JP2007079474A - Pattern forming material, pattern forming apparatus and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming material having high sensitivity and excellent developability and giving a high resolution pattern, and to provide a pattern forming apparatus equipped with the pattern forming material and a pattern forming method. <P>SOLUTION: The pattern forming material has on a support a photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator, wherein the sensitivity of the photosensitive layer is ≤20 mJ/cm<SP>2</SP>, and when the photosensitive layer is developed after exposure under the conditions of a line width of 10-40 μm and line/space (L/S)=1/1 and L/S=1/100 to obtain patterns, the difference in line width between a line pattern formed by the exposure under L/S=1/1 and a line pattern formed by the exposure under L/S=1/100 is ≤5 μm. The binder preferably has an I/O value of 0.5-0.8 and the polymerizable compound preferably has an I/O value of 0.5-1.5. The pattern forming apparatus and the pattern forming method using the pattern forming material are aso provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pattern forming material excellent in exposure sensitivity and resolution and suitable for dry film resist (DFR), etc., a pattern forming apparatus provided with the pattern forming material, and a pattern forming method using the pattern forming material. .

  Conventionally, when forming a permanent pattern such as a wiring pattern, a pattern forming material in which a photosensitive resin composition is formed on a support by applying and drying a photosensitive resin composition has been used. As the method for producing the permanent pattern, for example, a laminate is formed by laminating the pattern forming material on a substrate such as a copper clad laminate on which the permanent pattern is formed, and the photosensitive layer in the laminate is formed on the photosensitive layer. The permanent pattern is formed by exposing to light, developing the photosensitive layer after the exposure to form a pattern, and then performing an etching process or the like.

  The pattern forming material includes a polymerization inhibitor of a compound having a phenolic hydroxyl group, a fragrance, a heterocyclic ring, or an imino group in the photosensitive resin composition for the purpose of improving storage stability or improving the resolution. An added proposal has been made (see Patent Documents 1 to 4). However, in this case, nothing is disclosed about the point that the decrease in sensitivity can be suppressed by adding a sensitizer to the photosensitive resin composition (the photosensitive layer) or a highly sensitive dry resist film.

The photosensitive layer in the pattern forming material generally contains a binder, but paying attention to the I / O value (inorganic / organic ratio of the organic conceptual diagram) of the binder, the I / O value is a constant numerical value. If it is within the range, there is no disclosure or suggestion that the resolution and the tent property are excellent and the developability is also excellent. In addition, no proposal has been made to pay attention to the I / O value of the monomer, and the developability and resolution are excellent by adjusting the monomer I / O value and the binder I / O and adjusting the ratio thereof. Neither disclosed nor suggested.
In order to make the pattern forming material highly sensitive, proposals have been made to increase the concentration of a photopolymerization initiator added to the pattern forming material or to add a sensitizer. However, in this case, the degree of monomer polymerization in the cured film formed by exposure is low, the developer resistance is not sufficient, the line width is narrowed during development, and the developability and resolution may be reduced. . In particular, an isolated line pattern having a wide interval between adjacent line patterns is easily affected by a developing solution, so that the tendency to be thin is remarkable, and it is difficult to realize high resolution.

  Therefore, there is still provided a pattern forming material that has a high sensitivity, an excellent developability, and a high resolution pattern, a pattern forming apparatus including the pattern forming material, and a pattern forming method using the pattern forming material. However, the present situation is that further improvement and development is desired.

JP 2002-268211 A JP 2003-29399 A JP 2004-4527 A Japanese Patent Laid-Open No. 2004-4528

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention uses a pattern forming material that has a high sensitivity, is excellent in developability, and can obtain a high-resolution and high-definition pattern, a pattern forming apparatus including the pattern forming material, and the pattern forming material. An object is to provide a pattern forming method.

Means for solving the problems are as follows. That is, <1> a support and at least a photosensitive layer on the support, and the photosensitive layer contains at least a binder, a polymerizable compound, and a photopolymerization initiator, and the sensitivity of the photosensitive layer is 20 mJ / cm. ² or less of the pattern obtained by exposing and developing the photosensitive layer with a line width of 10 to 40 μm and a line / space (L / S) = 1/1 and L / S = 1/100. A pattern forming material having a line width difference of 5 μm or less between a line pattern formed by exposure with / S = 1/1 and a line pattern formed by exposure with L / S = 1/100 It is. In the pattern forming material according to <1>, the photosensitive layer includes the binder, the polymerizable compound, and the photopolymerization initiator, and the sensitivity of the photosensitive layer is 20 mJ / cm ² or less. L / S = 1/1 of the line pattern obtained by exposing and developing the layer with a line width of 10 to 40 μm, line / space (L / S) = 1/1 and L / S = 1/100. Since the difference in line width between the line pattern formed by the exposure of 1 and the line pattern formed by the exposure of L / S = 1/100 is 5 μm or less, high sensitivity and excellent developability, especially between the lines Even in the case of an isolated line pattern having a wide interval, it is possible to provide a pattern forming material that is less likely to be thinned, has excellent resolution, and provides a high-definition pattern.
<2> The pattern forming material according to <1>, wherein the binder has an I / O value of 0.5 to 0.8.
<3> The pattern forming material according to any one of <1> to <2>, wherein the polymerizable compound has an I / O value of 0.5 to 1.5.
<4> The pattern forming material according to any one of <1> to <3>, wherein a mass ratio of the binder and the polymerizable compound (binder / polymerizable compound) is 1 to 2.
<5> The pattern forming material according to any one of <1> to <4>, wherein the binder includes a copolymer, and the copolymer has a structural unit derived from at least one of styrene and a styrene derivative. is there.
<6> The pattern forming material according to any one of <1> to <5>, wherein the binder has a glass transition temperature of 80 ° C. or higher.
<7> The pattern forming material according to any one of <1> to <6>, wherein the binder has an acidic group.
<8> The pattern forming material according to any one of <1> to <7>, wherein the binder includes a vinyl copolymer.
<9> The pattern forming material according to any one of <1> to <8>, wherein the binder has an acid value of 100 to 250 mgKOH / g.
<10> The pattern forming material according to any one of <1> to <9>, wherein the polymerizable compound contains at least a compound having one polymerizable group in a molecule.
<11> The pattern forming material according to any one of <1> to <10>, wherein the polymerizable compound further includes a compound having two polymerizable groups in the molecule.
<12> The polymerizable compound according to <11>, wherein the polymerizable compound includes one or more compounds having one polymerizable group in the molecule and two or more compounds having two polymerizable groups in the molecule. It is a pattern forming material.
<13> The pattern forming material according to any one of <1> to <12>, wherein the polymerizable compound further includes a compound having three or more polymerizable groups in the molecule.
<14> The polymerizable compound has one or more compounds having one polymerizable group in the molecule, two or more compounds having two polymerizable groups in the molecule, and 3 polymerizable groups in the molecule. The pattern forming material according to <13>, comprising one or more compounds having a single structure.
<15> The pattern forming material according to any one of <1> to <14>, wherein the compound having at least one polymerizable group in the molecule has a polyalkylene oxide group.
<16> The pattern forming material according to any one of <1> to <15>, wherein the polymerizable compound includes a monomer having at least one of a urethane group and an aryl group.
<17> The photopolymerization initiator is a halogenated hydrocarbon derivative, phosphine oxide, hexaarylbiimidazole, oxime derivative, organic peroxide, thio compound, ketone compound, acylphosphine oxide compound, aromatic onium salt, and ketoxime ether. The pattern forming material according to any one of <1> to <16>, including at least one selected from the group consisting of:
<18> The pattern forming material according to any one of <1> to <17>, wherein the photosensitive layer has a thickness of 1 to 100 μm.
<19> The pattern forming material according to any one of <1> to <18>, wherein the support includes a synthetic resin and is transparent.
<20> The pattern forming material according to any one of <1> to <19>, wherein the support has an elongated shape.
<21> The pattern forming material according to any one of <1> to <20>, wherein the pattern forming material has a long shape and is wound in a roll shape.
<22> The pattern forming material according to any one of <1> to <21>, wherein the pattern forming material has a protective film on the photosensitive layer.

<23> After the photosensitive layer modulates the light from the light irradiation means by the light modulation means having n drawing parts for receiving and emitting the light from the light irradiation means, the emission surface in the drawing part The pattern forming material according to any one of <1> to <22>, wherein the pattern forming material is exposed to light that has passed through a microlens array in which microlenses having aspherical surfaces capable of correcting an aberration due to distortion of the lens. In the pattern forming material according to <23>, the light from the light irradiation unit is formed by the light modulation unit in which the photosensitive layer has n pixel portions that receive and emit light from the light irradiation unit. Then, the image is exposed to light passing through the microlens array in which the microlenses having the aspherical surface capable of correcting the aberration due to the distortion of the exit surface in the pixel portion are exposed. Aberration due to distortion of the exit surface in the element part is corrected, and exposure is performed with light in which distortion of an image formed on the pattern forming material is suppressed. As a result, since the pattern forming material is exposed with high definition, a high definition pattern can be formed by developing the photosensitive layer thereafter.
<24> After the photosensitive layer modulates the light from the light irradiation means by the light modulation means having n drawing elements for receiving and emitting the light from the light irradiation means, the peripheral portion of the drawing part The pattern forming material according to any one of <1> to <23>, wherein the pattern forming material is exposed with light that has passed through a microlens array in which microlenses having a lens opening shape to which light from the lens is not incident. In the pattern forming material according to <24>, the light from the light irradiation unit is formed by the light modulation unit having n pixel portions that receive and emit light from the light irradiation unit. The light modulated by the light modulation means passes through the microlens having a lens opening shape that does not allow the light from the peripheral part of the picture element part to enter, so that the peripheral part of the picture element part with large distortion, In particular, the light reflected at the four corners is not collected and distortion of the image formed on the photosensitive layer is suppressed. As a result, the photosensitive layer is exposed with high definition. Thereafter, when the photosensitive layer is developed, a high-definition pattern is formed.

<25> The pattern forming material according to any one of <1> to <24>,
A pattern forming apparatus comprising at least light irradiating means capable of irradiating light, and light modulating means for modulating light from the light irradiating means and exposing the photosensitive layer in the pattern forming material. is there. In the pattern forming apparatus according to <25>, the light irradiation unit irradiates light toward the light modulation unit. The light modulation unit modulates light received from the light irradiation unit. The light modulated by the light modulator is exposed to the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
<26> The light modulation means further includes a pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation means is emitted from the light irradiation means. It is a pattern formation apparatus as described in said <25> modulated according to. In the pattern forming apparatus according to <26>, since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit corresponds to the control signal generated by the pattern signal generation unit. Modulated.
<27> The light modulation means has n pixel parts, and forms any less than n pixel elements continuously arranged from the n pixel parts. The pattern forming apparatus according to any one of <25> to <26>, which can be controlled according to pattern information. In the pattern forming apparatus according to <27>, an arbitrary less than n pixel portions arranged continuously from the n pixel portions in the light modulation unit are controlled according to pattern information. Thereby, the light from the light irradiation means is modulated at high speed.
<28> The pattern forming apparatus according to any one of <25> to <27>, wherein the light modulation unit is a spatial light modulation element.
<29> The pattern forming apparatus according to <28>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<30> The pattern forming apparatus according to any one of <27> to <29>, wherein the picture element portion is a micromirror.
<31> The pattern forming apparatus according to any one of <25> to <30>, wherein the light irradiation unit is capable of combining and irradiating two or more lights. In the pattern forming apparatus according to <31>, since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the pattern forming material is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<32> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects and couples the laser beams emitted from the plurality of lasers to the multimode optical fiber. The pattern forming apparatus according to any one of <26> to <31>. In the pattern forming apparatus according to <32>, the light irradiation unit can condense the laser beams emitted from the plurality of lasers by the collective optical system and couple the laser beams to the multimode optical fiber. Thus, exposure is performed with exposure light having a deep focal depth. As a result, the pattern forming material is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<33> A pattern forming method comprising at least exposing the photosensitive layer in the pattern forming material according to any one of <1> to <24>. In the pattern forming method according to <33>, exposure is performed on the pattern forming material. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
<34> The pattern forming method according to <33>, wherein the pattern forming material is laminated on the substrate and exposed.
<35> The pattern forming method according to <34>, wherein the base is a printed wiring board.
<36> The pattern forming method according to any one of <33> to <35>, wherein the pattern forming material is laminated on the substrate while performing at least one of heating and pressing.
<37> The pattern forming method according to any one of <33> to <36>, wherein the exposure is performed imagewise based on pattern information to be formed.
<38> The pattern formation according to any one of <33> to <37>, wherein the exposure is performed using a light generated by generating a control signal based on pattern information to be formed and modulated in accordance with the control signal Is the method. In the pattern formation method according to <37>, a control signal is generated based on the pattern formation information to be formed, and light is modulated in accordance with the control signal.
<39> From <33> to <38, wherein the exposure is performed using light irradiation means for irradiating light and light modulation means for modulating light emitted from the light irradiation means based on pattern information to be formed. > The pattern forming method according to any one of the above.
<40> Exposure is performed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface of the picture element portion in the light modulation means after the light is modulated by the light modulation means. The pattern forming method according to <39>. In the pattern forming method according to <40>, the light modulated by the light modulation unit passes through the aspheric surface in the microlens array, so that the aberration due to the distortion of the emission surface in the pixel portion is corrected. The As a result, distortion of the image formed on the pattern forming material is suppressed, and exposure to the pattern forming material is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<41> The exposure according to <39>, wherein the exposure is performed through a microlens having a lens opening shape that does not allow light from a peripheral portion of a picture element portion in the light modulation unit to be incident after the light is modulated by the light modulation unit. This pattern forming method. In the pattern forming method according to <41>, the light modulated by the light modulation unit passes through a microlens having a lens opening shape that does not allow light from the peripheral portion of the pixel portion to enter, and thus distortion is large. The light reflected at the periphery of the image element, particularly at the four corners, is not collected, and distortion of the image formed on the photosensitive layer is suppressed. As a result, the photosensitive layer is exposed with high definition. Thereafter, when the photosensitive layer is developed, a high-definition pattern is formed.
<42> The pattern forming method according to <41>, wherein the microlens has an aspherical surface capable of correcting an aberration due to distortion of the exit surface in the pixel portion. In the pattern forming method according to <42>, the light modulated by the light modulation unit passes through the aspherical surface in the microlens array, whereby aberration due to distortion of the exit surface in the pixel portion is corrected. The distortion of the image formed on the pattern forming material is suppressed. As a result, the pattern forming material is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<43> The pattern forming method according to any one of <40> to <42>, wherein the aspherical surface is a toric surface. In the pattern forming method according to <43>, since the aspherical surface is a toric surface, the aberration due to the distortion of the radiation surface in the pixel portion is efficiently corrected, and an image formed on the pattern forming material is formed. Is effectively suppressed. As a result, the pattern forming material is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<44> The pattern forming method according to any one of <41> to <43>, wherein the microlens has a circular lens opening shape.
<45> The pattern forming method according to any one of <41> to <44>, wherein the lens opening shape is defined by providing a light shielding portion on the lens surface.
<46> The pattern forming method according to any one of <33> to <45>, wherein the exposure is performed through an aperture array. In the pattern forming method according to <46>, the extinction ratio is improved by performing exposure through the aperture array. As a result, the exposure is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<47> The pattern forming method according to any one of <33> to <46>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer. In the pattern forming method according to <47>, exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
<48> The pattern forming method according to any one of <33> to <47>, wherein the exposure is performed on a partial region of the photosensitive layer.
<49> The pattern forming method according to any one of <33> to <48>, wherein the photosensitive layer is developed after the exposure. In the pattern forming method according to <48>, a high-definition pattern is formed by developing the photosensitive layer after the exposure.
<50> The pattern formation method according to <49>, wherein a permanent pattern is formed after development.
<51> The pattern forming method according to <50>, wherein the permanent pattern is a wiring pattern, and the formation of the permanent pattern is performed by at least one of an etching process and a plating process.

  ADVANTAGE OF THE INVENTION According to this invention, the pattern formation material which can solve the problem in the past, is highly sensitive, is excellent in developability, and can obtain a high-definition and high-definition pattern, and pattern formation provided with this pattern formation material An apparatus and a pattern forming method using the pattern forming material can be provided.

(Pattern forming material)
The pattern forming material of the present invention may have a support, at least a photosensitive layer on the support, a protective film, and 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 as necessary. The number of photosensitive layers may be one or two or more.
The photosensitive layer has a sensitivity of 20 mJ / cm ² or less, and the photosensitive layer is exposed and developed with a line width of 10 to 40 μm at line / space (L / S) = 1/1 and L / S = 1/100. In the obtained pattern, the difference in line width between the line pattern formed by the exposure at L / S = 1/1 and the line pattern formed by the exposure at L / S = 1/100 is 5 μm or less. . Therefore, it is possible to provide a pattern forming material that is excellent in developer resistance, developability is improved, and a high-definition pattern with excellent resolution can be obtained.
The difference in line width is more preferably 5 μm or less, and particularly preferably 2 μm or less.
Here, the line pattern of L / S = 1/1 and L / S = 1/100 has a line width of 10 to 40 μm and a line / space (L / S) = 1 using the pattern forming apparatus of the present invention. / 10 and L / S = 1/100, and develop to form 10 line patterns each having a length of 20 cm. Then, for each of the 10 line patterns, the line widths of the upper end, the center, and the lower end in the thickness direction are measured at positions of 1 cm, 10 cm, and 19 cm from the end of each line pattern, and a total of 90 points are measured. Perform the measurement. The difference between the 90-point average value of the line width of the L / S = 1/1 line pattern measured in this way and the 90-point average value of the line width of the line pattern of L / S = 1/100 is calculated. .
As the method of measuring sensitivity, using the pattern forming apparatus of the present invention, by irradiating light of different light energy amount from 0.1 mJ / cm ² to 100 mJ / cm ² at ^{2 1/2} times the interval exposure Then, a part of the photosensitive layer was cured, developed and the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Next, a sensitivity curve is obtained by plotting the relationship between the light irradiation amount and the thickness of the cured layer. From the sensitivity curve thus obtained, the light energy when the thickness of the cured region is 0.5 μm in difference from the thickness of the photosensitive layer before exposure is the minimum light energy required to cure the photosensitive layer. The quantity, that is, the sensitivity of the photosensitive layer.

〔binder〕
There is no restriction | limiting in particular as said binder, According to the objective, it can select suitably.
Further, the I / O value of the binder is preferably 0.5 to 0.8, more preferably 0.5 to 0.65, and particularly preferably 0.5 to 0.6. preferable.
Moreover, it is preferable that the binder contains a copolymer, and the copolymer has a structural unit derived from at least one of styrene and a styrene derivative.

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

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

  The inorganic value of the copolymer is (inorganic value of the methacrylic acid) × (molar ratio of the methacrylic acid) and (inorganic value of the methyl methacrylate) × (molar ratio of the methyl methacrylate). And (the inorganic value of the styrene) × (molar ratio of the styrene).

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

  The organic value of the copolymer is (organic value of the methacrylic acid) × (molar ratio of the methacrylic acid) and (organic value of the methyl methacrylate) × (molar ratio of the methyl methacrylate). And (the organic value of the styrene) × (molar ratio of the styrene).

Since the methacrylic acid has 4 carbon atoms, the methyl methacrylate has 5 carbon atoms, and the styrene has 8 carbon atoms,
The organic value of the methacrylic acid is 20 (organic value of carbon atoms) × 4 (number of carbon atoms) = 80,
The organic value of the methyl methacrylate is 20 (organic value of carbon atoms) × 5 (number of carbon atoms) = 100,
The organic value of styrene is 20 (organic value of carbon atoms) × 8 (number of carbon atoms) = 160.
Therefore, the organic value of the copolymer has the following formula: 80 × 2 (molar ratio of the methacrylic acid) + 100 × 5 (molar ratio of the methyl methacrylate) + 160 × 3 (molar ratio of the styrene) By calculating, it is calculated to be 1140.

  Therefore, it can be seen that the I / O value of the copolymer is 645 (inorganic value of the copolymer) / 1140 (organic value of the copolymer), 0.566.

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

The acid value (acid group content) of the binder is not particularly limited as long as the I / O value is within the above numerical range, and can be appropriately selected according to the purpose. 250 mgKOH / g is preferable, 120 to 220 mgKOH / g is more preferable, and 150 to 220 mgKOH / g is particularly preferable.
When the acid value is less than 100 mgKOH / g, developability may be insufficient, resolution may be inferior, and permanent patterns such as wiring patterns may not be obtained with high definition. When the acid value exceeds 250 mgKOH / g In some cases, at least one of the pattern developer resistance and adhesion is deteriorated, the resolution and the tent property are inferior, and a permanent pattern such as a wiring pattern cannot be obtained with high definition.

In order to adjust both the I / O value and acid value of the binder so as to satisfy a certain numerical range, the type of monomer constituting the copolymer contained in the binder and the monomer are polymerized. It can adjust by selecting suitably at least any of the polymerization ratio (content) in the case.
For example, for the monomer constituting the copolymer contained in the binder, the proportion of the monomer having an acidic group is a mass%, and the monomer constituting the homopolymer having an I / O value of 0.35 or less. When the proportion of the monomer is b mass% and the proportion of the other monomer is c mass% (here, a + b + c = 100, c may be 0), peeling of the cured pattern after etching When the value of a is increased for the purpose of improving the property, the I / O value of the binder tends to increase. Therefore, the a, b, and c satisfy the relationship of a <(b + c). preferable.
Specifically, the copolymer contained in the binder preferably contains 25% by mass or more of a monomer constituting a homopolymer having an I / O value of 0.35 or less, and contains 30% by mass or more. It is more preferable.
Examples of the monomer constituting the homopolymer having an I / O value of 0.35 or less include styrene, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate.

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

  The vinyl copolymer having a carboxyl group can be obtained by copolymerizing at least (1) a vinyl monomer having a carboxyl group and (2) a monomer copolymerizable therewith.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono Examples include (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  The other copolymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid diesters. , Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes (eg styrene, styrene derivatives, etc.), (meth) acrylonitrile, complex substituted with vinyl groups Cyclic groups (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamido-2-methylpropanesulfonic acid, monophosphate ( 2-acryloyl Ciethyl ester), phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester), vinyl monomers having a functional group (for example, urethane group, urea group, sulfonamide group, phenol group, imide group) and the like. . Among these, the styrene and styrene are low in that the I / O value of the binder can be reduced, a permanent pattern such as a wiring pattern can be formed with high definition, and the tent property can be improved. Derivatives are preferred.

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meta ) Acrylate, diethylene glycol monoethyl ether (meth) 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-phenoxyethoxyethyl acrylate, Nylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples thereof include acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like can be mentioned.

  Examples of the styrenes include the styrene and the styrene derivatives (for example, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, Dichlorostyrene, chloromethylstyrene, bromostyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like).

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of the method for synthesizing a vinyl monomer having a urethane group or urea group as the functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group. Specifically, a monomer having an isocyanate group, Addition reaction with a compound containing one hydroxyl group or a compound having one primary or secondary amino group, addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate It is done.

Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (1) to (3).
However, in the structural formulas (1) to (3), R ¹ represents a hydrogen atom or a methyl group.

  Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.

Examples of the monomer having a hydroxyl group include compounds represented by the following structural formulas (4) to (12).
However, in the structural formulas (4) to (12), R ¹ represents a hydrogen atom or a methyl group, and n, n1, and n2 represent an integer of 1 or more.

  Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol). , N-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (eg, phenol, cresol, naphthol, etc.), and further containing substituents Examples thereof include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, acetoxyphenol, and the like.

  Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.

  Examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexyl). Amine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), Arylamines (aniline, toluylamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and amines containing further substituents (trifluoroethylamino) , Hexafluoro isopropyl amine, methoxyaniline, methoxypropylamine and the like) and the like.

As the other copolymerizable monomer, it is preferable to use a monomer constituting a homopolymer having an I / O value of 0.35 or less. For example, styrene, a styrene derivative, 2-ethylhexyl (meth) Acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Benzyl methacrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and the like. Among these, styrene and styrene derivatives are more preferable.
These other copolymerizable monomers may be used alone or in combination of two or more.

  The vinyl copolymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Moreover, it can prepare by utilizing superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.

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

  The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile). Examples thereof include peroxides such as azo compounds and benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

The content of the polymerizable compound having a carboxyl group in the vinyl copolymer is not particularly limited as long as the I / O value and the acid value are within the numerical range, and is appropriately selected according to the purpose. However, for example, 10 to 70 mass% is preferable, 15 to 65 mass% is more preferable, and 20 to 60 mass% is particularly preferable.
If the content is less than 10% by mass, the developability to alkaline water may be insufficient, and if it exceeds 70% by mass, the developer resistance of the cured part (image part) may be insufficient.

There is no restriction | limiting in particular as molecular weight of the binder which has the said carboxyl group, Although it can select suitably according to the objective, For example, 2,000-300,000 are preferable as a mass mean molecular weight, 4,000-150 1,000 is more preferable.
When the mass average molecular weight is less than 2,000, the strength of the film tends to be insufficient and stable production may be difficult, and when it exceeds 300,000, developability may be deteriorated.

  The binder which has the said carboxyl group may be used individually by 1 type, and may use 2 or more types together. Examples of the case where two or more binders are used in combination include, for example, a combination of two or more binders composed of different copolymer components, two or more binders having different mass average molecular weights, and two or more binders having different dispersities. Is mentioned.

  The binder having a carboxyl group may be partially or entirely neutralized with a basic substance. The binder may be used in combination with resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin.

  In addition, a resin that is soluble in an alkaline liquid described in Japanese Patent No. 2873889 can be used in combination. When these resins are used in combination, the content of the above-mentioned binder with respect to the total amount of the binder contained in the photosensitive layer can be appropriately selected according to the purpose. For example, 50% by mass or more is preferable, and 70% by mass or more. Is more preferable, and 90% by mass or more is particularly preferable.

As the binder having an I / O value of 0.5 to 0.8, 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 / styrene / ethyl acrylate copolymer (copolymer composition (mass ratio): 23/30/30/17), methacrylic acid / methyl Methacrylate / styrene / ethyl acrylate copolymer (copolymer composition (mass ratio): 25/25/4 / 5), methacrylic acid / methyl methacrylate / styrene / ethyl acrylate 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 / cyclohexyl methacrylate / 2-ethylhexyl methacrylate 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 (copolymer 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), Methacrylic acid / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 23/50/27), methacrylic acid / styrene / 2-ethylhexyl methacrylate Copolymer (copolymerization composition ratio (mass ratio): 29/60/11), methacrylic acid / styrene / 2-ethylhexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 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 ( Polymerization 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 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 / methyl methacrylate / 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 Polymer (copolymerization composition ratio (mass ratio): 25/29/46), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 20/53/27), methacrylic acid / methyl Methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 29/19/52), methacrylic acid / Methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 30/13/57), methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 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): 24/46/3 ), And the like.
Among these, methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 25/8/30/37), methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer (copolymer) Polymer composition (mass ratio): 23/8/15/54), methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer (copolymer composition (mass ratio): 25/25/45/5), methacryl Acid / methyl methacrylate / styrene / ethyl acrylate 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), methacrylic acid / 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 (copolymer group) 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 / 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 / cyclohexyl methacrylate Copolymer (copolymerization composition ratio (mass ratio): 31/64/5), methacrylic acid / styrene / cyclohexyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 25/15/60), methacrylic acid / Methyl methacrylate / styrene / butyl methacrylate copolymer (copolymerization composition ratio (mass ratio): 23/37/30/10), methacrylic acid / methyl methacrylate / styrene / butyl methacrylate copolymer (copolymerization composition ratio (mass ratio) ): 25/27/36/12), methacrylic acid / methyl methacrylate / styre / 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 (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), methacrylic acid / methyl methacrylate / styrene copolymer (co-polymer) Polymerization 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 (copolymerization composition ratio (mass ratio): 25/41/34), and methacrylic acid / methyl methacrylate / styrene copolymer ( Copolymerization composition ratio (mass ratio): 36/5/59) is preferable.
Further, methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate copolymer (copolymer composition (mass ratio): 25/8/30/37), methacrylic acid / methyl methacrylate / styrene / ethyl acrylate copolymer (copolymer) Combined composition (mass ratio): 25/25/45/5), methacrylic acid / styrene / methyl acrylate copolymer (copolymer composition (mass ratio): 29/61/10), methacrylic acid / styrene / ethyl acrylate Copolymer (copolymer composition (mass ratio): 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 / 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), methacryl 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) and methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization composition ratio (mass ratio): 25/41/34) are particularly preferable.

When the binder is a substance having a glass transition temperature, the glass transition temperature is not particularly limited and may be appropriately selected depending on the intended purpose. In view of at least one of the peelability of the support, 80 ° C. or higher is preferable, 100 ° C. or higher is more preferable, and 115 ° C. or higher is particularly preferable.
If the glass transition temperature is less than 80 ° C., the tack of the pattern forming material may increase or the peelability of the support may deteriorate.

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

[Polymerizable compound]
There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, For example, the monomer or oligomer which has at least any one of a urethane group and an aryl group is mentioned suitably. Moreover, it is preferable that these have 2 or more types of polymeric groups.
The I / O value of the polymerizable compound is preferably 0.5 to 1.5, more preferably 0.6 to 1.45, and particularly preferably 0.65 to 1.4. preferable.
In addition, a polymeric compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types of polymeric compounds simultaneously, let the weight average value be I / O value of said polymeric compound.
Moreover, as mass ratio (binder / polymerizable compound) of the said binder and polymeric compound, 1-2 are preferable, 1.05-1.65 are more preferable, 1.1-1.5 are especially preferable. When the mass ratio is less than 1, edge fusion (exudation of the photosensitive layer from the edge portion) may be deteriorated when the photosensitive layer is too soft and the pattern forming material is in roll form. However, if it is more than 2, lamination failure to the substrate may occur.

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

The compound preferably has a compound having at least one polymerizable group in the molecule, and the compound having at least one polymerizable group preferably has a polyalkylene oxide group.
Moreover, it is preferable that the said polymeric compound contains the compound which has at least any one of a urethane group and an aryl group.

-Compound having one polymerizable group in the molecule-
Examples of the compound having one polymerizable group in the molecule include, for example, the compounds exemplified as the raw material of the binder (a compound having a boiling point of 100 ° C. or higher at normal pressure is preferable, and a compound having a temperature of 150 ° C. or higher is more preferable. And the like are preferred.
Further, compounds having one polymerizable group in the molecule such as a dibasic mono ((meth) acryloyloxyalkyl ester) mono (halohydroxyalkyl ester) described in JP-A-6-236031 (for example, γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate, etc.), compounds described in Japanese Patent No. 2744443, International Publication No. 00/52529 pamphlet, Japanese Patent No. 2548016, etc. Can be mentioned.
Further, 3-phenoxy-2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, N-aryl substituted (meth) acrylamide (for example, N-phenyl (meth) acrylamide), N- Examples thereof include aralkyl-substituted (meth) acrylamide (for example, N-benzyl (meth) acrylamide), cyclohexanedimethanol monoacrylate, and the like.

Examples of the compound having one polymerizable group in the molecule include a compound having one polymerizable group in the molecule represented by the following structural formula (13) and having a polyalkylene oxide chain. Is preferred.
In the structural formula (13), R ₁ represents a hydrogen atom or a methyl group.
X represents an alkylene group having 2 to 6 carbon atoms, and preferably has a chain structure rather than a cyclic structure. The chain alkylene group may have a branch. Examples of the alkylene group include an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
n is an integer of 1 to 30, and when n is 2 or more, a plurality of (—X—O—) may be the same as or different from each other, and (—X—O—) may be When they are different, for example, a combination of an ethylene group and a propylene group can be used.

Examples of R ₂ include an alkyl group, an aryl group, and an aralkyl group, and these groups may be further substituted with a substituent.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group, and an octadecyl group. Is mentioned. The alkyl group may have a substituent, and may have a branch or a ring structure.
Examples of the aralkyl group include benzyl group and phenethyl group. The aralkyl group may have a substituent.
Examples of the aryl group include phenyl group, naphthyl group, tolyl group, xylyl group, ethylphenyl group, methoxyphenyl group, propylphenyl group, butylphenyl group, t-butylphenyl group, octylphenyl group, nonylphenyl group, Examples include chlorophenyl group, cyanophenyl group, dibromophenyl group, tribromophenyl group, biphenylyl group, benzylphenyl group, α-dimethyl-benzylphenyl group, and the like. The aryl group may have a substituent.

Examples of the substituent in the alkyl group, aralkyl group, and aryl group include a halogen atom, an aryl group, an alkenyl group, an alkoxy group, and a cyano group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
The aryl group preferably has a total carbon number of 6 to 20, and more preferably 6 to 14. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, and the like.
As said alkenyl group, C2-C10 is preferable and 2-6 are more preferable. Examples of the alkenyl group include ethynyl group, propenyl group, butyryl group and the like.
As said alkoxy group, 1-10 total carbon atoms which may be branched are preferable, and 1-5 are more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a 2-methylpropyloxy group, and a butoxy group.

Specific examples of the compound having one polymerizable group in the molecule represented by the structural formula (13) include compounds represented by the following structural formula. However, in the following formula, R represents a hydrogen atom or a methyl group. n represents an integer of 1 to 30, m and L each represents an integer of 1 or more, and m + L represents an integer of 1 to 30. Me represents a methyl group, and Bu represents a butyl group.

  The content of the compound having one polymerizable group in the molecule in the polymerizable compound is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and still more preferably 1 to 25% by mass. When the content is less than 1% by mass, the effect of improving peelability and development latitude may be insufficient, and when it exceeds 40% by mass, resolution, adhesion, tent property, etc. may deteriorate. is there.

-Compound having two polymerizable groups in the molecule-
The compound having two polymerizable groups in the molecule is not particularly limited as long as it has two polymerizable groups in the molecule, and can be appropriately selected according to the purpose. For example, a urethane group and an aryl group A compound (monomer or oligomer) having at least one of the above and having two polymerizable groups is preferred.

--A compound having a urethane group and two polymerizable groups--
The compound having a urethane group and two polymerizable groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a diisocyanate compound having two isocyanate groups in the molecule and Examples include adducts with vinyl monomers having a hydroxyl group in the molecule.

  Examples of the diisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, 3,3′dimethyl-4,4′-diphenyl. Examples thereof include diisocyanates such as diisocyanates; polyaddition products of the diisocyanates with bifunctional alcohols (in this case, both ends are isocyanate groups).

  Examples of the vinyl monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and 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, polypropylene glycol mono (meth) Examples include acrylate, dibutylene glycol mono (meth) acrylate, tributylene glycol mono (meth) acrylate, tetrabutylene glycol mono (meth) acrylate, octabutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, and the like. It is done.

Moreover, the one terminal (meth) acrylate compound of the diol body which has different alkylene oxide parts, such as the copolymer (random, block, etc.) of ethylene oxide and propylene oxide represented by following Structural formula (14), etc. are mentioned.

In the structural formula (14), R ¹ and R ² each represent a hydrogen atom or a methyl group.
X ₁ and X ₂ represent an alkylene oxide group, and these may be used alone or in combination of two or more. Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, and a group in which these are combined (may be combined in any of random or block). Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a combination thereof is preferable, and an ethylene oxide group and a propylene oxide group are particularly preferable.
In the structural formula (14), m1 and m2 represent an integer of 1 to 30, preferably 2 to 20, and more preferably 4 to 15.

In the structural formula (14), Y ₁ represents a divalent organic group having 2 to 30 carbon atoms. Examples of the organic group include an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group (—CO—), an oxygen atom (—O—), a sulfur atom (—S—), and an imino group (—NH—). ), A substituted imino group in which a hydrogen atom of an imino group is substituted with a monovalent hydrocarbon group, a sulfonyl group (—SO ₂ —), or a combination thereof. Among these, an alkylene group, an arylene group, or a group obtained by combining these is preferable.
The alkylene group may have a branched structure or a cyclic structure, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentylene group, hexylene group, trimethyl hexene. Preferred examples include xylene group, cyclohexylene group, heptylene group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, dodecylene group, octadecylene group, or any group represented by the following structural formula. It is done.

The arylene group may be substituted with a hydrocarbon group, and examples thereof include a phenylene group, a tolylene group, a diphenylene group, a naphthylene group, and a group represented by the following structural formula.
Examples of the group in which these are combined include a xylylene group.

  The alkylene group, arylene group, or a combination thereof may further have a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). ), Aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group (for example, Acetoxy group, butyryloxy group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group) and the like.

Preferred examples of the compound represented by the structural formula (14) include compounds represented by the following structural formulas (15) to (21).
However, in said structural formula (15)-(21), R represents a hydrogen atom or a methyl group. m and n represent an integer of 1 to 60.

--A compound having an aryl group and two polymerizable groups--
Examples of the compound having an aryl group and two polymerizable groups include at least one of a dihydric alcohol compound having an aryl group, a divalent amine compound having an aryl group, and an amino alcohol compound having an aryl group. Examples thereof include esters and amides of heel and unsaturated carboxylic acids.

Examples of the dihydric alcohol compound having an aryl group, the divalent amine compound having an aryl group, or the amino alcohol compound having an aryl group include polystyrene oxide, xylylene diol, di- (β-hydroxyethoxy) benzene, 1 , 5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 2,2-diphenyl-1,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1-phenyl-1,2-ethanediol, 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'-bi-2-naphthol, dihydroxynaphthalene, , 1′-methylene-di-2-naphthol, biphenol, 2,2′-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, hydroquinone, hydroxybenzyl alcohol, methylhydroquinone, resorcinol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino- 4-hydroxyphenyl sulfone and the like.
In addition to these, esterified products obtained from vinyl monomers containing hydroxyl groups in the molecule such as xylylene bis (meth) acrylamide and phthalic acid, diallyl phthalate, diallyl benzenedisulfonate, and cationic polymerizable dimers as polymerizable monomers. Vinyl ethers (for example, bisphenol A divinyl ether), epoxy compounds (for example, bisphenol A diglycidyl ether), vinyl esters (for example, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate), styrene compounds (For example, divinylbenzene, p-allyl styrene, p-isopropene styrene, etc.).
Among these, a compound represented by the following structural formula (22) is preferable.

In the structural formula (22), R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group.
In the structural formula (22), X ₅ and X ₆ each represent an alkylene oxide group, which may be used alone or in combination of two or more. Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, or a group obtained by combining these (may be combined in any of random or block). And the like. Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a group combining these is preferable, and an ethylene oxide group and a propylene oxide group are particularly preferable.

In the structural formula (22), m5 and m6 are preferably an integer of 1 to 60, more preferably an integer of 2 to 30, and particularly preferably an integer of 4 to 15.
In the structural formula (22), T represents a divalent linking group, and examples thereof include methylene, ethylene, MeCMe, CF ₃ CCF ₃ , CO, and SO ₂ .

In the structural formula (22), Ar ₁ and Ar ₂ represent an aryl group which may have a substituent, and examples thereof include a phenylene group and a naphthylene group. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, a halogen group, an alkoxy group, or a combination thereof.

Specific examples of the compound having an aryl group and two polymerizable groups include 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane; 2-bis [4-((meth) acryloxyethoxy) phenyl] propane, 2,2-bis (4-((meth) having 2 to 20 ethoxy groups substituted with one phenolic OH group ) Acryloyloxypolyethoxy) phenyl) propane (eg, 2,2-bis (4-((meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxy)) Phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Yloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecaethoxy) phenyl) propane), 2,2-bis [4-((meth) acryloxypropoxy) phenyl Propane; 2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane (for example, 2,2) having 2 to 20 ethoxy groups substituted with one phenolic OH group -Bis (4-((meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloyloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecap) Poxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane), or the polyether moiety of these compounds in the same molecule, a polyethylene oxide skeleton and a polypropylene oxide skeleton (For example, a compound described in WO 01/98832, a polymerizable compound having a bisphenol skeleton and a urethane group, and the like).
Examples of the polymerizable compound having a bisphenol skeleton and a urethane group include an isocyanate group and a polymerizable group in a compound having a hydroxyl group at the terminal obtained as an adduct such as bisphenol and ethylene oxide or propylene oxide, or a polyaddition product. Compounds (for example, 2-isocyanatoethyl (meth) acrylate, α, α-dimethyl-vinylbenzyl isocyanate, etc.), and the like. In addition, the compound which changed the part originating in the bisphenol A frame | skeleton into bisphenol F or bisphenol S etc. may be sufficient.

  Moreover, as a commercial item, Shin-Nakamura Chemical Co., Ltd. make, BPE-200, BPE-500, BPE-1000, etc. are mentioned, for example.

  These compounds having two polymerizable groups in the molecule may be used alone or in combination of two or more.

  The content of the compound having two polymerizable groups in the molecule in the polymerizable compound is preferably 60 to 99% by mass, more preferably 70 to 99% by mass, and still more preferably 75 to 99% by mass.

-Polymerizable compound having 3 or more polymerizable groups in the molecule-
The polymerizable compound having three or more polymerizable groups in the molecule is not particularly limited as long as it has three or more polymerizable groups in the molecule and can be appropriately selected according to the purpose. Methylolpropane tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, trimethylolethane tri (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta ( Α) β-unsaturated polyvalent glycidyl group-containing compounds such as acrylate, sorbitol hexa (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether Examples thereof include compounds obtained by adding carboxylic acid, diethylenetriamine tris (meth) acrylamide, and the like.

Examples of the compound having three or more polymerizable groups in the molecule include, for example, three or more polymerizable groups and a polyalkylene oxide chain in the molecule represented by the following structural formula (23). Also suitable are compounds.
However, in the structural formula (23), R ₁ represents either a hydrogen atom or a methyl group.
X represents an alkylene group which may have a branch having 2 to 6 carbon atoms, and the alkylene group may contain one kind or two or more kinds (for example, ethylene and propylene) in one molecule.
n represents an integer of 1 to 30. m represents an integer of 3 or more.
Y represents an m-valent (trivalent to hexavalent) organic group, and examples thereof include a group represented by the following structural formula.
However, Et represents an ethyl group.

Preferred examples of the compound represented by the structural formula (23) include compounds represented by the following structural formulas (24) to (25).
However, in the structural formulas (24) and (25), R _{1 to} R ₃ represent either a hydrogen atom or a methyl group.
X ₁ to X ₃ represents an optionally branched alkylene group having 2 to 6 carbon atoms, said alkylene group may in one in one molecule, two or more (e.g., ethylene and propylene) include May be.
n ₁ ~n ₃ represents an integer of 1 to 30.
R represents a monovalent organic group, and examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; and an aryl group such as a phenyl group and a naphthyl group.

As the compounds represented by the structural formulas (24) and (25), specifically, those represented by the following structural formulas are preferable. However, in the following structural formula, R represents a hydrogen atom or a methyl group. n1, n2, and n3 represent an integer of 1-30. m1, m2, and m3, and L1, L2, and L3 each represent an integer of 1 or more, and m1 + L1, m2 + L2, and m3 + L3 each represent an integer of 1-30.

  Moreover, as a compound which has three or more polymeric groups in the said molecule | numerator, the compound which has at least any one of a urethane group and an aryl group and has three or more polymeric groups is suitable, for example.

--A compound having a urethane group and having three or more polymerizable groups--
There is no restriction | limiting in particular as a compound which has the said urethane group and 3 or more polymeric groups, According to the objective, it can select suitably, For example, polyisocyanate which has 3 or more isocyanate groups in a molecule | numerator is mentioned. Examples include adducts of an isocyanate compound and a vinyl monomer having a hydroxyl group in the molecule.

  Examples of the polyisocyanate compound having three or more isocyanate groups in the molecule include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, Adducts of diisocyanates such as 3,3′dimethyl-4,4′-diphenyl diisocyanate and polyfunctional alcohols such as trimethylolpropane, pentaerythritol and glycerin, or polyfunctional alcohols obtained from these ethylene oxide adducts (Terminal is isocyanate group); Bullet or isocyanurate of the diisocyanate Like trimer.

  Examples of the vinyl monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and 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, polypropylene glycol mono (meth) Chryrate, dibutylene glycol mono (meth) acrylate, tributylene glycol mono (meth) acrylate, tetrabutylene glycol mono (meth) acrylate, octabutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, trimethylolpropane Examples include di (meth) acrylate and pentaerythritol tri (meth) acrylate. Moreover, the one terminal (meth) acrylate body of the diol body which has different alkylene oxide parts, such as a copolymer (random, a block, etc.) of ethylene oxide and propylene oxide, etc. are mentioned.

  Examples of the monomer having a urethane group include compounds having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate and tri (meth) acrylate of ethylene oxide-modified isocyanuric acid.

A compound having a urethane group together with three or more polymerizable groups, and a compound having a polyalkylene oxide chain are also preferably used. More specifically, examples of such a compound include those represented by the following structural formula (26).

In the structural formula (26), R ³ represents a hydrogen atom or a methyl group, respectively. X ₃ represents an alkylene oxide group, which may be used alone or in combination of two or more. m3 is an integer of 1 to 30, n is an integer of 3 or more, Y2 is a divalent organic group, and Z is an n-valent organic group.

Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, and a group in which these are combined (may be combined in any of random or block). Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a combination thereof is preferable, and an ethylene oxide group and a propylene oxide group are more preferable.
In Structural Formula (26), m3 represents an integer of 1 to 30, preferably 2 to 20, and more preferably 4 to 15.

In the structural formula (26), Y ₂ represents a divalent organic group having 2 to 30 carbon atoms. For example, an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group (—CO—), oxygen An atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group in which the hydrogen atom of the imino group is substituted with a monovalent hydrocarbon group, a sulfonyl group (—SO ₂ —) ) Or a combination of these, and the like. Among these, an alkylene group, an arylene group, or a combination of these is preferable.
The alkylene group may have a branched structure or a cyclic structure, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentylene group, hexylene group, trimethyl hexene. Preferred examples include xylene group, cyclohexylene group, heptylene group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, dodecylene group, octadecylene group, or any group represented by the following structural formula. It is done.

The arylene group may be substituted with a hydrocarbon group, and examples thereof include a phenylene group, a tolylene group, a diphenylene group, a naphthylene group, and a group represented by the following structural formula.
Examples of the group in which these are combined include a xylylene group.

  The alkylene group, arylene group, or a combination thereof may further have a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). ), Aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group (for example, Acetoxy group, butyryloxy group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group) and the like.

  In the structural formula (26), n represents an integer of 3 to 6, and 3, 4 or 6 is preferable from the viewpoint of feedability of raw materials for synthesizing a polymerizable monomer.

In the structural formula (26), Z represents an n-valent (trivalent to hexavalent) linking group, and examples thereof include any group represented by the following structural formula.
However, _{X 4} represents an alkylene oxide. m4 represents an integer of 1 to 20. n represents an integer of 3 to 6. A represents an n-valent (trivalent to hexavalent) organic group.

  Examples of A include an n-valent aliphatic group, an n-valent aromatic group, and an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group, an oxygen atom, a sulfur atom, an imino group, and an imino group. Are preferably a combination of a substituted imino group in which the hydrogen atom is substituted with a monovalent hydrocarbon group or a sulfonyl group, an n-valent aliphatic group, an n-valent aromatic group, or an alkylene group or arylene A group in which a group and an oxygen atom are combined is more preferable, and an n-valent aliphatic group, and a group in which an n-valent aliphatic group is combined with an alkylene group and an oxygen atom are particularly preferable.

  As the number of carbon atoms of A, for example, an integer of 1 to 100 is preferable, an integer of 1 to 50 is more preferable, and an integer of 3 to 30 is particularly preferable.

The n-valent aliphatic group may have a branched structure or a cyclic structure.
As a carbon atom number of the said aliphatic group, the integer of 1-30 is preferable, for example, the integer of 1-20 is more preferable, and the integer of 3-10 is especially preferable.
The number of carbon atoms of the 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 n-valent aliphatic group or aromatic group may further have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, Iodine atom), aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group ( Examples thereof include an acetoxy group, a butyryloxy group), an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group), an aryloxycarbonyl group (for example, a phenoxycarbonyl group), and the like.

The alkylene group may have a branched structure or a cyclic structure.
As a carbon atom number of the said alkylene group, the integer of 1-18 is preferable, for example, and the integer of 1-10 is more preferable.

The arylene group may be further substituted with a hydrocarbon group.
As the number of carbon atoms of the arylene group, an integer of 6 to 18 is preferable, and an integer of 6 to 10 is more preferable.

  As a carbon atom number of the monovalent hydrocarbon group of the said substituted imino group, the integer of 1-18 is preferable and the integer of 1-10 is more preferable.

Hereinafter, preferred examples of the A are as shown by the following structural formula.

Examples of the compound represented by the structural formula (26) include compounds represented by the following structural formulas (27) to (40).
However, in said structural formula (27)-(40), n, n1, n2 and m mean 1-60. l means 1-20. R represents a hydrogen atom or a methyl group.

--A compound having an aryl group and having three or more polymerizable groups--
Examples of the compound having an aryl group and having three or more polymerizable groups include trivalent or higher alcohol compounds having an aryl group, trivalent or higher amine compounds having an aryl group, and 3 having an aryl group. Examples include esters or amides of unsaturated carboxylic acids with at least one of higher-value amino alcohol compounds.

Examples of the trivalent or higher alcohol compound having an aryl group, a trivalent or higher amine compound, and a trivalent or higher amino alcohol compound include 1,2,4-benzenetriol, methylene-2,4,6-trihydroxy. Examples include benzoate, phloroglicinol, and pyrogallol.
In addition, compounds obtained by adding α, β-unsaturated carboxylic acid to glycidyl compounds such as novolak type epoxy resin and bisphenol A diglycidyl ether, trimellitic acid and the like and vinyl monomers containing a hydroxyl group in the molecule Examples include esterified products, triallyl trimellitic acid, and epoxy compounds (for example, novolac-type epoxy resins).
Furthermore, cationically polymerizable epoxy compounds (for example, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc.) can be used.

These compounds having three or more polymerizable groups may be used alone or in combination of two or more.
The content of the compound having three or more polymerizable groups in the molecule is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and still more preferably 1 to 25% by mass.

-Other polymerizable compounds-
For the pattern forming material of the present invention, a polymerizable compound other than the polymerizable compound may be used. For example, an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and an aliphatic polyhydric alcohol compound, an unsaturated carboxylic acid and a polyvalent amine compound Examples include amides.

  Examples of the monomer of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, and polyethylene glycol having 2 to 18 ethylene groups. Di (meth) acrylate (for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate , Tetradecaethylene glycol di (meth) acrylate, etc.), propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 18 propylene groups (for example, , Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) acrylate, etc.), neopentyl glycol di (meth) acrylate, ethylene oxide modified Neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1 4-cyclohexanediol di (meth) acrylate, 1,5-pentanediol (meth) acrylate, pentaerythritol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, di (meth) acrylate of alkylene glycol chain having at least one ethylene glycol chain / propylene glycol chain (for example, International Publication No. 01/98832 pamphlet), polybutylene glycol di (meth) acrylate, glycerin di (meth) acrylate, xylenol di (meth) acrylate and the like. It is.

  Among the (meth) acrylic acid esters, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meta) from the viewpoint of easy availability. ) Acrylate, di (meth) acrylate of alkylene glycol chain each having at least one ethylene glycol chain / propylene glycol chain, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, diglycerin di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,5-pe Butanediol (meth) acrylate, neopentyl glycol di (meth) acrylate.

  Examples of the ester (itaconic acid ester) of the itaconic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4- Examples include butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate.

  Examples of the ester (crotonate ester) of the crotonic acid and the aliphatic polyhydric alcohol compound include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Can be mentioned.

  Examples of the ester (isocrotonic acid ester) of the isocrotonic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diisocrotonate and pentaerythritol diisocrotonate.

  Examples of the ester of maleic acid and the aliphatic polyhydric alcohol compound (maleic acid ester) include ethylene glycol dimaleate, triethylene glycol dimaleate, and pentaerythritol dimaleate.

  Examples of the amide derived from the polyvalent amine compound and the unsaturated carboxylic acid include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, and octamethylene bis ( And (meth) acrylamide, diethylenetriamine bis (meth) acrylamide, and the like.

  In addition to the above, as the polymerizable compound, for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Compounds obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound such as hexanediol diglycidyl ether, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyester acrylates and polyester (meth) acrylate oligomers, epoxy compounds (for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ester, etc. Ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether) and (meth) acrylic acid reacted polyfunctional acrylates and methacrylates, Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308 (1984), photocurable monomers and oligomers, allyl esters (for example, diallyl phthalate, diallyl adipate, diallyl malonate, diallylamide (eg diallylacetamide, etc.), cations Polymerizable divinyl ethers (for example, butanediol-1,4-divinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether) , Dipropylene glycol divinyl ether, hexanediol divinyl ether, etc.), epoxy compounds (eg, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene) Glycol diglycidyl ether, hexanediol diglycidyl ether, etc.), oxetanes (eg, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, etc.), epoxy compounds, oxetanes (eg, WO01 / 2165) Compound, N-β-hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis (β-methacryloxyethyl) acrylamide And compounds having two different ethylenically unsaturated double bonds, such as allyl methacrylate.

Examples of the vinyl esters include divinyl succinate and divinyl adipate.
These polymerizable compounds may be used alone or in combination of two or more.

As content in the said photosensitive layer of the said polymeric compound, 5-90 mass% is preferable, for example, 15-60 mass% is more preferable, and 20-50 mass% is especially preferable.
If the content is 5% by mass, the strength of the tent film may be reduced, and if it exceeds 90% by mass, edge fusion during storage (exudation failure from the end of the roll) may be deteriorated. .

Specific examples of the monomer having an I / O value of 0.5 to 1.5 include, but are not limited to, compounds represented by the structural formulas shown below.
Examples of the compound include compounds represented by the following structural formulas exemplified in the specific examples of the compound represented by the structural formula (13).
However, in said formula, R represents a hydrogen atom or a methyl group. n represents an integer of 1 to 30, m and L each represents an integer of 1 or more, and m + L represents an integer of 1 to 30. Me represents a methyl group, and Bu represents a butyl group.

Examples of the monomer having an I / O value of 0.5 to 1.5 include compounds represented by the structural formulas (15) to (20). However, in this case, n in the structural formulas (15) to (20) represents an integer of 1 to 30.
Moreover, the compound represented by the following structural formula is also mentioned.
However, in the above structural formula, R represents a hydrogen atom or a methyl group, _{X 1} represents a _{(CH 2 CH 2 O) n} , X 2 represents _{(CH (CH 3) CH 2} O) m. n and m represent an integer of 1 to 30.

Furthermore, the compounds represented by the following structural formulas, which are given as specific examples of the compounds represented by the structural formulas (24) and (25), are also applicable. However, in the following structural formula, R represents a hydrogen atom or a methyl group. n1, n2, and n3 represent an integer of 1-30. m1, m2, and m3, and L1, L2, and L3 each represent an integer of 1 or more, and m1 + L1, m2 + L2, and m3 + L3 each represent an integer of 1-30.

  In addition, examples of the monomer having an I / O value of 0.5 to 1.5 include commercially available products such as BPE-200, BPE-500, and BPE-1000 manufactured by Shin-Nakamura Chemical Co., Ltd.

(Photopolymerization initiator)
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is visible from the ultraviolet region. It is preferable to have photosensitivity to the light, and it may be an activator that produces some kind of action with a photoexcited sensitizer and generates active radicals, and initiates cationic polymerization depending on the type of monomer. Initiator may be used.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, Examples include ketone compounds, acylphosphine oxide compounds, aromatic onium salts, and metallocenes. Among these, halogenated hydrocarbons having a triazine skeleton, oxime derivatives, ketone compounds, hexaarylbiimidazoles from the viewpoints of the sensitivity and storage stability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate. System compounds are preferred.

  Examples of the hexaarylbiimidazole include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-fluorophenyl)- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (3-methoxyphenyl) ) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (4-methoxyphenyl) biimidazole, 2,2'-bis (4-methoxyphenyl) -4 , 4 ', , 5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-trifluoromethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, compounds described in International Publication No. 00/52529 pamphlet, and the like.

  The biimidazoles are described in, for example, Bull. Chem. Soc. Japan, 33, 565 (1960); Org. It can be easily synthesized by the method disclosed in Chem, 36 (16) 2262 (1971).

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, F . C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, a US patent And the compounds described in the specification of No. 42122976.

  Wakabayashi et al., Bull. Chem. Soc. As a compound described in Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl)- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2, 4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-n-nonyl-4,6- Bis (trichloromethyl) 1,3,5-triazine, 2- (α, α, β- trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in British Patent 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6. -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) Examples include -4-amino-6-trichloromethyl-1,3,5-triazine.

  Examples of the compound described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

  Examples of the compound described in German Patent No. 3333724 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-Methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3 , 5-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloromethyl) ) -1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan) 2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 , 5-triazine and the like.

  F. above. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964) include, for example, 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (tribromomethyl); -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tri (bromomethyl) -1,3,5- Examples include triazine and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine.

  Examples of the compound described in JP-A-62-258241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Naphtyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropyl) Phenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloro Chill) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-281728 include 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2 , 6-Difluorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

  Examples of the compound described in JP-A-5-34920 include 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl]-. 1,3,5-triazine, trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4- Chlorophenyl) -4,6-bis (tribromomethyl) -s-triazine and the like.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl). -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-phenyl-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, , 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-tripromomethyl-5-styryl-1,3,4-oxadiazole, etc. ) And the like.

  Examples of the oxime derivative include compounds represented by the following structural formulas (41) to (74).

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

Examples of the metallocenes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, ⁵ -cyclopentadienyl-η ⁶ -cumenyl-iron (1 +)-hexafluorophosphate (1-), JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and Examples thereof include compounds described in US Pat. No. 3,615,455.

  Further, as photopolymerization initiators other than the above, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, and the like, polyhalogen compounds (for example, Carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, and JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206 , Coumarin compounds described in JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate) N-butyl acid, phenethyl 4-dimethylaminobenzoate, 4 Dimethylaminobenzoic acid 2-phthalimidoethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4-dimethylaminobenzaldehyde 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylami Aminofluoranes (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc.), acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6 -Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.).

  Further, vicinal polyketaldonyl compounds described in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, and US Pat. No. 2,722,512 are described. An aromatic acyloin compound substituted with α-hydrocarbon, a polynuclear quinone compound described in US Pat. Nos. 3,046,127 and 2,951,758, an organoboron compound described in JP-A-2002-229194, and a radical Generator, triarylsulfonium salt (for example, salt with hexafluoroantimony or hexafluorophosphate), phosphonium salt compound (for example, (phenylthiophenyl) diphenylsulfonium salt) (effective as a cationic polymerization initiator), International Publication No. 01/71428 Pamphlet Like onium salt compounds described.

  The said photoinitiator may be used individually by 1 type, and may use 2 or more types together. Examples of the combination of two or more include, for example, a combination of hexaarylbiimidazole and 4-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound described in Japanese Patent Publication No. 51-48516, and trihalomethyl- Combinations of s-triazine compounds, combinations of aromatic ketone compounds (such as thioxanthone) and hydrogen donors (such as dialkylamino-containing compounds and phenol compounds), combinations of hexaarylbiimidazole and titanocene, and coumarins And combinations of titanocene and phenylglycines.

  As content in the said photosensitive layer of the said photoinitiator, 0.1-30 mass% is preferable, 0.5-20 mass% is more preferable, 0.5-15 mass% is especially preferable.

-Other ingredients-
Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, color formers, colorants, and the like, and further adhesion promoters to the substrate surface and other auxiliary agents (for example, pigments, Conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension adjusting agents, chain transfer agents, etc.) may be used in combination. By appropriately containing these components, it is possible to adjust properties such as stability, photographic properties, print-out properties, and film properties of the target pattern forming material.

--- Sensitizer--
The sensitizer can be appropriately selected by visible light, ultraviolet light, visible light laser, or the like as a light irradiation means to be described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, Methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, chloroacrine) Don, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl)- 7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3 '-Carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7- Diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin Examples thereof include 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and others, and JP-A-5-19475, JP-A-7-271028, JP-A-2002-. No. 363206, JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, and the like.

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

As content in the said photosensitive layer of the said sensitizer, 0.05-30 mass% is preferable, 0.1-20 mass% is more preferable, 0.2-10 mass% is especially preferable.
When the content is less than 0.05% by mass, the sensitivity to active energy rays decreases, the exposure process takes time, and the productivity may decrease. When the content exceeds 30% by mass, the photosensitive layer May precipitate during storage.

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

As content of the said thermal-polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said polymeric compound of the said photosensitive layer, 0.005-2 mass% is more preferable, 0.01-1 mass% Is particularly preferred.
When the content is less than 0.001% by mass, stability during storage may be reduced, and when it exceeds 5% by mass, sensitivity to active energy rays may be reduced.

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

  As content in the said photosensitive layer of the said plasticizer, 0.1-50 mass% is preferable, 0.5-40 mass% is more preferable, 1-30 mass% is especially preferable.

--Coloring agent--
The color former may be added to give a visible image (printing function) to the photosensitive layer after exposure.
Examples of the color former include tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, tris (4- Diethylamino-2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolylmethane, tris (4-di Aminotriarylmethanes such as propylaminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine, etc. Aminoxanthines; 3,6-bis (diethyl Aminothioxanthenes such as mino) -9- (2-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9- Amino-9,10-dihydroacridine such as phenylacridine, 3,6-bis (benzylamino) -9,10-dividro-9-methylacridine; aminophenoxazine such as 3,7-bis (diethylamino) phenoxazine Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (4-dimethylamino) Aminophenylmethanes such as phenyl) anilinomethane; 4-amino-4 ′ Aminohydrocinnamic acids such as dimethylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis ( Ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; phenethylanilines such as N, N-diethyl-4-phenethylaniline; 10-acetyl-3,7-bis (dimethylamino) ) An acyl derivative of a leuco dye containing basic NH such as phenothiazine; a leuco-like compound which does not have an oxidizable hydrogen such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmentane but can be oxidized to a coloring compound; Leucoin digoid pigment; U.S. Pat. Nos. 3,042,515 and 3,043 Organic amines that can be oxidized to a colored form as described in US Pat. No. 517 (eg, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediamine (Phenylamine, N-vinylcarbazole) are mentioned, and among these, triarylmethane compounds such as leucocrystal violet are preferable.

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

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

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

  Examples of the colorant suitable for producing a color filter include C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 83, C.I. I. Pigment violet 23, and those described in JP-A-2002-162752 (0138) to (0141). There is no restriction | limiting in particular as an average particle diameter of the said coloring agent, Although it can select suitably according to the objective, For example, 5 micrometers or less are preferable and 1 micrometer or less is more preferable. Moreover, when producing a color filter, as said average particle diameter, 0.5 micrometer or less is preferable.

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

  As content in the said photosensitive layer of the said dye, 0.001-10 mass% is preferable, 0.01-5 mass% is more preferable, 0.1-2 mass% is especially preferable.

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

  Preferable examples of the adhesion promoter include adhesion promoters described in JP-A Nos. 5-11439, 5-341532, and 6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole Amino group-containing benzotriazole, silane coupling agents, and the like.

  As content in the said photosensitive layer of the said adhesion promoter, 0.001 mass%-20 mass% are preferable, 0.01-10 mass% is more preferable, 0.1 mass%-5 mass% are especially preferable.

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

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

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

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

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

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

--Surfactant--
In order to improve the surface unevenness generated when the pattern forming material of the present invention is produced, a known surfactant can be used in combination.
The surfactant can be appropriately selected from, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a fluorine-containing surfactant.

The content of the surfactant in the photosensitive layer is preferably 0.001 to 10% by mass.
When the content is less than 0.001% by mass, the effect of improving the surface shape may not be obtained, and when it exceeds 10% by mass, the adhesion may be deteriorated.

  There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 1-100 micrometers is preferable, 2-50 micrometers is more preferable, and 4-30 micrometers is especially preferable.

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

  The support is preferably made of synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

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

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

The pattern forming material may form a protective film on the photosensitive layer.
Examples of the protective film include those used for the support, paper, paper laminated with polyethylene, polypropylene, and the like. Among these, polyethylene film and polypropylene film are preferable.
There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable, 8-50 micrometers is more preferable, 10-30 micrometers is especially preferable.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

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

  It is preferable that the pattern forming material is wound around a cylindrical core, wound into a long roll, and stored. There is no restriction | limiting in particular as length of the said elongate pattern formation material, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. The roll-shaped pattern forming material may be slit into a sheet shape. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and use a low moisture-permeable material for packaging. Things are preferable.

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

<Other layers>
There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, layers, such as a cushion layer, a barrier layer, a peeling layer, an adhesive layer, a light absorption layer, a surface protective layer, are mentioned. . The said pattern formation material may have these layers individually by 1 type, may have 2 or more types, and may have 2 or more layers of the same kind.

  The photosensitive layer in the pattern forming material of the present invention modulates the light from the light irradiating means by means of a light modulating means having n picture elements for receiving and emitting light from the light irradiating means, A lens aperture shape that does not allow light that has passed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface in the pixel part to be incident or light from the peripheral part of the picture element part is not incident. It is preferable that exposure is performed with light passing through a microlens array in which microlenses are arranged. Details of the light irradiating means, the pixel part, the light modulating means, the aspherical surface, the microlens, and the microlens array will be described later.

[Method for producing pattern forming material]
The pattern forming material can be manufactured, for example, as follows.
First, the materials contained in the photosensitive layer and other layers are dissolved, emulsified or dispersed in water or a solvent to prepare a coating solution.

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

  Next, the coating liquid is applied onto the support and dried to form each layer, whereby a pattern forming material can be produced. For example, a photosensitive resin composition solution in which the components of the photosensitive layer are 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. Forming materials can be manufactured.

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

  The pattern forming material of the present invention is excellent in the effect of preventing unexposed film breakage, has high resolution, is excellent in tent properties and developability, and is excellent in releasability during etching. Can be suitably used for the formation of permanent patterns, for the production of liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, and for the formation of patterns for holograms, micromachines, proofs, etc. It can be suitably used for forming a fine wiring pattern. Moreover, it can use suitably for the pattern formation method and pattern formation apparatus of this invention.

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

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

[Exposure process]
The said exposure process is a process of exposing with respect to the photosensitive layer in the pattern formation material of this invention. The pattern forming material of the present invention is as described above.

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

  The substrate is not particularly limited, and is appropriately selected from known materials having high surface smoothness to those having an uneven surface and those having a hole (hole) such as a through hole or a via hole. However, a plate-like substrate (substrate) is preferable. Specifically, a known printed wiring board forming substrate (for example, a copper-clad laminate), a glass plate (for example, a soda glass plate), or a synthetic resin A film, paper, a metal plate, and the like. Among these, the copper-clad laminate is preferable in that it has excellent adhesion to a material containing copper.

The method for forming the laminate is not particularly limited and may be appropriately selected depending on the purpose. However, the pattern forming material may be laminated on the substrate while performing at least one of heating and pressing. preferable.
There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, a laminator (for example, Taisei Laminator company make, VP-II) vacuum laminator etc. Preferably mentioned.

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

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose.For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is generated. It is preferable to use.

  The digital exposure means is not particularly limited and may be appropriately selected depending on the purpose. For example, the light irradiation means for irradiating light, and the light irradiation means for irradiating based on the pattern information to be formed. Examples thereof include light modulation means for modulating light.

<Light modulation means>
The light modulating means is not particularly limited as long as it can modulate light, and can be appropriately selected according to the purpose. For example, it preferably has n pixel portions.
The light modulation means having the n picture elements is not particularly limited and can be appropriately selected according to the purpose. For example, a spatial light modulation element is preferable.

  Examples of the spatial light modulator include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), and modulates transmitted light by an electro-optic effect. An optical element (PLZT element), a liquid crystal optical shutter (FLC), etc. are mentioned, Among these, DMD is mentioned suitably.

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

Hereinafter, an example of the light modulation means will be described with reference to the drawings.
As shown in FIG. 1, in the DMD 50, a large number (for example, 1024 × 768) of micromirrors (micromirrors) 62, each constituting a pixel (pixel), are arranged in a lattice pattern on an SRAM cell (memory cell) 60. It is a mirror device arranged. In each pixel, a micromirror 62 supported by a support column is provided at the top, and a material having high reflectivity such as aluminum is deposited on the surface of the micromirror 62. In addition, the reflectance of the micromirror 62 is 90% or more, and the arrangement pitch is 13.7 μm as an example in both the vertical direction and the horizontal direction. A silicon gate CMOS SRAM cell 60 manufactured in a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke, and the entire structure is monolithic. ing.

  When a digital signal is written in the SRAM cell 60 of the DMD 50, the micromirror 62 supported by the support is tilted in a range of ± α degrees (for example, ± 12 degrees) with respect to the substrate side on which the DMD 50 is disposed with the diagonal line as the center. It is done. 2A shows a state where the micromirror 62 is tilted to + α degrees when the micromirror 62 is in the on state, and FIG. 2B shows a state where the micromirror 62 is tilted to −α degrees when the micromirror 62 is in the off state. Therefore, by controlling the inclination of the micro mirror 62 in each pixel of the DMD 50 as shown in FIG. 1 according to the pattern information, the laser light B incident on the DMD 50 is reflected in the inclination direction of each micro mirror 62. The

  FIG. 1 shows an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled to + α degrees or −α degrees. The on / off control of each micromirror 62 is performed by a controller 302 (see FIG. 12) connected to the DMD 50. Further, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 62 travels.

  Further, it is preferable that the DMD 50 is arranged with a slight inclination so that the short side forms a predetermined angle θ (for example, 0.1 ° to 5 °) with the sub-scanning direction. 3A shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not tilted, and FIG. 3B shows the scanning trajectory of the exposure beam 53 when the DMD 50 is tilted. Show.

In the DMD 50, a number of micromirror arrays in which a large number (for example, 1024) of micromirrors are arranged in the longitudinal direction are arranged in a short direction (for example, 756 sets). as shown, by tilting the DMD 50, the pitch P ₂ of the scanning locus of the exposure beams 53 from each micromirror (scan line), it becomes narrower than the pitch P ₁ of the scanning line in the case of not tilting the DMD 50, significant resolution Can be improved. On the other hand, the inclination angle of the DMD 50 is small, the scanning width _{W 2} in the case of tilting the DMD 50, which is substantially equal to the scanning width _{W 1} when not inclined DMD 50.

Next, a method for increasing the modulation speed in the optical modulation means (hereinafter referred to as “high-speed modulation”) will be described.
It is preferable that the light modulation means can control any less than n pixel parts arranged continuously from the n picture elements according to pattern information. There is a limit to the data processing speed of the light modulation means, and the modulation speed per line is determined in proportion to the number of pixels to be used. By using, the modulation speed per line is increased.

Hereinafter, the high-speed modulation will be further described with reference to the drawings.
When the laser light B is irradiated from the fiber array light source 66 to the DMD 50, the laser light reflected when the micromirror of the DMD 50 is in the on state is imaged on the pattern forming material 150 by the lens systems 54 and 58. In this manner, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the pattern forming material 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of used pixel elements of the DMD 50. . Further, when the pattern forming material 150 is moved at a constant speed together with the stage 152, the pattern forming material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region 170 is provided for each exposure head 166. Is formed.

  In this example, as shown in FIGS. 4A and 4B, the DMD 50 has 768 micromirror arrays in which 1024 micromirrors are arrayed in the main scanning direction. In this example, the controller 302 (see FIG. 12) performs control so that only a part of the micromirror rows (for example, 1024 × 256 rows) are driven.

  In this case, a micromirror array arranged at the center of the DMD 50 as shown in FIG. 4 (A) may be used, and a micromirror arranged at the end of the DMD 50 as shown in FIG. 4 (B). A column may be used. In addition, when a defect occurs in some of the micromirrors, the micromirror array to be used may be appropriately changed depending on the situation, such as using a micromirror array in which no defect has occurred.

  Since the data processing speed of the DMD 50 is limited and the modulation speed per line is determined in proportion to the number of pixels used, the modulation speed per line can be increased by using only a part of the micromirror array. Get faster. On the other hand, in the case of an exposure method 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 by the scanner 162 is finished and the rear end of the pattern forming material 150 is detected by the sensor 164, the stage 152 is moved upstream of the gate 160 along the guide 158 by the stage driving device 304. It returns to the origin on the side and is moved again along the guide 158 from the upstream side to the downstream side of the gate 160 at a constant speed.

  For example, in the case of using only 384 sets out of 768 sets of micromirror arrays, the modulation can be performed twice as fast per line as compared with the case of using all 768 sets. Also, when only 256 pairs are used in the 768 sets of micromirror arrays, modulation can be performed three times faster per line than when all 768 sets are used.

  As described above, according to the pattern forming method of the present invention, the micromirror array in which 1,024 micromirrors are arranged in the main scanning direction includes the DMD in which 768 sets are arranged in the subscanning direction. By controlling so that only a part of the micromirror rows are driven by the controller, the modulation rate per line becomes faster than when all the micromirror rows are driven.

  In addition, an example in which the DMD micromirror is partially driven has been described, but the length of the direction corresponding to the predetermined direction is reflected on the substrate longer than the length of the direction intersecting the predetermined direction according to the control signal. Even if a long and narrow DMD in which a large number of micromirrors capable of changing the surface angle are arranged in a two-dimensional manner is used, the number of micromirrors for controlling the angle of the reflecting surface is reduced. Can do.

  The exposure method is preferably performed while relatively moving the exposure light and the photosensitive layer, and in this case, it is preferable to use the high-speed modulation together. Thereby, high-speed exposure can be performed in a short time.

  In addition, as shown in FIG. 5, the entire surface of the pattern forming material 150 may be exposed by a single scan in the X direction by the scanner 162, and as shown in FIGS. 6A and 6B, the scanner 162. After the pattern forming material 150 is scanned in the X direction, the scanner 162 is moved one step in the Y direction, and scanning is performed in the X direction. Thus, the pattern forming material 150 is scanned a plurality of times. Alternatively, the entire surface may be exposed. In this example, the scanner 162 includes 18 exposure heads 166. Note that the exposure head includes at least the light irradiation unit and the light modulation unit.

  The exposure is performed on a partial area of the photosensitive layer to cure the partial area, and uncured areas other than the cured partial area are removed in a development step described later. A pattern is formed.

Next, an example of a pattern forming apparatus including the light modulation means will be described with reference to the drawings.
As shown in FIG. 7, the pattern forming apparatus including the light modulation means includes a flat plate stage 152 that holds a sheet-like pattern forming material 150 by adsorbing to the surface.
Two guides 158 extending along the stage moving direction are installed on the upper surface of the thick plate-like installation table 156 supported by the four legs 154. The stage 152 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by a guide 158 so as to be reciprocally movable. The pattern forming apparatus has a drive device (not shown) for driving the stage 152 along the guide 158.

  A U-shaped gate 160 is provided at the center of the installation table 156 so as to straddle the movement path of the stage 152. Each of the ends of the U-shaped gate 160 is fixed to both side surfaces of the installation table 156. A scanner 162 is provided on one side of the gate 160, and a plurality of (for example, two) detection sensors 164 for detecting the front and rear ends of the pattern forming material 150 are provided on the other side. . The scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152. The scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.

As shown in FIGS. 8 and 9B, the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in a substantially matrix of m rows and n columns (for example, 3 rows and 5 columns). ing. In this example, four exposure heads 166 are arranged in the third row in relation to the width of the pattern forming material 150. In addition, when showing each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure head 166 _mn .

An exposure area 168 by the exposure head 166 has a rectangular shape with a short side in the sub-scanning direction. Accordingly, as the stage 152 moves, a strip-shaped exposed region 170 is formed in the pattern forming material 150 for each exposure head 166. In addition, when showing the exposure area by each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure area 168 _mn .

Further, as shown in FIGS. 9A and 9B, each of the exposure heads in each row arranged in a line so that the strip-shaped exposed regions 170 are arranged in the direction orthogonal to the sub-scanning direction without gaps. These are arranged with a predetermined interval (natural number times the long side of the exposure area, twice in this example) in the arrangement direction. Therefore, can not be exposed portion between the exposure area _{168 11} in the first row and the exposure area _{168 12,} it can be exposed by the second row of the exposure area _{168 21} and the exposure area _{168 31} in the third row.

As shown in FIGS. 10 and 11, each of the exposure heads 166 _{11 to} 166 _mn serves as the light modulation means (spatial light modulation element that modulates each pixel) according to the pattern information. A digital micromirror device (DMD) 50 manufactured by Texas Instruments, USA is provided. The DMD 50 is connected to the controller 302 (see FIG. 12) including a data processing unit and a mirror drive control unit. The data processing unit of the controller 302 generates a control signal for driving and controlling each micromirror in the region to be controlled by the DMD 50 for each exposure head 166 based on the input pattern information. The area to be controlled will be described later. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the pattern information processing unit. The control of the angle of the reflecting surface will be described later.

  On the light incident side of the DMD 50, a fiber array light source 66 including a laser emitting section in which emission ends (light emitting points) of an optical fiber are arranged in a line along a direction corresponding to the long side direction of the exposure area 168, a fiber A lens system 67 for correcting the laser light emitted from the array light source 66 and condensing it on the DMD, and a mirror 69 for reflecting the laser light transmitted through the lens system 67 toward the DMD 50 are arranged in this order. In FIG. 10, the lens system 67 is schematically shown.

  As shown in detail in FIG. 11, the lens system 67 is inserted into the optical path of the light passing through the condenser lens 71 and the condenser lens 71 that collects the laser light B as the illumination light emitted from the fiber array light source 66. A rod-shaped optical integrator (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 mirror 69 side. 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 enter the DMD 50 as a light beam that is close to parallel light and has a uniform beam cross-sectional intensity. The shape and action of the rod integrator 72 will be described in detail later.

  The laser beam B emitted from the lens system 67 is reflected by the mirror 69 and irradiated to the DMD 50 via the TIR (total reflection) prism 70. In FIG. 10, the TIR prism 70 is omitted.

  An imaging optical system 51 that images the laser beam 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, but as shown in detail in FIG. 11, the imaging optical system 51 includes a first imaging optical system including lens systems 52 and 54 and lens systems 57 and 58. The optical system includes a second imaging optical system, a microlens array 55 inserted between these imaging optical systems, and an aperture array 59.

The microlens array 55 is formed by two-dimensionally arranging a large number of microlenses 55a corresponding to the pixels of the DMD 50. In this example, as described later, only 1024 × 256 rows of the 1024 × 768 rows of micromirrors of the DMD 50 are driven, and accordingly, 1024 × 256 rows of microlenses 55a are arranged. The arrangement pitch of the micro lenses 55a is 41 μm in both the vertical and horizontal directions. As an example, the microlens 55a has a focal length of 0.19 mm, an NA (numerical aperture) of 0.11, and is formed from the optical glass BK7. The shape of the micro lens 55a will be described in detail later.
The beam diameter of the laser beam B at the position of each microlens 55a is 41 μm.

  The aperture array 59 is formed by forming a large number of apertures (openings) 59 a corresponding to the respective micro lenses 55 a of the micro lens array 55. The diameter of the aperture 59a is, for example, 10 μm.

  The first imaging optical system forms an image on the microlens array 55 by enlarging the image by the DMD 50 three times. The second imaging optical system enlarges the image that has passed through the microlens array 55 by 1.6 times, and forms and projects the image on the pattern forming material 150. Therefore, as a whole, the image formed by the DMD 50 is enlarged and enlarged by 4.8 times, and is imaged and projected on the pattern forming material 150.

  A prism pair 73 is disposed between the second imaging optical system and the pattern forming material 150. By moving the prism pair 73 in the vertical direction in FIG. 11, an image on the pattern forming material 150 is obtained. The focus can be adjusted. In the figure, the pattern forming material 150 is sub-scanned in the direction of 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 forming method of the present invention When the pattern to be formed is an image pattern, it is a pixel, and when the light modulation means includes a DMD, it is a micromirror.
There is no restriction | limiting in particular as the number (the said n) of picture element parts which the said light modulation element has, It can select suitably according to the objective.
The arrangement of the picture element portions in the light modulation element is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably arranged in a two-dimensional form, and arranged in a lattice form. More preferably.

<Light irradiation means>
The light irradiation means is not particularly limited and may be appropriately selected depending on the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copier, fluorescent tube, LED, etc. , A known light source such as a semiconductor laser, or a means capable of synthesizing and irradiating two or more lights. Among these, a means capable of synthesizing and irradiating two or more lights is preferable.
The light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support. In particular, ultraviolet to visible light, electron beam, X-ray, laser beam, and the like can be mentioned. Of these, laser beam is preferable, and a laser combining two or more lights (hereinafter, referred to as “combined laser”). More preferred. Even when light irradiation is performed after the support is peeled off, the same light can be used.

The wavelength of the ultraviolet to visible light is preferably, for example, 300 to 1,500 nm, more preferably 320 to 800 nm, and particularly preferably 330 nm to 650 nm.
As a wavelength of the said laser beam, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330 nm-500 nm is still more preferable, 400 nm-450 nm is especially preferable.

  Examples of means capable of irradiating the combined laser include, for example, a plurality of lasers, a multimode optical fiber, and collective optics for condensing and coupling the laser beams respectively emitted from the plurality of lasers to the multimode optical fiber. Means having a system are preferred.

  Hereinafter, means (fiber array light source) capable of irradiating the combined laser will be described with reference to the drawings.

  As shown in FIG. 27 a, the fiber array light source 66 includes a plurality of (for example, 14) laser modules 64, and one end of the multimode optical fiber 30 is coupled to each laser module 64. An optical fiber 31 having the same core diameter as that of the multimode optical fiber 30 and a smaller cladding diameter than the multimode optical fiber 30 is coupled to the other end of the multimode optical fiber 30. As shown in detail in FIG. 27b, seven end portions of the multimode optical fiber 31 opposite to the optical fiber 30 are arranged along the main scanning direction orthogonal to the sub-scanning direction, and they are arranged in two rows to form a laser. An emission unit 68 is configured.

  As shown in FIG. 27b, the laser emitting portion 68 configured by the end portion of the multimode optical fiber 31 is sandwiched and fixed between two support plates 65 having a flat surface. In addition, a transparent protective plate such as glass is preferably disposed on the light emitting end face of the multimode optical fiber 31 for protection. The light exit end face of the multimode optical fiber 31 has high light density and is likely to collect dust and easily deteriorate. However, the protective plate as described above prevents the dust from adhering to the end face and deteriorates. Can be delayed.

  In this example, in order to arrange the emission ends of the optical fibers 31 having a small cladding diameter in a line without any gap, the multi-mode optical fiber 30 is disposed between two adjacent multi-mode optical fibers 30 in a portion having a large cladding diameter. Two exit ends of the optical fiber 31 coupled to two adjacent multi-mode optical fibers 30 where the exit ends of the optical fibers 31 coupled to the stacked multi-mode optical fibers 30 are adjacent to each other at a portion where the cladding diameter is large. Are arranged so as to be sandwiched between them.

  For example, as shown in FIG. 28, an optical fiber 31 having a length of 1 to 30 cm and having a small cladding diameter is coaxially connected to the tip portion of the multimode optical fiber 30 having a large cladding diameter on the laser light emission side. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 31 is fused and joined to the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 31 a of the optical fiber 31 is the same as the diameter of the core 30 a of the multimode optical fiber 30.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused to an optical fiber having a short cladding diameter and a large cladding diameter may be coupled to the output end of the multimode optical fiber 30 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 31 may be referred to as an emission end portion of the multimode optical fiber 30.

  The multimode optical fiber 30 and the optical fiber 31 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used. In the present embodiment, the multimode optical fiber 30 and the optical fiber 31 are step index type optical fibers, and the multimode optical fiber 30 has a cladding diameter = 125 μm, a core diameter = 50 μm, NA = 0.2, an incident end face. The transmittance of the coat is 99.5% or more, and the optical fiber 31 has a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2.

  In general, in the laser light in the infrared region, the propagation loss increases as the cladding diameter of the optical fiber is reduced. For this reason, a suitable cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, the cladding thickness {(cladding diameter−core diameter) / 2} is set to an infrared light having a wavelength band of 800 nm. The propagation loss hardly increases even if it is about ½ of the case of propagating infrared light and about ¼ of the case of propagating infrared light in the 1.5 μm wavelength band for communication. Therefore, the cladding diameter can be reduced to 60 μm.

  However, the cladding diameter of the optical fiber 31 is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber array light source is 125 μm, but the depth of focus becomes deeper as the clad diameter becomes smaller. Therefore, the clad diameter of the multimode optical fiber is preferably 80 μm or less, preferably 60 μm or less. More preferably, it is 40 μm or less. On the other hand, since the core diameter needs to 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 includes a combined laser light source (fiber array light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6, arrayed and fixed on the heat block 10. And LD7, collimator lenses 11, 12, 13, 14, 15, 16, and 17 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 20, and one multi-lens. Mode optical fiber 30. The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

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

  As shown in FIGS. 30 and 31, the combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements. The package 40 includes a package lid 41 created so as to close the opening thereof. After the deaeration process, a sealing gas is introduced, and the package 40 and the package lid 41 are closed by closing the opening of the package 40 with the package lid 41. 41. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by 41.

  A base plate 42 is fixed to the bottom surface of the package 40, and the heat block 10, a condensing lens holder 45 that holds the condensing lens 20, and the multimode optical fiber 30 are disposed on the top surface of the base plate 42. A fiber holder 46 that holds the incident end is attached. The exit end of the multimode optical fiber 30 is drawn out of the package from an opening formed in the wall surface of the package 40.

  Further, a collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held. An opening is formed in the lateral wall surface of the package 40, and wiring 47 for supplying a driving current to the GaN-based semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 31, in order to avoid complication of the figure, only the GaN-based semiconductor laser LD7 among the plurality of GaN-based semiconductor lasers is numbered, and only the collimator lens 17 among the plurality of collimator lenses is numbered. is doing.

  FIG. 32 shows a front shape of a mounting portion of the collimator lenses 11 to 17. Each of the collimator lenses 11 to 17 is formed in a shape obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the length direction is orthogonal to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 32).

  On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having a light emission width of 2 μm, and each of the laser beams B1 in a state in which the divergence angles in the direction parallel to and perpendicular to the active layer are 10 ° and 30 °, respectively. A laser emitting ~ B7 is used. These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.

Therefore, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the divergence angle is small with respect to the elongated collimator lenses 11 to 17 as described above. Incident light is incident in a state where the direction coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses 11 to 17 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2. 6 mm. 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.

The condensing lens 20 is obtained by cutting an area including the optical axis of a circular lens having an aspheric surface into a long and narrow shape in parallel planes, and is long in the arrangement direction of the collimator lenses 11 to 17, that is, in the horizontal direction and short in the direction perpendicular thereto. Is formed. This condenser lens 20 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 20 is also formed by molding resin or optical glass, for example.

  In addition, since the light emitting means for illuminating the DMD uses a high-intensity fiber array light source in which the output ends of the optical fibers of the combined laser light source are arranged in an array, it has a high output and a deep depth of focus. A pattern forming apparatus can be realized. Furthermore, since the output of each fiber array light source is increased, the number of fiber array light sources required to obtain a desired output is reduced, and the cost of the pattern forming apparatus can be reduced.

  In addition, since the cladding diameter at the exit end of the optical fiber is smaller than the cladding diameter at the entrance end, the diameter of the light emitting portion is further reduced, and the brightness of the fiber array light source can be increased. Thereby, a pattern forming apparatus having a deeper depth of focus can be realized. For example, even in the case of ultra-high resolution exposure with a beam diameter of 1 μm or less and a resolution of 0.1 μm or less, a deep depth of focus can be obtained, and high-speed and high-definition exposure is possible. Therefore, it is suitable for a thin film transistor (TFT) exposure process that requires high resolution.

  The light irradiating means is not limited to a fiber array light source including a plurality of the combined laser light sources, and for example, emits laser light incident from a single semiconductor laser having one light emitting point. A fiber array light source in which fiber light sources including optical fibers are arrayed can be used.

  Further, as the light irradiation means having a plurality of light emitting points, for example, as shown in FIG. 33, a laser in which a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 are arranged on the heat block 100. An array can be used. A chip-shaped multicavity laser 110 in which a plurality of (for example, five) light emitting points 110a shown in FIG. 34A is arranged in a predetermined direction is known. Since the multicavity laser 110 can arrange the light emitting points with high positional accuracy as compared with the case where the chip-shaped semiconductor lasers are arranged, it is easy to multiplex the laser beams emitted from the respective light emitting points. However, since the multicavity laser 110 is likely to be bent at the time of manufacturing the laser when the number of light emitting points increases, the number of light emitting points 110a is preferably 5 or less.

  As the light irradiation means, the multi-cavity laser 110 or a plurality of multi-cavity lasers 110 on the heat block 100 in the same direction as the arrangement direction of the light emitting points 110a of each chip as shown in FIG. An arrayed multi-cavity laser array can be used as a laser light source.

  The combined laser light source is not limited to one that combines laser beams emitted from a plurality of chip-shaped semiconductor lasers. For example, as shown in FIG. 21, a combined laser light source including a chip-shaped multicavity laser 110 having a plurality of (for example, three) light emitting points 110a can be used. The combined laser light source includes a multi-cavity laser 110, a single multi-mode optical fiber 130, and a condenser lens 120. The multi-cavity laser 110 can be composed of, for example, a GaN-based laser diode having an oscillation wavelength of 405 nm.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110 a of the multicavity laser 110 is collected by the condenser lens 120 and enters the core 130 a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  A plurality of light emitting points 110 a of the multicavity laser 110 are arranged in parallel within a width substantially equal to the core diameter of the multimode optical fiber 130, and a focal point substantially equal to the core diameter of the multimode optical fiber 130 is formed as the condenser lens 120. By using a convex lens of a distance or a rod lens that collimates the outgoing beam from the multi-cavity laser 110 only in a plane perpendicular to the active layer, the coupling efficiency of the laser beam B to the multi-mode optical fiber 130 can be increased. it can.

  As shown in FIG. 35, a multi-cavity laser 110 having a plurality of (for example, three) emission points is used, and a plurality of (for example, nine) multi-cavity lasers 110 are equidistant from each other on the heat block 111. A combined laser light source including the laser array 140 arranged in (1) can be used. The plurality of multi-cavity lasers 110 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 110a of each chip.

  This combined laser light source includes a laser array 140, a plurality of lens arrays 114 arranged corresponding to each multi-cavity laser 110, and a single rod arranged between the laser array 140 and the plurality of lens arrays 114. The lens 113, one multimode optical fiber 130, and a condenser lens 120 are provided. The lens array 114 includes a plurality of microlenses corresponding to the emission points of the multicavity laser 110.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110a of the plurality of multi-cavity lasers 110 is collected in a predetermined direction by the rod lens 113, and then each microlens of the lens array 114. It becomes parallel light. The collimated laser beam L is condensed by the condensing lens 120 and enters the core 130a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  Still another example of the combined laser light source will be described. In this combined laser light source, as shown in FIGS. 36A and 36B, a heat block 182 having an L-shaped cross section in the optical axis direction is mounted on a substantially rectangular heat block 180, and two heats are provided. A storage space is formed between the blocks. On the upper surface of the L-shaped heat block 182, a plurality of (for example, two) multi-cavity lasers 110 in which a plurality of light emitting points (for example, five) are arranged in an array form the light emitting points 110a of each chip. It is arranged and fixed at equal intervals in the same direction as the arrangement direction.

  A concave portion is formed in the substantially rectangular heat block 180, and a plurality of (for example, two) light emitting points (for example, five) are arranged in an array on the upper surface of the space side of the heat block 180. The multi-cavity laser 110 is arranged such that its emission point is located on the same vertical plane as the emission point of the laser chip arranged on the upper surface of the heat block 182.

  On the laser beam emission side of the multi-cavity laser 110, a collimator lens array 184 in which collimator lenses are arranged corresponding to the light emission points 110a of the respective chips is arranged. In the collimating lens array 184, the length direction of each collimating lens coincides with the direction in which the laser beam divergence angle is large (fast axis direction), and the width direction of each collimating lens is in the direction in which the divergence angle is small (slow axis direction). They are arranged to match. Thus, by collimating and integrating the collimating lenses, the space utilization efficiency of the laser light can be improved, the output of the combined laser light source can be increased, and the number of parts can be reduced and the cost can be reduced. .

  Further, on the laser light emitting side of the collimating lens array 184, there is one multimode optical fiber 130 and a condensing lens 120 that condenses and couples the laser light to the incident end of the multimode optical fiber 130. Has been placed.

  In the above-described configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110a of the plurality of multicavity lasers 110 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and condensed. The light is condensed by the lens 120 and enters the core 130 a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  As described above, the combined laser light source can achieve particularly high output by the multistage arrangement of multicavity lasers and the array of collimating lenses. By using this combined laser light source, a higher-intensity fiber array light source or bundle fiber light source can be configured, so that it is particularly suitable as a fiber light source constituting the laser light source of the pattern forming apparatus of the present invention.

  It should be noted that a laser module in which each of the combined laser light sources is housed in a casing and the emission end of the multimode optical fiber 130 is pulled out from the casing can be configured.

  In addition, the other end of the multimode optical fiber of the combined laser light source is coupled with another optical fiber having the same core diameter as the multimode optical fiber and a cladding diameter smaller than the multimode optical fiber. However, for example, a multimode optical fiber having a cladding diameter of 125 μm, 80 μm, 60 μm or the like may be used without coupling another optical fiber to the emission end.

Here, the pattern forming method of the present invention will be further described.
In each exposure head 166 of the scanner 162, laser light B1, B2, B3, B4, B5, B6 emitted in a divergent light state from each of the GaN-based semiconductor lasers LD1 to LD7 constituting the combined laser light source of the fiber array light source 66. , And B7 are collimated by corresponding collimator lenses 11-17. The collimated laser beams B <b> 1 to B <b> 7 are collected by the condenser lens 20 and converge on the incident end face of the core 30 a of the multimode optical fiber 30.

  In this example, the collimator lenses 11 to 17 and the condenser lens 20 constitute a condensing optical system, and the condensing optical system and the multimode optical fiber 30 constitute a multiplexing optical system. That is, the laser beams B1 to B7 collected as described above by the condenser lens 20 enter the core 30a of the multimode optical fiber 30 and propagate through the optical fiber to be combined with one laser beam B. The light is emitted from the optical fiber 31 coupled to the output end of the multimode optical fiber 30.

  In each laser module, when the coupling efficiency of the laser beams B1 to B7 to the multimode optical fiber 30 is 0.85 and each output of the GaN-based semiconductor lasers LD1 to LD7 is 30 mW, the light arranged in an array For each of the fibers 31, a combined laser beam B with an output of 180 mW (= 30 mW × 0.85 × 7) can be obtained. Therefore, the output from the laser emitting unit 68 in which the six optical fibers 31 are arranged in an array is about 1 W (= 180 mW × 6).

  In the laser emitting portion 68 of the fiber array light source 66, light emission points with high luminance are arranged in a line along the main scanning direction as described above. A conventional fiber light source that couples laser light from a single semiconductor laser to a single optical fiber has a low output, so that a desired output cannot be obtained unless multiple rows are arranged. Since the laser light source has a high output, a desired output can be obtained even with a small number of columns, for example, one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled on a one-to-one basis, a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser, and the core diameter is 50 μm and the cladding diameter is 125 μm. Since a multimode optical fiber having a numerical aperture (NA) of 0.2 is used, if an output of about 1 W (watt) is to be obtained, 48 multimode optical fibers (8 × 6) must be bundled. Narazu, the area of the light emitting region 0.62 mm ² because it is (0.675mm × 0.925mm), the luminance at laser emitting portion 68 is ^{1.6 × 10 6 (W / m} 2), 1 present optical fiber The luminance per hit is 3.2 × 10 ⁶ (W / m ² ).

On the other hand, when the light irradiating means is a means capable of irradiating a combined laser, an output of about 1 W can be obtained with six multimode optical fibers, and the area of the light emitting region at the laser emitting portion 68 can be obtained. Is 0.0081 mm ² (0.325 mm × 0.025 mm), the luminance at the laser emitting portion 68 is 123 × 10 ⁶ (W / m ² ), which is about 80 times higher than the conventional luminance. be able to. Further, the luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 28 times compared to the conventional one.

  Here, with reference to FIGS. 37A and 37B, the difference in depth of focus between the conventional exposure head and the exposure head of the present embodiment will be described. The diameter of the light emission region of the bundled fiber light source of the conventional exposure head in the sub-scanning direction is 0.675 mm, and the diameter of the light emission region of the fiber array light source of the exposure head in the sub-scanning direction is 0.025 mm. As shown in FIG. 37A, in the conventional exposure head, since the light emitting area of the light irradiating means (bundle-shaped fiber light source) 1 is large, the angle of the light beam incident on the DMD 3 is increased, and as a result, the scanning surface 5 is moved. The angle of the incident light beam increases. For this reason, the beam diameter tends to increase with respect to the light condensing direction (shift in the focus direction).

  On the other hand, as shown in FIG. 37B, in the exposure head in the pattern forming apparatus of the present invention, the diameter of the light emitting region of the fiber array light source 66 in the sub-scanning direction is small, so that it passes through the lens system 67 and enters the DMD 50. As a result, the angle of the light beam incident on the scanning surface 56 is reduced. That is, the depth of focus becomes deep. In this example, the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus substantially corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot. This effect on the depth of focus is more prominent and effective as the required light quantity of the exposure head is larger. In this example, the size of one pixel projected on the exposure surface is 10 μm × 10 μm. The DMD is a reflective spatial light modulator, but FIGS. 37A and 37B are developed views for explaining the optical relationship.

  Pattern information corresponding to the exposure pattern is input to a controller (not shown) connected to the DMD 50 and temporarily stored in a frame memory in the controller. This pattern information is data representing the density of each pixel constituting the image as binary values (whether or not dots are recorded).

  The stage 152 having the pattern forming material 150 adsorbed on the surface thereof is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device (not shown). When the leading edge of the pattern forming material 150 is detected by the detection sensor 164 attached to the gate 160 while the stage 152 passes under the gate 160, the pattern information stored in the frame memory is sequentially read out for a plurality of lines. Then, a control signal is generated for each exposure head 166 based on the pattern information read by the data processing unit. Then, each of the micromirrors of the DMD 50 is controlled on and off for each exposure head 166 based on the generated control signal by the mirror drive control unit.

  When the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the micromirror of the DMD 50 is in the on state is coupled onto the exposed surface 56 of the pattern forming material 150 by the lens systems 54 and 58. Imaged. In this manner, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the pattern forming material 150 is exposed in the number of pixel units (exposure area 168) substantially equal to the number of used pixel elements of the DMD 50. . Further, when the pattern forming material 150 is moved at a constant speed together with the stage 152, the pattern forming material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region 170 is provided for each exposure head 166. Is formed.

<Microlens array>
The exposure is preferably performed using the modulated light through a microlens array, and may be performed through an aperture array, an imaging optical system, or the like.

  The microlens array is not particularly limited and may be appropriately selected depending on the purpose.For example, the microlens array having an aspherical surface capable of correcting aberration due to the distortion of the exit surface in the pixel part, A microlens array having a lens aperture shape that does not allow light from the peripheral portion of the picture element portion to be incident is preferably used.

  There is no restriction | limiting in particular as said aspherical surface, Although it can select suitably according to the objective, For example, a toric surface is preferable.

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

FIG. 13A shows each of DMD 50, light irradiation means 144 for irradiating the DMD 50 with laser light, lens systems (imaging optical systems) 454, 458, and DMD 50 for enlarging and imaging the laser light reflected by the DMD 50. A microlens array 472 in which a large number of microlenses 474 are arranged corresponding to the picture element portion, an aperture array 476 in which a large number of apertures 478 are provided corresponding to each microlens of the microlens array 472, and a laser that has passed through the aperture An exposure head composed of lens systems (imaging optical systems) 480 and 482 for forming an image of light on an exposed surface 56 is shown.
Here, FIG. 14 shows a result of measuring the flatness of the reflection surface of the micromirror 62 constituting the DMD 50. In the figure, the same height positions of the reflecting surfaces are shown connected by contour lines, and the pitch of the contour lines is 5 nm. Note that the x direction and the y direction shown in the figure are two diagonal directions of the micromirror 62, and the micromirror 62 rotates around the rotation axis extending in the y direction as described above. 15A and 15B show the height position displacement of the reflecting surface of the micromirror 62 along the x direction and the y direction, respectively.

  As shown in FIGS. 14 and 15, there is distortion on the reflection surface of the micromirror 62, and when attention is paid particularly to the center of the mirror, distortion in one diagonal direction (y direction) is different from that in the other diagonal line. It is larger than the distortion in the direction (x direction). For this reason, the problem that the shape in the condensing position of the laser beam B condensed with the micro lens 55a of the micro lens array 55 may be distorted may occur.

  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. Hereinafter, this point will be described in detail.

  FIGS. 16A and 16B respectively show the front and side shapes of the entire microlens array 55 in detail. These drawings also show the dimensions of each part of the microlens array 55, and the unit thereof is mm. In the pattern forming method of the present invention, as described above with reference to FIG. 4, the 1024 × 256 rows of micromirrors 62 of the DMD 50 are driven. A row of 1024 microlenses 55a arranged in the direction is arranged in parallel in the vertical direction. In FIG. 9A, the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and k in the vertical direction.

  17A and 17B show the front shape and the side shape of one microlens 55a in the microlens array 55, respectively. In FIG. 9A, the contour lines of the micro lens 55a are also shown. The end surface of each microlens 55a on the light emitting side has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62. More specifically, the micro lens 55a is a toric lens, and has a radius of curvature Rx = −0.125 mm in a direction optically corresponding to the x direction and a radius of curvature Ry = − in a direction corresponding to the y direction. 0.1 mm.

  Therefore, the condensing state of the laser beam B in the cross section parallel to the x direction and the y direction is roughly as shown in FIGS. 18A and 18B, respectively. That is, when the cross section parallel to the x direction is compared with the cross section parallel to the y direction, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. .

  19A, 19B, 19D, and 19D show simulation results of the beam diameter in the vicinity of the condensing position (focal position) of the microlens 55a when the microlens 55a has the above shape. For comparison, FIGS. 20a, 20b, 20c, and 20d show the results of a similar simulation when the microlens 55a has a spherical shape with a radius of curvature Rx = Ry = −0.1 mm. In addition, the value of z in each figure has shown the evaluation position of the focus direction of the micro lens 55a with the distance from the beam emission surface of the micro lens 55a.

The surface shape of the microlens 55a used for the simulation is calculated by the following calculation formula.
In the above formula, Cx means the curvature in the x direction (= 1 / Rx), Cy means the curvature in the y direction (= 1 / Ry), and X is the lens optical axis in the x direction. The distance from O means Y, and Y means the distance from the lens optical axis O in the y direction.

  19A to 19D and FIGS. 20A to 20D, in the pattern forming method of the present invention, the microlens 55a is focused on the micro lens 55a with a focal length in a cross section parallel to the y direction. By using a toric lens smaller than the distance, distortion of the beam shape in the vicinity of the condensing position is suppressed. If so, the pattern forming material 150 can be exposed to a higher-definition image without distortion. It can also be seen that the embodiment shown in FIGS. 19a to 19d has a wider region with a smaller beam diameter, that is, a greater depth of focus.

  In addition, when the magnitude relationship of the distortion of the center part in the x direction and the y direction of the micromirror 62 is opposite to the above, the focal length in the cross section parallel to the x direction is in the cross section parallel to the y direction. If the microlens is made up of a toric lens that is smaller than the focal length, similarly, a higher-definition image without distortion can be exposed to the pattern forming material 150.

  In addition, the aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is disposed such that only light having passed through the corresponding microlens 55a is incident on each aperture 59a. That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to increase the extinction ratio.

  Originally, if the diameter of the aperture 59a of the aperture array 59 installed for the above purpose is reduced to some extent, an effect of suppressing the distortion of the beam shape at the condensing position of the microlens 55a can be obtained. However, in such a case, the amount of light blocked by the aperture array 59 is increased, and the light use efficiency is reduced. On the other hand, when the microlens 55a has an aspherical shape, the light utilization efficiency is kept high because the light is not blocked.

  In the pattern forming method of the present invention, the micro lens 55a which is a toric lens having different curvatures in the x direction and the y direction optically corresponding to the two diagonal directions of the micro mirror 62 is applied. 38A and 38B, the xx direction and yy optically corresponding to the two side directions of the rectangular micromirror 62 are shown in FIGS. A microlens 55a ′ composed of toric lenses having different curvatures in directions may be applied.

  In the pattern forming method of the present invention, the microlens 55a may have a secondary aspherical shape or a higher order (4th, 6th,...) Aspherical shape. By adopting the higher order aspherical shape, the beam shape can be further refined. Furthermore, it is possible to adopt a lens shape in which the curvatures in the x direction and the y direction described above coincide with each other in accordance with the distortion of the reflection surface of the micromirror 62. Hereinafter, examples of such lens shapes will be described in detail.

39A and 39B, the microlens 55a ″ showing the front shape and the side shape with contour lines, respectively, has the same curvature in the x direction and the y direction, and the curvature is equal to the curvature Cy of the spherical lens. The spherical lens shape that is the basis of the lens shape of the microlens 55a ″ is, for example, the lens height (lens) according to the following equation (Equation 2). A curved surface in which the position in the optical axis direction) z is defined is adopted.
FIG. 40 is a graph showing the relationship between the lens height z and the distance h when the curvature Cy = (1 / 0.1 mm).

Then, the curvature Cy of the spherical lens shape is corrected according to the following formula (Equation 3) in accordance with the distance h from the lens center to obtain the lens shape of the microlens 55a ″.

Also in the calculation formula (Formula 3), the meaning of z is the same as the above-described calculation formula (Formula 2). Here, the curvature Cy is corrected using the fourth-order coefficient a and the sixth-order coefficient b. . The lens height z and the distance h when the curvature Cy = (1 / 0.1 mm), the fourth-order coefficient a = 1.2 × 10 ³ , and the sixth-order coefficient a = 5.5 × 10 ⁷ are described. The relationship is shown in a graph in FIG.

  In the embodiment described above, the end surface on the light emission side of the micro lens 55a is an aspherical surface (toric surface). However, one of the two light passing end surfaces is a spherical surface and the other is a cylindrical surface. Thus, the microlens array can be configured to obtain the same effect as the above embodiment.

  Furthermore, in the embodiment described above, the microlens 55a of the microlens array 55 has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62. Such an aspherical shape is adopted. Instead, the same effect can be obtained even if each microlens constituting the microlens array has a refractive index distribution that corrects aberration due to distortion of the reflection surface of the micromirror 62.

  An example of such a microlens 155a is shown in FIG. (A) and (B) of the same figure respectively show the front shape and side shape of the micro lens 155a, and the external shape of the micro lens 155a is a parallel plate shape as shown in the figure. The x and y directions in the figure are as described above.

  23A and 23B schematically show the condensing state of the laser beam B in the cross section parallel to the x direction and the y direction by the micro lens 155a. The microlens 155a has a refractive index distribution that gradually increases outward from the optical axis O. In the drawing, the broken line shown in the microlens 155a indicates that the refractive index is predetermined from the optical axis O. The position changed with the pitch is shown. As shown in the figure, when the cross section parallel to the x direction and the cross section parallel to the y direction are compared, the ratio of the refractive index change of the microlens 155a is larger in the latter cross section, and the focal length is larger. It is shorter. Even when a microlens array composed of such a gradient index lens is used, it is possible to obtain the same effect as when the microlens array 55 is used.

  In addition, in the microlens whose surface shape is aspherical like the microlens 55a previously shown in FIGS. 17 and 18, the refractive index distribution as described above is given together, and both by the surface shape and the refractive index distribution. The aberration due to the distortion of the reflection surface of the micromirror 62 may be corrected.

Next, another example of the microlens array will be described with reference to the drawings. As shown in FIG. 42, the microlens array of this example is formed by arranging microlenses having a lens opening shape that does not allow light from the peripheral portion of the picture element portion to enter.

  As described above with reference to FIGS. 14 and 15, there is distortion on the reflection surface of the micromirror 62 of the DMD 50, but the amount of change in the distortion gradually increases from the center of the micromirror 62 toward the periphery. Has a trend. The amount of change in peripheral distortion in one diagonal direction (y direction) of the micromirror 62 is larger than the amount of change in peripheral distortion in another diagonal direction (x direction), and the above-described tendency is more remarkable. .

  The microlens array of this example is applied to cope with the above-described problem. In the microlens array 255, the microlenses 255a arranged in an array have a circular lens opening. Therefore, as described above, the laser light B reflected at the peripheral portion of the reflecting surface of the micromirror 62 having a large distortion, particularly at the four corners, is not condensed by the microlens 255a, and the condensing position of the condensed laser light B is reduced. Can be prevented from being distorted. Therefore, a higher-definition image without distortion can be exposed on the photosensitive layer 150.

  In the microlens array 255, as shown in FIG. 42, the back surface of the transparent member 255b holding the microlens 255a (which is usually formed integrally with the microlens 255a), that is, the microlens 255a. A light-shielding mask 255c is formed on the surface opposite to the surface on which the lens openings are formed so as to fill the outer regions of the lens openings of the plurality of microlenses 255a separated from each other. By providing such a mask 255c, the laser beam B reflected at the periphery of the reflecting surface of the micromirror 62, particularly at the four corners, is absorbed and blocked there, so the shape of the focused laser beam B Is more reliably prevented from being distorted.

  In the microlens array 255, the opening shape of the microlens is not limited to the circular shape described above. For example, as shown in FIG. 43, a microlens array in which a plurality of microlenses 455a having elliptical openings are arranged in parallel. As shown in FIG. 44, a microlens array 555 formed by arranging a plurality of microlenses 555a having polygonal (quadrangle in the illustrated example) openings can be used. The microlenses 455a and 555a are formed by cutting out a part of a normal axisymmetric spherical lens into a circular shape or a polygonal shape, and have a light collecting function similar to that of a normal axisymmetric spherical lens.

  Furthermore, in the present invention, a microlens array as shown in FIGS. 45A, 45B and 45C can be applied. The microlens array 655 shown in FIG. 6A is such that a plurality of microlenses 655a similar to the microlenses 55a, 455a and 555a are in close contact with the surface of the transparent member 655b on the side where the laser beam B is emitted. A mask 655c similar to the mask 255c is formed on the surface on which the laser beam B is incident in parallel. Note that the mask 255c in FIG. 42 is formed in the outer portion of the lens opening, whereas the mask 655c is provided in the lens opening. In the microlens array 755 shown in FIG. 5B, a plurality of microlenses 755a are arranged in parallel with each other on the surface of the transparent member 455b on the side where the laser beam B is emitted, and the microlens 755a is disposed between the microlenses 755a. Then, a mask 755c is formed. In the microlens array 855 shown in FIG. 5C, a plurality of microlenses 855a are arranged in parallel with each other on the surface of the transparent member 855b on the side where the laser beam B is emitted, and the periphery of each microlens 855a is arranged. A mask 855c is formed on the portion.

  The masks 655c, 755c, and 855c all have a circular opening as in the above-described mask 255c, so that the opening of the microlens is defined as a circle.

  FIG. 17 shows a configuration in which a lens opening shape that does not allow light from the periphery of the micromirror 62 of the DMD 50 to enter by providing a mask, such as the microlenses 255a, 455a, 555a, 655a, and 755a described above. An aspherical lens that corrects aberration due to the distortion of the surface of the micromirror 62 like the microlens 55a described above, or a lens having a refractive index distribution that corrects the aberration like the microlens 155a shown in FIG. It is also possible to employ them. By doing so, the effect of preventing the distortion of the exposure image due to the distortion of the reflection surface of the micromirror 62 is synergistically enhanced.

  In particular, as shown in FIG. 45C, in the configuration in which the mask 855c is formed on the lens surface of the microlens 855a in the microlens array 855, the microlens 855a has the above-described aspherical shape and refractive index distribution. When the imaging position of the first imaging optical system such as the lens systems 52 and 54 shown in FIG. 11 is set on the lens surface of the microlens 855a, The light utilization efficiency is increased, and the photosensitive layer 150 can be exposed with higher intensity light. That is, at that time, the first imaging optical system refracts the light so that stray light due to the distortion of the reflection surface of the micromirror 62 is focused at one point at the imaging position of the optical system. If the mask 855c is formed, light other than stray light is not shielded, and light use efficiency is improved.

  In each of the above microlens array examples, the aberration due to the distortion of the reflection surface of the micromirror 62 constituting the DMD 50 is corrected. However, in the pattern forming method of the present invention using a spatial light modulation element other than the DMD. If there is distortion on the surface of the picture element portion of the spatial light modulator, the present invention can be applied to correct the aberration due to the distortion and prevent the beam shape from being distorted.

Next, the imaging optical system will be further described.
In the exposure head, when the laser beam is irradiated from the light irradiation means 144, the cross-sectional area of the beam line reflected in the ON direction by the DMD 50 is enlarged several times (for example, two times) by the lens systems 454 and 458. The The enlarged laser light is condensed by each microlens of the microlens array 472 so as to correspond to each pixel part of the DMD 50 and passes through the corresponding aperture of the aperture array 476. The laser light that has passed through the aperture is imaged on the exposed surface 56 by the lens systems 480 and 482.

  In this imaging optical system, the laser light reflected by the DMD 50 is magnified several times by the magnifying lenses 454 and 458 and projected onto the exposed surface 56, so that the entire image area is widened. At this time, if the microlens array 472 and the aperture array 476 are not arranged, as shown in FIG. 13B, one pixel size (spot size) of each beam spot BS projected onto the exposed surface 56 is set. MTF (Modulation Transfer Function) characteristics representing the sharpness of the exposure area 468 are reduced depending on the size of the exposure area 468.

  On the other hand, when the microlens array 472 and the aperture array 476 are arranged, the laser light reflected by the DMD 50 is condensed corresponding to each pixel part of the DMD 50 by each microlens of the microlens array 472. Accordingly, as shown in FIG. 13C, even when the exposure area is enlarged, the spot size of each beam spot BS can be reduced to a desired size (for example, 10 μm × 10 μm), and the MTF characteristics are obtained. It is possible to perform high-definition exposure while preventing a decrease in the image quality. The exposure area 468 is tilted because the DMD 50 is tilted and disposed in order to eliminate the gap between the pixels.

  In addition, the aperture array can shape the beam so that the spot size on the surface to be exposed 56 is constant even if the beam is thick due to the aberration of the micro lens. Thus, crosstalk between adjacent picture elements can be prevented by passing through the aperture array.

  Further, by using a high-intensity light source, which will be described later, as the light irradiating means 144, the angle of the light beam incident on each microlens of the microlens array 472 from the lens 458 becomes small. The incident can be prevented. That is, a high extinction ratio can be realized.

<Other optical systems>
In the pattern forming method of the present invention, it may be used in combination with other optical systems appropriately selected from known optical systems, for example, a light amount distribution correcting optical system composed of a pair of combination lenses.
The light amount distribution correcting optical system changes the light flux width at each exit position so that the ratio of the light flux width at the peripheral portion to the light flux width at the central portion close to the optical axis is smaller on the exit side than on the incident side. When the DMD is irradiated with the parallel light beam from the light irradiation means, the light amount distribution on the irradiated surface is corrected so as to be substantially uniform. Hereinafter, 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 entire luminous flux widths (total luminous flux widths) H0 and H1 are the same for the incident luminous flux and the outgoing luminous flux will be described. In FIG. 24A, the portions denoted by reference numerals 51 and 52 virtually indicate the entrance surface and the exit surface in the light quantity distribution correction optical system.

  In the light quantity distribution correcting optical system, it is assumed that the light flux widths h0 and h1 of the light beam incident on the central portion near the optical axis Z1 and the light flux incident on the peripheral portion are the same (h0 = hl). The light quantity distribution correcting optical system expands the light flux width h0 of the incident light flux at the central portion with respect to the light having the same light flux width h0, h1 on the incident side, and conversely changes the incident light flux at the peripheral portion. On the other hand, the light beam width h1 is reduced. That is, the width h10 of the outgoing light beam at the center and the width h11 of the outgoing light beam at the periphery are set to satisfy h11 <h10. In terms of the ratio of the luminous flux width, the ratio “h11 / h10” of the luminous flux width in the peripheral portion to the luminous flux width in the central portion on the emission side is smaller than the ratio (h1 / h0 = 1) on the incident side ( (H11 / h10) <1).

  By changing the light flux width in this way, the light flux in the central part, which normally has a large light quantity distribution, can be utilized in the peripheral part where the light quantity is insufficient, and the overall light utilization efficiency is not reduced. In addition, the light quantity distribution on the irradiated surface is made substantially uniform. The degree of uniformity is, for example, such that the unevenness in the amount of light in the effective area is within 30%, preferably within 20%.

  The operations and effects of the light quantity distribution correcting optical system are the same when the entire luminous flux width is changed between the incident side and the exit side (FIGS. 24B and 24C).

  FIG. 24B shows a case where the entire light flux width H0 on the incident side is “reduced” to the width H2 and emitted (H0> H2). Even in such a case, the light quantity distribution correcting optical system has the same light beam width h0, h1 on the incident side, and the light beam width h10 in the central part is larger than that in the peripheral part on the emission side. Conversely, the luminous flux width h11 at the peripheral part is made smaller than that at the central part. Considering the reduction rate of the light beam, the reduction rate with respect to the incident light beam in the central part is made smaller than that in the peripheral part, and the reduction rate with respect to the incident light beam in the peripheral part is made larger than that in the central part. Also in this case, the ratio “H11 / H10” of the light flux width in the peripheral portion to the light flux width in the central portion is smaller than the ratio (h1 / h0 = 1) on the incident side ((h11 / h10) <1). .

  FIG. 24C shows a case where the entire light flux width H0 on the incident side is “enlarged” to the width H3 and emitted (H0 <H3). Even in such a case, the light quantity distribution correcting optical system has the same light beam width h0, h1 on the incident side, and the light beam width h10 in the central part is larger than that in the peripheral part on the emission side. Conversely, the luminous flux width h11 at the peripheral part is made smaller than that at the central part. Considering the expansion rate of the light beam, the expansion rate for the incident light beam in the central portion is made larger than that in the peripheral portion, and the expansion rate for the incident light beam in the peripheral portion is made smaller than that in the central portion. Also in this case, the ratio “h11 / h10” of the light flux width in the peripheral portion to the light flux width in the central portion is smaller than the ratio (h1 / h0 = 1) on the incident side ((h11 / h10) <1). .

  As described above, the light quantity distribution correcting optical system changes the light beam width at each emission position, and the ratio of the light beam width in the peripheral part to the light beam width in the central part near the optical axis Z1 is larger on the outgoing side than on the incident side. Since the light having the same luminous flux width on the incident side is larger on the outgoing side, the luminous flux width in the central portion is larger than that in the peripheral portion, and the luminous flux width in the peripheral portion is smaller than that in the central portion. Become smaller. As a result, it is possible to make use of the light beam at the center part to the peripheral part, and it is possible to form a light beam cross-section with a substantially uniform light amount distribution without reducing the light use efficiency of the entire optical system.

Next, an example of specific lens data of a pair of combination lenses used as the light quantity distribution correcting optical system will be shown. In this example, lens data in the case where the light amount distribution in the cross section of the emitted light beam is a Gaussian distribution as in the case where the light irradiation means is a laser array light source is shown. When one semiconductor laser is connected to the incident end of the single mode optical fiber, the light quantity distribution of the emitted light beam from the optical fiber becomes a Gaussian distribution. The pattern forming method of the present invention can be applied to such a case. Further, the present invention can be applied to a case where the light amount in the central portion near the optical axis is larger than the light amount in the peripheral portion, for example, by reducing the core diameter of the multi-mode optical fiber and approaching the configuration of the single mode optical fiber.
Table 1 below shows basic lens data.

  As can be seen from Table 1, the pair of combination lenses is composed of two rotationally symmetric aspherical lenses. If the light incident side surface of the first lens disposed on the light incident side is the first surface and the light exit side surface is the second surface, the first surface is aspherical. In addition, when the surface on the light incident side of the second lens disposed on the light emitting side is the third surface and the surface on the light emitting side is the fourth surface, the fourth surface is aspherical.

In Table 1, the surface number Si indicates the number of the i-th surface (i = 1 to 4), the curvature radius ri indicates the curvature radius of the i-th surface, and the surface interval di indicates the i-th surface and the i + 1-th surface. The distance between surfaces on the optical axis is shown. The unit of the surface interval di value is millimeter (mm). The refractive index Ni indicates the value of the refractive index with respect to the wavelength of 405 nm of the optical element having the i-th surface.
Table 2 below shows the aspheric data of the first surface and the fourth surface.

The aspheric data is expressed by a coefficient in the following formula (A) that represents the aspheric shape.

In the above formula (A), each coefficient is defined as follows.
Z: Length of a perpendicular line (mm) drawn from a point on the aspheric surface at a height ρ from the optical axis to the tangent plane (plane perpendicular to the optical axis) of the apex of the aspheric surface
ρ: Distance from optical axis (mm)
K: conic coefficient C: paraxial curvature (1 / r, r: paraxial radius of curvature)
ai: i-th order (i = 3 to 10) aspheric coefficient In the numerical values shown in Table 2, the symbol “E” indicates that the next numerical value is a “power exponent” with 10 as the base. The numerical value represented by the exponential function with the base 10 is multiplied by the numerical value before “E”. For example, “1.0E-02” indicates “1.0 × 10 ⁻² ”.

  FIG. 26 shows a light amount distribution of illumination light obtained by the pair of combination lenses shown in Tables 1 and 2. The horizontal axis indicates coordinates from the optical axis, and the vertical axis indicates the light amount ratio (%). For comparison, FIG. 25 shows a light amount distribution (Gaussian distribution) of illumination light when correction is not performed. As can be seen from FIG. 25 and FIG. 26, the light amount distribution correction optical system corrects the light amount distribution that is substantially uniform as compared with the case where correction is not performed. Thereby, it is possible to perform exposure with uniform laser light without reducing the use efficiency of light, without causing any unevenness.

[Other processes]
There is no restriction | limiting in particular as said other process, Although selecting suitably from the process in well-known pattern formation is mentioned, For example, a image development process, an etching process, a plating process, etc. are mentioned. These may be used alone or in combination of two or more.
The development step is a step of forming a pattern by exposing the photosensitive layer in the pattern forming material by the exposure step, curing the exposed region of the photosensitive layer, and then developing by removing an uncured region. is there. Since the pattern forming material of the present invention is excellent in preventing the unexposed film from being broken, even when the support is peeled off from the photosensitive layer for the development, the unexposed portion of the photosensitive layer which is not cured is a hole. In this case, the device is not broken and peeled off, and it is possible to prevent contamination of the apparatus due to minute peeling pieces of the photosensitive layer and a decrease in pattern resolution.

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

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

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

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

The etching step can be performed by a method appropriately selected from known etching methods.
There is no restriction | limiting in particular as an etching liquid used for the said etching process, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, Examples thereof include a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide-based etching solution. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor.
A permanent pattern can be formed on the surface of the substrate by removing the pattern after performing the etching process in the etching step.
There is no restriction | limiting in particular as said permanent pattern, According to the objective, it can select suitably, For example, a wiring pattern etc. are mentioned suitably.

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

[Method of manufacturing printed wiring board and color filter]
The pattern forming method of the present invention can be suitably used for the production of a printed wiring board, particularly for the production of a printed wiring board having a hole such as a through hole or a via hole, and for the production of a color filter. Hereinafter, an example of a method for manufacturing a printed wiring board and a method for manufacturing a color filter using the pattern forming method of the present invention will be described.

-Manufacturing method of printed wiring board-
In particular, as a method of manufacturing a printed wiring board having a hole portion such as a through hole or a via hole, (1) the pattern forming material is placed on the printed wiring board forming substrate having the hole portion as the base, and the photosensitive layer is (2) The photosensitive layer is cured by irradiating a desired region from the opposite side of the laminate to the base, and (3) ) Remove the support, cushion layer and barrier layer in the pattern forming material from the laminate, and (4) develop the photosensitive layer in the laminate to remove the uncured portion in the laminate. Can be formed.

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

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

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

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

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

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

  At this time, when the support, the cushion layer, and the barrier layer are not yet peeled, the support, the cushion layer, and the barrier layer are peeled from the laminate (peeling step).

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

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

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

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

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

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

-Color filter manufacturing method-
When the photosensitive layer in the pattern forming material of the present invention is bonded onto a substrate such as a glass substrate and the support, cushion layer and barrier layer are peeled from the pattern forming material, the charged support (film) and There is a problem that the human body may receive an unpleasant electric shock, or dust may adhere to the charged support. For this reason, it is preferable to provide a conductive layer on the support or to perform a treatment for imparting conductivity to the support itself. When the conductive layer is provided on the support on the side opposite to the cushion layer, it is preferable to provide a hydrophobic polymer layer in order to improve scratch resistance.

  Next, a pattern forming material having a red photosensitive layer in which the photosensitive layer is colored red, green, blue, and black, a pattern forming material having a green photosensitive layer, a pattern forming material having a blue photosensitive layer, and black A pattern forming material having a photosensitive layer is prepared. Using the pattern forming material having the red photosensitive layer for red pixels, a red photosensitive layer is laminated on the surface of the substrate to form a laminate, and then exposed and developed imagewise to form red pixels. After forming red pixels, the laminate is heated to cure the uncured portion. This is performed in the same manner for the green and blue pixels to form each pixel.

  The formation of the laminate may be performed by laminating the pattern forming material on the glass substrate, or directly applying a photosensitive resin composition solution for manufacturing the pattern forming material to the surface of the glass substrate, You may laminate | stack a photosensitive layer, a barrier layer, a cushion layer, and a support body on the said glass substrate by making it dry. In addition, when arranging three types of pixels of red, green, and blue, any arrangement such as a mosaic type, a triangle type, and a four-pixel arrangement type may be used.

  A pattern forming material having the black photosensitive layer is laminated on the surface on which the pixels are formed, and back exposure is performed from the side where the pixels are not formed, and development is performed to form a black matrix. By heating the laminate in which the black matrix is formed, the uncured portion can be cured and a color filter can be produced.

  Since the pattern forming method of the present invention uses the pattern forming material of the present invention, liquid crystal structures such as various patterns, formation of permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, partition walls, etc. It can be suitably used for the production of members, holograms, micromachines, proofs, etc., and can be particularly suitably used for 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 forms various patterns, forms permanent patterns such as wiring patterns, color filters, column materials, rib materials, spacers, partition walls, and other liquid crystals. It can be suitably used for the production of structural members, holograms, micromachines, proofs, etc., and can be particularly suitably used for the formation of high-definition wiring patterns.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
Example 1
-Production of pattern forming material-
A photosensitive resin composition solution having the following composition was applied to a polyethylene terephthalate film having a thickness of 20 μm as the support and dried to form a photosensitive layer having a thickness of 15 μm, thereby producing the pattern forming material.

[Composition of photosensitive resin composition solution]
Methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 25/29/46, mass average molecular weight: 43,000, Tg: 127 ° C., acid value 163 mg KOH / g, I / O value : 0.55) 15 parts by mass / monomer (manufactured by Toagosei Co., Ltd., M270, I / O value: 0.41) 14 parts by mass / B-CIM (manufactured by Hodogaya Chemical) 2.17 parts by mass / 2-mercaptobenz 0.23 parts by mass of imidazole, 0.02 parts by mass of malachite green oxalate, 0.26 parts by mass of leuco crystal violet, 40 parts by mass of methyl ethyl ketone
-1-methoxy-2-propanol 20 mass parts In the said photosensitive composition, mass ratio of a binder and a polymeric compound is 1.07.

  The prepared pattern forming material was peeled off, and the peeled portion was examined by measuring the thickness of the pattern forming material after peeling. .

A polyethylene film having a thickness of 20 μm was laminated as the protective film on the photosensitive layer of the pattern forming material. Next, a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-67, no through-hole, copper thickness 12 μm) whose surface is chemically polished is prepared as the substrate, and the copper-clad laminate In addition, a laminator (MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.) is used while peeling the protective film of the pattern forming material so that the photosensitive layer of the pattern forming material is in contact with the copper clad laminate. Thus, a laminate was prepared in which the copper-clad laminate, the photosensitive layer, the barrier layer, the cushion layer, and the polyethylene terephthalate film (support) were laminated in this order. When the maximum height (Rz) defined in JIS B 0601 was measured on the surface of the copper clad laminate on which the photosensitive layer was laminated, the Rz was 3 μm.
The pressure bonding conditions were a pressure roll temperature of 105 ° C., a pressure roll pressure of 0.3 MPa, and a laminating speed of 1 m / min.

  The manufactured laminate was evaluated for the shortest development time, sensitivity, and resolution as follows. The results are shown in Tables 3 and 3.

<Resolution>
(1) Measuring method of shortest development time The polyethylene terephthalate film (support), cushion layer and barrier layer are peeled off from the laminate, and 1% by mass sodium carbonate at 30 ° C. is formed on the entire surface of the photosensitive layer on the copper clad laminate. The aqueous solution was sprayed at a pressure of 0.15 MPa, and the time required from the start of spraying of the sodium carbonate aqueous solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time.
As a result, the shortest development time was 8 seconds.

(2) Measurement of sensitivity Using a pattern forming apparatus having a laser light source of 405 nm as the light irradiation means from the polyethylene terephthalate film (support) side to the photosensitive layer of the pattern forming material in the laminate. Exposure was performed by irradiating with different light energy amounts from 1 mJ / cm ² to 100 mJ / cm ^{2 at} intervals of 2 ^1/2 times to cure a part of the photosensitive layer. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support), cushion layer and barrier layer were peeled off from the laminate, and an aqueous sodium carbonate solution (30 ° C, 30 ° C, 1 mass%) was sprayed at a spray pressure of 0.15 MPa for twice the shortest development time determined in (1) above, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Next, a sensitivity curve is obtained by plotting the relationship between the light irradiation amount and the thickness of the cured layer. From the sensitivity curve thus obtained, the amount of light energy when the thickness of the cured region becomes 0.5 μm in the difference from the thickness of the photosensitive layer provided above (15 μm) is necessary for curing the photosensitive layer. The minimum amount of light energy was used. As a result, the amount of light energy necessary for curing the photosensitive layer was 10 mJ / cm ² . The pattern forming apparatus includes a light modulating unit made of the DMD and includes the pattern forming material.

(3) Resolution measurement (measurement of line width of line pattern of L / S = 1/1 and L / S = 1/100)
The laminate was prepared under the same method and conditions as the method (1) for evaluating the shortest development time, and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate film (support) of the laminate, exposure was performed at L / S = 20/20 using the pattern forming apparatus, and 10 line patterns each having a length of 20 cm were obtained. On the other hand, the other laminates were exposed at L / S = 20/2000 using the pattern forming apparatus, and 10 line patterns each having a length of 20 cm were obtained. The exposure amount at this time is twice the minimum light energy amount necessary for curing the photosensitive layer of the pattern forming material measured in (2). After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support), the cushion layer, and the barrier layer were peeled off from the laminate. Twice the shortest development time obtained in (1) above with a sodium carbonate aqueous solution (30 ° C., 1% by mass) as the developer at a spray pressure of 0.15 MPa on the entire surface of the photosensitive layer on the copper clad laminate. The uncured area was dissolved and removed by spraying. The surface of the copper-clad laminate with a cured resin pattern thus obtained was observed with an optical microscope, and for each of the 10 line patterns with a length of 20 cm for each cured film, 1 cm from the end of each line pattern. At the positions of 10 cm and 19 cm, the line widths at the upper end, the center, and the lower end in the thickness direction were measured, and a total of 90 points were measured. The difference between the average value of 90 line widths of the L / S = 20/20 line pattern and the average value of 90 line widths of the L / S = 20/200 line pattern was calculated. . When the difference is 5 μm or less, a high resolution and high definition pattern can be obtained.

<Development time>
The polyethylene terephthalate film (support) is peeled off from the laminate, and a 1% by mass sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. The time required from the start of spraying until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time. The shorter the shortest development time, the better the developability.
As a result, the shortest development time was 8 seconds.

(Example 2)
In Example 1, the composition ratio of the binder in the photosensitive resin composition was methacrylic acid / methyl methacrylate / styrene copolymer = 25/45/30, the binder I / O value was 0.71, and the monomer As in Example 1, except that UAT1 / BPE500 / M270 (all monomers manufactured by Shin-Nakamura Chemical Co., Ltd.) (mass ratio) = 45/10/10 was used and the I / O value of the monomer was 0.97. Thus, a pattern forming material was manufactured. The mass ratio of the binder and the polymerizable compound in Example 2 is 1.9.
<Evaluation>
Next, using the obtained pattern forming material, the sensitivity, the shortest development time, and the resolution were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 3)
In Example 1, the composition ratio of the binder in the photosensitive resin composition is methacrylic acid / methyl methacrylate / styrene copolymer = 29/0/71, the binder I / O value is 0.42, and the monomer As in Example 1, except that UAT1 / BPE500 / M270 (all monomers manufactured by Shin-Nakamura Chemical Co., Ltd.) (mass ratio) = 45/10/10 was used and the I / O value of the monomer was 0.97. Thus, a pattern forming material was manufactured. The mass ratio of the binder and the polymerizable compound in Example 3 is 1.1.
<Evaluation>
Next, using the obtained pattern forming material, the sensitivity, the shortest development time, and the resolution were evaluated in the same manner as in Example 1. The results are shown in Table 3.

Example 4
In Example 1, the composition ratio of the binder in the photosensitive resin composition is methacrylic acid / methyl methacrylate / styrene copolymer = 25/29/46, the I / O value of the binder is 0.55, the monomer A pattern forming material was produced in the same manner as in Example 1 except that UAT1 / BPE500 / M270 = 45/10/10 was used and the I / O value of the monomer was 0.97. The mass ratio of the binder and the polymerizable compound in Example 3 is 1.25.

(Example 5)
In Example 1, the composition ratio of the binder in the photosensitive resin composition is methacrylic acid / methyl methacrylate / styrene copolymer = 25/29/46, the I / O value of the binder is 0.55, the monomer A pattern forming material was produced in the same manner as in Example 1 except that BPE500 / M270 = 19/81 was used and the I / O value of the monomer was 0.52.

(Example 6)
In Example 1, the binder composition ratio in the photosensitive resin composition was methacrylic acid / methyl methacrylate / styrene copolymer = 25/45/30, and the I / O value of the binder was 0.71. Except for this, a pattern forming material was produced in the same manner as in Example 1.

(Example 7)
Using the pattern forming material of Example 1, evaluation of sensitivity, development time, and resolution was performed in the same manner as in Example 1 except that the pattern forming apparatus was replaced with a pattern forming apparatus described below. . The results are shown in Table 3.

<< Pattern Forming Apparatus >>
27 to 32 as the light irradiating means, and 768 pairs of micromirror arrays in which 1024 micromirrors are arranged in the main scanning direction shown in FIG. 4 as the light modulating means are arranged in the sub-scanning direction. The microlens array 472 in which the DMD 50 controlled to drive only 1024 × 256 rows and the microlenses 474 whose one surface is a toric surface shown in FIG. A pattern forming apparatus having optical systems 480 and 482 for imaging light passing through the array onto the pattern forming material and the pattern forming material was used. The DMD 50 is connected to the controller 302 including the data processing unit and the mirror drive control unit shown in FIG. Based on the input pattern information, the data processing unit of the controller 302 can generate a control signal for driving and controlling each micromirror in the region to be controlled by the DMD 50 for each exposure head 166. The drive control unit can control the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the pattern information processing unit.
The exposure in the pattern forming apparatus was performed while relatively moving the exposure light and the photosensitive layer in the pattern forming material.

The toric surface of the microlens described below was used.
First, in order to correct the distortion on the exit surface of the microlens 474 as the picture element portion of the DMD 50, the strain on the exit surface was measured. The results are shown in FIG. In FIG. 14, the same height positions of the reflecting surfaces are shown connected by contour lines, and the pitch of the contour lines is 5 nm. Note that the x direction and the y direction shown in the figure are two diagonal directions of the micromirror 62, and the micromirror 62 rotates around a rotation axis extending in the y direction. 15A and 15B show the height position displacement of the reflecting surface of the micromirror 62 along the x direction and the y direction, respectively.

  As shown in FIGS. 14 and 15, there is distortion on the reflection surface of the micromirror 62, and when attention is paid particularly to the center of the mirror, distortion in one diagonal direction (y direction) is different from that in the other diagonal line. It can be seen that the distortion is larger than the distortion in the direction (x direction). Therefore, it can be seen that the shape of the laser beam B collected by the microlens 55a of the microlens array 55 is distorted in this state.

  FIGS. 16A and 16B show the front shape and the side shape of the entire microlens array 55 in detail. In these drawings, the dimensions of each part of the microlens array 55 are also entered, and the unit thereof is mm. As described above with reference to FIG. 4, the 1024 × 256 micromirrors 62 of the DMD 50 are driven. Correspondingly, the microlens array 55 has 1024 microlenses arranged in the horizontal direction. The 55a rows are arranged in parallel in 256 rows in the vertical direction. In FIG. 9A, the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and k in the vertical direction.

  17A and 17B show a front shape and a side shape of one microlens 55a in the microlens array 55, respectively. In FIG. 9A, the contour lines of the micro lens 55a are also shown. The end surface of each microlens 55a on the light emitting side has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62. More specifically, the micro lens 55a is a toric lens, and has a radius of curvature Rx = −0.125 mm in a direction optically corresponding to the x direction and a radius of curvature Ry = − in a direction corresponding to the y direction. 0.1 mm.

  Therefore, the condensing state of the laser beam B in the cross section parallel to the x direction and the y direction is roughly as shown in FIGS. 18A and 18B, respectively. That is, when the cross section parallel to the x direction is compared with the cross section parallel to the y direction, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. I understand that.

  19A, 19B, 19C, and 19D show simulation results of the beam diameter in the vicinity of the condensing position (focal position) of the microlens 55a when the microlens 55a has the above shape. For comparison, FIGS. 20a, 20b, 20c, and 20d show the results of a similar simulation when the microlens 55a has a spherical shape with a radius of curvature Rx = Ry = −0.1 mm. In addition, the value of z in each figure has shown the evaluation position of the focus direction of the micro lens 55a with the distance from the beam emission surface of the micro lens 55a.

The surface shape of the microlens 55a used for the simulation is calculated by the following calculation formula.

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

  As is apparent when comparing FIGS. 19a to 19d and FIGS. 20a to 20d, the microlens 55a includes a toric lens in which the focal length in the cross section parallel to the y direction is smaller than the focal length in the cross section parallel to the x direction. As a result, distortion of the beam shape in the vicinity of the condensing position is suppressed. As a result, the pattern forming material 150 can be exposed to a higher definition pattern without distortion. Moreover, it turns out that the area | region where a beam diameter is small is wider, ie, the depth of focus is larger in this embodiment shown to FIG.

  In addition, the aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is disposed such that only light having passed through the corresponding microlens 55a is incident on each aperture 59a. That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to increase the extinction ratio.

(Comparative Example 1)
In Example 1, the composition ratio of the binder in the photosensitive resin composition is methacrylic acid / methyl methacrylate / styrene copolymer = 29/0/71, the binder I / O value is 0.42, and the monomer A pattern forming material was produced in the same manner as in Example 1 except that M270 (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used and the I / O value of the monomer was 0.41. The mass ratio of the binder of Comparative Example 1 and the polymerizable compound is 2.1.
<Evaluation>
Next, using the obtained pattern forming material, the sensitivity, the shortest development time, and the resolution were evaluated in the same manner as in Example 1. The photosensitive layer of Comparative Example 1 was too hard to be developed, and the shortest development time and resolution could not be evaluated. The results are shown in Table 3.

(Comparative Example 2)
In Example 1, the composition ratio of the binder in the photosensitive resin composition was methacrylic acid / methyl methacrylate / styrene copolymer = 25/45/30, the binder I / O value was 0.71, and the monomer A pattern forming material was produced in the same manner as in Example 1 except that UAT1 (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used and the I / O value of the monomer was 1.8. The mass ratio of the binder and the polymerizable compound in Comparative Example 2 is 1.9.
<Evaluation>
Next, using the obtained pattern forming material, the sensitivity, the shortest development time, and the resolution were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Comparative Example 3)
A pattern forming material was produced in the same manner as in Example 1 except that 0.23 parts by mass of 2-mercaptobenzimidazole was not added.
<Evaluation>
Next, using the obtained pattern forming material, the sensitivity, the shortest development time, and the resolution were evaluated in the same manner as in Example 1. The results are shown in Table 3.

From the results of Table 3, in the pattern forming materials of Examples 1 to 7, the sensitivity of the photosensitive layer is 20 mJ / cm ² or less, and a line pattern formed by exposure with L / S = 1/1; It was found that the line width difference from the line pattern formed by exposure with S = 1/100 was 5 μm or less, the development time was short, the developability was excellent, and a high-resolution and high-definition pattern was obtained. Moreover, the I / O value of a binder is 0.5-0.7, or Examples 1-4 whose I / O value of a monomer is 0.5-1.5 are the difference of the said line | wire width. Is less than 1 μm and has excellent resolution. In particular, Example 4 in which both the I / O value of the binder and the I / O value of the monomer are within the above range has a small difference in line width and is extremely excellent in resolution. I found out.
On the other hand, in Comparative Example 1, the photosensitive layer is too hard to be developed, and in Comparative Example 2, the line pattern of L / S = 1/1 and the line pattern of L / S = 1/100. The difference in line width was more than 5 μm. In Comparative Example 3, the difference in line width between the line pattern with L / S = 1/1 and the line pattern with L / S = 1/100 was 5 μm or less, but the sensitivity was low.

The pattern forming material of the present invention has high sensitivity, excellent developability, and a high resolution and high definition pattern can be obtained. For this reason, it is suitable for use in the formation of various patterns, the formation of permanent patterns such as wiring patterns, the production of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, and partition walls, the production of holograms, micromachines, and proofs. In particular, it can be suitably used for forming a high-definition wiring pattern.
In addition, since the pattern forming apparatus of the present invention includes the pattern forming material of the present invention, various patterns are formed, permanent patterns such as wiring patterns are formed, color filters, pillar materials, rib materials, spacers, partition walls, etc. It can be suitably used for the production of liquid crystal structure members, holograms, micromachines, proofs, and the like, and can be particularly suitably used for the formation of high-definition wiring patterns.
In addition, since the pattern forming method of the present invention uses the pattern forming material of the present invention, liquid crystal such as various patterns, permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, partition walls, etc. It can be suitably used for the production of structural members, the production of holograms, micromachines, proofs, and the like, and can be particularly suitably used for the formation of high-definition wiring patterns.

FIG. 1 is an example of a partially enlarged view showing a configuration of a digital micromirror device (DMD). 2A and 2B are examples of explanatory diagrams for explaining the operation of the DMD. FIGS. 3A and 3B are examples of plan views showing the arrangement of the exposure beam and the scanning line in a case where the DMD is not inclined and in a case where the DMD is inclined. 4A and 4B are examples of diagrams illustrating examples of DMD usage areas. FIG. 5 is an example of a plan view for explaining an exposure method in which the pattern forming material is exposed by one scanning by the scanner. 6A and 6B are examples of plan views for explaining an exposure method for exposing a pattern forming material by a plurality of scans by a scanner. FIG. 7 is an example of a schematic perspective view illustrating an appearance of an example of the pattern forming apparatus. FIG. 8 is an example of a schematic perspective view illustrating the configuration of the scanner of the pattern forming apparatus. FIG. 9A is an example of a plan view showing an exposed region formed in the pattern forming material, and FIG. 9B is an example of a diagram showing an array of exposure areas by each exposure head. FIG. 10 is an example of a perspective view showing a schematic configuration of an exposure head including light modulation means. FIG. 11 is an example of a sectional view in the sub-scanning direction along the optical axis showing the configuration of the exposure head shown in FIG. FIG. 12 is an example of a controller that controls DMD based on pattern information. FIG. 13A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system, and FIG. 13B shows the exposure when a microlens array or the like is not used. FIG. 13C is an example of a plan view showing a light image projected on a surface to be exposed when a microlens array or the like is used. FIG. 14 is an example of a diagram showing the distortion of the reflection surface of the micromirror constituting the DMD with contour lines. FIGS. 15A and 15B are examples of graphs showing the distortion of the reflection surface of the micromirror in the two diagonal directions of the mirror. FIG. 16 is an example of a front view (A) and a side view (B) of a microlens array used in the pattern forming apparatus. FIG. 17 is an example of a front view (A) and a side view (B) of a microlens constituting a microlens array. FIG. 18 is an example of a schematic diagram illustrating a condensing state by a microlens in one cross section (A) and another cross section (B). FIG. 19a is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens of the present invention. FIG. 19B is an example of a diagram showing the same simulation result as that in FIG. 19A at another position. FIG. 19c is an example of a diagram showing the same simulation result as in FIG. 19a at another position. FIG. 19d is an example of a diagram showing the same simulation result as in FIG. 19a at another position. FIG. 20a is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens in the conventional pattern forming method. FIG. 20b is an example of a diagram showing the same simulation result as in FIG. 20a at another position. FIG. 20c is an example of a diagram showing the same simulation result as in FIG. 20a for another position. FIG. 20d is an example of a diagram illustrating simulation results similar to those in FIG. 20a at different positions. FIG. 21 is an example of a plan view showing another configuration of the combined laser light source. FIG. 22 shows an example of a front view (A) and an example of a side view (B) of the microlens constituting the microlens array. FIG. 23 is an example of a schematic diagram illustrating a light condensing state by the microlens of FIG. 22 in one cross section (A) and another cross section (B). FIG. 24 is an example of an explanatory diagram about the concept of correction by the light quantity distribution correction optical system. FIG. 25 is an example of a graph showing the light amount distribution when the light irradiation means has a Gaussian distribution and the light amount distribution is not corrected. FIG. 26 is an example of a graph showing the light amount distribution after correction by the light amount distribution correcting optical system. 27A (A) is a perspective view showing the configuration of the fiber array light source, FIG. 27A (B) is an example of a partially enlarged view of FIG. 27A, and FIGS. 27A (C) and (D) are lasers. It is an example of the top view which shows the arrangement | sequence of the light emission point in an emission part. FIG. 27 b is an example of a front view showing the arrangement of light emitting points in the laser emission part of the fiber array light source. FIG. 28 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 29 is an example of a plan view showing the configuration of the combined laser light source. FIG. 30 is an example of a plan view showing the configuration of the laser module. FIG. 31 is an example of a side view showing the configuration of the laser module shown in FIG. 32 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 33 is an example of a perspective view showing a configuration of a laser array. FIG. 34A is an example of a perspective view showing a configuration of a multi-cavity laser, and FIG. 34B is a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. It is an example. FIG. 35 is an example of a plan view showing another configuration of the combined laser light source. FIG. 36A is an example of a plan view showing another configuration of the combined laser light source, and FIG. 36B is an example of a cross-sectional view along the optical axis of FIG. FIGS. 37A and 37B are examples of cross-sectional views along the optical axis showing the difference between the depth of focus in the conventional exposure apparatus and the depth of focus by the pattern forming method (pattern forming apparatus) of the present invention. FIG. 38 is a front view (A) and a side view (B) showing another example of the microlens array constituting the macro array. FIG. 39 shows an example of a front view (A) and an example of a side view (B) of a microlens array constituting a macro array. FIG. 40 is a graph showing a spherical lens shape example. FIG. 41 is a graph showing another lens surface shape example. FIG. 42 is a perspective view showing another example of the microlens array. FIG. 43 is a plan view showing another example of the microlens array. FIG. 44 is a plan view showing another example of the microlens array. 45A to 45C are longitudinal sectional views showing other examples of the microlens array.

Explanation of symbols

LD1-LD7 GaN-based semiconductor laser 10 Heat block 11-17 Collimator lens 20 Condensing lens 30-31 Multimode optical fiber 44 Collimator lens holder 45 Condensing lens holder 46 Fiber holder 50 Digital micromirror device (DMD)
52 Lens system 53 Reflected light image (exposure beam)
54 Lens of second imaging optical system 55 Micro lens array 55a Micro lens 55a 'Micro lens array 55a "Micro lens array 56 Surface to be exposed (scanning surface)
57 Lens of second imaging optical system 58 Lens of second imaging optical system 59 Aperture array 64 Laser module 66 Fiber array light source 67 Lens system 68 Laser emitting unit 69 Mirror 70 Prism 73 Combination lens 74 Imaging lens 100 Heat block 110 Multicavity laser 111 Heat block 113 Rod lens 120 Condensing lens 130 Multimode optical fiber 130a Core 140 Laser array 144 Light irradiation means 150 Photosensitive layer 152 Stage 155a Microlens 156 Installation table 158 Guide 160 Gate 162 Scanner 164 Sensor 166 Exposure head 168 Exposure area 170 Exposed area 180 Heat block 184 Collimating lens array 255 Micro lens array 255a Micro 302 Controller 304 Stage drive device 355 Micro lens array 355a Micro lens 454 Lens system 455 Micro lens array 455a Micro lens 468 Exposure area 472 Micro lens array 474 Micro lens 476 Aperture array 478 Aperture 480 Lens system 555 Micro lens array 555a Micro lens 655 Micro lens array 655a Micro lens 755 Micro lens array 755a Micro lens

Claims (20)

A support and at least a photosensitive layer on the support, the photosensitive layer including at least a binder, a polymerizable compound, and a photopolymerization initiator, and the sensitivity of the photosensitive layer is 20 mJ / cm ² or less. The pattern obtained by exposing and developing the photosensitive layer at a line width of 10 to 40 μm at a line / space (L / S) = 1/1 and L / S = 1/100, and the L / S = 1. A pattern forming material having a line width difference of 5 μm or less between a line pattern formed by exposure at / 1 and a line pattern formed by exposure at L / S = 1/100.   The pattern forming material according to claim 1, wherein the binder has an I / O value of 0.5 to 0.8.   The pattern forming material according to claim 1, wherein the polymerizable compound has an I / O value of 0.5 to 1.5.   The pattern forming material according to claim 1, wherein a mass ratio of the binder and the polymerizable compound (binder / polymerizable compound) is 1 to 2.   The pattern forming material according to claim 1, wherein the binder includes a copolymer, and the copolymer has a structural unit derived from at least one of styrene and a styrene derivative.   The pattern forming material according to claim 1, wherein the binder has a glass transition temperature of 80 ° C. or higher.   The pattern forming material according to claim 1, wherein the binder has an acid value of 70 to 250 mg KOH / g.   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 photopolymerization initiator is selected from halogenated hydrocarbon derivatives, phosphine oxides, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, acyl phosphine oxide compounds, aromatic onium salts and ketoxime ethers. The pattern forming material according to claim 1, comprising at least one selected from the group consisting of: The pattern forming material according to claim 1 is provided,
A pattern forming apparatus comprising: a light irradiating means capable of irradiating light; and a light modulating means for modulating light from the light irradiating means and exposing the photosensitive layer in the pattern forming material.   A pattern forming method comprising at least exposing the photosensitive layer in the pattern forming material according to claim 1.   The pattern forming method according to claim 11, wherein the exposure is performed using light modulated by the control signal generated based on the pattern information to be formed.   The exposure is performed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface of the picture element portion in the light modulation means after the light is modulated by the light modulation means. The pattern forming method according to any one of 11 to 12.   The exposure is performed through a microlens array in which microlenses having a lens opening shape in which light from a peripheral portion of a picture element portion in the light modulation unit is not incident after the light is modulated by the light modulation unit. The pattern formation method in any one of 13 to 13.   14. The pattern forming method according to claim 11, wherein the microlens has an aspherical surface capable of correcting aberration due to distortion of the exit surface in the pixel portion.   The pattern forming method according to claim 13, wherein the aspherical surface is a toric surface.   The pattern forming method according to claim 14, wherein the microlens has a circular lens opening shape.   The pattern forming method according to claim 14, wherein the lens opening shape is defined by providing a light shielding portion on the lens surface.   The pattern forming method according to claim 11, wherein the photosensitive layer is developed after the exposure. The pattern forming method according to claim 19, wherein a permanent pattern is formed after the development.