 42, 2924 (1969), which is mentioned above, may be, for example, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5. -three , 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-(4-tolyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2,4,6-gin (trichloromethyl)-1,3,5-three 2-methyl-4,6-bis(trichloromethyl)-1,3,5-three 2-n-indenyl-4,6-bis(trichloromethyl)-1,3,5-three And 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-1,3,5-three Wait.

The compound described in the above-mentioned British Patent No. 1,388,492 may be, for example, 2-styryl-4,6-bis(trichloromethyl)-1,3,5-three. ,2-(4-methylstyryl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-three 2-(4-methoxystyryl)-4-amino-6-trichloromethyl-1,3,5-three Wait.

The compound described in JP-A-53-133428 can be, for example, 2-(4-methoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3. 5-three , 2-(4-ethoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-[4-(2-ethoxyethyl)-naphthalen-1-yl]-4,6-bis(trichloromethyl)-1,3,5-three ,2-(4,7-Dimethoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3,5-three And 2-(ethylindolin-5-yl)-4,6-bis(trichloromethyl)-1,3,5-three Wait.

The compound described in the above-mentioned German Patent No. 3337024 can be, for example, 2-(4-styrylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three. , 2-(4-(4-methoxystyryl)phenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(1-naphthyl-extended vinylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three 2-chlorostyrylphenyl-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-thiophene-2-extended vinylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-thiophene-3-vinylidenephenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-furan-2-extended vinylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three And 2-(4-benzofuran-2-strandylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three Wait.

The compound described in the above-mentioned FC Schaefer et al., J. Org. Chem.; 29, 1527 (1964), for example, may be 2-methyl-4,6-bis(tribromomethyl)-1,3,5-three. , 2,4,6-gin (tribromomethyl)-1,3,5-three , 2,4,6-gin(dibromomethyl)-1,3,5-three 2-amino-4-methyl-6-tris(bromomethyl)-1,3,5-three And 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-three Wait.

The compound described in JP-A-62-58241 can be, for example, 2-(4-phenylethynylphenyl)-4,6-bis(trichloromethyl)-1,3,5-trid. , 2-(4-naphthyl-1-ethynylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-(4-triethynyl)phenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-(4-methoxyphenyl)ethynylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-(4-(4-isopropylphenylethynyl)phenyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-(4-(4-ethylphenylethynyl)phenyl)-4,6-bis(trichloromethyl)-1,3,5-three Wait.

The compound described in JP-A-H05-281728 can be, for example, 2-(4-trifluoromethylphenyl)-4,6-bis(trichloromethyl)-1,3,5-trid. ,2-(2,6-difluorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-(2,6-dichlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-(2,6-dibromophenyl)-4,6-bis(trichloromethyl)-1,3,5-three Wait.

The compound described in JP-A-H05-34920 can be, for example, 2,4-bis(trichloromethyl)-6-[4-(N,N-diethoxycarbonylmethylamino)- 3-bromophenyl]-1,3,5-three Trihalomethyl-s-three as described in the specification of U.S. Patent No. 4,239,850 Compound, and 2,4,6-parade (trichloromethyl)-s-three 2-(4-chlorophenyl)-4,6-bis(tribromomethyl)-s-three Wait.

The compound described in the specification of the above-mentioned U.S. Patent No. 4,212,976, for example, may be a compound described in the specification of U.S. Patent No. 4,212,976, for example, a compound having an oxadiazole skeleton (e.g., 2-trimethylmethyl-5-phenyl-) 1,3,4-oxadiazole, 2-trimethylmethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1- Naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-tribromomethyl-5-benzene 1,3,4-oxadiazole, 2-tribromomethyl-5-(2-naphthyl)-1,3,4-oxadiazole; 2-trichloromethyl-5-styryl -1,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4 -Methoxystyryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl -5-(4-n-butoxystyryl)-1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.) .

The anthracene derivative which can be used in the present invention is, for example, a compound represented by the following structural formulae (36) to (69).

[化40]

Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, and 4-methoxybenzophenone. 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid Or its tetramethyl ester, 4,4'-bis(dialkylamino)benzophenone (such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-double Dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone, 4- Methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylamino group Acetophenone, benzyl, hydrazine, 2-tert-butyl fluorene, 2-methyl hydrazine, phenanthrenequinone, xanthone, thioxanthone, 2-chloro-thioxanthone, 2,4- Diethylthioxanthone, anthrone, 2-benzyl-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinyl-1-propanone, 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer, benzene Infant, benzoin ethers (such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), 吖Pyridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, and the like.

As the above metallocene derivative, for example, it may be bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl). -Phenyl)titanium, η ⁵ -cyclopentadiene-η ⁶ - cumenyl-iron (1+)-hexafluorophosphate (1-), JP-A-53-133428, JP 59-17-19 The compound described in the Japanese Patent Publication No. 57-6096, and the specification of U.S. Patent No. 3,615,455.

Further, examples of the photopolymerization initiator other than the above may be an acridine derivative (for example, 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)heptane, etc.), N-benzene. Acridine or the like, a polyhalogen compound (for example, carbon tetrabromide, phenyltribromomethylhydrazine, phenyltrichloromethane, etc.), coumarins (such as 3-(2-benzofuranylmethyl) -7-diethylamino coumarin, 3-(2-benzofurancarbenyl)-7-(1-pyrrolidinyl)coumarin, 3-anisyl-7-diethyl Amino coumarin, 3-(2-methoxybenzimidyl)-7-diethylamino coumarin, 3-(4-dimethylaminobenzimidyl)-7-di Ethylamine coumarin, 3,3'-carbonylbis(5,7-di-n-propoxycoumarin), 3,3'-carbonylbis(7-diethylaminocoumarin) , 3-benzylidene-7-methoxycoumarin, 3-(2-furanyl)-7-diethylaminocoumarin, 3-(4-diethylamino cinnamon Mercapto)-7-diethylamino coumarin, 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzylidene-5,7-dipropoxy Bean, 7-benzotriazol-2-ylcoumarin, and Japanese Patent Laid-Open No. 5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-36320 A coumarin compound or the like described in JP-A-2002-363208, JP-A-2002-363209, and the like, and an amine such as ethyl 4-dimethylaminobenzoate or 4-dimethylamine. N-butyl benzoate, phenylethyl 4-dimethylaminobenzoate, 2-nonylaminoethyl 4-dimethylaminobenzoate, 2-methyl 4-dimethylaminobenzoate Propylene methoxyethyl ester, pentamethylene bis(4-dimethylamino benzoate), phenylethyl ester of 3-dimethylaminobenzoic acid, pentamethyl ester, 4-dimethyl Aminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzimidyl) acetate, 4 - piperidinyl acetophenone, 4-dimethylaminobenzoin, N,N-dimethyl-4-toluidine, N,N-diethyl-3-phenylethylamine, triphenylmethylamine Diphenylmethylbenzene Amine, N-methyl-N-phenylbenzylamine, 4-bromo-N,N-dimethylaniline, tri-dodecylamine, amine-based hydrocarbons (ODB, ODBII, etc.), crystal violet Ester, leuco crystal violet, etc.), fluorenylphosphine oxides (such as bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzoate) Mercapto) 2,4,4-trimethyl-pentylphenylphosphine oxide, LucirinTPO, etc.).

Further, for example, the vicinal polyketal nitrile compound described in the specification of U.S. Patent No. 2,367,660, the affinity ether compound described in the specification of U.S. Patent No. 2,448,828, and the aromatic group substituted by α-hydrocarbyl group described in the specification of U.S. Patent No. 2,725,512 The agonist compound, the specification of the U.S. Patent No. 3,046,127, and the polynuclear ruthenium compound described in the specification No. 2,591,758, the organoboron compound described in JP-A-2002-229194, the radical generator, and the triarylsulfonium salt (e.g., a salt of cesium fluoride or a hexafluorophosphate), a sulfonium salt compound (such as a (phenylphenylsulfonylphenyl) diphenyl sulfonium salt) (effective as a cationic polymerization initiator), and a sulfonium salt described in WO01/71428 Compounds, etc.

These photopolymerization initiators may be used alone or in combination of two or more. In the case of a combination of two or more types, for example, a combination of a hexaaryldiimidazole and a 4-aminoketone described in the specification of U.S. Patent No. 3,549,367, a benzothiazole compound and a trihalogenated methyl group described in Japanese Patent Publication No. Sho 51-48516- S-three Combination of a compound, a combination of an aromatic ketone compound (for example, thioxanthone), a hydrogen donor (for example, a dialkylamine-containing compound, a phenol compound, etc.), a hexaaryldiimidazole and a titanium chloride-based catalyst Combination of coumarins, titanium chloride-based catalysts and phenylglycines.

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, particularly preferably from 0.5 to 15% by mass.

-Other ingredients -

The above other components such as a sensitizer, a thermal polymerization inhibitor, a plasticizer, a color developer, a colorant, etc., may also be used in combination with an adhesion promoter on the surface of the substrate and other auxiliary agents (such as pigments, conductive particles, fillers). , defoamers, flame retardants, leveling agents, stripping accelerators, antioxidants, perfumes, thermal crosslinkers, surface tension modifiers, chain transfer agents, etc.). By appropriately containing these components, the properties of the desired pattern forming material such as stability, photographic properties, printability, film properties, and the like can be adjusted.

--sensitizer --

The sensitizer can be appropriately selected from visible light rays, ultraviolet-visible lasers, and the like which are light irradiation means to be described later.

The sensitizer is excited by an active energy ray, and can generate a radical or an acid by interacting with other substances (for example, a radical generator, an acid generator, etc.) (for example, energy movement, electron movement, etc.). Useful base.

The sensitizer is not particularly limited and may be appropriately selected from known sensitizers, and may be, for example, known polynuclear aromatics (e.g., ruthenium, osmium, triphenylene), xanthene ( Such as luciferin, eosin, erythrosine, rhodamine B, rose red), quinoline blue (such as hydrazine carbonyl quinoline blue, thiacarbonylquinoline blue, oxacarbonylquinoline blue), part Cyanines (such as phthalocyanine, carbonyl phthalocyanine), thiophene Class , methylene blue, toluidine blue), acridine (such as acridine orange, chlorsulfurin, acridine yellow), anthraquinones (such as hydrazine), titanium dioxide (such as titanium dioxide), acridone (such as acridine) Ketone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc., coumarin (eg 3-(2-benzofuran) -7-diethylamino coumarin, 3-(2-benzofuranyl)-7-(1-pyrrolidinyl)coumarin, 3-benzylidene-7-di Ethylamino coumarin, 3-(2-methoxybenzimidyl)-7-diethylamino coumarin, 3-(4-dimethylaminobenzimidyl)-7 -diethylamino coumarin, 3,3'-carbonyl bis(5,7-di-n-propoxycoumarin), 3,3'-carbonyl bis(7-diethylamine coumarin , 3-benzylidene-7-methoxycoumarin, 3-(2-furanyl)-7-diethylaminocoumarin, 3-(4-diethylamine Cinnamyl)-7-diethylamino coumarin, 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzylidene-5,7-dipropoxy Base coumarin, etc., such as, for example, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-36 A coumarin compound or the like described in each of the publications such as No. 3,208 and JP-A-2002-363209.

The combination of the photopolymerization initiator and the sensitizer is, for example, an electron transfer type initiator system described in JP-A-2001-305734 ((1) Electron-supply-type initiator and sensitizing dye, (2) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye, and an electron-accepting initiator (ternary priming system).

The content of the sensitizer is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, particularly preferably 0.2 to 10% by mass based on the total amount of the components in the photosensitive composition.

When the content is less than 0.05% by mass, the sensitivity to the active energy ray is lowered, the exposure process takes time, and the productivity is lowered. When the content exceeds 30% by mass, the sensitizer is chromatographed from the photosensitive layer during storage.

-- Thermal polymerization inhibitor --

The above thermal polymerization inhibitor is added to prevent thermal polymerization or polymerization over time of the above polymerizable compound.

The above thermal polymerization inhibitor may be, for example, 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, tert-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methyl Oxy-2-hydroxybenzophenone, cuprous chloride, thiophene, chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2'- Methylene bis(4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methyl blue, copper and organic chelating agent reactants, Methyl salicylate, and thiophene a nitroso compound, a chelating compound of a nitroso compound and A1, and the like.

The content of the above-mentioned polymerizable compound is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, particularly preferably 0.01 to 1% by mass, based on the polymerizable compound of the photosensitive layer.

When the content is less than 0.001 by mass, the stability at the time of storage is lowered, and when it exceeds 5% by mass, the sensitivity to the active energy ray is lowered.

-- Plasticizer --

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

As the above plasticizer, for example, dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, bismuth citrate- Tridecyl ester, butyl benzyl phthalate, diisononyl phthalate, diphenyl phthalate, diallyl citrate, octyl octyl phthalate, etc.; triethylene glycol Diacetate, tetraethylene glycol diacetate, dimethyl glucose decanoate, ethyl decyl ethyl glycolate, methyl hydrazine Alcohol esters such as ethyl glycolate, butyl decyl butyl glycolate, triethylene glycol dicaprylate, etc.; phosphates such as trishydroxymethylphenyl phosphate and triphenyl phosphate; - decylamines such as toluene sulfonamide, benzene sulfonamide, N-n-butyl benzene sulfonamide, N-n-butyl acetamide, diisobutyl adipate, dioctyl adipate Aliphatic esters of esters, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, dioctyl phthalate, dioctyl selenite, dibutyl maleate, etc. Terpolymers: triethyl citrate, tributyl citrate, glycerol triethyl decyl acrylate, butyl laurate, 4,5-dicyclooxycyclohexane-1,2-dicarboxylic acid An alcohol such as octyl ester or the like, polyethylene glycol or polypropylene glycol.

The content of the plasticizer is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 40% by mass, particularly preferably from 1 to 30% by mass, based on the total components of the photosensitive layer.

--Reagent--

The developer is added to provide an image (printer function) on the photosensitive layer after exposure.

The above color developing agent is, for example, ginseng (4-dimethylaminophenyl)methane (leuco crystal violet), ginseng (4-diethylaminophenyl)methane, ginseng (4-dimethylamino group- 2-methylphenyl)methane, ginseng (4-diethylamino-2-methylphenyl)methane, bis(4-dibutylaminophenyl)-[4-(2-cyanoethyl) Aminotriaryl group such as methylaminophenyl]methane, bis(4-dimethylaminophenyl)-2-quinolinylmethane or bis(4-dipropylaminophenyl)methane Methane; 3,6-bis(dimethylamino)-9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9-(2-chlorinated phenyl Astragalus and the like; 3,6 bis(diethylamino)-9-(2-ethoxycarbonylphenyl)thioxanthone, 3,6-bis(dimethylamino) Aminothioxanthone such as thioxanthone; 3,6-bis(diethylamino)-9,10-dihydro-9-phenyl acridine, 3,6-bis(benzylamine) Amino-9,10-dihydroacridines such as -9,10-dihydro-9-methyl acridine; 3,7-bis(diethylamino) phenoxy Amine Aminophenothiazoles such as 3,7-bis(ethylamino)phenothiazole; 3,7-bis(diethylamino)-5-hexyl-5,10-dihydrobenzene Aminodihydrophene Aminophenylmethanes such as bis(4-dimethylaminophenyl)anilinyl methane; 4-amino-4'-dimethylaminodiphenylamine, 4-amino-α, β -Aminohydrocinnamic acid such as methyl dicyanohydrocinnamate; 1-(2-naphthyl)-2-phenylindole Wait Amino-2,3-dihydroindoles of 1,4-bis(ethylamino)-2,3-dihydroindoles; N,N-diethyl-4-phenethyl Phenylethylaniline such as aniline; 10-ethylindolyl-3,7-bis(dimethylamino)phenothiphenyl a sulfhydryl derivative containing a basic NH leuco dye; oxidized to a color-developing compound by oxidation of ginseng (4-diethylamino-2-methylphenyl)ethoxycarbonyl decane or the like without hydrogen a leuco compound; a leuco quinone pigment; an oxidative chromogenic organic amine (eg, 4,4'-ethylenediamine, diphenylamine, N,N-) as described in U.S. Patent No. 3,042,515 and the same as No. 3,042,517. Among them, dimethylaniline, 4,4'-methylenediaminetriphenylamine, and N-vinylcarbazole are preferable, and among these, a triarylmethane-based compound such as leuco crystal violet is preferable.

Further, when the color developing agent is used for the purpose of coloring the leuco body or the like, it is generally known to be combined with a halogen compound.

The above halogen compound is, for example, a halogenated hydrocarbon (e.g., carbon tetrabromide, iodoform, vinyl bromide, methyl bromide, bromopentane, bromoisopentane, iodopentane, brominated isobutylene, iodine butane, diphenylmethane bromide, Hexachloromethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3- Tribromopropane, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropane, hexachlorocyclopentadiene, dibromocyclohexane, 1,1,1 - trichloro-2,2-bis(4-chlorophenyl)ethane, etc.; halogenated alcohol compounds (eg 2,2,2-trichloroethanol, tribromoethanol, 1,3-dichloro-2-propane) Alcohol, 1,1,1-trichloro-2-propanol, di(iodohexamethyl)aminoisopropanol, tribromo-butanol, 2,2,3-trichlorobutane-1 , 4-diol, etc.; halogenated carbonyl compounds (eg 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1 , 1,1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc.; halogenated ether compounds (such as 2-bromoethyl) Methyl ether, 2-bromoethyl ether, bis(2-bromoethyl)ether, 1,2-dichloroethylether, etc.; halogenated ester compounds (eg bromoacetate, ethyl trichloroacetate, trichloro) a homopolymer and a copolymer of trichloroethyl acetate, 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, ethyl α,β-dichloroacrylate, etc.; a halogenated vinyl decylamine compound (eg, vinyl chloroamine, bromoethylene decylamine, dichloroethylene decylamine, dibromoethmonium amide, trichloroethylene) Enamine, tribromoethylene decylamine, trichloroethyl trichloroethylene decylamine, 2-bromoisopropionate decylamine, 2,2,2-trichloropropionate decylamine, N-chlorosuccinimide, N-bromosuccinimide, etc.; compounds having sulfur or phosphorus (such as tribromomethylphenylhydrazine, 4-nitrophenyltribromomethylhydrazine, 4-chlorophenyltribromomethylhydrazine, ginseng ( 2,3-dibromopropyl)phosphate, etc., 2,4-bis(trichloromethyl)6-phenyltriazole, etc. The organohalogen compound has two or more halogens bonded to the same carbon atom. The halogen compound of the atom is preferably a halogen compound having three or more halogen atoms bonded to one carbon atom. The above organohalogen compound may be used alone or in combination of two or more. Preferably, tribromomethylphenylhydrazine and 2,4-bis(trichloromethyl)-6-phenyltriazole are used.

The content of the above-mentioned color developing agent is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, particularly preferably 0.1 to 5% by mass based on the total components of the photosensitive layer. Further, the content of the halogen compound is preferably 0.001 to 5% by mass, and more preferably 0.005 to 1% by mass, based on the total amount of the photosensitive layer.

--Colorant--

The coloring agent is not particularly limited, and may be appropriately selected according to the purpose, for example, a conventional pigment or dye such as red, green, blue, yellow, purple, magenta, cyan, or black, specifically For example, Victoria Pure Blue BO (CI42595), 槐 yellow (CI41000), fat-soluble 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 carmine red FBB (CI Pigment Red 146), Hestam Bam Red ESB (CI Pigment Red 19), Permanent Ruby Red FBH (CI Pigment Red 11), Fast Pink B Spira (CI Pigment Red 81), Monaston Larufastel Blue (CI Pigment Blue 15), Morrow Brighton Farston Black B (CI Pigment Black 1), carbon black.

Further, the coloring agent suitable for the production of a color filter may be, 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 (0138) to (0141) of JP-A-2002-162752. on The average radius of the coloring agent is not particularly limited and may be appropriately selected depending on the purpose, and is, for example, preferably 5 μm or less, more preferably 1 μm or less. Further, in the case of producing a color filter, the average particle diameter is preferably 0.5 μm or less.

--dye--

In the above-mentioned photosensitive layer, a dye may be used for the purpose of coloring the photosensitive resin composition in order to improve handleability, or for imparting storage stability.

As the dye, for example, it may be brilliant green (for example, sulfate thereof), ruthenium, ethyl violet, red fresh sodium salt B, methyl green, crystal violet, basic magenta, phenol phenolphthalein, 1,3-diphenyl. Base three 1,2-dihydroxy ruthenium S, thymol phenolphthalein, methyl violet 2B, quinoline red, rose red, Mitanier yellow, thyme sulfophenolphthalein, xylenol blue, methyl orange, orange Color IV, diphenyl caseinazole, 2,7-dichlorofluorescein, p-methyl red, Congo red, Benzo red 4B, α-naphthyl-red, naple blue A, phenacetin , methyl violet, malachite green, by-product magenta, oil blue #603 (Orient Chemical Industry Co., Ltd.), rhodamine B, rhodamine 6G, Victoria pure blue BOH, etc., such as cationic dyes (such as peacock Green oxalate, malachite green sulfate, etc.) are preferred. The counter cation of the cationic dye may be a residue of an organic acid or an inorganic acid, such as a residue (anion) of bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid, toluenesulfonic acid or the like.

The content of the dye is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, particularly preferably 0.1 to 2% by mass, based on the total amount of the photosensitive layer.

--Intimate accelerator --

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

The adhesion promoters described in, for example, Japanese Laid-Open Patent Publication No. Hei 5- No. Hei. Specifically, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinylmethyl-1-phenyl - triazole-2-thione, 3-morpholinylmethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinylmethyl-thiadiazole-2- Thiol, 2-mercapto-5-methylthiothiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amine-containing benzotriazole, decane coupling agent, and the like.

The content of the adhesion promoter is preferably 0.001% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass based on the total components of the photosensitive layer.

The photosensitive layer may contain, for example, an organic sulfur compound, a peroxide, a redox compound, an azo or a diazo compound, a photoreducible dye, or an organic halogen compound described in Chapter 5 of the "Photosensitive System". Wait.

As the above organic sulfur compound, for example, di-n-butyl sulfide, diphenylmethyl disulfide, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, thiophene, ethyltrichloromethane sulfate, 2 may be used. - mercaptobenzimidazole and the like.

The above peroxide is, for example, di-tert-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide.

The redox-based compound is a combination of a peroxide and a reducing agent, and is, for example, a ferrous ion, a persulfate ion, an iron ion, a peroxide, or the like.

The above azo and diazo compounds are, for example, α,α'-azobisisobutyronitrile, 2-azobis-2-methylbutyronitrile, and 4-aminodiphenylamine diazonium.

The photoreducible pigments are, for example, rose bengal, red bright red, eosin, acridine yellow, riboflavin, and laurel purple.

- Surfactant - In the production of the above-mentioned pattern forming material of the present invention, a conventional surfactant may be added in order to improve the resulting surface streaks.

The surfactant may be appropriately selected, for example, from an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or a fluorine-containing surfactant.

The content of the surfactant is preferably 0.001 to 10% by mass based on the solid content of the photosensitive resin composition.

When the content is less than 0.001% by mass, the surface-improving effect cannot be obtained, and when it is more than 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, for example, preferably 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 according to the purpose. It is preferred that the photosensitive layer can be peeled off and the light transmittance is good, and the smoothness of the surface is better.

The support is preferably made of a synthetic resin and is transparent, such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (methyl). Alkylate, poly(meth)acrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamine, polyimine, Various plastic films such as vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose film, and nylon film, among which polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

The thickness of the support is not particularly limited and may be appropriately selected depending on the purpose, and is, for example, preferably 2 to 150 μm, more preferably 5 to 100 μm, and particularly preferably 8 to 50 μm.

The shape of the support is not particularly limited, and may be appropriately selected depending on the purpose, and is preferably elongated. The length of the above-mentioned elongated support is not particularly limited, and may be, for example, a length of 10 m to 20,000 m.

The pattern forming material may also form a protective film on the photosensitive layer.

The protective film is, for example, a user of the above-mentioned support, paper, paper having a layer of polyethylene or polypropylene laminated thereon, and among these, a polyethylene film or a polypropylene film is preferable.

The thickness of the protective film is not particularly limited and may be appropriately selected depending on the purpose, and is, for example, preferably 5 to 100 μm, more preferably 8 to 50 μm, and particularly preferably 10 to 30 μm.

As a combination of the above support and a protective film (support/protective film), for example, polyethylene terephthalate/polypropylene, polyethylene terephthalate/polyethylene, polyvinyl chloride/cellophane, polyfluorene Imine/polypropylene, polyethylene terephthalate/polyethylene terephthalate, and the like. Further, by at least one of the support and the protective film, the relationship of the above-mentioned adhesive force can be satisfied. The surface treatment of the support may be carried out in order to improve the adhesion to the photosensitive layer, for example, coating of the underlayer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high-frequency irradiation treatment, glow discharge treatment, active electricity Slurry irradiation treatment, laser irradiation treatment, and the like.

Further, the static friction coefficient of the support and the protective film is preferably from 0.3 to 1.4, more preferably from 0.5 to 1.2.

When the static friction coefficient is less than 0.3, the overwinding is likely to cause a winding deviation when rolled into a roll shape, and when it is more than 1.4, it is difficult to roll into a good roll shape.

The pattern forming material is preferably wound into a roll shape in a roll shape, for example, by winding it into a roll. The length of the long strip-shaped pattern forming material is not particularly limited, and may be, for example, suitably selected from the range of 10 m to 20,000 m. Further, in order to facilitate the slicing process by the user, the elongated body in the range of 100 m to 1,000 m can be formed into a roll shape. Furthermore, in this case, it is preferable to roll the said support body to the outermost side. Further, the roll-shaped pattern forming material may be cut into a sheet shape. In the case of storage, end face protection, and prevention of edge melting, it is preferable to provide a separator on the end surface (particularly, a moisture-proof person, a desiccant is added), and a material having a low moisture permeability is used in packaging. good.

In order to adjust the adhesion between the protective film and the photosensitive layer, the protective film may be subjected to a surface treatment. In the above surface treatment, for example, an undercoat layer made of a polymer of polyorganosiloxane, fluorinated polyolefin, polyvinyl fluoride, polyvinyl alcohol or the like is formed on the surface of the protective film. The formation of the undercoat layer can be carried out by applying the coating liquid of the above polymer to the surface of the protective film, followed by drying at 30 to 150 ° C (especially 50 to 120 ° C) for 1 to 30 minutes.

<Other layers>

The other layer is not particularly limited and may be appropriately selected depending on the purpose, and may be, for example, a layer of a buffer layer, a barrier layer, a release layer, an adhesive layer, a light absorbing layer, a surface protective layer, or the like. The pattern forming material may have one type alone or two or more types of these layers.

In the above-described photosensitive layer of the pattern forming material of the present invention, it is preferable to use a light modulation mechanism having n pixel portions for receiving and emitting light from the light irradiation means, and the light irradiation means is provided from the light irradiation means. After the light is modulated, it is exposed by light having a microlens array in which aspherical microlenses capable of correcting aberrations due to distortion of the exit surface of the pixel portion are arranged. Details of the light irradiation means, the pixel portion, the light modulation means, the aspherical surface, the microlens, and the microlens array will be described later.

[Method of Manufacturing Pattern Forming Material]

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

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

The coating solvent is not particularly limited and may be appropriately selected according to the purpose, and may be, for example, an alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol or n-hexanol. ; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, propionic acid Esters of esters, dimethyl phthalate, ethyl benzoate and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene , halogenated hydrocarbons such as chloroform, 1,1,1-trichloroethane, dichloromethane, monochlorobenzene, etc.; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy Ethers such as benzyl-2-propanol; dimethylformamide, dimethylacetamide, dimethyl hydrazine, cyclobutyl hydrazine, and the like. These may be used alone or in combination of two or more. In addition, conventional surfactants may also be added.

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

The coating method of the above-described composition for pattern formation is not particularly limited, and may be appropriately selected according to the purpose, and may be, for example, a spray method, a roll coating method, a rotary coating method, a slit coating method, or extrusion coating. Various coating methods such as a cloth method, a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.

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

Since the pattern forming material of the present invention is excellent in resolution and shielding properties, and also excellent in developability and excellent in peeling property during etching, it can be applied to formation of various patterns, formation of permanent patterns such as wiring patterns, and color filter. For the production of liquid crystal structural members such as a light sheet, a column, a rib, a spacer, and a partition, a pattern for forming a hologram, a micromachine, or a verification, etc., it is particularly applicable to formation of a high-definition wiring pattern. Moreover, it can be suitably applied to the pattern forming method and the pattern forming apparatus of the present invention.

(pattern forming device and pattern forming method)

The pattern forming apparatus of the present invention includes the pattern forming material of the present invention, and has at least a light irradiation mechanism and a light modulation mechanism.

The pattern forming method of the present invention includes at least an exposure step, including other steps that are appropriately selected.

Further, the above-described pattern forming apparatus of the present invention is as described in 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 pattern forming material relating to 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 according to the purpose, for example, preferably for a laminate formed by forming the pattern forming material on a substrate. .

The substrate is suitably selected from those of the conventional materials, and the surface smoothness is high, and the surface has irregularities, and a plate-shaped substrate (substrate) is preferable. Specifically, for example, a conventional printed wiring board forming substrate is used. (for example, copper area laminate), glass plate (for example, soda glass plate, etc.), synthetic resin film, paper, metal plate, and the like. Among these, the above-mentioned copper area laminate is preferable from the viewpoint of excellent adhesion to the copper-containing material.

The method for forming the layered body is not particularly limited, and may be appropriately selected according to the purpose, and at least one of heating and pressurizing the pattern forming material on the substrate is preferable.

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

The pressurized pressure is not particularly limited and may be appropriately selected depending on the purpose, and is, for example, preferably 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 according to the purpose, and examples thereof include a laminator, a vacuum laminator, and the like.

The apparatus for performing at least one of the above-described heating and pressurization is not particularly limited, and may be appropriately selected according to the purpose, and may be, for example, a laminator (for example, Taiseilaminator, Co., Ltd.). VP-II) and so on.

The above exposure system is not particularly limited and may be appropriately selected depending on the purpose, and may be, for example, digital, analog exposure, etc., among which digital exposure is preferred.

The above-mentioned digital exposure is not particularly limited and may be appropriately selected depending on the purpose, and may be, for example, digital, analog exposure, etc., among which digital exposure is preferred.

The above-described digital exposure mechanism is not particularly limited, and may be appropriately selected according to the purpose. For example, it is preferably a light irradiation mechanism that irradiates light, and is irradiated from the light irradiation mechanism based on the formed pattern information. The light is used as a mechanism for modulation.

<Light modulation means>

The light modulation means is not particularly limited as long as the light can be modulated, and may be appropriately selected according to the purpose. For example, it is preferable to have n pixel portions.

The light modulation mechanism having the n pixel portions is not particularly limited, and may be appropriately selected depending on the purpose. For example, a spatial light modulation element is preferable.

The spatial light modulation element may be, for example, a digital microlens device (DMD) or a MEMS (micro electro mechanical system) type spatial light modulation element (SLM; special light modulator), which is modulated by electro-optical effects. An optical element (PLZT element) that transmits light, a liquid crystal shutter (FLC), etc., among these, is preferably a DMD.

Further, it is preferable that the optical modulation means has a pattern signal forming means for generating a control signal based on the formed pattern information. In this case, the optical modulation mechanism changes the light in accordance with a control signal generated by the pattern signal generating means.

The above control signal is not particularly limited and may be appropriately selected according to the purpose, for example, a data signal is suitable.

Hereinafter, an example of the above-described optical modulation mechanism will be described with reference to the drawings.

As shown in FIG. 1, the DMD 50 is a micro lens (microlens) 62 in which a plurality of (for example, 1024 × 768) pixels (pixels) are arranged in a grid on the SRAM cell (memory cell) 60. The resulting microlens device. In each of the pixels, a microlens 62 supported by a pillar is provided on the uppermost portion, and a material having a high reflectance such as aluminum is vapor-deposited on the surface of the microlens 62. Further, the reflectance of the microlens 62 is 90% or more, and the arrangement pitch is 13.7 μm in one example in the longitudinal direction and the lateral direction. Further, the CMOS SRAM cell 60 which is disposed on the production line of a general semiconductor memory via a pillar including a hinge and a yoke directly under the microlens 62 is formed in a single piece.

When a digital signal is input to the SRAM cell 60 of the DMD 50, the microlens 62 supported by the pillar is tilted within a range of ±α degrees (for example, ±12 degrees) on the substrate side on which the DMD 50 is disposed, centering on the diagonal. Fig. 2A shows a state in which the microlens 62 is in an open state and is tilted by +α degrees, and Fig. 2B shows a state in which the microlens 62 is in a closed state and tilted by -α degrees. Therefore, according to the pattern information, by controlling the inclination of the microlenses 62 in the respective pixels of the DMD 50, the laser beams B incident on the DMD 50 are each reflected toward the oblique direction of the microlenses 62.

Further, Fig. 1 shows an example in which a part of the DMD 50 is enlarged and the microlens 62 is controlled to +α degrees or -α degrees. The switching control of each microlens 62 is performed by the above controller 302 connected to the DMD 50. . Further, an optical absorber (not shown) is disposed in a direction in which the laser light B reflected by the microlens 62 in the closed state is performed.

Further, the DMD 50 is preferably disposed such that the short side is slightly inclined toward the scanning direction and the specific angle θ (for example, 0.1 to 5 degrees). Fig. 3A shows a scanning trajectory of a reflected light image (exposure beam) 53 by each microlens when the DMD 50 is not tilted, and Fig. 3B shows a scanning trajectory of the exposure light beam 53 when the DMD 50 is tilted.

The DMD 50 has a plurality of (for example, 1024) microlenses arranged in the longitudinal direction and an array (for example, 756 sets) of microlens arrays arranged in the short side direction. As shown in FIG. 3B, each microlens is made by tilting the DMD 50. When the distance P ₂ between the scanning trajectories (scanning lines) of the exposure light beam 53 is such that the DMD 50 is not inclined, the distance P ₁ between the scanning lines is narrow, and the resolution can be greatly improved. On the other hand, since the tilt angle of the DMD 50 is small, the scan width W ₂ when the DMD 50 is tilted is approximately the same as the scan width W ₁ when the DMD 50 is not tilted.

Next, a method for accelerating the modulation speed of the above-described optical modulation mechanism (hereinafter also referred to as "high-speed modulation") will be described.

Preferably, the light modulation mechanism may correspond to the pattern information to control any of the n pixels that are consecutively arranged in the n pixels. The data processing speed of the optical modulation mechanism is limited, and since the modulation speed of each of the pixels is determined in proportion to the pixel portion to be used, each of the pixels is made by using only any of the pixel elements that are continuously arranged in less than n pixels. The modulation speed is faster.

In the following, the above-described high-speed modulation will be described with reference to the drawings.

When the laser array light source 66 causes the laser light B to illuminate the DMD 50, the laser light reflected by the microlens of the DMD 50 in the open state is imaged on the pattern forming material 150 by the lens systems 54, 58. The laser light thus emitted from the fiber array light source 66 is switched by each of the pixels, and the pattern forming material 150 is exposed in approximately the same number of pixel units (exposure range 168) as the number of pixels of the DMD 50. Further, by the pattern forming material 150 and the stage 152 moving at a certain speed at the same time, the pattern forming material 150 is scanned by the scanner 162 in the direction opposite to the moving direction of the stage, and the strip exposure completion area is formed in each of the exposure heads 166. 170.

Further, as shown in FIG. 4A and FIG. 4B, for example, the DMD 50 has 1024 microlenses arranged in the main scanning direction and 768 microlens arrays arranged in the sub-scanning direction, and this example is provided by the controller 302 (see the Figure 12) Controlling only a portion of the microlens column (e.g., 1024 x 256 columns).

In this case, the microlens array disposed at the central portion of the DMD 50 shown in Fig. 4A may be used, or the microlens array disposed at the end of the DMD 50 shown in Fig. 4B may be used. Further, when a defect occurs in a part of the microlens, a microlens array or the like which does not cause a defect is used, and the microlens array to be used can be appropriately changed as appropriate.

The data processing speed of the DMD50 is limited. Since the modulation speed of each strip is determined by using the number of pixels used, only a part of the microlens array is used to speed up the modulation of each strip. On the other hand, in the exposure mode in which the exposure head is continuously moved relative to the exposure surface, it is not necessary to use all the pixels in the sub-scanning direction.

When the sub-scan of the pattern forming material 150 is completed by the scanner 162, and the rear end of the pattern forming material 150 is detected by the inductor 164, the platform 152 is returned to the most upstream side of the gate 160 along the guide 158 by the platform driving device 304. The origin is then moved from the upstream side of the gate 160 to the downstream side at a constant speed along the guide 158.

For example, when only 384 sets are used in the 768 sets of microlens arrays, each of the strips becomes twice as fast as when the 768 sets are all used. Moreover, when only 256 sets are used in the 768 sets of microlens rows, each of the strips becomes 3 times faster than when the 768 sets are all used.

As described above, the pattern forming method of the present invention includes 1024 microlenses arranged in the main scanning direction and 768 sets of microlens arrays arranged in the sub-scanning direction, and the controller controls only a part of the microlens array to be driven, and The modulation speed of each strip is faster than when all the microlens trains are driven.

In addition, an example of a microlens for partially driving a DMD is described. Even if a length corresponding to a direction of a specific direction is longer than a length of a direction intersecting the specific direction, the angle of the reflection surface can be changed depending on each control signal. When the microlenses are arranged in a two-dimensional arrangement of the elongated DMD, the number of microlenses that control the angle of the reflecting surface is reduced, and the modulation speed can be increased in the same manner.

Further, the above-described exposure method is preferably performed while moving the exposed light to the side of the photosensitive layer, and in this case, it is preferably used in combination with the above-described high-speed modulation. Thereby, high-speed exposure can be performed in a short time.

In addition, as shown in FIG. 5, the scanner 162 may be scanned once in the X direction to fully expose the pattern forming material 150, such as 6A and 6B, after the patterning material 150 is scanned in the X direction by the scanner 162, the scanner 162 is moved in the Y direction by one step and scanned in the X direction, and scanning and moving are repeated. The secondary scan exposes the patterning material 150 in its entirety. Moreover, in this example, the scanner 162 is provided with 18 exposure heads 166. Further, the exposure head has at least the above-described light irradiation mechanism and the above-described modulation mechanism.

In the above-described exposure, the partial region is hardened by a partial region of the photosensitive layer, and an unhardened region other than the hardened portion is removed in a developing step to be described later to form a pattern.

Next, an example of a pattern forming apparatus including the above-described light modulation mechanism will be described with reference to the drawings.

The pattern forming apparatus including the above-described light modulation mechanism includes a flat plate-like platform 152 that adsorbs and holds the sheet-like pattern forming material 150 on the surface as shown in FIG.

On the upper surface of the thick plate-like setting table 156 supported by the four leg portions 154, two guide members 158 which are stretched in the direction in which the platform moves are provided. The platform 152 is disposed in the longitudinal direction thereof toward the platform moving direction, and is supported by the guide 158 to move back and forth. Moreover, the above-described patterning device has a driving device that is not shown in the drawing when the stage 152 is driven along the guide 158.

A moving path that can span the platform 152 is disposed on a central portion of the setting table 156. Font gate 160. The ends of the font gates 160 are each fixed to both sides of the setting table 156. Clamping the One side of the font gate 160 is provided with a scanner 162, and the other side is provided with a plurality of (for example, two) detection sensors 164 for detecting the front end and the rear end of the pattern forming material 150. The scanner 162 and the detecting sensor 164 are each disposed on the gate 160 and fixedly disposed above the moving path of the platform 152. Moreover, the scanner 162 and the detection sensor 164 are connected to a controller that controls these without being shown.

As shown in FIGS. 8 and 9B, the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in an approximately matrix form in m rows and n columns (for example, three rows and five columns). In this example, four exposure heads 166 are arranged in the third row in relation to the width of the pattern forming material 150. Further, when the exposure heads arranged in the nth row of the mth row are to be represented, they are indicated by the exposure head 166 _mn .

The exposure range 168 of the exposure head 166 is a rectangular shape in which the sub-scanning direction is a short side. Therefore, with the movement of the mesa 152, each of the exposure heads 166 forms a strip-shaped exposure completion region 170 on the pattern forming material 150. Further, when the exposure range of each of the exposure heads arranged in the mth row and the nth column is to be expressed, it is represented by an exposure range of 168 _mn .

Further, as shown in FIGS. 9A and 9B, the strip exposure completion region 170 is arranged side by side with no gap in the direction orthogonal to the sub-scanning direction, and each line of the line-up exposure heads is arranged at a specific interval toward the arrangement direction (exposure range The natural length of the long side is several times, in this case 2 times). Therefore, the portion of the first row between the exposure range 168 ₁₁ and the exposure range 168 ₁₂ that is not exposed can be exposed by the exposure range 168 ₂₁ of the second row and the exposure range 168 _{31 of} the third row.

Each of the exposure heads 166 ₁₁ to 166 _{mn is provided} with a digital microlens device (DMD) 50 manufactured by Texas Instruments Co., Ltd. as the above-mentioned optical modulation mechanism depending on the pattern information (as shown in FIGS. 10 and 11). Space light modulation components for each pixel modulation). The DMD 50 is connected to the controller 302 (see Fig. 12) including the data processing unit and the lens drive control unit. The data processing unit of the controller 302 generates, based on the input pattern information, a control signal for driving control of each microlens within the control range of the DMD 50. Moreover, the relevant control area is as follows. Further, the lens drive control unit controls the angle of the reflection surface of each of the microlenses of the DMD 50 based on the control signal generated by the pattern information processing unit. Further, the angle control of the reflecting surface will be described later.

On the light incident side of the DMD 50, a fiber array light source 66 having a laser emitting end portion (light emitting point) arranged in a row along the longitudinal direction of the corresponding exposure region 168 is arranged in order, and the fiber array light source 66 is emitted from the fiber array light source 66. The laser light is corrected, the lens system 67 condensed on the DMD, and the lens 69 that reflects the laser light transmitted through the lens system 67 toward the DMD 50. Moreover, Fig. 10 schematically shows a lens system 67.

The lens system 67 is shown in detail in Fig. 11, and the rod-shaped optical integration of the condensing lens 71 that condenses the laser light B emitted from the fiber array light source 66 as the illumination light and the light path of the light that has passed through the condensing lens 71 is shown. The device (hereinafter referred to as a rod integrator) 72 and an imaging lens 74 disposed in front of the rod integrator 72, that is, on the side of the lens 69. The condensing lens 71, the rod integrator 72, and the imaging lens 74 cause the laser light emitted from the fiber array light source 66 to form near-parallel light and a light beam having a uniform intensity in the beam cross section is incident on the DMD 50. The shape or function of the rod integrator 72 will be described in detail below.

The laser light B emitted from the lens system 67 is reflected by the lens 69 and is irradiated to the DMD 50 via TIR (total reflection) 稜鏡70. Moreover, the TIR 稜鏡 70 is omitted in FIG.

Further, an imaging optical system 51 that images the laser light B reflected by the DMD 50 on the pattern forming material 150 is disposed on the light reflection side of the DMD 50. The imaging optical system 51 is schematically shown in FIG. 10, and the first imaging optical system formed by the lens systems 52 and 54 and the second imaging optical system formed by the lens systems 57 and 58 are shown in detail in FIG. The microlens array 55 and the aperture array 59 interposed between the imaging optical systems are formed.

The microlens array 55 is formed by arranging a plurality of microlenses 55a corresponding to respective pixels of the DMD 50 in a quadratic shape. In this example, since only 1024 × 256 columns are driven in the 1024 × 768 column microlenses of the DMD 50 as described below, the microlenses 55a corresponding thereto are arranged in 1024 × 256 columns. Further, the arrangement pitch of the microlenses 55a was 41 μm both in the longitudinal direction and in the lateral direction. One of the microlenses 55a is formed of, for example, an optical glass BK7 with a focal length of 0.19 mm and a NA (number of openings) of 0.11. Further, the shape of the microlens 55a will be described in detail later. Further, the beam diameter of the laser beam B located in each of the microlenses 55a is 41 μm.

Further, the aperture array 59 is formed by a plurality of apertures 59a corresponding to the respective microlenses 55a of the microlens array 55. The diameter of the opening 59a is, for example, 10 μm.

The first imaging optical system is formed by magnifying the image by three times by the DMD 50 and imaging the microlens array 55. Then, the second imaging optical system expands the image by 1.6 times via the microlens array 55, and images and projects onto the pattern forming material 150. Therefore, the image is enlarged by 4.8 times, imaged, and projected onto the pattern forming material 150 by the DMD 50 as a whole.

Further, a pair of yokes 73 is disposed between the second image forming optical system and the pattern forming material 150, and by moving the pair of shins 73 in the vertical direction in FIG. 11, the image on the pattern forming material 150 can be adjusted. focus. Further, in the same figure, the pattern forming material 150 is sub-scanned in the direction of the arrow F.

The pixel portion is not particularly limited as long as it can receive and emit light from the light irradiation means, and can be appropriately selected according to the purpose. For example, the pattern formed by the pattern forming method of the present invention is The image pattern is a pixel, and the micro-lens is used when the light modulation mechanism contains DMD.

The number of the pixel portions having the above-described light modulation element (the above n) is particularly limited and can be appropriately selected depending on the purpose.

The arrangement of the pixel portions in the above-mentioned optical modulation element is particularly limited, and may be appropriately selected according to the purpose. For example, it is preferably arranged in a two-dimensional shape, and is preferably arranged in a lattice shape.

<Light Irradiation Mechanism>

The light irradiation means is not particularly limited and may be appropriately selected depending on the purpose, such as a fluorescent tube, a carbon lamp, a halogen lamp, a photoreceptor, or the like, such as a fluorescent tube, an LED, or a semiconductor laser. A light source or a mechanism for synthesizing and irradiating two or more kinds of light is preferable, and among them, a mechanism for synthesizing two or more types of light can be preferably used.

The light irradiated from the light irradiation means may be an electromagnetic wave or an ultraviolet ray which is activated by the photopolymerization initiator or the sensitizer used for the support and the package, for example, when the light is irradiated through the support. Among the light, the electron beam, the X-ray, the laser light, and the like, it is preferable that the laser light is combined with a laser that combines two or more types of light (hereinafter referred to as "composite-wave laser"). Further, when the support is peeled off and light is irradiated, the same light can be used.

The wavelength of the ultraviolet to visible light is, for example, preferably 300 to 1500 nm, more preferably 320 to 800 nm, and particularly preferably 330 to 650 nm.

The wavelength of the above-mentioned laser light is, for example, preferably 200 to 1500 nm, more preferably 300 to 800 nm, particularly preferably 330 to 500 nm, and particularly preferably 400 to 450 nm.

As a means for illuminating the complex wave, for example, it is preferable to have a plurality of kinds of lasers, a multimode fiber, and a collecting optical system that combines the laser light irradiated from each of the plurality of laser beams to the multimode fiber. mechanism.

Hereinafter, a mechanism (fiber array light source) that can illuminate the composite wave will be described with reference to the drawings.

As shown in FIG. 27A, the fiber array light source 66 is provided with a plurality of (for example, 14) laser modules 64, and one end of the multimode fiber 30 is coupled to each of the laser modules 64. On the other end of the multimode fiber 30, the core fiber 30 is the same as the multimode fiber 30, and the cladding fiber 30 is a small fiber 31. As shown in Fig. 27B, the end portion on the opposite side to the optical fiber 30 of the multimode optical fiber 31 is a laser emitting portion 68 which is arranged in parallel in the main scanning direction perpendicular to the sub-scanning direction and arranged in two rows. Composition.

As shown in Fig. 27B, the laser emitting portion 68 formed at the end of the multimode optical fiber 31 is sandwiched and fixed by two support plates 65 having a flat surface. Moreover, on the light exit end face of the multimode fiber 31, for protection It is preferable to arrange a transparent protective plate such as glass. The light-emitting end face of the multimode fiber 31 is easy to collect dust and deteriorate due to high optical density. However, by arranging the above-mentioned protective plate, dust can be prevented from adhering to the end face and the deterioration can be delayed.

In this example, in order to arrange the exit ends of the optical fibers 31 having a small cladding diameter in one column without voids, a multimode optical fiber is laminated between two adjacent multimode optical fibers 30 having a large cladding diameter. 30. The exit end of the optical fiber 31 combined with the multi-mode optical fiber 30 of the laminated layer is sandwiched between two exit ends of the optical fiber 31 of the two multimode optical fibers 30 adjacent to the adjacent portion having a large cladding diameter. Arrange.

For example, as shown in Fig. 28, the optical fiber can be obtained by coaxially combining optical fibers 31 having a small cladding diameter of 1 to 30 cm in length at the front end portion of the laser light exiting side of the multimode optical fiber 30 having a large cladding diameter. The incident end faces of the two fiber-optic fibers 31 are melt-bonded on the exit end faces of the multimode fibers 30 so that the central axes of the two fibers are uniformly aligned. As described above, the diameter of the core 31a of the optical fiber 31 is the same as the diameter of the core 30a of the multimode optical fiber 30.

Further, a short optical fiber having an optical fiber having a small cladding diameter can be melted on an optical fiber having a short length and a large cladding diameter, and bonded to the exit end of the multimode optical fiber 30 via a ferrule or a connector. By using a connector or the like to be detachable and combined, the front end portion can be easily exchanged when the optical fiber having a small cladding diameter is broken, and the cost required for repairing the exposure head can be reduced. Further, the optical fiber 31 is sometimes referred to as an exit end portion of the multimode optical fiber 30 in the following.

The multimode fiber 30 and the optical fiber 31 are a step index type fiber, a graded index type fiber, and a composite type fiber. For example, a step index type optical fiber manufactured by Mitsubishi Electric Wire Co., Ltd. can be used. Type of this implementation The medium multimode fiber 30 and the optical fiber 31 are step index type fibers, and the multimode fiber 30 series cladding diameter = 125 μm, core diameter = 50 μm, NA = 0.2, transmittance of the incident end face coating = 99.5% or more, and the optical fiber 31 system Cladding diameter = 60 μm, core diameter = 50 μm, NA = 0.2.

In general, the transmission loss of the laser light in the infrared region to the cladding diameter of the optical fiber increases. Therefore, the appropriate cladding diameter is determined depending on the wavelength range of the laser light. Moreover, the shorter the wavelength, the less the transmission loss, and the laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, even if the thickness of the cladding layer {(cladding diameter-core diameter)/2} is about infrared rays transmitting a wavelength range of 800 nm. At 1/2 of the time, it is about 1/4 of the infrared ray in the wavelength range of 1.5 μm for communication, and the transmission loss hardly increases at all. Therefore, the cladding diameter can be made small to be 60 μm.

However, the cladding diameter of the optical fiber 31 is not limited to 60 μm. The cladding diameter of the optical fiber used in the conventional fiber array light source is 125 μm. However, the deeper the depth of the cladding is, the deeper the depth of the cladding is, so the cladding diameter of the multimode fiber is preferably 80 μm or less, more preferably 60 μm or less, and 40 μm. The best of the following. Further, since the core diameter must be at least 3 to 4 μm, the cladding diameter of the optical fiber 31 is preferably 10 μm or more.

The laser module 64 is constructed by a composite laser light source (fiber array light source) as shown in FIG. The composite laser light source is composed of a plurality of (for example, seven) sheet-shaped transverse multimode or single-mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6, and LD7 arranged and fixed on the heating region 10. And collimating lenses 11, 12, 13, 14, 15, 16, and 17, respectively, corresponding to the GaN-based semiconductor lasers LD1 to LD7, and one collecting lens 20, and one multimode fiber 30 Composition. And half The number of conductor lasers is not limited to seven. For example, a multimode fiber having a cladding diameter of 60 μm, a core diameter of 50 μm, and a NA of 0.2 allows 20 semiconductor laser light to be incident, which can achieve the necessary amount of light for the exposure head, and can further reduce the number of optical fibers.

The GaN-based semiconductor lasers LD1 to LD7 have the same oscillation wavelength (for example, 405 nm) and the maximum output is the same (for example, a multimode laser is 100 mW and a single mode laser is 30 mW). Further, the GaN-based semiconductor lasers LD1 to LD7 may use a laser having an oscillation wavelength other than 405 nm in the wavelength range of 350 nm to 450 nm.

As shown in Figs. 30 and 31, the composite laser light source is housed in a box-shaped envelope 40 that is open at the top side together with other optical elements. The encapsulant 40 is provided with an encapsulation cover 41 for closing the opening, and after the degassing treatment, the sealing gas is introduced, and the opening of the encapsulation 40 is covered by the encapsulation cover 41, and the envelope 40 is covered by the encapsulation 40. The composite wave laser light source is gas-tightly sealed in a sealed space (sealing space) formed by the envelope cover 41.

The substrate 42 is fixed to the bottom surface of the encapsulant 40, and the heating zone 10, the condensing lens holder 45 for holding the condensing lens 20, and the fiber holding the incident end of the multimode fiber 30 are fixed on the substrate 42. 46. The exit end of the multimode fiber 30 is pulled out from the opening formed by the wall surface of the envelope 40 to the outside of the envelope.

Further, a collimator lens holder 44 is disposed on the side of the heating zone 10 to hold the collimator lenses 11-17. An opening is formed in the lateral wall surface of the encapsulant 40, and the wiring 47 for supplying the driving current to the GaN-based semiconductor lasers LD1 to LD7 is pulled out to the outside of the envelope.

Further, in Fig. 31, in order to avoid complication of the pattern, only the GaN-based semiconductor laser LD7 is numbered among a plurality of GaN-based semiconductor lasers, and of the plurality of collimating lenses, only the collimator lens 17 is numbered.

Fig. 32 is a view showing the front shape of the mounting portion of the above-described collimating lenses 11 to 17. Each of the collimator lenses 11 to 17 is formed by cutting an optical axis of a circular lens having an aspherical surface into a slender shape in a parallel plane. The elongated shape collimating lens can be formed, for example, by molding a resin or an optical glass. The collimator lenses 11 to 17 are arranged in close contact with each other in the arrangement direction of the light-emitting points so that the longitudinal direction thereof is orthogonal to the arrangement direction of the light-emitting points of the GaN-based semiconductor lasers LD1 to LD7 (the horizontal direction in FIG. 32).

On the other hand, each of the GaN semiconductor lasers LD1 to LD7 is made to have an active layer having a light-emitting width of 2 μm, a direction parallel to the active layer, and an angle of expansion of a vertical direction of, for example, 10° and 30°, respectively. B1~B7 luminous laser. These GaN-based semiconductor lasers LD to LD7 are arranged such that the light-emitting points in the direction parallel to the active layer are arranged side by side.

Therefore, the laser beams B1 to B7 emitted from the respective light-emitting points are aligned with the longitudinal direction in the direction in which the enlargement angle is large for each of the elongated collimating lenses 11 to 17, and the direction and the width direction (and the length) are small. Incident in a state where the direction is perpendicular). In short, the width of each of the collimating lenses 11 to 17 is 1.1 mm and the length is 4.6 mm, and the beam diameters in the horizontal direction and the vertical direction of the laser beams B1 to B7 incident thereon are 0.9 mm and 2.6 mm, respectively. Further, each of the collimator lenses 11 to 17 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

In the condensing lens 20, the region including the optical axis of the aspherical circular lens is cut into a slender shape in a parallel plane, and the alignment directions of the collimator lenses 11 to 17, that is, the horizontal direction is the long side, and the direction perpendicular thereto is short. The shape of the sides is formed. The condensing lens 20 has a focal length f ₂ = 23 mm and NA = 0.2. The condensing lens 20 is formed, for example, by molding a resin or an optical glass.

Further, in the light irradiation mechanism for illuminating the DMD, since the exit end portions of the optical fibers using the composite wave laser light source are arranged in a line-like high-intensity fiber array light source, pattern formation with high output and deep depth of focus can be realized. Device. Further, by increasing the output of each of the fiber array light sources, it is required to reduce the number of fiber array light sources necessary for obtaining a desired output, thereby reducing the cost of the pattern forming apparatus.

Further, since the cladding diameter of the exit end of the optical fiber is smaller than the cladding diameter of the incident end, the diameter of the light-emitting portion is required to be small, and the fiber array light source is brightened. Thereby, a pattern forming device having a deep depth of focus can be realized. For example, when the beam diameter is 1 μm or less and the resolution is 0.1 μm or less, the deep focus depth can be obtained, and the exposure can be performed at high speed and high definition. Moreover, it is suitable for an exposure step of a thin film transistor (TFT) which must have high resolution.

Further, the light irradiation means is not limited to the above-described fiber array light source including a plurality of composite laser light sources, and for example, one optical fiber having laser light emitted from a single semiconductor laser having one light-emitting point can be used. A fiber array light source in which fiber sources are arranged.

Further, as a light irradiation means having a plurality of light-emitting points, for example, as shown in Fig. 33, a plurality of (for example, 7) can be used in the heating zone 100. Laser arrays of chip semiconductor lasers LD1~LD7. Further, a plurality of sheet-like multi-slot lasers 110 in which a plurality of (for example, five) light-emitting points 110a are arranged in a specific direction as shown in Fig. 34A are known. The multi-slot laser 110 can easily align the positions of the light-emitting points as compared with the case where the sheet-like semiconductor lasers are arranged, so that the laser light complexes emitted from the respective light-emitting points are easily generated. However, when the number of light-emitting points is increased, the multi-slot laser 110 is likely to be bent during laser manufacturing, so that the number of the light-emitting points 110a is preferably five or less.

As the light irradiation means, it is possible to arrange the plurality of multi-slot lasers 110 in the same direction as the arrangement direction of the light-emitting points 110a of the respective wafers in the heating zone 100 as shown in the multi-slot laser 110 or the 34B. A multi-slot laser array is used as a laser source.

In addition, the composite wave laser source is not limited to laser light composites that are emitted from a plurality of chip semiconductor lasers. For example, as shown in Fig. 21, a composite laser light source having a sheet-shaped multi-slot laser 110 having a plurality of (for example, three) light-emitting points 110a can be used. The composite laser light source includes a multi-slot laser 110, a multimode optical fiber 130, and a collecting lens 120. The multi-slot laser 110 can be configured, for example, by oscillating a GaN-based laser diode having a wavelength of 405 nm.

In the above configuration, the laser light B emitted from the plurality of light-emitting points 110a of the multi-slot lasers 110 is condensed by the condensing lens 120 and incident on the core 130a of the multimode optical fiber 130. The laser light incident on the core 130a moves in the optical fiber and is combined into one emission.

By arranging the plurality of light-emitting points 110a of the multi-slot laser 110 in a width approximately equal to the core diameter of the multimode fiber 130, and using a convex lens having a focal length approximately equal to the core diameter of the multimode fiber 130, Or, the exiting beam from the multi-slot laser 110 can be used as a collecting lens only in a rod lens that is parallelized in the plane perpendicular to the active layer, thereby improving the bonding efficiency of the laser light B to the multimode fiber 130.

Further, as shown in FIG. 35, a multi-slot laser 110 having a plurality of (for example, three) light-emitting points can be used, and a plurality of (for example, nine) multi-grooves arranged at equal intervals in the heating region 111 are provided. A composite laser light source that emits a laser array 140 of 110. The plurality of multi-slot lasers 110 are arranged and fixed in the same direction as the arrangement direction of the light-emitting points 110a of the respective wafers.

The composite laser light source includes a laser array 140, a plurality of lens arrays 114 arranged corresponding to the multi-slot lasers 110, and one rod lens 113 disposed between the laser array 140 and the plurality of lens columns 114, A multimode optical fiber 130 and a collecting lens 120 are formed. The lens array 114 is provided with a plurality of microlenses corresponding to the light-emitting points of the multi-slot laser 110.

In the above configuration, the laser light B emitted from the plurality of light-emitting points 110a of the plurality of multi-slot lasers 110 is condensed in a specific direction by the rod lens 113, and is parallelized by the respective microlenses of the lens array 114. . The collimated laser light L is concentrated by the collecting lens 120 and incident on the core 130a of the multimode optical fiber 130. The laser light incident on the core 130a moves in the optical fiber and is combined into one emission.

In addition, an example of another composite wave source is shown. As shown in FIGS. 36A and 36B, the composite-wave laser light source has a heating region 182 having an L-shaped cross section in the optical axis direction on the rectangular heating region 180, and a storage space is formed in the two heating intervals. On the L-shaped heating zone 182, a plurality of light-emitting points (for example, five) are arranged in a row (for example, 2) The multi-slot lasers 110 are arranged and fixed at equal intervals in the same direction as the arrangement direction of the light-emitting points 110a of the respective wafers.

A concave portion is formed on the rectangular heating region 180, and a plurality of (for example, two) multi-slot lasers 110 arranged in a plurality of light-emitting points (for example, five) are arranged on the space side of the heating region 180 at a light-emitting point thereof. The heating areas 182 are arranged on the same vertical plane as the light-emitting points of the laser wafers arranged.

On the laser exit side of the multi-slot laser 110, a collimator lens array 184 in which collimating lenses are arranged for the light-emitting points 110a of the respective wafers is disposed. The collimator lens array 184 is in the direction in which the length direction of each collimating lens is larger than the angle of enlargement of the laser light (the direction of the speed axis), and the direction of the width of each collimating lens is smaller than the angle of expansion of the laser light (late axis). The direction is consistently configured. By linearizing and integrating the collimator lens, the space utilization efficiency of the laser light can be improved, and the high output power of the composite laser light source can be reduced, the number of parts can be reduced, and the cost can be reduced.

Further, on the laser light exit side of the collimator lens array 184, a multimode fiber 130 and a collecting lens 120 for condensing and combining the laser light at the incident end of the multimode fiber 130 are disposed.

In the above configuration, the laser beams B respectively emitted by the plurality of light-emitting points 110a of the plurality of multi-slot lasers 110 arranged on the laser regions 180 and 182 are respectively optically parallelized by the collimator lens array 184. The light is collected by the collecting lens 120 and incident on the core 130a of the multimode optical fiber 130. The laser light incident on the core 130a moves in the optical fiber and is combined into one emission.

The composite wave laser light source described above is arranged in a plurality of stages of a multi-slot laser and arrayed by a collimating lens as described above, and in particular, can be made high in output. Since the composite laser light source can be used to form a higher-intensity fiber array light source or fiber bundle light source, it is particularly suitable to use a fiber light source as a laser light source constituting the pattern forming device of the present invention.

Further, each of the composite laser light sources described above may be housed in a case, and an exit end portion of the multimode optical fiber 130 may be pulled out from the case to constitute a laser module.

In addition, an example is described in which the other end of the multimode fiber of the composite laser light source is combined with a core fiber having the same core diameter and a larger cladding fiber diameter, so that the fiber array light source is brighter. However, for example, a multimode optical fiber having a cladding diameter of 125 μm, 80 μm, 60 μm or the like which is not bonded to other optical fibers at the exit end may be used.

Here, the above-described pattern forming method of the present invention will be further described.

Each of the exposure heads 166 of the scanner 162 emits laser beams B1, B2, B3, B4, and B5 from the GaN-based semiconductor lasers LD1 to LD7 constituting the composite laser light source of the optical fiber array light source 66 in a divergent light state. , B6 and B7, each of which is converted into parallel light by the corresponding collimating lenses 11-17. The laser beams B1 to B7 which are converted into parallel light are collected by the collecting lens 20 and bundled into the incident end faces of the core 30a of the multimode optical fiber 30.

In this example, the condensing optical system is constituted by the collimating lenses 11 to 17 and the condensing lens 20, and the concentrating optical system and the multimode optical fiber 30 constitute a composite optical system. That is, the laser beams B1 to B7 condensed by the condensing lens 20 as described above are incident on the core 30a of the multimode fiber 30. The fiber is moved within the optical fiber and combined into one laser beam B, and is emitted from the optical fiber 31 coupled to the exit end of the multimode fiber 30.

In each of the laser modules, the combination efficiency of the laser beams B1 to B7 to the multimode fiber 30 is 0.85, and when the output power of the GaN semiconductor lasers LD1 to LD7 is 30 mW, the respective fibers 31 arranged in an array are arranged. A composite wave laser beam B of 180 mW (= 30 mW × 0.85 × 7) can be obtained. Therefore, the output of the laser emitting portion 68 in which the six optical fibers 31 are arranged in an array is about 1 W (180 mW × 6).

At the laser exit portion 68 of the fiber array light source 66, the high-intensity light-emitting points are arranged in a line along the main scanning direction. A conventional optical fiber source that combines laser light from a single semiconductor laser into one fiber has a low output, and needs to arrange a plurality of columns to obtain a desired output, and the above composite laser light source has a high output, so even a few Columns such as 1 column can also get the desired output.

For example, a conventional fiber source that combines a semiconductor laser with an optical fiber in a one-to-one relationship typically uses a laser output of about 30 mW (microwatt) as a semiconductor laser, using a core diameter of 50 μm, a cladding diameter of 125 μm, and NA ( numerical aperture) as much as 0.2-mode fiber as the optical fiber, is obtained when it is about 1W (watt) of the output, must be bundled into a multimode optical fiber 48 (8 × 6), the range of the light emitting area of 0.62mm ² (0.675mm × 0.925 mm), the luminance of the laser exit portion 68 is 1.6 × 10 ⁶ (W/m ² ), and the luminance per one optical fiber is 3.2 × 10 ⁶ (W/m ² ).

On the other hand, in the case where the light irradiation means is a mechanism capable of irradiating a composite laser beam, since the output of about 1 W is obtained by six multimode optical fibers, the area of the light-emitting range of the laser emission portion 68 is 0.0081 mm ^{2 .} (0.325 mm × 0.025 mm), the luminance of the laser emitting portion 68 is 123 × 10 ⁶ (W/m ² ), which is about 80 times higher than that of the conventional one. Further, the luminance per one optical fiber is 90 × 10 ⁶ (W/m ² ), which is about 28 times higher than that of the conventional one.

Here, the difference between the conventional exposure head and the depth of focus of the exposure head of the present embodiment will be described with reference to Figs. 37A and 37B. The diameter of the light-emitting region of the bundled fiber light source of the conventional exposure head has a diameter of 0.675 mm in the sub-scanning direction, and the diameter of the light-emitting region of the fiber array light source of the exposure head has a diameter of 0.025 mm. As shown in Fig. 37A, in the conventional exposure head, since the light-emitting range (beam-shaped fiber light source) 1 has a large light-emitting range, the beam angle incident on the DMD 3 becomes large, and as a result, the beam angle incident on the scanning surface 5 becomes large. Therefore, the beam diameter tends to become too thick in the collecting direction (deviation of the focus direction).

On the other hand, as shown in Fig. 37B, the exposure head in the pattern forming apparatus of the present invention has a small beam diameter in the sub-scanning direction of the light-emitting region of the fiber array light source 66, so that the beam angle incident on the DMD 50 through the lens system 67 is small. As a result, the beam angle incident on the scanning surface 56 becomes small. That is, the depth of focus becomes deeper. Further, the DMD is a reflective spatial light modulation element, and the 37A and 37B are diagrams for explaining the optical relationship.

Corresponding to the pattern information of the exposure pattern, a frame is connected to a controller that is not displayed in the figure of the DMD 50, and is directly recorded in a frame memory in the controller. The pattern information is data indicating the density of each pixel constituting the image as a binary value (record with or without dots).

The platform 152 on which the pattern forming material 150 is adsorbed on the surface is moved from the upstream side to the downstream side of the gate 160 at a constant speed along the guide 158 by a driving means not shown. When the platform 152 passes through the gate 160, when the front end of the pattern forming material 150 is detected by the detecting sensor 164 attached to the gate 160, the pattern information recorded in the frame memory is sequentially read in the order of each number. A control signal is generated in each of the exposure heads 166 based on the pattern information read by the data processing unit. Then, the respective switches of the microlenses of the DMD 50 of each of the exposure heads 166 are controlled by the lens drive control unit based on the generated control signals.

When the fiber array light source 66 illuminates the laser light on the DMD 50, the laser light reflected by the microlens of the DMD 50 in the open state is imaged on the exposed surface 56 of the pattern forming material 150 via the lens systems 54, 58. The laser light thus emitted from the fiber array light source 66 is switched by each pixel, and the pattern forming material 150 is exposed in the same number of pixel units (exposure range 168) as the number of pixels used by the DMD 50. Further, the pattern forming material 150 is simultaneously moved at a constant speed with the mesa 152, and the pattern forming material 150 is scanned by the scanner 162 in a direction opposite to the moving direction of the mesa, and a strip-shaped exposure completion region is formed in each of the exposure heads 166. 170.

<Microlens array>

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

The microlens array is not particularly limited, and may be appropriately selected according to the purpose. Aspherical microlens due to aberration caused by distortion of the exit surface in the above pixel portion

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

Hereinafter, the drawings relating to the microlens array, the aperture array, the imaging optical system, and the like described above will be described.

Fig. 13A shows a lens system (imaging optical system) 454 and 458 in which the DMD 50, the light irradiation mechanism 144 that irradiates the DMD 50 with the laser light, and the laser light reflected by the DMD 50 are enlarged, and the respective pixel portions corresponding to the DMD 50 are arranged. The microlens array 472 of the microlenses 474, the microlenses corresponding to the microlens array 472 are provided with an opening array 476 of a plurality of openings 478, and a lens system (imaging optical system) for imaging the laser light passing through the openings to the exposed surface 56. An exposure head composed of 480 and 482.

Here, Fig. 14 shows the result of measuring the flatness of the reflecting surface of the microlens 62 constituting the DMD 50. In the same figure, the height position of the reflecting surface is connected by a contour line, and the distance between the contour lines is 5 nm. Further, the x direction and the y direction shown in the figure are two diagonal directions of the microlens 62, and the microlens 62 is rotated around the rotation axis extending in the y direction as described above. Further, the 15A and 15B drawings each show the displacement of the height of the reflection surface of the microlens 62 along the x direction and the y direction.

As shown in Fig. 14, Fig. 15A and Fig. 15B, there is distortion on the reflecting surface of the microlens 62, especially when observing the central portion of the lens, the distortion of one diagonal direction (y direction) is different. The distortion in the diagonal direction (x direction) is large. Therefore, the microlens array The condensing position of the laser beam B condensed by the microlens 55a of 55 causes a shape distortion problem.

In the pattern forming method of the present invention, in order to prevent the above problem, the microlens 55a of the microlens array 55 has a special shape different from the conventional one. This point is explained in detail below.

FIGS. 16A and 16B show the front shape and the side surface shape of the entire microlens array 55 in detail. In these figures, the dimensions of the respective portions of the microlens array 55 are also described, and the units are in mm. In the pattern forming method of the present invention, the 1024 x 256 columns of microlenses 62 of the DMD 50 are driven as described above with reference to Fig. 4, and the microlens array 55 is arranged 1024 columns in the horizontal direction and the vertical direction, respectively. And 256 rows of microlenses 55a are formed. Further, in Fig. 16A, the side-by-side order of the microlenses 55 is denoted by j in the lateral direction and denoted by k in the longitudinal direction.

Further, the 17A and 17B drawings each show the front shape and the side surface shape of one microlens 55a in the microlens array 55. Further, the contour line of the microlens 55a is shown together in Fig. 17A. The end surface of the light exit surface of each microlens 55a is an aspherical shape for correcting aberration due to distortion of the reflecting surface of the microlens 62. More specifically, the microlens 55a is a toric lens having a curvature radius Rx=−0.125 mm corresponding to the x-direction optical and a curvature radius Ry=−0.1 mm corresponding to the y direction.

Therefore, the condensed state of the laser light B in the cross section parallel to the x direction and the y direction is approximately as shown in Figs. 18A and 18B. That is, in a section parallel to the x direction and a section parallel to the y direction In the inner comparison, the microlens 55a in the latter cross section has a small radius of curvature and a short focal length.

When the microlens 55a has the above shape, the beam diameter in the vicinity of the condensing position (focus position) of the microlens 55a is calculated by computer simulation as shown in Figs. 19A to D. Further, for comparison, when the microlens 55a has a spherical shape having a radius of curvature Rx = Ry = -0.1 mm, the results of performing the same simulation calculation are as shown in Figs. 20A to D. Further, the value of z in each figure is such that the evaluation position of the focus direction of the microlens 55a is expressed by the distance from the beam exit surface of the microlens 55a.

Further, the surface shape of the microlens 55a used in the above simulation calculation is calculated by the following calculation formula.

In the above calculation formula, Cx represents the curvature in the x direction (=1/Rx), Cy represents the curvature in the y direction (=1/Ry), and X represents the distance from the optical axis O of the lens in the x direction, and the Y system The distance from the optical axis O of the lens in the y direction.

Comparing FIGS. 19A to D and 20A to D, the pattern forming method of the present invention has a small focal length in the cross section parallel to the x direction in which the microlens 55a is parallel to the y direction. The curved lens suppresses the distortion of the shape of the beam near the condensing position. Thereby, an image having no distortion and higher definition can be exposed on the pattern forming material 150. Further, in the present embodiment shown in Figs. 19A to D, it is understood that the range in which the beam diameter is small is wide, that is, the depth of focus is large.

Further, regarding the magnitude relationship between the distortion of the central portion of the microlens 62 in the x direction and the y direction, contrary to the above, the focal length in the cross section parallel to the x direction is smaller than the focal length in the cross section parallel to the y direction. When the toric lens constitutes the microlens, the undistorted, finer image can be exposed to the patterning material 150 in the same manner.

Further, the array of openings 59 arranged in the vicinity of the condensing position of the microlens array 55 is arranged such that only light passing through the corresponding microlens 55a is incident on each opening 59a. That is, by providing the opening array 59, it is possible to prevent light from the adjacent microlenses 55a not corresponding thereto from being incident on the respective openings 59a, and the extinction ratio can be improved.

When the diameter of the opening 59a of the opening array 59 provided for the above purpose is a small value, the effect of suppressing the distortion of the beam shape in the condensing position of the microlens 55a can be obtained. However, this increases the amount of light blocked by the aperture array 59 and reduces the light use efficiency. On the other hand, when the microlens 55a has an aspherical shape, since the light is not blocked, the light use efficiency can be ensured to be high.

Further, in the pattern forming method of the present invention, the microlens 55a may have a 2-dimensional aspherical shape or an aspherical shape of a higher order (4th order, 6th order...). By adopting the above-described high-dimensional aspherical shape, a more high-definition beam shape can be obtained.

Further, in the embodiment described above, the end surface on the light exit side of the microlens 55a is an aspherical surface (toric surface), and the microlens array is formed by one of the two light passage end faces being a spherical surface, and the other is a toric microlens. The same effects as in the above embodiment can be obtained.

Further, in the above-described embodiment, the microlens 55a of the microlens array 55 is an aspherical shape for correcting aberrations due to distortion of the reflecting surface of the microlens 62, but only the microlenses constituting the microlens array. The same effect can be obtained by using the refractive index distribution for correcting the aberration due to the distortion of the reflecting surface of the microlens 62 instead of using the aspherical shape.

An example of the microlens 155a is shown in Figs. 22A and 22B. The front surface shape and the side surface shape of the microlens 155a are shown in each of Figs. 22A and 22B. As shown in the figure, the outer shape of the microlens 155a is a parallel plate shape. Moreover, the x and y directions in the same figure are as described above.

Further, FIGS. 23A and 23B schematically show the condensed state of the laser beam B in the cross section parallel to the x direction and the y direction by the microlens 155a. The microlens 155a has a refractive index distribution which gradually increases from the optical axis O toward the outside, and the broken line shown in the microlens 155a in the same figure indicates a position which changes from the optical axis O by a certain equal pitch. As shown in the figure, in the cross section parallel to the x direction and the cross section parallel to the y direction, the refractive index change ratio of the microlens 155a in the latter section is large, and the focal length is short. The same effect as the above-described microlens array 55 can be obtained by using the microlens array composed of the refractive index distribution type lens.

Further, in the microlens having the aspherical surface shape of the microlens 55a shown in FIGS. 17 and 18, the refractive index distribution as described above is simultaneously obtained, and both of the surface shape and the refractive index distribution can be corrected. The aberration caused by the distortion of the reflecting surface of the microlens 62.

Further, in the above-described embodiment, the aberration due to the distortion of the reflecting surface of the microlens 62 constituting the DMD 50 can be corrected, but in the pattern forming method of the present invention using the spatial light modulation element other than the DMD, even the space When there is distortion on the surface of the pixel portion of the light modulation element, the aberration of the distortion can be corrected by using the present invention, and the shape of the beam can be prevented from being deformed.

Next, the above imaging optical system will be further explained.

When the exposure head is irradiated with the laser beam by the light irradiation means 144, the cross-sectional area of the beam line reflected by the DMD 50 in the opening direction is expanded several times (for example, twice) via the lens systems 454 and 458. The expanded laser light is concentrated by the respective microlenses of the microlens array 472 corresponding to the respective pixel portions of the DMD 50 through the openings corresponding to the array of openings 476. The exposed laser light is imaged onto the exposed surface 56 via lens systems 480, 482.

In the imaging optical system, the laser light reflected by the DMD 50 is projected on the exposure surface 56 by being expanded by several times by the enlarged lenses 454 and 458, so that the entire image range is expanded. At this time, if the microlens array 472 and the aperture array 476 are not disposed, as shown in FIG. 13B, the pixel size (dot size) of each beam spot BS projected on the exposure surface 56 corresponds to the exposure range 468. In the case of the size, the MTF (modulation transfer function) characteristic indicating the sharpness of the exposure range 468 is lowered.

On the other hand, in the case where the microlens array 472 and the aperture array 476 are disposed, the laser light reflected by the DMD 50 is concentrated by the respective microlenses of the microlens array 472 corresponding to the respective pixel portions of the DMD 50. Thereby, as shown in FIG. 13C, even when the exposure range is enlarged, each beam spot BS The dot size can still be reduced to a desired size (for example, 10 μm × 10 μm) to prevent a decrease in MTF characteristics and to perform high-definition exposure. Further, the inclination of the exposure range 468 is such that the DMD 50 is obliquely arranged so that there is no gap between the pixels.

Moreover, even if the light beam is thickened due to the aberration of the microlens, the beam size can be shaped by the aperture array on the exposed surface 56 to a certain size, while the aperture array is provided by corresponding to each pixel. To prevent crosstalk between adjacent pixels.

Further, by using the high-intensity light source in the light irradiation means 144, since the angle of the light beam incident on the respective lenticular surfaces of the microlens array 472 from the lens 458 becomes small, it is possible to prevent the light beams of the adjacent pixels from being incident. That is, a high extinction ratio can be achieved.

<Other optical systems>

In the pattern forming method of the present invention, other optical systems suitably selected from conventional optical systems, such as a light amount distribution correcting optical system formed by a pair of combined lenses, and the like can be used in combination.

In the light-quantity-dispensing optical system, when the beam width of the peripheral portion is closer to the incident side than the beam width near the central portion of the optical axis, the beam width of each of the emission positions is smaller and smaller at the emission side, so that the self-light is irradiated. When the parallel beam of the mechanism is irradiated to the DMD, the light quantity distribution on the illuminated surface is corrected to be approximately uniform. In the following, the light quantity distribution correcting optical system will be described with reference to the drawings.

First, as shown in Fig. 24A, the case where the incident beam and the outgoing beam are the same for the entire beam width (full beam width) H0, H1 will be described. Moreover, in Fig. 24A, the parts indicated by the symbols 51 and 52 are The incident surface and the outgoing surface of the light quantity distribution correcting optical system are imaginarily displayed.

In the light amount distribution correction optical system, the light beam incident on the center portion close to the optical axis Z1 is the same as the beam widths h0 and h1 of the light beam incident on the peripheral portion (h0=h1). In the light quantity distribution correcting optical system, for the light of the same beam width h0 and h1 on the incident side, the incident beam of the central portion expands the beam width h0, and conversely, the incident beam of the peripheral portion reduces the beam width h1. effect. In other words, the width h10 of the outgoing beam of the central portion and the width h11 of the outgoing beam of the peripheral portion, h11 < h10. When the ratio of the beam width is expressed as a ratio of the beam width, the ratio of the beam width of the peripheral portion to the beam width at the center of the emission side is smaller than that of the incident side (h1/h0 = 1). (h11/h10) <1).

By changing the beam width, the light beam at the central portion where the light amount distribution is increased is generally generated in the peripheral portion where the amount of light is insufficient, and the light amount distribution of the illuminated surface is approximately equalized without reducing the overall light use efficiency. The degree of homogenization, for example, the light amount unevenness within the effective range is within 30%, preferably within 20%.

The action and effect of the light amount distribution correcting optical system are the same when the entire beam widths of the incident side and the exit side are changed (Fig. 24B and Fig. 24C).

Fig. 24B shows a case where the beam width H0 of the entire incident side is reduced to the width H2 and is emitted (H0 > H2). In this case, the light amount distribution correction optical system has the same beam width h0 and h1 on the incident side, and the beam width h10 at the center of the emission side is compared with the peripheral portion. Larger, on the other hand, the beam width h11 of the peripheral portion is smaller than that of the central portion. When the reduction ratio of the light beam is considered, the reduction ratio of the incident light beam at the center portion is smaller than that of the peripheral portion, and the reduction ratio of the incident light beam at the peripheral portion is larger than that of the central portion. At this time, the ratio "h11/h10" of the beam width of the peripheral portion to the beam width of the center portion is smaller than that of the incident side (h1/h0=1) ((h11/h10)<1) .

Fig. 24C shows the case where the entire beam width H0 on the incident side is increased to the width H3 and incident (H0 < H3). In this case, the light amount distribution correction optical system has the same beam width h0 and h1 on the incident side, and the beam width h10 at the center of the emission side is larger than that of the peripheral portion, and the beam width h11 of the peripheral portion is opposite. Smaller effect compared to the central part. When the expansion ratio of the light beam is considered, the enlargement rate of the incident light beam at the center portion is larger than that of the peripheral portion, and the enlargement rate of the incident light beam at the peripheral portion is smaller than that of the central portion. At this time, the ratio "h11/h10" of the beam width of the peripheral portion to the beam width of the center portion is smaller than that of the incident side (h1/h0 = 1) ((h11/h10)<1) .

As described above, in the light amount distribution correcting optical system, since the beam width at each of the emission positions is changed, the beam width close to the central portion of the optical axis Z1 is smaller when the ratio of the beam width of the peripheral portion is smaller than that on the incident side. Therefore, the light having the same beam width on the incident side has a larger beam width at the center of the exit side than when the peripheral portion is larger, and the beam width at the peripheral portion is smaller than that of the center portion. Thereby, the light beam at the center portion can be generated in the peripheral portion, and the beam cross section in which the light amount distribution is approximately uniform can be formed without reducing the light use efficiency of the entire optical system.

Next, an example of specific lens data as a pair of combined lenses used as the above-described light amount distribution correction optical system is shown. This example shows lens data when the light-irradiating light source has a Gaussian distribution in the cross section of the outgoing light beam when the light-emitting means is a laser array light source. Moreover, when one semiconductor laser is connected to the incident end of the single mode fiber, the light quantity distribution of the light beam emitted from the fiber is Gaussian. The pattern forming method of the present invention can also be used in this case. Further, when the core diameter of the multimode optical fiber is small, the amount of light near the central portion of the optical axis such as the vicinity of the configuration of the single mode fiber can be used when the amount of light is larger than that of the peripheral portion.

The basic lens data is shown in Table 1 below.

As can be seen from Table 1, a pair of combined lenses are composed of two rotationally symmetrical aspherical lenses. When the light incident side surface of the first lens disposed on the light incident side is the first surface, and the light emitting side surface is the second surface, the first surface has an aspherical shape. Further, when the light incident side surface of the second lens disposed on the light exit side is the third surface, and the light emitting surface is the fourth surface, the fourth surface has an aspherical shape.

In Table 1, the surface number Si indicates the number of the i-number (i=1 to 4) plane, the bending radius ri is the bending radius of the i-numbered surface, and the surface spacing di is the i-numbered surface and the i+1-numbered surface. The area spacing on the optical axis. The unit of the face spacing di value is micrometer (mm). The refractive index Ni represents a value of a refractive index for a wavelength of 405 nm of an optical element having an i-numbered surface.

Table 2 below shows aspherical data of the first surface and the fourth surface.

The data of the above aspherical surface is represented by a coefficient of the following formula (A) indicating an aspherical shape.

In the above formula (A), each coefficient is specifically defined as follows.

Z: the length of the vertical line (mm) from the point on the aspheric surface from the height ρ position of the optical axis to the junction plane of the aspherical vertex (the plane perpendicular to the optical axis)

ρ: distance from the optical axis (mm)

K: Cone coefficient

C: paraxial curvature (1/r, r: paraxial radius of curvature)

Ai: the aspheric coefficient of the i-th (i=3~10)

In the numerical values shown in Table 2, the symbol "E" indicates the "index" of the subsequent value from the base 10, and the numerical value indicated by the exponential function at the base of 10 indicates the multiplication of the values before "E". For example, when "1.0E-02", it means "1.0×10 ^-2 ".

Fig. 26 is a view showing the light amount distribution of the illumination light obtained by the pair of combined lenses shown in the above Tables 1 and 2. Here, the horizontal axis represents the coordinates from the optical axis, and the vertical axis represents the light amount ratio (%). Moreover, for comparison, Fig. 25 shows the light amount distribution (Gaussian distribution) of the illumination light when no correction is performed. As can be seen from Figs. 25 and 26, when the optical system is corrected by the light amount distribution correction, a substantially uniform light amount distribution can be obtained as compared with the case where no correction is performed. Thereby, uneven exposure can be performed with uniform laser light without lowering the light use efficiency.

[other steps]

The other steps described above are not particularly limited, and may be appropriately selected from the steps in the formation of a conventional pattern, 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 and curing the exposure range of the photosensitive layer, thereby removing the uncured region to develop a pattern.

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

The development mechanism is not particularly limited as long as it is developed using a developing liquid, and may be appropriately selected according to the purpose, for example, a mechanism for spraying the developing liquid and a mechanism for applying the developing liquid. a mechanism immersed in the above developing solution or the like. These may be used alone or in combination of two or more.

Further, the developing unit may include a developing liquid exchange mechanism for exchanging the developing liquid, a developing liquid supply unit for supplying the developing liquid, and the like.

The above-mentioned developing liquid system is not particularly limited, and may be appropriately selected according to the purpose, and may be, for example, an alkaline liquid, an aqueous developing solution, or an organic solvent. Among them, a weakly alkaline aqueous solution is preferable. The alkali component of the weakly alkaline liquid is, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, potassium phosphate, or coke. Potassium phosphate, borax, and the like.

The pH of the above weakly alkaline aqueous solution is, for example, preferably from about 8 to 12, more preferably from about 9 to 11. The weakly basic 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 developing solution can be appropriately selected in combination with the developing property of the photosensitive layer, and is preferably, for example, about 25 ° C to 40 ° C.

The above-mentioned developing solution may be used in combination with a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diamethylenetrimonium, triamethyleneamine, morpholine, triethanolamine, etc.), Or an organic solvent that promotes imaging (such as alcohols, ketones, esters, ethers, guanamines, lactones) and many more. Further, the developing solution may be a water-based developing solution in which water or an aqueous alkali solution is mixed with an organic solvent, or may be a single organic solvent.

The etching step can be carried out by a method appropriately selected from a conventional etching treatment method.

The etching liquid used for the etching treatment is not particularly limited, and may be appropriately selected according to the purpose. For example, when the metal layer is formed of copper, it is a copper chloride solution, a ferric chloride solution, an alkali etching solution, or As the hydrogen peroxide-based etching solution or the like, it is preferable to use a ferric chloride solution among the etching factors.

After the etching process by the etching step described above, the pattern is removed, and a permanent pattern can be formed on the surface of the substrate.

The permanent pattern is not particularly limited and may be appropriately selected depending on the purpose, and for example, a wiring pattern or the like is suitable.

The plating step can be carried out by an appropriate method selected from a conventional plating treatment.

The plating treatment is, for example, copper plating such as copper sulfate plating or copper pyrophosphate plating, welding plating such as rapid solder plating, Watt bath (nickel sulfate-nickel chloride) plating, and nickel sulfonate. Gold plating, hard gold plating, soft gold plating, etc.

After the plating treatment by the plating step described above, the pattern is removed, and an unnecessary portion is removed by an etching treatment or the like as needed, and a permanent pattern can be formed on the surface of the substrate.

[Manufacturing method of printed wiring board and color filter]

The above pattern forming method of the present invention can be used for the manufacture of printed wiring boards, particularly with through holes or via holes (via The manufacture of printed wiring boards for holes in holes and the like, and the manufacture of color filters. Hereinafter, an example of a method of manufacturing a printed wiring board and a method of manufacturing a color filter using the pattern forming method of the present invention will be described.

-Manufacturing method of printed wiring board -

In particular, the method of producing a printed wiring board having a hole portion such as a through hole or a via hole can be made by using the pattern forming material on the printed wiring board forming substrate having the hole portion as the substrate. The photosensitive layer is formed by laminating the positional relationship on the substrate side, and (2) is irradiated with light in a desired region on the side opposite to the substrate of the laminate to harden the photosensitive layer, and (3) is removed from the laminate. The support, the buffer layer, and the barrier layer in the pattern forming material, and (4) developing the photosensitive layer of the laminate, and removing the uncured portion of the laminate to form a pattern.

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

Then, in order to obtain a printed wiring board, the above-described formed pattern can be used to perform etching or plating treatment on the printed wiring board forming substrate (for example, conventional subtraction or addition (such as semi-addition, full addition). In the above, in order to form a printed wiring board by a masking process which is advantageous for industrial use, the above-described subtraction method is preferable. After the above treatment, the cured resin remaining on the printed wiring board forming substrate is peeled off, and In the case of subtraction, a desired printed wiring board can be produced by etching the copper thin film portion after peeling. Further, the multilayer printed wiring board can be produced in the same manner as in the above-described method of manufacturing the printed wiring board.

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

First, a substrate for forming a printed wiring board having a through hole and having a surface covered with a metal plating layer is prepared. In the substrate for forming a printed wiring board, for example, a substrate on which a copper-plated layer is formed on an insulating substrate such as a copper-area substrate or a glass-epoxy resin, or an interlayer insulating film is formed on the substrate to form a copper-plated layer. Substrate (stacked substrate).

When the protective layer is provided on the pattern-shaped layer material, the protective film is peeled off and pressed by a pressure roller to connect the photosensitive layer of the pattern forming material to the surface of the substrate for forming a printed wiring board (layering step) ). Thereby, a laminate having the above-described substrate for forming a printed wiring board and a laminate is provided in this order.

The lamination 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 in this case, heating (60 to 140 ° C) good.

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

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

Further, the substrate for forming a printed wiring board may be heated in advance or laminated under reduced pressure.

In the formation of the laminated body, the pattern forming material may be laminated on the printed wiring board forming substrate, or a photosensitive resin composition solution for producing the pattern forming material may be directly applied to the printed wiring board. On the surface of the substrate and dried, a photosensitive layer, a barrier layer, a buffer layer, and a support are laminated on the substrate for forming a printed wiring board.

Then, light is irradiated from the surface opposite to the substrate of the above laminated body to harden the photosensitive layer. Further, at this time, if 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 point in time, when the support, the buffer layer, and the barrier layer have not been peeled off, the support, the buffer layer, and the barrier layer are peeled off from the laminate (peeling step).

Then, the uncured region of the photosensitive layer on the substrate for forming a printed wiring board is dissolved and removed by an appropriate developing solution to form a pattern of the hardened layer for forming a wiring pattern and the hardened layer for protecting the metal layer of the via hole, and A metal layer is exposed on the surface of the printed wiring board forming substrate (developing step).

Further, it is necessary to carry out a treatment for promoting the hardening reaction of the hardened portion by post-heat treatment or post-exposure treatment in the case of post-development. The development process can be either the wet development method described above or the dry development method.

Next, the metal layer exposed on the surface of the printed wiring board forming substrate is dissolved and removed by an etching solution (etching step). Since the opening of the through hole is covered with the cured resin composition (masking film), the etching liquid does not corrode the metal plating in the through hole, and the metal plating of the through hole remains in a specific shape. Thereby, a wiring pattern can be formed on the printed wiring board forming substrate.

The etching liquid is not particularly limited and may be appropriately selected according to the purpose. For example, in the case where the metal layer is formed of copper, it is a copper chloride solution, a ferric chloride solution, an alkali etching solution, or a hydrogen peroxide system. The etching solution or the like is preferably a ferric chloride solution among the etching factors.

Then, the hardened layer (hardened material removing step) which is a release sheet is removed from the printed wiring board forming substrate by a strong alkali aqueous solution or the like.

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

The pH of the above aqueous strong alkali solution is, for example, preferably from about 12 to 14, more preferably from about 13 to about 14.

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

Further, the printed wiring board may be a printed wiring board having a plurality of layers.

Furthermore, the pattern forming material may be used not only in the etching process but also in the plating process. The plating method is, for example, copper plating such as copper sulfate plating or copper pyrophosphate plating, solder plating such as rapid solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfonate, and the like. Gold plating such as hard gold plating or soft gold plating.

-Manufacturing method of color filter -

The photosensitive layer of the pattern forming material of the present invention is bonded to a substrate such as a glass substrate, and when the support forming body, the buffer layer, and the barrier layer are peeled off from the pattern forming material, the support (film) with static electricity causes the human body to feel There is a problem that dust or the like adheres to an uncomfortable contact inductance or a support body with static electricity. Therefore, it is preferable to provide a conductive layer on the support and to perform a process of making the support itself conductive. Further, when the conductive layer is provided on the support opposite to the buffer layer, it is preferable to provide a hydrophobic polymer layer in order to improve the scratch resistance.

Then, a pattern forming material having a red photosensitive layer for coloring each of the photosensitive layers by red, green, blue, and black, a pattern forming material having a green photosensitive layer, and a pattern forming material having a blue photosensitive layer, A pattern forming material of a black photosensitive layer. The pattern forming material having the red photosensitive layer for red pixels is used, and the red photosensitive layer is formed into a laminate on the surface of the substrate, and then exposed to an image pattern to be developed to form a red pixel. After the red pixel is formed, the above laminated body is heated to harden the uncured portion. The green and blue pixels are also performed in the same manner to form each pixel.

The layered body may be formed by laminating the pattern forming material on the glass substrate, or may directly apply a solution of the photosensitive resin composition for producing the pattern forming material to the surface of the glass substrate and dry it. On the glass substrate, a photosensitive layer, a barrier layer, a buffer layer, and a support are laminated. Further, when three kinds of pixels such as red, green, and blue are arranged, they can be arranged in a mosaic type, a triangle type, or a four-pixel configuration type.

A pattern forming material having the above-described black photosensitive layer is laminated on the surface on which the above-mentioned pixel is formed, and a back side exposure and development are performed from the side where no pixel is formed to form a black matrix. The uncured portion can be hardened by heating the laminate in which the black matrix is formed to produce a color filter.

According to the pattern forming method of the present invention, since the pattern forming material of the present invention is used, permanent pattern formation, color filter, pillar, rib, spacer, and partition wall for forming various patterns, wiring patterns, and the like can be used. Manufacturing of liquid crystal structural parts, holograms, etc. The manufacture of micromachines, verification, etc., is particularly suitable for use in high-definition wiring pattern formation. Since the pattern forming apparatus of the present invention includes the pattern forming material of the present invention, it can be used for permanent pattern formation such as various pattern formation and wiring patterns, color filters, pillars, ribs, spacers, partition walls, and the like. The manufacture of liquid crystal structural members, the manufacture of holograms, micromachines, and verification are particularly suitable for use in high-definition wiring pattern formation.

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto.

(Example 1)

On the polyethylene terephthalate film having a thickness of 20 μm as the support, a photosensitive resin composition solution composed of the following composition was applied and dried to form a photosensitive layer having a thickness of 15 μm, followed by the photosensitive layer. A 20 μm-thick polyethylene film as the above protective film was laminated thereon to fabricate the above-mentioned pattern forming material.

[Composition of photosensitive resin composition solution]

Further, the I/O value of the above-mentioned methacrylic acid/methyl methacrylate/styrene copolymer (copolymer composition (mass ratio): 24/46/30) as the above-mentioned binder is 0.645 when calculated as described above. .

In the structural formula (70), m + n = 10. Further, the structural formula (70) is an example of a compound represented by the above structural formula (35).

As the substrate, a copper-area laminate (without via holes and a copper thickness of 12 μm) which has been ground, washed, and dried is prepared, and the photosensitive layer of the pattern forming material is bonded to the surface of the copper-area laminate. In the form of a copper-area laminate, the protective film of the pattern forming material is peeled off, and a layering machine (MODEL8B-720-PH, manufactured by Dacheng Laminator Co., Ltd.) is laminated to prepare the copper-area laminate and the photosensitive layer. The laminate in which the support is laminated in order.

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

With respect to the laminated body produced as described above, the developability, the resolution, the etching property, the peeling property of the cured pattern after etching, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

<developmentality>

The support was peeled off from the laminate, and a 1% by mass aqueous solution of sodium carbonate at 30 ° C was sprayed at a pressure of 0.15 MPa on the entire surface of the photosensitive layer on the copper area layer, and the spraying from the sodium carbonate aqueous solution was started until the copper area was measured. The time required for the above-mentioned photosensitive layer on the laminate to be dissolved and removed is regarded as the shortest development time. The shorter the short development time, the better the imaging performance.

As a result, the above shortest development time is 10 seconds.

<resolution>

(1) Determination of sensitivity

In the photosensitive layer of the pattern forming material in the laminate, a pattern forming device having a 405 nm laser light source is used as the light irradiation means from the support side, and the irradiation is performed at 0.1 1/ ² /cm ² at intervals of 2 ^1/2 . The light of different light energies up to 100 mJ/cm ^{2 is} exposed to light to harden a part of the photosensitive layer. After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and the sodium carbonate aqueous solution (30 ° C, 1 mass %) was sprayed on the entire surface of the photosensitive layer on the copper area layer layer at a pressure of 0.15 MPa. Further, it was sprayed twice as long as the shortest development time obtained by the above evaluation of development, 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 irradiation of light and the thickness of the hardened layer is plotted to obtain a sensitivity curve. According to the sensitivity curve thus obtained, the light energy when the thickness of the hardened region became 15 μm was used as the light energy required to cure the photosensitive layer. As a result, the light energy required for hardening the above photosensitive layer was 3 mJ/cm ² . Further, the pattern forming apparatus includes a light modulation mechanism formed by the DMD, and includes the pattern forming material.

(2) Determination of resolution

The laminate was prepared under the same conditions and conditions as those for evaluation of the above-mentioned developability, and allowed to stand at room temperature (23 ° C, 55% RH) for 10 minutes. From the above-mentioned support body of the obtained laminated body, the above-described pattern forming apparatus was used to expose the line widths of 5 μm to 20 μm in line width/gap=1/1 and 1 μm on the scale, and the line width was 20 μm to 50 μm on the scale of 5 μm. The exposure of each line width up to now. The exposure amount at this time is the light energy required for curing the photosensitive layer of the pattern forming material measured by the above-described sensitivity measurement (1). After standing at room temperature for 10 minutes, the support was peeled off from the above laminated body. On the entire surface of the photosensitive layer on the copper area layer, an aqueous solution of sodium carbonate (30 ° C, 1% by mass) was sprayed at a pressure of 0.15 MPa as the above-mentioned developing solution, and the shortest development time obtained by the above (1) was obtained. Spray twice to dissolve and remove the unhardened area. The surface of the copper-area laminate having the cured resin pattern thus obtained was observed with an optical microlens, and the minimum line width without abnormalities such as clogging or waviness on the line of the cured resin pattern was measured and used as the resolution. The smaller the resolution coefficient value, the better.

<etching property>

Using a laminate having a pattern formed by the above-described resolution measurement, a ferric chloride etchant (iron chloride-containing etching solution, 40° wave beauty) was applied at 0.25 MPa on the surface of the copper-area laminate exposed to the laminate. (Baume) The liquid temperature was 40 ° C. and sprayed for 36 seconds, and the copper layer which was not exposed in the exposed region of the hardened layer was removed by etching to carry out an etching treatment. Then, by spraying a 2% by mass aqueous sodium hydroxide solution to remove the pattern formed as described above, a printed wiring board having a copper layer wiring pattern as the permanent pattern on the surface thereof is prepared. The wiring pattern on the printed wiring board was observed with an optical microlens, and the minimum line width of the wiring pattern was measured. The smaller the minimum line width, the higher the fine wiring pattern can be obtained, and the more excellent the etching property.

<Removability of hardened pattern>

In the photosensitive layer of the pattern forming material in the laminate, a pattern forming device having a 405 nm laser light source is used as the light irradiation means from the support side, and light of 10 mJ/cm ² of light energy is irradiated for overall exposure. The photosensitive layer is cured. After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and under the same conditions as the above evaluation method, the photosensitive layer of the laminate was sprayed with a sodium carbonate aqueous solution in a hardened pattern. Like, wash it and then dry it. The thus obtained copper-area layer with a hardened pattern was placed in a 3 mass% aqueous sodium hydroxide solution for immersion. The time (peeling time) required from the start of the immersion of the copper-area laminate having the above-described hardened pattern to the completion of the removal of the cured resin pattern on the copper-area layer was evaluated by the following criteria. The shorter the peeling time, the better the peelability.

- Evaluation benchmark -

○. . . Stripping time is less than 60 seconds

△. . . Stripping time is 60~300 seconds

×. . . Stripping time is more than 300 seconds

<shielding>

A laminate for the evaluation of the shielding property was prepared in the same manner as the laminate described above, except that the copper-area laminate in the laminate was changed to a copper-area laminate having 200 through-holes having a diameter of 2 mm. Leave at °C for 5 minutes under conditions of °C and relative humidity of 55%. Next, the above-described pattern forming apparatus is used to expose the entire photosensitive layer in the laminated body to the support of the laminated body prepared as described above. The exposure amount at this time is the light energy required for the hardening of the photosensitive layer of the pattern forming material measured in (2) of the above-described resolution evaluation. After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and the aqueous solution of sodium carbonate was sprayed at a pressure of 0.15 MPa on the entire surface of the photosensitive layer on the copper-area layer (30 ° C, 1% by mass). It is sprayed as the above-mentioned developing solution and twice as long as the shortest developing time obtained in (1) of the above evaluation of the resolution. The hardened layer (masking film) formed on the opening of the through hole in the copper area layer plate thus obtained was observed by a microscope to have defects such as peeling or breakage, and the incidence of defects was calculated.

<exposure speed>

Using the pattern forming apparatus described above, the relative moving speed of the exposed light and the photosensitive layer is changed, and the formation speed of a general wiring pattern is obtained. The exposure is performed on the support layer side of the pattern forming material in the laminated body prepared as described above. Moreover, the faster the setting speed is, the more efficiently the pattern is formed.

(Example 2)

The above methacrylic acid/methyl methacrylate/ in the above-mentioned photosensitive resin composition solution as the above-mentioned binder in Example 1. Styrene copolymer (copolymer composition ratio (mass ratio): 24/46/30) was changed to methacrylic acid/styrene copolymer (copolymer composition ratio (mass ratio): 29/71, mass average molecular weight: 63,100, A pattern forming material and a laminate were produced in the same manner as in Example 1 except that the acid value was 189 (mgKOH/g).

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

In addition, the I/O value of the above-mentioned methacrylic acid/styrene copolymer (copolymer composition ratio (mass ratio): 29/71) as the above-mentioned binder is 0.447 when calculated as described above, and the shortest development time is For 12 seconds, the light energy required for the hardening of the photosensitive layer was 3 mJ/cm ² .

(Reference Example 3)

The above methacrylic acid/methyl methacrylate/styrene copolymer (copolymer composition ratio (mass ratio): 24/46/ in the above-mentioned photosensitive resin composition solution as the above-mentioned binder in Example 1. 30) The same procedure as in Example 1 except that the composition of the acrylic acid/styrene copolymer (copolymer composition ratio (mass ratio): 21/79, mass average molecular weight: 30,000, acid value: 137 (mgKOH/g)) was changed. A pattern forming material and a laminate are produced.

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

In addition, the I/O value of the above-mentioned methacrylic acid/styrene copolymer (copolymer composition ratio (mass ratio): 21/79) as the above-mentioned binder is 0.340 as calculated as described above, and the shortest development time is For 15 seconds, the light energy required for the hardening of the photosensitive layer was 3 mJ/cm ² .

(Example 4)

The above methacrylic acid/methyl methacrylate/styrene copolymer (copolymer composition ratio (mass ratio): 24/46/ in the above-mentioned photosensitive resin composition solution as the above-mentioned binder in Example 1. 30) Change to methacrylic acid / methyl methacrylate / styrene / 2-ethylhexyl methacrylate copolymer (copolymer composition ratio (mass ratio): 36/5/45/14, mass average molecular weight: A pattern forming material and a laminate were produced in the same manner as in Example 1 except that 82,000 and an acid value: 235 (mgKOH/g).

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

Further, as the above-mentioned binder, the above-mentioned methacrylic acid/methyl methacrylate/styrene/2-ethylhexyl methacrylate copolymer (copolymer composition ratio (mass ratio): 36/5/45/14) The I/O value is 0.614 when calculated as described above, the shortest development time is 10 seconds, and the light energy required for curing the photosensitive layer is 3 mJ/cm ² .

(Reference example 5)

The above methacrylic acid/methyl methacrylate/styrene copolymer (copolymer composition ratio (mass ratio): 24/46/ in the above-mentioned photosensitive resin composition solution as the above-mentioned binder in Example 1. 30) changed to a methacrylic acid/styrene/methyl acrylate copolymer (copolymer composition ratio (mass ratio): 22/58/20, mass average molecular weight: 35,000, acid value: 143 (mgKOH/g)), A pattern forming material and a laminate were produced in the same manner as in Example 1.

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

Further, the I/O value of the above methacrylic acid/styrene/methyl acrylate copolymer (copolymer composition ratio (mass ratio): 22/58/20) as the above-mentioned binder was 0.473 as calculated as described above. The shortest development time is 11 seconds, and the light energy required for the hardening of the photosensitive layer is 3 mJ/cm ² .

(Example 6)

The above methacrylic acid/methyl methacrylate/styrene copolymer (copolymer composition ratio (mass ratio): 24/46/ in the above-mentioned photosensitive resin composition solution as the above-mentioned binder in Example 1. 30) Change to methacrylic acid/methyl methacrylate/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/25/37/13, mass average molecular weight: A pattern forming material and a laminate were produced in the same manner as in Example 1 except that the acid value was 1,500 (mgKOH/g).

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

Further, as the above-mentioned binder, the above-mentioned methacrylic acid/methyl methacrylate/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/25/37/) The I/O value was 0.561 as calculated above, the shortest development time was 10 seconds, and the light energy required for curing the photosensitive layer was 3 mJ/cm ² .

(Example 7)

The above methacrylic acid/methyl methacrylate/styrene copolymer (copolymer composition ratio (mass ratio): 24/46/ in the above-mentioned photosensitive resin composition solution as the above-mentioned binder in Example 1. 30) Change to methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 29/19/52, mass average molecular weight: 61,800, acid value: 189 (mgKOH/g)) In the same manner as in Example 1, a pattern forming material and a laminate were produced.

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

In addition, the I/O value of the above-mentioned methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 29/19/52) as the above-mentioned binder is calculated as described above. It is 0.552, the shortest development time is 10 seconds, and the light energy required for the hardening of the photosensitive layer is 3 mJ/cm ² .

(Example 8)

The above methacrylic acid/methyl methacrylate/styrene copolymer (copolymer composition ratio (mass ratio): 24/46/ in the above-mentioned photosensitive resin composition solution as the above-mentioned binder in Example 1. 30) Change to methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 31/5/64, mass average molecular weight: 46,400, acid value: 202 (mgKOH/g)) In the same manner as in Example 1, a pattern forming material and a laminate were produced.

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

In addition, the I/O value of the above-mentioned methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 31/5/64) as the above-mentioned binder is calculated as described above. It is 0.501, the shortest development time is 10 seconds, and the light energy required for the hardening of the photosensitive layer is 3 mJ/cm ² .

(Example 9)

The above methacrylic acid/methyl methacrylate/styrene copolymer (copolymer composition ratio (mass ratio): 24/46/ in the above-mentioned photosensitive resin composition solution as the above-mentioned binder in Example 1. 30) Change to methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 29/31/40, mass average molecular weight: 58,900, acid value: 189 (mgKOH/g)) In the same manner as in Example 1, a pattern forming material and a laminate were produced.

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

In addition, the I/O value of the above-mentioned methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 29/31/40) as the above-mentioned binder is calculated as described above. It is 0.627, the shortest development time is 9 seconds, and the light energy required for the hardening of the photosensitive layer is 3 mJ/cm ² .

(Embodiment 10)

The above methacrylic acid/methyl methacrylate/styrene copolymer (copolymer composition ratio (mass ratio): 24/46/ in the above-mentioned photosensitive resin composition solution as the above-mentioned binder in Example 1. 30) Change to methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 25/41/34, mass average molecular weight: 55,300, acid value A pattern forming material and a laminate were produced in the same manner as in Example 1 except for 163 (mgKOH/g).

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

In addition, the I/O value of the above-mentioned methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 25/41/34) as the above-mentioned binder is calculated as described above. It is 0.627, the shortest development time is 14 seconds, and the light energy required for the hardening of the photosensitive layer is 3 mJ/cm ² .

(Example 11)

In the same manner as in Example 7, except that the pattern forming apparatus described above was changed to the pattern forming apparatus described below, the pattern forming material and the laminated body produced were used to evaluate the developability, the resolution, and the etching property. The peeling property of the hardened pattern, the shielding property, and the exposure speed. The results are shown in Table 3.

Further, the I/O value of the above methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 29/19/52) as the above-mentioned binder is as in Example 7. It is shown as 0.552, the shortest development time is 10 seconds, and the light energy required for the hardening of the photosensitive layer is 3 mJ/cm ² .

<<Pattern forming device>>

A composite laser light source having the 27th to 32th drawings is used as the light irradiation mechanism, and as shown in FIGS. 4A and 4B, the microlens is arranged in 1024 in the main scanning direction, and the microlens is in the sub-scanning direction. The array is arranged in 768 sets, and only DMD50 driven by 1024×256 columns is used as the above-mentioned optical modulation mechanism, and the side shown in FIG. 13A is complex. The curved microlens 474 is arranged in an array of microlens arrays 472, and the patterning means for imaging the optical systems 480, 482 of the pattern forming material by the light of the microlens array. The DMD 50 is connected to a controller 302 including a data processing unit and a lens drive control unit shown in FIG. The data processing unit of the controller 302 is based on the input pattern information, and each of the exposure heads 166 can generate a control signal for driving and controlling each microlens within a range that the DMD 50 should control. Further, the lens driving control unit is patterned. The control signal generated by the information processing unit is used as a reference, and each of the exposure heads 166 can control the angle of the reflection surface of each microlens of the DMD 50.

Further, the exposure in the pattern forming apparatus is performed by moving the exposed light to the side of the photosensitive layer in the pattern forming material.

Further, the toric surface of the above microlens is used as described below.

First, in order to correct the distortion of the exit surface of the microlens 474 which is the above-described pixel portion of the DMD 50, the distortion of the exit surface is measured. The result is shown in Figure 14. In Fig. 14, the same height positions of the reflecting surfaces are connected by contour lines, and the distance between the contour lines is 5 nm. Further, the x-direction and the y-direction shown in the same figure are two diagonal directions of the microlens 62, and the microlens 62 is rotated around the rotary shaft that is stretched in the y direction. Further, the 15A and 15B drawings each show the displacement of the height of the reflection surface of the microlens 62 along the x direction and the y direction.

As shown in Fig. 14, Fig. 15A and Fig. 15B, there is distortion on the reflecting surface of the microlens 62, and in particular, when the central portion of the lens is observed, the distortion in one diagonal direction (y direction) is higher than the other. The distortion in the diagonal direction (x direction) is large. Therefore, the microlens array A problem of shape distortion occurs in the condensing position of the laser light B condensed by the microlens 55a of 55.

FIGS. 16A and 16B show the front shape and the side surface shape of the entire microlens array 55 in detail. In these figures, the dimensions of the various portions of the microlens array 55 are also described, and the units are in mm. First, referring to the 1024 x 256 columns of microlenses 62 of the DMD 50, as described above with reference to FIGS. 4A and 4B, the microlens array 55 is arranged side by side in the horizontal direction, and the microlenses 55a are arranged vertically. The direction 256 columns are arranged side by side. Further, in Fig. 4A, the lateral direction of the microlens array 55 is represented by j, and the longitudinal direction is represented by k.

Further, FIGS. 17A and 17B show the front shape and the side shape of each of the microlens arrays 55a in the microlens array 55. Further, the contour line of the microlens 55a is collectively shown in Fig. 17A. The end face of the light exit surface of each microlens 55a is an aspherical shape for correcting aberration due to distortion of the reflecting surface of the microlens 62. More specifically, the microlens 55a is a buckling lens, and corresponds to the curvature radius Rx of the x-direction optical direction of -0.125 mm, and the radius of curvature Ry of the y direction is -0.1 mm.

Therefore, the condensed state of the laser light B in the cross section parallel to the x direction and the y direction is approximately as shown in Figs. 18A and 18B. That is, when the cross section parallel to the x direction is compared with the inside of the cross section parallel to the y direction, the microlens 55a in the latter cross section has a small radius of curvature and a short focal length.

Further, when the microlens 55a has the above shape, the beam diameter near the condensing position (focus position) of the microlens 55a is obtained by a computer The simulation results are shown in Figures 19A-D. Further, for comparison, in the case where the microlens 55a has a spherical shape having a radius of curvature Rx = Ry = -0.1 mm, the same simulation calculation is performed, and the results are shown in Figs. 20A to D. Further, the value of z in each figure is such that the evaluation position of the focus direction of the microlens 55a is expressed by the distance from the beam exit surface of the microlens 55a.

Further, the surface shape of the microlens 55a used in the above simulation calculation is calculated by the following calculation formula.

In the above calculation formula, Cx represents the curvature in the x direction (=1/Rx), Cy represents the curvature in the y direction (=1/Ry), and X represents the distance from the optical axis O of the lens in the x direction, and the Y system The distance from the optical axis O of the lens in the y direction.

Comparing the 19A-D and 20A-D, the pattern forming method of the present invention has a toric surface having a small focal length in the cross section parallel to the x direction by the microlens 55a parallel to the y direction. The lens controls the distortion of the beam shape near its condensing position. Thereby, an image having no distortion and higher definition can be exposed on the pattern forming material 150. Further, in the present embodiment shown in Figs. 19A to 10D, it is understood that the region having a small beam diameter is wide, that is, the depth of focus is large.

In addition, the array of openings 59 disposed in the vicinity of the condensing position of the microlens array 55 is such that only the corresponding micro vias are provided in the respective openings 59a. The light of the lens 55a is arranged to be incident. That is, by providing the opening array 59, it is possible to prevent light from the adjacent adjacent microlens 55a from entering the respective openings 59a, and the extinction ratio can be improved.

(Embodiment 12)

In the same manner as in Example 9, except that the above-described pattern forming apparatus was changed to the pattern forming apparatus of Example 11, the pattern forming material and the laminated body were used, and the developing property, the resolution, and the etching were evaluated. Peelability, shielding properties, and exposure speed of the sexual and hardened patterns. The results are shown in Table 3.

Further, the I/O value of the above methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 29/31/40) as the above-mentioned binder is as in Example 9. It is shown as 0.627, the shortest development time is 9 seconds, and the light energy required for the hardening of the photosensitive layer is 3 mJ/cm ² .

(Example 13)

In the same manner as in the tenth embodiment except that the pattern forming apparatus was changed to the pattern forming apparatus of the eleventh embodiment, the pattern forming material and the laminated body were used, and the developing property, the resolution, and the etching were evaluated. Peelability, shielding properties, and exposure speed of the sexual and hardened patterns. The results are shown in Table 3.

Further, the I/O value of the above methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 25/41/34) as the above-mentioned binder is as in Example 10. It is shown as 0.627, the shortest development time is 10 seconds, and the light energy required for the hardening of the photosensitive layer is 3 mJ/cm ² .

(Comparative Example 1)

The methacrylic acid/styrene copolymer (copolymer composition ratio (mass ratio): 29/71) in the above photosensitive resin composition solution as the above-mentioned binder was changed to methacrylic acid/A in Example 1 The methyl acrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 18/50/32, mass average molecular weight: 47,300, acid value: 117 (mgKOH/g)) was the same as in Example 1. A pattern forming material and a laminate are produced.

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

In addition, the I/O value of the above-mentioned methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 18/50/32) as the above-mentioned binder is calculated as described above. It is 0.569, the shortest development time is 25 seconds, and the light energy required for the hardening of the photosensitive layer is 3 mJ/cm ² .

(Comparative Example 2)

The methacrylic acid/styrene copolymer (copolymer composition ratio (mass ratio): 29/71) in the above photosensitive resin composition solution as the above-mentioned binder was changed to methacrylic acid/A in Example 1 The methyl acrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 25/45/30, mass average molecular weight: 35,000, acid value: 163 (mgKOH/g)) was the same as in Example 1. A pattern forming material and a laminate are produced.

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

In addition, the I/O value of the above-mentioned methacrylic acid/methyl methacrylate/styrene copolymer (copolymerization composition ratio (mass ratio): 25/45/30) as the above-mentioned binder is calculated as described above. It is 0.655, the shortest development time is 10 seconds, and the light energy required for the hardening of the photosensitive layer is 3 mJ/cm ² .

(Comparative Example 3)

The methacrylic acid/styrene copolymer (copolymer composition ratio (mass ratio): 29/71) in the above photosensitive resin composition solution as the above-mentioned binder was changed to methacrylic acid/A in Example 1 Methyl methacrylate/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 40/30/15/15, mass average molecular weight: 50,200, acid value: 261 (mgKOH/ In the same manner as in Example 1, except for g)), a pattern forming material and a laminate were produced.

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

Further, as the above-mentioned binder, the above-mentioned methacrylic acid/methyl methacrylate/styrene/2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 40/30/15/15) The I/O value is 0.871 when calculated as described above, the shortest development time is 5 seconds, and the light energy required for curing the photosensitive layer is 3 mJ/cm ² .

(Comparative Example 4)

In addition to the methacrylic/styrene copolymer (copolymer) in the above photosensitive resin composition solution as the above-mentioned binder in Example 1. Composition ratio (mass ratio): 29/71) changed to methacrylic acid/methyl methacrylate/2-ethylhexyl acrylate/butyl acrylate copolymer (copolymerization composition ratio (mass ratio): 19/61/ In the same manner as in Example 1, except that 10/10, mass average molecular weight: 60,700, acid value: 124 (mgKOH/g), a pattern forming material and a laminate were produced.

Using the produced pattern forming material and the laminate, the developing property, the resolution, the etching property, the peeling property of the cured pattern, the shielding property, and the exposure speed were evaluated. The results are shown in Table 3.

Further, as the above-mentioned binder, the above methacrylic acid/methyl methacrylate/2-ethylhexyl acrylate/butyl acrylate copolymer (copolymerization composition ratio (mass ratio): 19/61/10/10) The I/O value was 0.765 as calculated above, the shortest development time was 15 seconds, and the light energy required for curing the photosensitive layer was 3 mJ/cm ² .

As is clear from the results of Table 3, the pattern forming materials of Examples 1 to 13 have an I/O value in the range of 0.300 to 0.650 and an acid value in the range of 130 to 250 (mgKOH/g). It is excellent in etching property and shielding property, and the shortest development time is short, the image forming property is excellent, and the peeling property of the hardened pattern is excellent. Further, Examples 11 to 13 using a pattern forming apparatus having a toric surface have better resolution than Examples 1 to 10, and the exposure speed is faster.

[Industry use possibility]

In the pattern forming material of the present invention, the I/O value and the glass transition temperature of the binder contained in the photosensitive layer are all within a certain numerical range, so that the resolution and the shielding property are excellent, and the developing property is also excellent. Moreover, by suppressing the occurrence of edge melting, it can be applied to the formation of various patterns, the formation of permanent patterns such as wiring patterns, the manufacture of liquid crystal structural members such as color filters, pillars, ribs, spacers, and partition walls. , holography, micro-machines, manufacturing of verification, etc., in particular, can be applied to the formation of high-definition wiring patterns. Since the pattern forming apparatus of the present invention includes the pattern forming material of the present invention, it can be applied to formation of various patterns, formation of permanent patterns such as wiring patterns, color filters, pillars, ribs, spacers, and partition walls. The manufacture of liquid crystal structural members, holograms, micro-machines, verification manufacturing, and the like are particularly suitable for use in the formation of high-definition wiring patterns. Since the pattern forming method of the present invention uses the pattern forming material of the present invention, it can be applied to formation of various patterns, formation of permanent patterns such as wiring patterns, color filters, pillars, ribs, spacers, and partition walls. The manufacture of liquid crystal structural members, holograms, micro-machines, verification manufacturing, and the like are particularly applicable to the formation of high-definition wiring patterns.

Claims (14)

A pattern forming material characterized by having at least a photosensitive layer on a support, the photosensitive layer comprising a binder, a polymerizable compound and a photopolymerization initiator, and the I/O value of the binder is 0.350 to 0.650, and the acid value is 130 to 250 (mgKOH/g), and the binder contains a copolymer containing 30% by mass or more of a monomer constituting a homopolymer having an I/O value of 0.35 or less. For example, in the pattern forming material of claim 1, wherein the I/O value of the bonding agent is 0.350 to 0.630. The pattern forming material according to claim 1, wherein the acid value of the binder is 150 to 230 (mgKOH/g). 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 according to claim 1, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group. The pattern forming material according to claim 1, wherein the photopolymerization initiator comprises a halogenated hydrocarbon derivative, a hexaaryldiimidazole, an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, and At least one selected from the group of metallocenes. A pattern forming device characterized by comprising a pattern forming material, wherein the pattern forming material has at least a photosensitive layer on a support, the photosensitive layer comprising a binder, a polymerizable compound, and a photopolymerization initiator, and the I/ of the binder The O value is 0.350 to 0.650, and the acid value is 130 to 250 (mgKOH/g), and the binder contains a copolymer, and the copolymer 30% by mass or more of a monomer constituting a homopolymer having an I/O value of 0.35 or less, and having at least a light irradiation mechanism capable of irradiating light, and modulating light from the light irradiation means to form the pattern A light modulation mechanism that exposes the photosensitive layer of the material. A pattern forming method comprising at least exposing a photosensitive layer of a pattern forming material, wherein the pattern forming material has at least a photosensitive layer on a support, the photosensitive layer comprising a binder, a polymerizable compound, and a photopolymerization initiator The binder has an I/O value of 0.350 to 0.650 and an acid value of 130 to 250 (mgKOH/g), and the binder contains a copolymer having a constituent I/O value of 30% by mass or more. A monomer of a homopolymer of 0.35 or less. The pattern forming method of claim 8, wherein the photosensitive layer is provided with a light modulation mechanism having n pixel portions for receiving and emitting light from the light irradiation mechanism. After the light is modulated, it is exposed by light having a microlens array in which aspherical microlenses capable of correcting aberrations due to distortion of the exit surface of the pixel portion are arranged. The pattern forming method of claim 8, wherein the exposure is based on the formed pattern information to generate a control signal, and the light is modulated using the light corresponding to the control signal. The pattern forming method of claim 8, wherein the exposure is modulated by the light modulation mechanism, and the distortion is caused by the distortion of the exit surface of the pixel portion that can be corrected by the light modulation mechanism. The microlens array in which the aspherical microlenses are arranged is performed. The pattern forming method of claim 11, wherein the aspherical surface is a toric surface. The pattern forming method of claim 8, wherein the developing of the photosensitive layer is performed after the exposure is performed. The pattern forming method of claim 13, wherein the permanent pattern is formed after the development is performed.