JP4651524B2 - Pattern forming material, pattern forming apparatus and pattern forming method - Google Patents

Description

  The present invention relates to a pattern forming material suitable for dry film resist (DFR) and the like, and a pattern forming apparatus 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 layer is formed by applying and drying a photosensitive composition on a support 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. (See Patent Documents 1 and 2).

In order to obtain the permanent pattern with high definition and efficiency, it is required to improve sensitivity, improve the shape of the resist pattern, increase the strength of the tent film, and the like. For the purpose of improving the sensitivity, for example, a technique in which a photosensitive composition contains a polycarboxylic acid together with a sensitizer has been proposed (see Patent Document 3). However, in this photosensitive composition, the main purpose is to perform high-speed photoprinting and to extend the lifetime mainly using polycarboxylic acid, and it has been unclear how much the sensitivity is improved.
As a technique for clarifying that the sensitivity is improved by containing a carboxylic acid, for example, a polymerizable composition containing a carboxylic acid that is decarboxylated by heat development has been proposed (see Patent Document 4). However, in this polymerizable composition, heat development is performed as described above, and it is not clear whether the sensitivity can be improved similarly when irradiated with light. Further, no consideration is given to making the shape of the resist pattern good. Furthermore, when a polycarboxylic acid compound is used, there is a problem that the strength of the tent film is weakened.
As a technique capable of improving the sensitivity when irradiated with light, for example, a photosensitive composition containing N-phenylglycine or the like as a hydrogen donor, that is, a chain transfer agent has been proposed (Patent Literature). 5). However, this photosensitive composition has a problem that the shape of the resist pattern is deteriorated due to the molecular weight of the N-phenylglycine being as low as about 151. Also, the improvement in sensitivity is not always sufficient.

  Therefore, by containing carboxylic acid, a high sensitivity, a good resist pattern shape can be obtained, and the tent film strength is strong, and a pattern forming material capable of forming a high-definition and high-aspect-ratio pattern, and A pattern forming apparatus and a pattern forming method using a pattern forming material have not yet been provided, and the present situation is that further improvement and development are desired.

International Publication No. 01/071428 Pamphlet JP 2004-252421 A JP-A-8-254821 Japanese Patent Laid-Open No. 2004-310000 JP 2003-50459 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention provides a pattern-forming material that can form a high-definition, high-aspect-ratio pattern with high sensitivity, good resist pattern shape, strong tent film strength, by containing carboxylic acid. Another object is to provide a pattern forming apparatus and a pattern forming method using the pattern forming material.

Means for solving the problems are as follows. That is,
<1> A photosensitive layer formed using a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, and a monocarboxylic acid compound having a molecular weight of 180 to 2,000,
When the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 50 mJ / cm ^2. A pattern forming material characterized by the following. In the pattern forming material according to <1>, since the photosensitive composition contains a monocarboxylic acid compound, the strength of the tent film can be increased. Moreover, since the molecular weight of the monocarboxylic acid compound is set to 180 to 2,000, a high sensitivity and good resist pattern shape can be obtained. By using such a pattern forming material, the photosensitive layer is exposed with high definition, and then, when the photosensitive layer is developed, a pattern with high definition and high aspect ratio is formed.
<2> The pattern forming material according to <1>, wherein the monocarboxylic acid compound includes a group represented by the following structural formula (1).
In the structural formula (1), X is a divalent linking group selected from —O—, —S—, —SO ₂ —, —NH—, —N (R ³ ) —, and —CO—. R ³ represents a hydrogen atom or a monovalent substituent. R ¹ and R ² each independently represents a hydrogen atom or a monovalent substituent. Note that the ^{R 1} and ^R 2, ^{R 1} and at least one and ^{R 3} of ^{R 2,} may be bonded to form a ring structure.
<3> The pattern forming material according to any one of <1> to <2>, wherein the monocarboxylic acid compound is a compound represented by the following structural formula (2).
However, in said structural formula (2), A represents an aromatic group or a heterocyclic group. R ¹ and R ² each independently represents a hydrogen atom or a monovalent substituent. Note that at least one of R ¹ and R ² , R ¹ and R ² and at least one of X ¹ , R ¹ and R ² and A, A and X may be bonded to each other to form a ring structure. X ¹ represents a divalent linking group selected from —O—, —S—, —SO ₂ —, —NH—, —N (R ³ ) —, and —CO—, and R ³ represents hydrogen. Represents an atom or a monovalent substituent. In the pattern forming material according to <3>, by containing a monocarboxylic acid compound represented by the following structural formula (2), the sensitivity can be further improved, and the shape of the resist pattern Can also be good.
<4> The aspect ratio (d / L) between the line width (L; μm) of the pattern after exposure and development and the film thickness (d; μm) of the pattern is 1.0 to 5.0 < The pattern forming material according to any one of <1> to <3>.
<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 (Tg) of 80 ° C. or higher.
<7> The pattern forming material according to any one of <1> to <6>, wherein the polymerizable compound includes a monomer having at least one of a urethane group and an aryl group.
<8> The photopolymerization initiator is selected from halogenated hydrocarbon derivatives, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, metallocenes, and acylphosphine oxide compounds. The pattern forming material according to any one of <1> to <7>, including at least one selected from the group consisting of:
<9> The photosensitive composition includes a thermal crosslinking agent, and the binder includes at least one of an epoxy acrylate compound, and a vinyl copolymer having a (meth) acryloyl group and an acidic group in a side chain. The pattern forming material according to any one of <1> to <8>.
<10> The thermal crosslinking agent according to <9>, wherein the thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. Pattern forming material.
<11> The pattern forming material according to any one of <1> to <10>, wherein the photosensitive composition includes a sensitizer, and the sensitizer is a hetero-fused ring ketone.
<12> The pattern forming material according to any one of <1> to <11>, further including at least a support and a photosensitive layer formed on the support.
<13> The pattern forming material according to <12>, wherein the support has a thermoplastic resin layer and a photosensitive layer in this order.

<14> The pattern forming material according to any one of <1> to <13>, wherein the binder has an acid value of 70 to 250 (mgKOH / g).
<15> The pattern forming material according to any one of <1> to <14>, wherein the photosensitive layer has a thickness of 1 to 100 μm.
<16> The pattern forming material according to any one of <1> to <15>, wherein the photosensitive layer contains 10 to 90% by mass of a binder and 5 to 90% by mass of a polymerizable compound.
<17> The pattern forming material according to any one of <12> to <16>, wherein the support includes a synthetic resin and is transparent.
<18> The pattern forming material according to any one of <12> to <17>, wherein the support has a long shape.
<19> The pattern forming material according to any one of <12> to <18>, wherein the pattern forming material has a long shape and is wound in a roll shape.
<20> The pattern forming material according to any one of <12> to <19>, having a protective film on the photosensitive layer in the pattern forming material.

<21> The pattern forming material according to any one of <1> to <20> is provided,
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 <21>, 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.
<22> The light modulation means further includes 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 <21> modulated according to. In the pattern forming apparatus according to <22>, since the light modulation unit includes the pattern signal generation unit, light emitted from the light irradiation unit corresponds to a control signal generated by the pattern signal generation unit. Modulated.
<23> The light modulation means includes n pixel parts, and forms any less than n pixel parts arranged continuously from the n pixel parts. The pattern forming apparatus according to any one of <21> to <22>, which is controllable according to pattern information. In the pattern forming apparatus according to <23>, any less than n pixel parts arranged continuously from the n pixel parts in the light modulation unit are controlled according to pattern information. Thereby, the light from the light irradiation means is modulated at high speed.
<24> The pattern forming apparatus according to any one of <21> to <23>, wherein the light modulation unit is a spatial light modulation element.
<25> The pattern forming apparatus according to <24>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<26> The pattern forming apparatus according to any one of <23> to <25>, wherein the picture element portion is a micromirror.
<27> The pattern forming apparatus according to any one of <21> to <26>, wherein the light irradiation unit is capable of combining and irradiating two or more lights. In the pattern forming apparatus according to <27>, 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 exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<28> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects laser beams irradiated from the plurality of lasers and couples them to the multimode optical fiber. <21> to the pattern forming apparatus according to any one of <27>. In the pattern forming apparatus according to <28>, the light irradiation unit can condense the laser beams irradiated 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 exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<29> After laminating the photosensitive layer in the pattern forming material according to any one of <1> to <20> on the surface of the substrate under at least one of heating and pressurization, The pattern forming method includes at least performing exposure.
<30> The pattern forming method according to <29>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
<31> The pattern forming method according to any one of <29> to <30>, wherein the exposure is performed imagewise based on pattern information to be formed.

<32> Exposure has light irradiation means, and n (where n is a natural number of 2 or more) two-dimensionally arranged pixel parts that receive and emit light from the light irradiation means, An exposure head provided with a light modulation means capable of controlling the picture element portion in accordance with pattern information, wherein the column direction of the picture element portion forms a predetermined set inclination angle θ with respect to the scanning direction of the exposure head. Using an exposure head arranged as follows:
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
The pattern forming method according to any one of <29> to <31>, wherein the exposure head is moved relative to the photosensitive layer in a scanning direction. In the pattern forming method according to <32>, the exposure head is subjected to N-exposure (where N is a natural number of 2 or more) among the usable pixel parts by the used pixel part specifying unit. The pixel part to be used is specified, and the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in exposure. By performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction, the exposure head is formed on the exposed surface of the photosensitive layer due to a shift in the mounting position or mounting angle of the exposure head. Variations in the resolution of the pattern and unevenness in density are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<33> The exposure is performed by a plurality of exposure heads, and the drawing element specifying unit is related to the exposure of the head-to-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The pattern forming method according to <32>, wherein, among the element parts, the image element part used for realizing N double exposure in the inter-head connection region is designated. In the pattern forming method according to <33>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designation unit is an overlapped exposure region on the exposed surface formed by the plurality of exposure heads. Of the picture element parts involved in the exposure of the head-to-head connection area, the picture element part used for realizing the N-fold exposure in the head-to-head connection area is designated, so that the mounting position and attachment of the exposure head are specified. Variations in resolution and density unevenness of the pattern formed in the connecting area between the heads on the exposed surface of the photosensitive layer due to the angle shift are leveled. As a result, the photosensitive layer is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<34> The exposure is performed by a plurality of exposure heads, and the used picture element specifying means is involved in exposure other than the inter-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The pattern forming method according to <33>, wherein the image element portion to be used for realizing N double exposure in an area other than the inter-head connection area in the image element area is designated. In the pattern forming method according to <34>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. Of the picture element parts involved in the exposure other than the inter-head connection area, the attachment position of the exposure head is specified by designating the picture element part used for realizing the N-fold exposure in the areas other than the inter-head connection area. Variations in the resolution and density unevenness of the pattern formed in areas other than the head-to-head connection area on the exposed surface of the photosensitive layer due to the mounting angle deviation are equalized. As a result, the photosensitive layer is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<35> When the set inclination angle θ is N, the number N of the multiple exposures, the number s of the pixel parts in the column direction, the interval p of the pixel parts in the column direction, and the exposure head tilted. the relative row direction pitch δ of pixel parts in the direction perpendicular to the scanning direction, the following equation with respect to theta _ideal satisfying spsinθ _ideal ≧ Nδ, which is set so as to satisfy the relation of θ ≧ θ _ideal <32> to <34>.
<36> The pattern forming method according to any one of <32> to <34>, wherein N in N-fold exposure is a natural number of 3 or more. In the pattern forming method according to <36>, multiple drawing is performed when N in N double exposure is a natural number of 3 or more. As a result, due to the effect of filling, variations in the resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to a shift in the mounting position and mounting angle of the exposure head are more precisely leveled.

<37> Use pixel part designation means,
A light spot position detecting means for detecting a light spot position as a pixel unit that is generated by the picture element unit and constitutes an exposure area on the exposed surface;
<32> to <36>, further comprising: a pixel part selection unit that selects a pixel part to be used for realizing N double exposure based on a detection result by the light spot position detection unit. This is a pattern forming method.
<38> The pattern forming method according to any one of <32> to <37>, wherein the used pixel part specifying unit specifies the used pixel part used for realizing the N double exposure in a line unit. is there.

<39> Based on at least two light spot positions detected by the light spot position detection means, an actual direction formed by the column direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted. The inclination angle θ ′ is specified, and the picture element selection means selects the use picture element part so as to absorb the error between the actual inclination angle θ ′ and the set inclination angle θ. The pattern forming method according to any one of the above.
<40> The actual inclination angle θ ′ is an average value, a median value, and a plurality of actual inclination angles formed by the row direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is inclined. The pattern forming method according to <39>, wherein the pattern forming method is any one of a maximum value and a minimum value.
<41> The pixel part selection means derives a natural number T close to t satisfying a relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <37> to <40> in which the pixel elements in the first to the Tth rows are selected as the used pixel elements in a line element (where m represents a natural number of 2 or more). The pattern forming method according to any one of the above.
<42> The pixel part selection means derives a natural number T close to t satisfying a relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m In the picture element part arranged in a row (where m represents a natural number of 2 or more), the picture element part from line (T + 1) to m-th line is specified as an unused picture element part, and the unused picture element part is specified. The pattern forming method according to any one of <37> to <41>, wherein the picture element part excluding the element part is selected as a use picture element part.

<43> In a region including at least an overlapped exposure region on an exposed surface formed by a plurality of pixel part columns,
(1) Means for selecting a used pixel portion so that a total area of an overexposed region and an underexposed region is minimized with respect to an ideal N-multiple exposure,
(2) Means for selecting a pixel part to be used so that the number of pixel units in an overexposed area and the number of pixel units in an underexposed area are equal to each other with respect to an ideal N double exposure;
(3) Means for selecting a pixel part to be used so that the area of an overexposed area is minimized and an underexposed area does not occur with respect to an ideal N double exposure, and (4) Ideal From the above <37>, which is one of means for selecting a pixel part to be used so that the area of an underexposed area is minimized and an overexposed area does not occur with respect to typical N double exposure It is the pattern formation method as described in <42>.
<44> In the joint region between the heads, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads,
(1) With respect to the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connection region, the total area of the overexposed region and the underexposed region is minimized. Means for identifying a used pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
(2) Involvement in the exposure of the head-to-head connecting region so that the number of pixel units in the overexposed region and the number of pixel units in the underexposed region are equal to the ideal N-double exposure. Means for identifying an unused pixel part from the pixel part to be selected, and selecting the pixel part excluding the unused pixel part as a used pixel part;
(3) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the overexposed region is minimized and the underexposed region is not generated. A means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part; and
(4) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the underexposed region is minimized and the region that is overexposed is not generated. , Means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
The pattern forming method according to any one of <37> to <43>, which is any of the above.
<45> The pattern forming method according to <44>, wherein the unused pixel parts are specified in units of rows.

<46> In order to specify a used pixel part in the used pixel part specifying means, among N pixel exposures that can be used, with respect to N of N double exposure, a pixel part sequence for each (N-1) column The pattern forming method according to any one of <32> to <45>, wherein the reference exposure is performed by using only the image element portion that constitutes. In the pattern forming method according to <46>, in order to specify the used pixel part in the used pixel part specifying unit, among the usable pixel elements, N of N double exposures (N -1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.
<47> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel elements, a N / N line pixel part row is configured for N of N multiple exposures. The pattern forming method according to any one of <32> to <45>, wherein the reference exposure is performed using only the pixel part. In the pattern forming method according to <47>, in order to designate a used pixel part in the used pixel part designating unit, among the usable picture element parts, 1 / Reference exposure is performed using only the pixel part constituting the pixel part column for every N rows, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<48> From the above <32> to <47>, the used pixel part specifying unit includes a slit and a photodetector as a light spot position detecting unit, and an arithmetic unit connected to the photodetector as a pixel unit selecting unit. The pattern forming method according to any one of the above.
<49> The pattern forming method according to any one of <32> to <48>, wherein N in N-exposure exposure is a natural number of 3 or more and 7 or less.

<50> 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. The pattern forming method according to <32> to <49>, wherein the pattern is modulated according to the method. In the pattern forming method according to <50>, since the light modulation unit includes the pattern signal generation unit, light emitted from the light irradiation unit corresponds to a control signal generated by the pattern signal generation unit. Modulated.
<51> The pattern forming method according to any one of <32> to <50>, wherein the light modulation unit is a spatial light modulation element.
<52> The pattern forming method according to <51>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<53> The pattern forming method according to any one of <32> to <52>, wherein the picture element portion is a micromirror.
<54> From the above <32> to <32> having conversion means for converting the pattern information so that the dimension of the predetermined part of the pattern represented by the pattern information matches the dimension of the corresponding part that can be realized by the designated used pixel part 53>.

<55> The pattern forming method according to any one of <32> to <54>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the pattern forming method according to <55>, 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.
<56> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams irradiated from the plurality of lasers and couples the laser beams to the multimode optical fiber. The pattern forming method according to any one of <32> to <55>. In the pattern forming method according to <56>, 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.

  <57> The pattern forming method according to any one of <30> to <56>, wherein the base material is a printed wiring board.

<58> The pattern forming method according to any one of <30> to <57>, wherein the photosensitive layer is developed after the exposure. In the pattern forming method according to <58>, a high-definition pattern is formed by developing the photosensitive layer after the exposure.
<59> The pattern forming method according to <58>, wherein a permanent pattern is formed after development.
<60> The pattern forming method according to <59>, 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.
<61> The pattern forming method according to <59>, wherein after the development, the photosensitive layer is cured.
<62> The pattern forming method according to <61>, wherein the curing process is at least one of an entire surface exposure process and an entire surface heat treatment performed at 120 to 200 ° C.
<63> The pattern forming method according to any one of <61> to <62>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed. In the pattern forming method according to <63>, since at least one of the protective film, the interlayer insulating film, and the solder resist pattern is formed, the wiring is externally provided due to the insulating property, heat resistance, and the like of the film. Protected from impact and bending.

  According to the present invention, conventional problems can be solved, and by containing a carboxylic acid, a high sensitivity and good resist pattern shape can be obtained, and the tent film strength is strong, high definition, and high aspect ratio. And a pattern forming apparatus and a pattern forming method using the pattern forming material.

(Pattern forming material)
The pattern forming material of the present invention has a photosensitive layer formed using a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, and a monocarboxylic acid compound having a molecular weight of 180 to 2,000. When exposing and developing the photosensitive layer, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 50 mJ / cm ² . .

As the pattern forming material, the aspect ratio (d / L) between the line width (L; μm) of the pattern after exposure and development and the film thickness (d; μm) of the pattern is 1.0 to 5. 0 is preferable, 1.1 to 3.0 is more preferable, and 1.2 to 2.5 is particularly preferable.
When the aspect ratio (d / L) is less than 1.0, a high-resolution wiring pattern (for example, Cu) may not be obtained. When the aspect ratio (d / L) exceeds 5.0, it is difficult to achieve both sensitivity and compatibility. There is.
The film thickness (d; μm) of the pattern is preferably 1 to 100 μm, and more preferably 5 to 50 μm.

<Photosensitive layer>
The photosensitive layer contains at least a binder, a polymerizable compound, a photopolymerization initiator, and a monocarboxylic acid compound having a molecular weight of 180 to 2,000, and other components such as a thermal crosslinking agent and a sensitizer as necessary. It is formed using the photosensitive composition containing this.
As the photosensitive layer, a photosensitive layer constituting an etching resist layer used when forming a wiring pattern and the like, and a solder resist layer used when forming a protective film, an interlayer insulating film, a solder resist pattern, etc. Any photosensitive layer may be used.

In the case where the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 50 mJ / cm ² . There is preferably 0.2~40mJ / cm ^2, more preferably 0.5~30mJ / cm ^2.
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs exceeds 50 mJ / cm ^2, increases the time necessary for exposure, processing speed is slow Sometimes.

Here, “the minimum energy of light used in the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development” is so-called development sensitivity, for example, when the photosensitive layer is exposed. It can be determined from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for the exposure and the thickness of the cured layer generated by the development process following the exposure.
The thickness of the cured layer increases as the amount of exposure increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
Here, when the thickness of the cured layer and the thickness of the photosensitive layer before the exposure are within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.
The method for measuring the thickness of the cured layer and the photosensitive layer before the exposure is not particularly limited and may be appropriately selected depending on the intended purpose. 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.

-Monocarboxylic acid compound-
The molecular weight of the monocarboxylic acid compound contained in the photosensitive layer is 180 to 2,000, more preferably 190 to 1,500, and particularly preferably 200 to 1,000.
When the molecular weight of the monocarboxylic acid is less than 180, a good resist pattern shape may not be obtained, and when it exceeds 2,000, the sensitivity of the photosensitive layer may be lowered.
On the other hand, the photosensitive layer containing a polycarboxylic acid compound has a detrimental effect on the strength of the tent film.

  The monocarboxylic acid compound is not particularly limited as long as it has a molecular weight of 180 to 2,000, and can be appropriately selected according to the purpose. For example, the monocarboxylic acid compound includes a group containing a group represented by the following structural formula (1). Preferred examples include carboxylic acid compounds.

In the structural formula (1), X is a divalent linking group selected from —O—, —S—, —SO ₂ —, —NH—, —N (R ³ ) —, and —CO—. R ³ represents a hydrogen atom or a monovalent substituent. R ¹ and R ² each independently represents a hydrogen atom or a monovalent substituent. Note that the ^{R 1} and ^R 2, ^{R 1} and at least one and ^{R 3} of ^{R 2,} may be bonded to form a ring structure.

  The monocarboxylic acid compound containing the group represented by the structural formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. However, the sensitivity can be further improved and the resist obtained From the viewpoint of improving the shape of the pattern, for example, a monocarboxylic acid compound represented by the following structural formula (2) is preferably exemplified.

However, in said structural formula (2), A represents an aromatic group or a heterocyclic group. R ¹ and R ² each independently represents a hydrogen atom or a monovalent substituent. Note that at least one of R ¹ and R ² , R ¹ and R ² and at least one of X ¹ , R ¹ and R ² and A, A and X may be bonded to each other to form a ring structure. X ¹ represents a divalent linking group selected from —O—, —S—, —SO ₂ —, —NH—, —N (R ³ ) —, and —CO—, and R ³ represents hydrogen. Represents an atom or a monovalent substituent.

Examples of the aromatic group include a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.
Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and the like. In these, a phenyl group and a naphthyl group are more preferable.
The aromatic group may have a substituent. Examples of the aromatic group having such a substituent include a hydrogen atom as a substituent on a ring-forming carbon atom of an aryl group described below. And those having a group consisting of a monovalent non-metallic atomic group other than the above. As said substituent, what was shown as a substituent in the below-mentioned alkyl group, substituted alkyl group, substituted alkyl group, etc. are mentioned, for example.

Examples of the heterocyclic group include a pyrrole ring group, a furan ring group, a thiophene ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a pyrazole ring group, an isoxazole ring group, an isothiazole ring group, and an indazole ring. Group, benzisoxazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, pyridine ring group, quinoline ring group, Isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidene ring group, phenanthridine ring group, carbazole ring group, purine ring group, Piperidine ring group, piperazine ring group, morpholine ring group, indole ring group, Ndorijin ring group, a chromene ring group, a cinnoline ring group, an acridine ring group, a phenothiazine ring group, a tetrazole ring group, a triazine ring group, and the like.
The heterocyclic group may have a substituent, and the heterocyclic group having such a substituent excludes a hydrogen atom as a substituent on a ring-forming carbon atom of an aryl group described later. Those having a group consisting of a monovalent nonmetallic atomic group are used. As said substituent, what was shown as a substituent in the below-mentioned alkyl group, a substituted alkyl group, a substituted alkyl group, etc. can be mentioned, for example.

--Monovalent substituent represented by R ¹ and R ^2-
In the structural formulas (1) and (2), examples of the monovalent substituent represented by R ¹ and R ² include a halogen atom, an amino group that may have a substituent, an alkoxycarbonyl group, and a hydroxyl group. An ether group, a thiol group, a thioether group, a silyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, etc., each of which may have a substituent.

Examples of the alkyl group that may have a substituent (hereinafter also referred to as a substituted alkyl group) include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. It is done.
Specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group Group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl Group, 2-norbornyl group, and the like. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.

Examples of the substituent that such an alkyl group can have include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom.
Specifically, for example, halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino Group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkyl Carbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, Acylthio group, acylamino group, N-alkylacyl group Group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′- Alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl -N-alkylureido group, N ', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl -N-alkylureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl- -Arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N- di arylcarbamoyl group, N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO 3 _H) and its conjugate base (Referred to as sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinaimoyl group, N-arylsulfinamoyl group, N, N- Diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N - diaryl sulfamoyl group, (referred to as phosphonato group) N- alkyl -N- arylsulfamoyl group, a phosphono group _(-PO 3 _{H 2)} and its conjugated base group, a dialkyl phosphono group _(-PO 3 (alkyl ₂ ) “alkyl = alkyl group, the same shall apply hereinafter”, diarylphosphono group (—PO 3 (Aryl) ₂ ) “aryl = aryl group, the same shall apply hereinafter”, alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ (alkyl)) and its conjugate base group (Referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base Group (referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ ( alkyl) (aryl)), monoalkyl phosphono group _(-OPO 3 H _(alkyl)) and its Conjugate base (referred to as alkylphosphonato group) group, (referred to as aryl phosphite Hona preparative group) monoarylphosphono group (-OPO 3 H _(aryl)) and its conjugated base group, a cyano group, a nitro group, an aryl Group, alkenyl group, alkynyl group, heterocyclic group, silyl group, and the like.

Examples of the alkyl group in the substituent include the same as the specific examples of the alkyl group which may have a substituent.
Examples of the aryl group in the substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a chloromethylphenyl group, a hydroxyphenyl group, and a methoxyphenyl group. Group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, methoxycarbonylphenyl group, ethoxy Phenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphonatopheny Group, and the like.

Examples of the alkenyl group in the substituent include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like.
Examples of the alkynyl group in the substituent include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group, and the like.
Examples of the heterocyclic group in the substituent include a pyridyl group and a piperidinyl group.
Examples of the silyl group in the substituent include a trimethylsilyl group.
The substituent may include an acyl group (R ⁰¹ CO—), and examples of the acyl group include those in which R ⁰¹ is a hydrogen atom, the above alkyl group, an aryl group, or the like. .

  Among the substituents that the alkyl group may have, a halogen atom (—F, —Br, —Cl, —I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N , N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N Alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphosphonato group, phosphonooxy group , A phosphonatoxy group, an aryl group, and an alkenyl group are more preferable.

  In addition, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms described above. Among these, a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, a cyclic alkylene group having 5 to 10 carbon atoms, and the like are preferable.

  Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and an isopropoxymethyl group. , Butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetra Methylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group , Carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl Group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyl Cutyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxy Propyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2 -Butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. are mentioned.

Examples of the aryl group include a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.
Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and the like. Among these, a phenyl group and a naphthyl group are more preferable.

  Examples of the aryl group which may have the substituent (hereinafter also referred to as a substituted aryl group) include, for example, a monovalent non-hydrogen atom other than a hydrogen atom as a substituent on the ring-forming carbon atom of the aryl group. The thing which has group which consists of metal atom groups, etc. are mentioned. Among these, those shown as the substituents in the aforementioned alkyl group, substituted alkyl group, and substituted alkyl group are preferable.

  Specific examples of the substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl group. , Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, methoxycarbonyl group Nyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl- N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfa Moylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphospho Honatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2- A propynylphenyl group, a 2-butynylphenyl group, a 3-butynylphenyl group, and the like are preferable.

Examples of the alkenyl group and alkynyl group (—C (R ⁰² ) ═C (R ⁰³ ) (R ⁰⁴ ) and —C≡C (R ⁰⁵ )) that may have a substituent include, for example, R ^{And 02} , R ⁰³ , R ⁰⁴ , and R ⁰⁵ each having a monovalent nonmetallic atomic group.
Examples of R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ include a hydrogen atom, a halogen atom, an alkyl group, an alkyl group that may have a substituent, and an aryl group.
Specifically, those shown as the above example can be mentioned. Among these, a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group, and a cyclic alkyl group are preferable.

  Preferable specific examples of such alkenyl group, substituted alkenyl group, alkynyl group and substituted alkynyl group include vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group and 1-octenyl group. 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1 -Propynyl group, 1-butynyl group, phenylethynyl group, and the like.

  Examples of the heterocyclic group which may have a substituent include a pyridyl group exemplified as a substituent for a substituted alkyl group.

Examples of the oxy group (R ⁰⁶ O—) (hereinafter also simply referred to as a substituted oxy group) contained in the above-described substituent include, for example, R ⁰⁶ is a monovalent nonmetallic atomic group excluding a hydrogen atom. The thing etc. which are groups are mentioned.
Examples of the substituted oxy group include an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N, N-dialkylcarbamoyloxy group, and an N, N-diaryl. Preferred examples include carbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, phosphonooxy group, phosphonatoxy group, and the like.

Examples of the alkyl group and aryl group in the substituted oxy group include those described above as the substituted alkyl group and substituted aryl group.
In addition, the substituted oxy group may contain an acyl group (R ⁰⁷ CO—). Examples of the acyl group include those in which R ⁰⁷ is an alkyl group or an aryl group listed above. Can be mentioned. Among these, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable.
Specifically, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, benzyloxy group, allyloxy group, phenethyloxy group, carboxyethyloxy group, Methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy group, tolyloxy group Xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group, bromophenyloxy group Shi group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, phosphonatoxy group, and the like.

Among the amino groups contained in the above-described substituents, those containing an amide group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) (hereinafter also referred to as a substituted amino group) include, for example, Examples include those in which R ⁰⁸ , R ⁰⁹ and R ⁰¹⁰ are each a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. R ⁰⁹ and R ⁰¹⁰ may combine to form a ring.
Examples of the substituted amino group include an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, an acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N′-alkyl-N′-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, '-Dialkyl-N'-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl-N-alkylureido group, N ', N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxy Carbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, Etc. Examples of the alkyl group and aryl group in these include those described above as the alkyl group and aryl group, and acyl groups (R ⁰⁷ CO—) in acylamino groups, N-alkylacylamino groups, and N-arylacylamino groups. R ^{07 is} also as described above. Among these, an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group are preferable.
Specific examples include a methylamino group, an ethylamino group, a diethylamino group, a morpholino group, a piperidino group, a pyrrolidino group, a phenylamino group, a benzoylamino group, and an acetylamino group.

The substituent may include a sulfonyl group (R ⁰¹¹ —SO ₂ —). Examples of the sulfonyl group include a group in which R ⁰¹¹ is a monovalent nonmetallic atomic group.
Examples of such a sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group and substituted aryl group.
Specific examples include a butylsulfonyl group, a phenylsulfonyl group, a chlorophenylsulfonyl group, and the like.

Wherein the substituents, sulfonato group as the conjugated base anion group of a sulfo group _{(-SO 3 H) (-SO 3} -) may be contained. The sulfonate group is usually preferably used with a counter cation.
There is no restriction | limiting in particular as this counter cation, Usually, what is known can be selected suitably and can be used, for example, various oniums (Ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums) Etc.), metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ²⁺ etc.), and the like.

The substituent may include a carbonyl group (R ⁰¹³ —CO—). As the carbonyl group, for example, a group in which R ⁰¹³ is a monovalent nonmetallic atomic group can be used.
Examples of such a carbonyl group include formyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group and the like can be mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group and aryl group.
Among these, formyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group are more preferable, formyl group, acyl group An alkoxycarbonyl group and an aryloxycarbonyl group are particularly preferable.
Specifically, for example, formyl group, acetyl group, benzoyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N-methylcarbamoyl group, N -Phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like are preferable.

The substituent may include a sulfinyl group (R ⁰¹⁴ —SO—). Examples of the sulfinyl group include those in which R ⁰¹⁴ is a group composed of a monovalent nonmetallic atomic group.
Examples of such sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, sulfinamoyl groups, N-alkylsulfinamoyl groups, N, N-dialkylsulfinamoyl groups, N-arylsulfinamoyl groups, N, N -A diarylsulfinamoyl group, an N-alkyl-N-arylsulfinamoyl group, etc. are mentioned suitably. Examples of the alkyl group and aryl group in these include those described above as the alkyl group and aryl group. Among these, an alkylsulfinyl group and an arylsulfinyl group are more preferable.
Specific examples include a hexylsulfinyl group, a benzylsulfinyl group, a tolylsulfinyl group, and the like.

The substituent may include one in which one or two hydroxyl groups on the phosphono group are substituted with another organic oxo group (hereinafter also referred to as a substituted phosphono group).
Examples of the substituted phosphono group include the aforementioned dialkylphosphono group, diarylphosphono group, alkylarylphosphono group, monoalkylphosphono group, monoarylphosphono group, and the like. Among these, a dialkylphosphono group and a diarylphosphono group are more preferable.
Specific examples include a diethylphosphono group, a dibutylphosphono group, a diphenylphosphono group, and the like.

The substituent includes a phosphonate group (—PO ₃ H _{2 —,} —PO) as a conjugated base anion group derived from acid first dissociation or acid second dissociation of a phosphono group (—PO ₃ H _{2). 3} H-) may be included. The phosphonate group is usually preferably used with a counter cation.
There is no restriction | limiting in particular as this counter cation, Usually, what is known can be selected suitably and can be used, for example, various oniums (Ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums) ), Metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.), and the like.

The phosphonate group may be a conjugated base anion group in which one of the phosphono groups is substituted with one organic oxo group.
Examples of such a phosphonate group include the above-mentioned monoalkylphosphono group (—PO ₃ H (alkyl)), a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)), and the like.

--X and X ^1-
X in the structural formula (1) and X ¹ in the structural formula (2) are —O—, —S—, —SO ₂ —, —NH—, —N (R ³ ) —, and —CO—. represents a divalent linking group selected from, among these, -O -, - S -, - NH -, - N (R 3) - are preferred, -N ^{(R 3)} - from the viewpoint of sensitivity Particularly preferred.

Here, R ^{3 in} X represents a hydrogen atom or a monovalent substituent, and such a monovalent substituent has the same meaning as R ¹ and R ² in the structural formula (1).
In particular, R ³ is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, each of which may have a substituent.
In addition, R ³ preferably has at least one of —CO ₂ — and —CON (R ⁸ ) — in the structure, and an ester structure represented by the following formula (3-1) And a structure containing an amide structure represented by the following formula (3-2) are particularly preferred. In both cases, a structure containing an amide structure represented by the formula (3-2) is most preferred.

However, in said formula (3-1) and (3-2), R < ⁶ >, R < ⁷ > and R < ⁸ > represent a hydrogen atom or a monovalent substituent each independently, Z is a monovalent substituent. Represents. Such a monovalent substituent is synonymous with R ¹ and R ² in the structural formula (1) and the structural formula (2).

  Preferred examples of the specific monocarboxylic acid compound represented by the structural formula (2) include those represented by the following compounds (A-1) to (A-80).

Although there is no restriction | limiting in particular as content of the said monocarboxylic acid compound, From the viewpoint of ensuring sufficient sensitivity improvement effect and ensuring the excellent removability of an unexposed part, it is in photosensitive composition solid content. It is preferable that it is 0.01-10 mass% with respect to all the components, It is more preferable that it is 0.05-8 mass%, It is most preferable that it is 0.1-5 mass%.
When the content of the monocarboxylic acid compound is within this range, there is an advantage that a highly sensitive pattern forming material can be obtained and the film physical properties before and after curing are excellent.

(1) Photosensitive layer for etching resist The photosensitive layer for etching resist contains at least a monocarboxylic acid compound having a molecular weight of 180 to 2,000, a binder, a polymerizable compound, and a photopolymerization initiator. And a photosensitive composition containing other appropriately selected components such as a sensitizer.

-Binder-
The binder is preferably, for example, swellable with an alkaline liquid, and more preferably soluble in an alkaline liquid.
As the binder exhibiting swellability or solubility with respect to the alkaline liquid, for example, those having an acidic group are preferably mentioned.

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

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

Examples of the vinyl 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-Acryllo 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 styrenes (styrene and styrene derivatives) are preferable in that a permanent pattern such as a wiring pattern can be formed with high definition and the tent property can be improved.

  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, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples include methylstyrene, 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 the vinyl monomer having a 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 and a compound containing one hydroxyl group. Alternatively, an addition reaction with a compound having one primary or secondary amino group, an addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate can be given.

  Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (4) to (6).

However, in the structural formulas (4) to (6), 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 (7) to (15).

However, in the above structural formula (7) ~ (15), R 1 represents a hydrogen atom or a methyl radical, n represents 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.

  Examples of the other copolymerizable monomers other than those described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic. Preferable examples include 2-ethylhexyl acid, styrene, chlorostyrene, bromostyrene, and hydroxystyrene.

  The said other copolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

  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.

There is no restriction | limiting in particular as content rate of the polymeric compound which has a carboxyl group in the said vinyl copolymer, Although it can select suitably according to the objective, For example, 5-50 mol% is preferable, 10-40 mol % Is more preferable, and 15 to 35 mol% is particularly preferable.
If the content is less than 5 mol%, the developability to alkaline water may be insufficient, and if it exceeds 50 mol%, the developer resistance of the cured portion (image portion) 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, as the binder, a resin soluble in an alkaline liquid described in Japanese Patent No. 2873890 can be used.

There is no restriction | limiting in particular in content of the said binder in the said photosensitive layer, Although it can select suitably according to the objective, For example, 10-90 mass% is preferable, 20-80 mass% is more preferable, 40-80 Mass% is particularly preferred.
When the content is less than 10% by mass, alkali developability and adhesion 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.

When the binder is a substance having a glass transition temperature (Tg), the glass transition temperature is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tack and edge of the pattern forming material 80 degreeC or more is preferable, 100 degreeC or more is more preferable, and 120 degreeC or more is especially preferable from the viewpoint of at least any one of suppression of fusion and the peelability improvement of the said support body.
When the glass transition temperature is less than 80 ° C., tack and edge fusion of the pattern forming material may increase, or the peelability of the support may deteriorate.

The acid value of the binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 70 to 250 mgKOH / g, more preferably 90 to 200 mgKOH / g, and particularly preferably 100 to 180 mgKOH / g. preferable.
When the acid value is less than 70 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 developer resistance and adhesion of the pattern deteriorates, and a permanent pattern such as a wiring pattern cannot be obtained with high definition.

-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.

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

--Monomer having urethane group--
The monomer having a urethane group is not particularly limited as long as it has a urethane group, and can be appropriately selected depending on the purpose. For example, JP-B-48-41708, JP-A-51-37193, JP-B-5 -50737, Japanese Patent Publication No. 7-7208, Japanese Patent Application Laid-Open No. 2001-154346, Japanese Patent Application Laid-Open No. 2001-356476, and the like. For example, a polyisocyanate compound having two or more isocyanate groups in the molecule And an adduct of a vinyl monomer having a hydroxyl group in the molecule.

  Examples of the polyisocyanate compound having two 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, A diisocyanate such as 3,3′dimethyl-4,4′-diphenyl diisocyanate; a polyaddition product of the diisocyanate with a bifunctional alcohol (in this case, both ends are isocyanate groups); a burette or isocyanurate of the diisocyanate; Trimer; the diisocyanate or diisocyanates and trimethylolpropane, pe Taeritoritoru, polyfunctional alcohols such as glycerin, or the like adducts of other functional alcohol obtained of such these ethylene oxide adducts and the like.

  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.

  In addition, examples of the monomer having a urethane group include compounds having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate, di (meth) acrylated isocyanurate, and tri (meth) acrylate of ethylene oxide-modified isocyanuric acid. Is mentioned. Among these, the compound represented by the following structural formula (16) or the structural formula (17) is preferable, and it is particularly preferable that at least the compound represented by the structural formula (17) is included from the viewpoint of tent properties. Moreover, these compounds may be used individually by 1 type, and may use 2 or more types together.

In the structural formulas (16) and (17), R ^{1 to} R ³ each represent a hydrogen atom or a methyl group. X ₁ to X ₃ represents an alkylene oxide, may be alone or in combination of two or more thereof.

  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 the structural formulas (16) and (17), m1 to m3 represent an integer of 1 to 60, preferably 2 to 30, and more preferably 4 to 15.

In the structural formulas (16) and (17), Y ¹ and Y ² represent 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—), an oxygen 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, Preferred examples include a sulfonyl group (—SO ₂ —) or a combination thereof, and among these, an alkylene group, an arylene group, or a combination thereof 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. Preferable examples include a xylene group, a cyclohexylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, a nonylene group, a decylene group, a dodecylene group, an octadecylene group, or any of the groups shown below.

  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 the groups shown below.

  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, fluorine atom, chlorine atom, 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 (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 formulas (16) and (17), n represents an integer of 3 to 6, and 3, 4 or 6 is preferable from the viewpoint of raw material supply ability for synthesizing a polymerizable monomer.

  In the structural formulas (16) and (17), Z represents an n-valent (3 to 6-valent) linking group, and examples thereof include any of the groups shown below.

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 (3-6 valent) 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.

  Preferred examples of A are as follows.

  Examples of the compounds represented by the structural formulas (16) and (17) include compounds represented by the following structural formulas (18) to (37).

  However, in said structural formula (18)-(37), n, n1, n2 and m mean 1-60, l means 1-20, R represents a hydrogen atom or a methyl group. .

--Monomer having an aryl group--
The monomer having an aryl group is not particularly limited as long as it has an aryl group, and can be appropriately selected depending on the purpose. For example, a polyhydric alcohol compound having a aryl group, a polyvalent amine compound, and a polyvalent Examples thereof include esters or amides of at least one of amino alcohol compounds and an unsaturated carboxylic acid.

  Examples of the polyhydric alcohol compound, polyamine compound or polyhydric 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-tetra Methyl-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, 1,1′-methylene-di-2-naphth 1,2,4-benzenetriol, biphenol, 2,2′-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, hydroquinone, hydroxybenzyl alcohol, methyl hydroquinone, methylene-2,4,6-trihydroxybenzoate, phloroglicinol, pyrogallol, resorcinol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, α -(1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino-4-hydroxyphenylsulfone and the like can be mentioned. In addition, compounds obtained by adding α, β-unsaturated carboxylic acid to glycidyl compounds such as xylylene bis (meth) acrylamide, novolac epoxy resin and bisphenol A diglycidyl ether, phthalic acid, trimellitic acid, etc. Esterified products obtained from vinyl monomers containing hydroxyl groups in the molecule, diallyl phthalate, triallyl trimellitic acid, diallyl benzenedisulfonate, cationically polymerizable divinyl ethers (for example, bisphenol A divinyl ether), epoxy as a polymerizable monomer Compound (for example, novolac type epoxy resin, bisphenol A diglycidyl ether, etc.), vinyl ester (for example, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate, etc.), styrene Compounds such as divinylbenzene, p-allylstyrene, p-isopropenestyrene, and the like. Among these, a compound represented by the following structural formula (38) is preferable.

In the structural formula (38), R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group.

In the structural formulas, X ₅ and X ₆ represent an alkylene oxide group, which may be used alone or in combination of two or more. As the alkylene oxide group, for example, an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, a group combining these (which 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 group combining these is preferable, and an ethylene oxide group and a propylene oxide group are more preferable.

  In the structural formula (38), 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 (38), 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 (38), Ar ¹ and Ar ² represent an aryl group which may have a substituent, and examples thereof include phenylene and naphthylene. 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 monomer having an aryl group include 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 2,2-bis [4-((meth)). (Acryloxyethoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane having 2 to 20 ethoxy groups substituted with one phenolic OH group ( For example, 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) acryloyloxydecaet) C) 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 (e.g. 2,2-bis (2) having 2 to 20 ethoxy groups substituted with one phenolic OH group 4-((meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxy) Pentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecapropoxy) phenyl Propane, 2,2-bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane, or the like, or a polyether moiety of these compounds contains both a polyethylene oxide skeleton and a polypropylene oxide skeleton in the same molecule Compound having a bisphenol skeleton and a urethane group (for example, a compound described in WO01 / 98832 or a commercially available product, Shin-Nakamura Chemical Co., Ltd., BPE-200, BPE-500, BPE-1000) Compound. These compounds may be compounds obtained by changing the part derived from the bisphenol A skeleton to bisphenol F or bisphenol S.

  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. Examples thereof include compounds (for example, 2-isocyanatoethyl (meth) acrylate, α, α-dimethyl-vinylbenzyl isocyanate, etc.).

-Other polymerizable monomers-
In the pattern forming method of the present invention, a polymerizable monomer other than the monomer containing the urethane group and the monomer having an aryl group may be used in combination as long as the characteristics as the pattern forming material are not deteriorated.

  Examples of the polymerizable monomer other than the monomer containing a urethane group and the monomer containing an aromatic ring include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) And an ester of an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and a polyvalent amine compound.

  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 tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ) Ether, trimethylolethane tri (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol (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, 1,2,4-butanetriol tri (meth) acrylate, 1,5-bentanediol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate Rate, sorbitol hexa (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate A di (meth) acrylate of an alkylene glycol chain having at least one ethylene glycol chain / propylene glycol chain (for example, a compound described in WO01 / 98832), at least one of ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate, polybutylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate Examples include relate and xylenol di (meth) acrylate.

  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, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol triacrylate, penta Erythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (Meth) acrylate, diglycerin di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1, Preference is given to 5-pentanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate added with ethylene oxide, and the like.

  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 of the isocrotonic acid and the aliphatic polyhydric alcohol compound (isocrotonate ester) include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like.

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

  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 tris (meth) acrylamide, and diethylenetriamine bis (meth) acrylamide.

  In addition to the above, as the polymerizable monomer, for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Compound obtained by adding α, β-unsaturated carboxylic acid to glycidyl group-containing compound such as hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, Polyester acrylate and polyester (meth) acrylate as described in JP-B-6183, JP-B-49-43191 and JP-B-52-30490. Rate oligomers, epoxy compounds (for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether , Pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc.) and (meth) acrylic acid and other polyfunctional acrylates and methacrylates such as epoxy acrylates, Journal of Japan Adhesion Association vol. Photocurable monomers and oligomers and allyl esters described in page (1984) (eg diallyl phthalate, diallyl adipate, malonic acid) Allyl, diallylamidodiallylacetamide, etc.), cationically polymerizable divinyl ethers (for example, butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, Hexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerin trivinyl ether, etc.), epoxy compounds (eg, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, Diethylene glycol diglycidyl ether, dipropylene glycol di Glycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc.), oxetanes (for example, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl Benzene, etc.), epoxy compounds, oxetanes (for example, compounds described in WO01 / 22165), N-β-hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis (β-methacryloxy) And compounds having two or more different ethylenically unsaturated double bonds such as ethyl) acrylamide and allyl methacrylate.

  Examples of the vinyl esters include divinyl succinate and divinyl adipate.

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

If necessary, the polymerizable monomer may be used in combination with a polymerizable compound (monofunctional monomer) containing one polymerizable group in the molecule.
Examples of the monofunctional monomer include the compounds exemplified as the raw material of the binder, and the dibasic mono ((meth) acryloyloxyalkyl ester) mono (halohydroxyalkyl ester) described in JP-A-6-236031. Monofunctional monomers such as γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate, etc., compounds described in Japanese Patent No. 2744443, WO00 / 52529 pamphlet, Japanese Patent No. 2548016, etc. Is mentioned.

As content of the polymeric compound in the said photosensitive layer, 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. .
Moreover, as content of the polyfunctional monomer which has 2 or more of the said polymeric groups in a polymeric compound, 5-100 mass% is preferable, 20-100 mass% is more preferable, 40-100 mass% is especially preferable. .

-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, aromatic onium salts, and metallocenes. Among these, halogenated hydrocarbons having a triazine skeleton, oxime derivatives, ketone compounds, hexaarylbiimidazoles from the viewpoints of sensitivity and storage stability of the photosensitive layer, and 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 WO00 / 52529, 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 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  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, and 2-(alpha, alpha, beta-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in the 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)- 4-amino-6-trichloromethyl-1,3,5-triazine and the like can be mentioned.

  Examples of the compounds 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- Examples include triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in the specification of German Patent 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, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine etc. are mentioned.

  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 compounds described in JP-A-62-258241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- Naphthyl-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-isopropylphenyl) Ethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) Le) -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- Examples include triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  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) Examples include -4,6-bis (tribromomethyl) -s-triazine.

  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) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole and the like).

  Examples of the oxime derivative suitably used in the present invention include compounds represented by the following structural formulas (39) to (72).

  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 And 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, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206 No., JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate) N-butyl acid, 4-dimethylaminobenzoic acid phenethyl, 4-dimethyl 2-phthalimidoethyl tilaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, 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, tridodecylamine, amino Nofluoranes (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, etc.) (effective as a cationic polymerization initiator), WO01 / 71428 Onium Such compounds.

  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 of the photoinitiator in the said photosensitive layer, 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, known thermal polymerization inhibitors, surfactants, plasticizers, color formers, colorants, and the like, and adhesion promoters to the substrate surface and other auxiliaries. (For example, pigments, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.) may be used in combination. In addition, by appropriately containing these components, properties such as stability, photographic properties, print-out properties, and film properties of the target pattern forming material can be adjusted.
Among these, in the case of exposing and developing the photosensitive layer, from the viewpoint of improving the minimum energy (sensitivity) of the light that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development, for example, It is particularly preferred to use a sensitizer together.

There is no restriction | limiting in particular as said sensitizer, According to the said light irradiation means (For example, visible light, an ultraviolet light, visible light laser etc.), it can select suitably. When the light irradiation means is combined with a laser of 380 to 420 nm, a sensitizer having a maximum absorption wavelength of 380 to 450 nm is preferable.
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

--- Sensitizer--
The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, Methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin, acriflavine, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane), anthraquinones (eg anthraquinone), squalium Kind (For example, squalium), acridones (for example, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 2-chloro-10-butylacridone, etc.), coumarin (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-fluoro Yl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, etc.) And thioxanthone compounds (thioxanthone, isopropyl thioxanthone, 2,4-hour ethyl thioxanthone, 1-chloro-4-propyloxythioxanthone, Quantacure QTX, etc.) and the like, as well as JP-A-5-19475 and JP-A-7-271028. No., JP-A 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, and the like. Compounds with condensed rings or heterocycles ( Ring compounds) are preferred, hetero condensed ring systems ketone compounds, and acridines are more preferred. Among the hetero-fused ketone compounds, an acridone compound and a thioxanthone compound are particularly preferable.

  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 of the said sensitizer, 0.01-4 mass% is preferable with respect to all the components of the photosensitive resin composition for pattern formation materials, 0.02-2 mass% is more preferable, 0.05- 1% by mass is particularly preferred.
When the content is less than 0.01% by mass, the sensitivity may decrease, and when the content exceeds 4% by mass, the shape of the pattern may be deteriorated.

--- 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, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

The content of the thermal polymerization inhibitor is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and 0.01 to 1% by mass with respect to the polymerizable compound of the photosensitive layer. 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.

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

--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 3,042 Organic amines that can be oxidized to a colored form as described in No. 517 (for example, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediaminetriphenylamine, N-vinylcarbazole), and among these, triarylmethane compounds such as leuco crystal violet are preferable.

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

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

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

  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 resin composition for pattern forming material for improving the 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, etc. Victoria Pure Blue BOH can be cited, among these cationic dyes (e.g., Malachite Green oxalate, malachite green sulfates) are preferable. The counter anion of the cationic dye may be a residue of an organic acid or an inorganic acid, for example, a residue such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid, toluenesulfonic acid ( Anion) and the like.

  The content of the dye is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and particularly preferably 0.1 to 2% by mass with respect to all components of the photosensitive layer.

-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.

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

  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 added.
The surfactant can be appropriately selected from, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a fluorine-containing surfactant.

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

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

(2) Photosensitive layer for solder resist The solder resist photosensitive layer includes at least a monocarboxylic acid compound having a molecular weight of 180 to 2,000, a binder, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent. It is formed using the photosensitive composition containing the other component suitably selected as needed.

-Binder-
The binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A Nos. 51-131706, 52-94388, 64-62375, and JP-A-2 -97513, JP-A-3-289656, JP-A-61-2243869, JP-A-2002-296976, etc., an epoxy acrylate compound having an acidic group, and a (meth) acryloyl group in the side chain and Examples thereof include a vinyl copolymer having an acidic group, an epoxy acrylate compound and a vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain, and a maleic anhydride copolymer.
Further, the same binders as exemplified as the binder contained in the etching photosensitive layer can be used.

  The epoxy acrylate compound is a compound having a skeleton derived from an epoxy compound and containing an ethylenically unsaturated double bond and a carboxyl group in the molecule. Such a compound can be obtained, for example, by a method of reacting a polyfunctional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.

  Examples of the polyfunctional epoxy compound include a bixylenol type or bisphenol type epoxy resin (“YX4000; manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton (“TEPIC; NISSAN CHEMICAL INDUSTRY CO., LTD. "ALALDITE PT810; Ciba Specialty Chemicals" etc.), bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac Type epoxy resin, cresol novolac type epoxy resin, halogenated phenol novolak type epoxy resin, glycidylamine type epoxy resin (for example, tetraglycidyldiaminodiphenylmethane), hydantoy Type epoxy resin, cycloaliphatic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink and Chemicals”, etc.), epoxy resins having a dicyclopentadiene skeleton (“ HP-7200, HP-7200H; manufactured by Dainippon Ink Chemical Co., Ltd., etc.); a polyphenol compound obtained by a condensation reaction of a phenol compound such as phenol, o-cresol, naphthol and an aromatic aldehyde having a phenolic hydroxyl group; D Reaction product with chlorohydrin; Reaction product of polyphenol compound obtained by addition reaction of phenol compound with diolefin compound such as divinylbenzene or dicyclopentadiene and epichlorohydrin; Ring-opening polymerization product of 4-vinylcyclohexene-1-oxide Epoxidized with peracetic acid, etc .; epoxy resin having a heterocyclic ring such as triglycidyl isocyanurate; glycidyl methacrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), cyclohexyl Copolymerized epoxy resin of maleimide and glycidyl methacrylate; epoxy resin obtained by glycidyl etherification of one kind selected from phenol and cresol and p-hydroxybenzaldehyde condensate; bis (glycidyloxyphenyl) fluore Bis (glycidyloxyphenyl) adamantane type epoxy resin, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of carboxyl group-containing monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, Acrylic acid dimer; in addition, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic acid anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic anhydride; halogen Examples thereof include reaction products with carboxylic acid compounds, ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. Furthermore, commercially available products include Aronix M-5300, M-5400, M-5500 and M-5600 manufactured by Toa Synthetic Chemical Industry Co., Ltd., NK Esters CB-1 and CBX- manufactured by Shin-Nakamura Chemical Co., Ltd. 1, HOA-MP and HOA-MS manufactured by Kyoeisha Yushi Chemical Co., Ltd., Biscoat # 2100 manufactured by Osaka Organic Chemical Industry Co., Ltd., etc. can be used. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polybasic acid anhydride include succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, dodecenyl succinic anhydride, nonenyl succinic anhydride, Maleic anhydride, methylmaleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cisaccot anhydride , Phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydro Phthalic anhydride, Hydrochlorendic acid and dibasic anhydrides such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride Polybasic acid anhydrides such as 3,3 ′, 4,4′-benzophenonetetracarboxylic acid can also be used. These may be used individually by 1 type and may use 2 or more types together.
Each is reacted in order to obtain an epoxy acrylate, and the ratio of reacting them is 0.8 to 1.2 equivalents of carboxyl groups of the carboxyl group-containing monomer, preferably 1 equivalent of epoxy groups of the polyfunctional epoxy compound. Is 0.9-1.1 equivalent, 0.1-1.0 equivalent of polybasic acid anhydride, preferably 0.3-1.0 equivalent.

  Also, compounds obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton (a compound having no carboxyl group) described in JP-A-5-70528 can be used as the epoxy acrylate of the present invention.

  The molecular weight of the epoxy acrylate compound is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000. When the molecular weight is less than 1,000, the tackiness of the surface of the photosensitive layer may become strong, and the film quality may become brittle or the surface hardness may deteriorate after curing of the photosensitive layer described later. If it exceeds 1,000, developability may deteriorate. Also, synthesis of the resin becomes difficult.

  An acrylic resin having at least one polymerizable group such as an acidic group or a double bond described in JP-A-6-295060 can also be used. Specifically, at least one polymerizable double bond in the molecule, for example, an acrylic group such as (meth) acrylate group or (meth) acrylamide group, various polymerizations such as carboxylic acid vinyl ester, vinyl ether, allyl ether, etc. Sex double bonds can be used. More specifically, acrylic resins containing carboxyl groups as acidic groups, glycidyl esters of unsaturated fatty acids such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, and epoxy groups such as cyclohexene oxide in the same molecule and (meth) Examples thereof include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound having an acryloyl group. In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group, a hydroxyalkyl ( Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as (meth) acrylate.

  Furthermore, as the binder, a vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain can be used. Specifically, for example, (1) a vinyl monomer having an acidic group, (2 ) Obtained by vinyl (co) polymerization of a vinyl monomer having a functional group that can be used for the polymer reaction described later, if necessary, and (3) other copolymerizable vinyl monomer if necessary A polymer is synthesized, and (4) a (meth) acryloyl group and a functional group reactive to at least one of an acidic group in the (co) polymer or a functional group available for polymer reaction It can be obtained by polymer reaction with a compound having

There is no restriction | limiting in particular as an acidic group of the vinyl monomer which has said (1) 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, These Among these, a carboxyl group is preferable. 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 a monomer having a 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 ( And (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like. Moreover, these monomers may be used individually by 1 type, and may use 2 or more types together.
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.

  In the vinyl monomer having a functional group usable for the polymer reaction of (2), the functional group usable for the polymer reaction is a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, Etc. Moreover, the carboxyl group and acid anhydride group of the above-mentioned (1) are also mentioned as usable functional groups.

  Examples of the vinyl monomer having a hydroxyl group include compounds represented by the structural formulas (7) to (15).

  Examples of the vinyl monomer having an amino group include vinyl benzylamine and aminoethyl methacrylate.

  Examples of the monomer having an isocyanate group include compounds represented by the structural formulas (4) to (6).

  Examples of the vinyl monomer having an epoxy group include glycidyl (meth) acrylate and a compound represented by the following structural formula (73).

However, in said structural formula (73), R represents either H or Me.

Examples of the vinyl monomer having an acid halide group include (meth) acrylic acid chloride.
Examples of the vinyl monomer having an active halide group include chloromethylstyrene.
Moreover, each said monomer may be used individually by 1 type, and may use 2 or more types together.

  The other copolymerizable monomer used as necessary in (3) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters and crotonic acid. Esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes (eg, styrene, styrene derivatives, etc.), (Meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamide-2 -Methylpropanesulfonic acid, Vinyl monomers having mono (2-acryloyloxyethyl ester) acid, mono (1-methyl-2-acryloyloxyethyl ester) phosphate, and functional groups (eg, urethane group, urea group, sulfonamide group, imide group) Etc.

  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-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) 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, nonylphenoxy polyethylene glycol ( (Meth) acrylate, dicyclopentanyl (meth) acrylate, dis Clopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) 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, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include the styrene, the styrene derivatives (for example, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, Bromostyrene, hydroxystyrene protected with a group deprotectable 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 a 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, and a hydroxyl group An addition reaction with a compound containing 1 or a compound having one primary or secondary amino group, an addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate. .

Examples of the monomer having an isocyanate group include compounds represented by the structural formulas (4) to (6), as in the above-described (2).
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 structural formulas (7) to (15) in the same manner as shown in (2) above.

  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.

Moreover, these monomers may be used individually by 1 type, and may use 2 or more types together.
By vinyl (co) polymerizing these, a (co) polymer containing an acid group, an acid anhydride group and, if necessary, a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, etc. can get. The vinyl (co) polymer can be prepared by copolymerizing corresponding monomers according to a conventional 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.
With respect to the (co) polymer thus obtained, as the above (4), an acidic group in these copolymers and, if necessary, a hydroxyl group, an amino group, an isocyanate group, a glycidyl group, an acid halide It is obtained by polymer-reacting a functional group having reactivity with at least one of the groups and a compound having a (meth) acryloyl group.

As the compound having a (meth) acryloyl group and a functional group reactive to at least one of the acidic group in the (co) polymer of the above (4) or a functional group available for polymer reaction The compounds shown in (2) above can be used.
Examples of combinations of functional groups in performing these polymer reactions include, for example, a combination of a copolymer having an acidic group (such as a carboxyl group) and a vinyl monomer having an epoxy group, and a copolymer having an amino group and an epoxy group. A combination of vinyl monomers having an amino group, a combination of a copolymer having an amino group and a vinyl monomer having an isocyanate group, a combination of a copolymer having a hydroxyl group and a vinyl monomer having an isocyanate group, a copolymer having a hydroxyl group and an acid halide group A combination of vinyl monomers having an amino group, a combination of a copolymer having an amino group and a vinyl monomer having an active halide group, a combination of a copolymer having an acid anhydride group and a vinyl monomer having a hydroxyl group, a copolymer having an isocyanate group A combination of a monomer and a vinyl monomer having an amino group, an isocyanate group Combinations of vinyl monomer having a copolymer and a hydroxyl group of the combination of the vinyl monomer having a copolymer and an amino group having an active halide groups, and the like. Two or more of these combinations may be used in combination.

Examples of commercially available binders include “Kaneka Resin AX; manufactured by Kaneka Chemical Industry Co., Ltd.”, “CYCLOMER A-200; manufactured by Daicel Chemical Industries, Ltd.”, “CYCLOMER M”. -200; manufactured by Daicel Chemical Industries, Ltd. "," SPCP1X, SPCP2X, SPCP3X; manufactured by Showa Polymer Co., Ltd. "can be used.
Furthermore, a reaction product of hydroxyalkyl acrylate or hydroxyalkyl methacrylate described in JP-A No. 50-59315 and any of polycarboxylic acid anhydride and epihalohydrin can be used.

  Further, a compound obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton described in JP-A-5-70528, a polyamide (imide) resin described in JP-A-11-288087, and JP-A-2-097502 Polyimide precursors described in Japanese Patent Laid-Open No. 11-282155, and the like can be used. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The molecular weight of the acrylic resin, epoxy acrylate having a fluorene skeleton, polyamide (imide), amide group-containing styrene / acid anhydride copolymer, or polyimide precursor is preferably 3,000 to 500,000, 5,000-100,000 are more preferable. When the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may be deteriorated. If it exceeds 1,000, developability may deteriorate.

As the binder, a copolymer obtained by reacting one or more primary amine compounds with an anhydride group of a maleic anhydride copolymer can also be used. The copolymer is a maleamic acid-based copolymer having at least a maleamic acid unit B having a maleic acid half amide structure and a unit A not having the maleic acid half amide structure, represented by the following structural formula (74). It is preferably a coalescence.
The unit A may be one type or two or more types. For example, when the unit B is one type, when the unit A is one type, the maleamic acid-based copolymer means a binary copolymer, and the unit A is 2 When it is a seed, the maleamic acid-based copolymer means a terpolymer.
The unit A is an aryl group which may have a substituent and a vinyl monomer described later, and the glass transition temperature (Tg) of the homopolymer of the vinyl monomer is less than 80 ° C. A combination with the vinyl monomer (c) is preferred.

In the Structural Formula (74), R ³ and R ⁴ represents a hydrogen atom or a lower alkyl group. x and y represent the mole fraction of the repeating unit. For example, when the unit A is one, x is 85 to 50 mol%, and y is 15 to 50 mol%.

In the structural formula (74), as R ¹ , for example, (—COOR ¹⁰ ), (—CONR ¹¹ R ¹² ), an aryl group which may have a substituent, (—OCOR ¹³ ), (—OR ¹⁴ ), substituents such as (—COR ¹⁵ ). Here, said R < ¹⁰ > -R < ¹⁵ > represents either a hydrogen atom (-H), the alkyl group which may have a substituent, an aryl group, and an aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.
Examples of R ^{10 to} R ¹⁵ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, allyl, n-hexyl, and cyclohexyl. 2-ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, chlorophenyl and the like.
Specific examples of R ¹ include benzene derivatives such as phenyl, α-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl; n-propyloxycarbonyl, n- Examples include butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, n-butyloxycarbonyl, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyloxycarbonyl and the like.

Examples of R ² include an alkyl group, an aryl group, and an aralkyl group that may have a substituent. These may have a cyclic structure or a branched structure. Specific examples of R ² include benzyl, phenethyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, α-methylbenzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2- (p-tolyl) ethyl, β-methylphenethyl, 1-methyl-3-phenylpropyl, 2-chlorobenzyl, 3-chlorobenzyl, 4- Chlorobenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 4-bromophenethyl, 2- (2-chlorophenyl) ethyl, 2- (3-chlorophenyl) ethyl, 2- (4-chlorophenyl) ethyl, 2- (2-fluorophenyl) ethyl, 2- (3-fluorophenyl) ethyl, 2- (4-fluorophenyl) ethyl, -Fluoro-α, α-dimethylphenethyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 2-methoxyphenethyl, 3-methoxyphenethyl, 4-methoxyphenethyl, methyl, ethyl, propyl , I-propyl, butyl, t-butyl, sec-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, lauryl, phenyl, 1-naphthyl, methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl 2-butoxyethyl, 2-cyclohexyloxyethyl, 3-ethoxypropyl, 3-propoxypropyl, 3-isopropoxypropylamine and the like.

  The binder is, in particular, (a) maleic anhydride, (b) an aromatic vinyl monomer, and (c) a vinyl monomer, the glass transition temperature (Tg) of the homopolymer of the vinyl monomer. ) Is preferably a copolymer obtained by reacting a primary amine compound with an anhydride group of a copolymer comprising a vinyl monomer having a temperature of less than 80 ° C. A copolymer comprising the component (a) and the component (b) can obtain a high surface hardness of the photosensitive layer described later, but it may be difficult to ensure laminating properties. Moreover, in the copolymer which consists of this (a) component and this (c) component, although lamination property can be ensured, it may become difficult to ensure the said surface hardness.

-(B) Aromatic vinyl monomer-
The aromatic vinyl monomer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the surface hardness of the photosensitive layer formed using the pattern forming material of the present invention can be increased. In this respect, a compound having a glass transition temperature (Tg) of the homopolymer of 80 ° C. or higher is preferable, and a compound of 100 ° C. or higher is more preferable.
Specific examples of the aromatic vinyl monomer include styrene (homopolymer Tg = 100 ° C.), α-methylstyrene (homopolymer Tg = 168 ° C.), 2-methylstyrene (homopolymer Tg = 136 ° C.). ), 3-methylstyrene (homopolymer Tg = 97 ° C.), 4-methylstyrene (homopolymer Tg = 93 ° C.), 2,4-dimethylstyrene (homopolymer Tg = 112 ° C.) Preferably mentioned. These may be used individually by 1 type and may use 2 or more types together.

-(C) Vinyl monomer--
The vinyl monomer needs to have a glass transition temperature (Tg) of a homopolymer of the vinyl monomer of less than 80 ° C., preferably 40 ° C. or less, and more preferably 0 ° C. or less.
Examples of the vinyl monomer include n-propyl acrylate (homopolymer Tg = −37 ° C.), n-butyl acrylate (homopolymer Tg = −54 ° C.), pentyl acrylate, or hexyl acrylate (homopolymer acrylate). Tg = −57 ° C.), n-butyl methacrylate (Tg of homopolymer = −24 ° C.), n-hexyl methacrylate (Tg of homopolymer = −5 ° C.), and the like. These may be used individually by 1 type and may use 2 or more types together.

-Primary amine compound-
Examples of the primary amine compound include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, 6-phenyl-1-hexylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3-phenylpropylamine, 2-chloro Benzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4-bromophenethylamine, 2- (2-chlorophenyl) ethylamine, 2- ( 3-Chlorophenyl) ethyla Min, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethyl Phenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methylamine, ethylamine, propylamine, 1 -Propylamine, butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, aniline, octylaniline, anisi Gin, 4-chloroaniline, 1-naphthylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine, 3- Examples thereof include propoxypropylamine and 3-isopropoxypropylamine. Among these, benzylamine and phenethylamine are particularly preferable.
The said primary amine compound may be used individually by 1 type, and may use 2 or more types together.

  The reaction amount of the primary amine compound needs to be 0.1 to 1.2 equivalents relative to the anhydride group, and preferably 0.1 to 1.0 equivalents. When the reaction amount exceeds 1.2 equivalents, the solubility may be significantly deteriorated when one or more primary amine compounds are reacted.

  The content of the (a) maleic anhydride in the binder is preferably 15 to 50 mol%, more preferably 20 to 45 mol%, particularly preferably 20 to 40 mol%. When the content is less than 15 mol%, alkali developability cannot be imparted, and when it exceeds 50 mol%, alkali resistance deteriorates and synthesis of the copolymer becomes difficult, resulting in a normal permanent pattern. Formation may not be possible. In this case, the content of (b) the aromatic vinyl monomer and (c) the vinyl monomer having a glass transition temperature (Tg) of the homopolymer of less than 80 ° C. in the binder is 20 respectively. -60 mol% and 15-40 mol% are preferable. When the content satisfies the numerical range, both surface hardness and laminating properties can be achieved.

  The molecular weight of the acrylic resin, epoxy acrylate having a fluorene skeleton, polyamide (imide), a compound obtained by reacting an anhydride group of the maleic anhydride copolymer with a primary amine compound, or a binder such as a polyimide precursor, 3,000 to 500,000 are preferable, and 5,000 to 100,000 are more preferable. When the molecular weight is less than 3,000, the tackiness of the surface of the photosensitive layer may become strong, and after curing of the photosensitive layer described later, the film quality may become brittle or the surface hardness may be deteriorated. If it exceeds 1,000, developability may deteriorate.

  5-80 mass% is preferable and, as for solid content in the said pattern formation material solid content of the said binder, 10-70 mass% is more preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. When it exceeds 50% by mass, the exposure sensitivity is increased. May decrease.

-Polymerizable compound-
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. However, the polymerizable compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. A compound is preferable, and the same compounds as those exemplified as the polymerizable compound contained in the photosensitive layer for etching resist can be used. For example, at least one selected from monomers having a (meth) acryl group is preferable. It is mentioned in.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Poly (functional) alcohols such as tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc., which are subjected to addition reaction with ethylene oxide and propylene oxide, and converted to (meth) acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50- Urethane acrylates described in JP-A-6034, JP-A-51-37193, etc .; JP-A-48-64183, JP-B-49-43191, JP-B-52-30 Polyester acrylates described in each publication of such 90 No.; and epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  5-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. If the solid content is less than 5% by mass, problems such as deterioration of developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.

-Photopolymerization initiator-
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. The thing similar to what was illustrated as a photoinitiator contained can be used.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
Particularly preferred examples of the photopolymerization initiator include halogenated carbonization having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton capable of supporting laser light having a wavelength of 405 nm in the exposure described later. Examples include a composite photoinitiator, a hexaarylbiimidazole compound, or titanocene, which is a combination of a hydrogen compound and an amine compound as a sensitizer described later.

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

-Thermal crosslinking agent-
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the pattern forming material, developability, etc. For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.
Examples of the epoxy compound having at least two oxirane groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resins ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, Hydrogenated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200") , HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (diglycidyl phthalate) Ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy resin (3,4) Epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc. )), Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy Resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products are “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”) "HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc."), polyphenol compounds obtained by addition reaction of phenol compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene, and epichlorohydrin Reaction product of 4-vinylcyclohexene-1-oxide ring-opened polymer with peracetic acid or the like, epoxy resin having a linear phosphorus-containing structure, epoxy resin having a cyclic phosphorus-containing structure, α-methyl Stilbene liquid crystal epoxy resin, dibenzoyloxybenzene liquid crystal epoxy resin, azophenyl liquid crystal epoxy resin, azomethine phenyl liquid crystal epoxy resin, binaphthyl liquid crystal epoxy resin, azine epoxy resin, glycidyl methacrylate copolymer epoxy resin (“CP − 50S, CP-50M; manufactured by NOF Corporation, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, etc. Although it is mentioned, it is not restricted to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

In addition to the epoxy compound having at least two oxirane groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group in the β-position can be used, and the β-position is an alkyl group. Particularly preferred are compounds containing an epoxy group substituted with a (specifically, a β-alkyl-substituted glycidyl group or the like).
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.

From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the β-position is substituted with β-alkyl in all epoxy groups in the total amount of the epoxy compound contained in the photosensitive composition. The proportion of glycidyl groups is preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more.
The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, β-butylglycidyl group. Among these, a β-methylglycidyl group is preferred from the viewpoint of improving the storage stability of the photosensitive resin composition and the ease of synthesis.

  As the epoxy compound containing an epoxy group having an alkyl group at the β-position, for example, an epoxy compound derived from a polyhydric phenol compound and a β-alkylepihalohydrin is preferable.

  The β-alkylepihalohydrin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepifluorohydrin, etc. Β-methyl epihalohydrin, β-ethyl epichlorohydrin, β-ethyl epibromohydrin, β-ethyl epihalohydrin, such as β-ethyl epihalohydrin, β-propyl epichlorohydrin, β-propyl epibromohydrin Β-propyl epihalohydrin such as phosphorus and β-propyl epifluorohydrin; β-butyl epihalohydrin such as β-butyl epichlorohydrin, β-butyl epibromohydrin, β-butyl epifluorohydrin; . Among these, β-methylepihalohydrin is preferable from the viewpoint of reactivity with the polyhydric phenol and fluidity.

  The polyhydric phenol compound is not particularly limited as long as it is a compound containing two or more aromatic hydroxyl groups in one molecule, and can be appropriately selected according to the purpose. For example, bisphenol A, bisphenol F Bisphenol compounds such as bisphenol S, biphenol compounds such as biphenol and tetramethylbiphenol, naphthol compounds such as dihydroxynaphthalene and binaphthol, phenol novolac resins such as phenol-formaldehyde polycondensates, cresol-formaldehyde polycondensates 1 1-10 monoalkyl-substituted phenol-formaldehyde polycondensate, xylenol-formaldehyde polycondensate, etc., dialkyl-substituted phenol-formaldehyde polycondensate having 1 to 10 carbon atoms, bisphenol A-formalde De polycondensates such bisphenol compounds of - formaldehyde polycondensates, phenol and copolycondensates of monoalkyl-substituted phenol and formaldehyde having 1 to 10 carbon atoms, and phenolic compounds and polyaddition products of divinylbenzene. Among these, when selecting for the purpose of improving fluidity | liquidity and storage stability, the said bisphenol compound is preferable, for example.

Examples of the epoxy compound containing an epoxy group having an alkyl group at the β-position include di-β-alkyl glycidyl ether of bisphenol A, di-β-alkyl glycidyl ether of bisphenol F, and di-β-alkyl glycidyl of bisphenol S. Di-β-alkyl glycidyl ethers of bisphenol compounds such as ethers; di-β-alkyl glycidyl ethers of biphenols such as di-β-alkyl glycidyl ethers of biphenols and di-β-alkyl glycidyl ethers of tetramethylbiphenol; dihydroxynaphthalene Β-alkyl glycidyl ethers of naphthol compounds such as di-β-alkyl glycidyl ether of dinaphthol, di-β-alkyl glycidyl ether of binaphthol; poly- of phenol-formaldehyde polycondensate β-alkyl glycidyl ether; poly-β-alkyl glycidyl ether of monoalkyl-substituted phenol-formaldehyde polycondensate having 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ether of cresol-formaldehyde polycondensate; xylenol-formaldehyde C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate poly-β-alkyl glycidyl ether such as poly-β-alkyl glycidyl ether of condensate; poly-β-alkyl glycidyl ether of bisphenol A-formaldehyde polycondensate Bisphenol compounds such as poly-β-alkyl glycidyl ethers of formaldehyde polycondensates; poly-β-alkyl glycidyl ethers of polyaddition products of phenol compounds and divinylbenzene; The
Among these, a bisphenol compound represented by the following structural formula (i), a β-alkyl glycidyl ether derived from a polymer obtained from the bisphenol compound and epichlorohydrin, and the following structural formula (ii) Phenol compound-formaldehyde polycondensate poly-β-alkyl glycidyl ether is preferred.

However, in said structural formula (i), R represents either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.
In the Structural Formula (ii), R represents any of an alkyl group having 1 to 6 carbon hydrogen and carbon, R "represents either hydrogen atoms, and CH _3, n is from 0 to 20 Represents an integer.
These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more. It is also possible to use together an epoxy compound having at least two oxirane rings in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

  Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, oligomers or copolymers thereof, and compounds having an oxetane group , Novolak resin, poly (p-hydroxystyrene), potassium Bisphenols, calixarenes, calixresorcinarenes, ether compounds with hydroxyl group resins such as silsesquioxane, etc. In addition, unsaturated monomers having an oxetane ring and alkyl (meth) acrylates And a copolymer thereof.

Moreover, in order to accelerate the thermal curing of the epoxy compound or the oxetane compound, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N , N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivatives Cyclic amidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenyl) Midazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), S- Triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric An acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
Solid content in the said pattern formation material solid content of the said epoxy compound, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally.

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene). Diisocyanate, bis (4-isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate, trimethylolpropane, pentalithol tol Polyfunctional alcohols such as glycerin; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; hexamethylene diisocyanate, hexamethylene-1,6-di Isocyanate and cyclic trimers thereof derivatives; and the like.

Furthermore, for the purpose of improving the storage stability of the pattern forming material of the present invention, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include alcohols (eg, isopropanol, tert-butanol, etc.), lactams (eg, ε-caprolactam, etc.), phenols (eg, phenol, cresol, p-tert-butylphenol, p-sec). -Butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (eg, dialkyl malonate, Methyl ethyl ketoxime, acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime, etc.). In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, a melamine derivative can be used as the thermal crosslinking agent. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

  1-50 mass% is preferable and, as for solid content in the said pattern formation material solid content of the said thermal crosslinking agent, 3-30 mass% is more preferable. When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 50% by mass, developability and exposure sensitivity may be deteriorated.

-Other ingredients-
Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, colorants (coloring pigments or dyes), extender pigments, and the like, and further adhesion promoters to the substrate surface and other components. Auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.) may be used in combination.
These components may be the same as those contained in the photosensitive layer for etching resist, and by appropriately containing these, properties such as the stability, photographic properties, film physical properties, etc. of the target pattern forming material are adjusted. can do.

  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>
The pattern forming material preferably includes at least a support and the photosensitive layer formed on the support, and optionally has other layers such as a thermoplastic resin layer as necessary.
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 10-20,000 m is mentioned.

<Protective film>
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, interlayer adhesion can be adjusted by surface-treating at least one of the support and the 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 discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

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, and when it exceeds 1.4, it is difficult to wind into a good roll. 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 10-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 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>
The other layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a layer such as a thermoplastic resin layer, a barrier layer, a release layer, an adhesive layer, a light absorption layer, or a surface protective layer may be used. Can be mentioned. The pattern forming material may have one kind of these layers or two or more kinds.

<< Thermoplastic resin layer >>
The thermoplastic resin layer (hereinafter also referred to as a cushion layer) is not particularly limited and may be appropriately selected depending on the intended purpose. There may be.

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

The softening point (Vicat) of the thermoplastic resin in this case is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 80 ° C. or lower.
As the thermoplastic resin having a softening point of 80 ° C. or less, in addition to the above-mentioned thermoplastic resin, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, October 1968) Among those organic polymers having a softening point of about 80 ° C. or less as issued on the 25th), those soluble in an alkaline liquid can be mentioned. In addition, even in an organic polymer substance having a softening point of 80 ° C. or higher, various plasticizers compatible with the organic polymer substance are added to the organic polymer substance so that a substantial softening point is 80 ° C. or lower. It is also possible to lower it.

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

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

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

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

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

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

There is no restriction | limiting in particular as an ethylene copolymerization ratio in the copolymer which uses the said ethylene as an essential copolymerization component, According to the objective, it can select suitably, For example, 60-90 mass% is preferable, and 60-80 % By mass is more preferable, and 65 to 80% by mass is particularly preferable.
When the ethylene copolymerization ratio is less than 60% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. When the amount exceeds 90% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer becomes too small, so that the cushion layer and the photosensitive layer are very easily peeled off, including the cushion layer. It may be difficult to manufacture the pattern forming material.

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

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

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

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

The method for applying the photosensitive resin composition solution 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, and an extrusion coating method. And various coating methods such as a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

<Formation of laminate>
When pattern formation is performed using the pattern forming material of the present invention, a laminate is formed by laminating a photosensitive layer of the pattern forming material on a substrate.

  The substrate is not particularly limited and can be appropriately selected from known materials having high surface smoothness to those having an uneven surface. A plate-like substrate (substrate) is preferred. Specifically, known printed wiring board forming substrates (for example, copper-clad laminates), glass plates (for example, soda glass plates), synthetic resin films, paper, metal plates, and the like can be given.

  There is no restriction | limiting in particular as a layer structure in the said laminated body, According to the objective, it can select suitably, For example, the layer structure which has the said base material, the said photosensitive layer, and the said support body in this order is preferable. In addition, when the said pattern formation material has the protective film mentioned above, it is preferable to peel this protective film and to laminate | stack so that a photosensitive layer may overlap with the said base material.

The method for forming the laminate is not particularly limited and may be appropriately selected. The embodiment in which the photosensitive composition of the pattern forming material is applied on the substrate and dried to form a laminate, An embodiment in which the pattern forming material is laminated on the material while performing at least one of heating and pressing is preferable.
There is no restriction | limiting in particular as said heating temperature, According to the objective, it can select suitably, For example, 70-130 degreeC is preferable and 80-110 degreeC is more preferable.
There is no restriction | limiting in particular as said pressurization pressure, According to the objective, it can select suitably, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 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, heat press, a heat roll laminator (For example, Taisei Laminator company make, VP-II) ), A vacuum laminator (for example, MVLP500, manufactured by Meiki Seisakusho) and the like are preferable.

  The pattern forming material of the present invention is advantageous in that the exposure sensitivity is high, the resolution is excellent, the light can be exposed with a smaller amount of light, and the exposure speed increases, so that the processing speed increases. Furthermore, even with high sensitivity, the effect of preventing light fogging with a light source such as a safelight is high, and a high-definition pattern can be obtained.

  The pattern forming material of the present invention has high sensitivity, a good resist pattern shape can be obtained, and the tent film strength is strong, and a high-definition and high aspect ratio pattern can be formed. It can be suitably used for the formation of permanent patterns such as wiring patterns, for the production of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, and for the formation of patterns such as holograms, micromachines, and proofs. In particular, it can be suitably used in the pattern forming method of the present 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 such as an appropriately selected development step.
In addition, the said pattern formation apparatus of this invention is clarified through description of the said pattern formation method of this invention.

<Exposure process>
The said exposure process is a process of exposing with respect to the photosensitive layer in the pattern formation material of this invention. The pattern forming material and the base material of the present invention are as described above.

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

  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 used. For example, the photosensitive layer is arranged in a two-dimensional array of n (where n is a natural number of 2 or more) that receives and emits light from the light irradiation means and the light irradiation means. An exposure head provided with a light modulation unit capable of controlling the drawing unit according to pattern information, wherein the column direction of the drawing unit is relative to the scanning direction of the exposure head. An exposure head arranged so as to form a predetermined set inclination angle θ is used, and the exposure head is subjected to N double exposure (where N is 2) among the usable pixel parts by the use pixel part specifying means. The natural number above) Designate the element part, and control the element part for the exposure head so that only the element part specified by the element part for specifying the used element part is involved in the exposure by the element part controlling unit. A method is preferred in which the exposure head is moved relative to the photosensitive layer in the scanning direction.

In the present invention, “N double exposure” means that the exposed surface is irradiated with a straight line parallel to the scanning direction of the exposure head in almost all of the exposed region on the exposed surface of the photosensitive layer. This means exposure by setting that intersects N light spot rows (pixel rows). Here, the “light spot array (pixel array)” is a direction in which the angle formed with the scanning direction of the exposure head is smaller in the array of light spots (pixels) as pixel units generated by the pixel unit. Refers to a sequence of Note that the arrangement of the picture element portions is not necessarily a rectangular lattice shape, and may be, for example, an arrangement of parallelograms. Here, “substantially all areas” of the exposure area is described as a straight line parallel to the scanning direction of the exposure head by tilting the pixel part rows at both side edges of each picture element part. Since the number of drawing element rows of the used drawing element parts to be crossed decreases, even if it is used to connect a plurality of exposure heads in such a case, it is parallel to the scanning direction due to errors in the mounting angle and arrangement of the exposure heads. The number of pixel parts in the used pixel part that intersect with a straight line may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is only a fraction of the resolution. However, due to errors such as the mounting angle and the arrangement of the picture element parts, the pitch of the picture element parts along the direction orthogonal to the scanning direction does not exactly match the pitch of the picture element parts of other parts, and is parallel to the scanning direction. The number of used pixel parts that intersect with the straight line may increase or decrease within a range of ± 1. It is an order. In the following description, N multiple exposures where N is a natural number of 2 or more are collectively referred to as “multiple exposure”. Furthermore, in the following description, “N-fold drawing” and “N-fold exposure” are used as terms corresponding to “N-double exposure” and “multiple exposure” for the embodiment in which the exposure apparatus or exposure method of the present invention is implemented as a drawing apparatus or drawing method. The term “multiple drawing” shall be used.
N in the N-fold exposure is not particularly limited as long as it is a natural number of 2 or more, and can be appropriately selected according to the purpose. However, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is more preferable. .

An example of a pattern forming apparatus according to the pattern forming method of the present invention will be described with reference to the drawings.
The pattern forming apparatus is a so-called flat-bed type exposure apparatus, and as shown in FIG. 1, a sheet-like photosensitive material 12 (hereinafter, “ A flat moving stage 14 that holds the photosensitive layer 12 by adsorption to the surface. Two guides 20 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 18 supported by the four legs 16. The stage 14 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 20 so as to be reciprocally movable. The pattern forming apparatus 10 is provided with a stage driving device (not shown) that drives the stage 14 along the guide 20.

  A U-shaped gate 22 is provided at the center of the installation base 18 so as to straddle the movement path of the stage 14. Each end of the U-shaped gate 22 is fixed to both side surfaces of the installation base 18. A scanner 24 is provided on one side across the gate 22, and a plurality of (for example, two) sensors 26 that detect the front and rear ends of the photosensitive material 12 are provided on the other side. The scanner 24 and the sensor 26 are respectively attached to the gate 22 and fixedly arranged above the moving path of the stage 14. The scanner 24 and the sensor 26 are connected to a controller (not shown) that controls them.

  Here, for explanation, an X axis and a Y axis orthogonal to each other are defined in a plane parallel to the surface of the stage 14 as shown in FIG.

  A slit formed in a “<” shape that opens in the direction of the X-axis at the upstream edge (hereinafter sometimes simply referred to as “upstream”) along the scanning direction of the stage 14. 10 are formed at equal intervals. Each slit 28 includes a slit 28 a located on the upstream side and a slit 28 b located on the downstream side. The slit 28a and the slit 28b are orthogonal to each other, and the slit 28a has an angle of −45 degrees and the slit 28b has an angle of +45 degrees with respect to the X axis.

  The position of the slit 28 is substantially coincident with the center of the exposure head 30. Further, the size of each slit 28 is set to sufficiently cover the width of the exposure area 32 by the corresponding exposure head 30. Further, the position of the slit 28 may be substantially coincident with the center position of the overlapping portion between the adjacent exposed regions 34. In this case, the size of each slit 28 is set so as to sufficiently cover the width of the overlapping portion between the exposed regions 34.

  In the position below each slit 28 inside the stage 14, single cell type light detection as a light spot position detecting means for detecting a light spot as a pixel unit in a used pixel part designation process described later. A vessel (not shown) is incorporated. In addition, each photodetector is connected to an arithmetic unit (not shown) as a pixel part selection means for selecting the pixel part in the used pixel part specifying process described later.

  The operation form of the pattern forming apparatus at the time of exposure may be a form in which exposure is continuously performed while constantly moving the exposure head, or each movement destination position while the exposure head is moved stepwise. The exposure head may be stationary to perform the exposure operation.

<< Exposure head >>
Each exposure head 30 is connected to the scanner 24 so that each pixel portion (micromirror) row direction of an internal digital micromirror device (DMD) 36 described later forms a predetermined set inclination angle θ with the scanning direction. It is attached. Therefore, the exposure area 32 by each exposure head 30 is a rectangular area inclined with respect to the scanning direction. As the stage 14 moves, a strip-shaped exposed region 34 is formed in the photosensitive layer 12 for each exposure head 30. In the example shown in FIGS. 2 and 3B, the scanner 24 includes ten exposure heads arranged in a substantially matrix of 2 rows and 5 columns.
In the following description, when the individual exposure heads arranged in the m-th row and the n-th column are indicated, the exposure head 30 _mn is indicated, and exposure by the individual exposure heads arranged in the m-th row and the n-th column is performed. When an area is indicated, it is expressed as an exposure area 32 _mn .

Further, as shown in FIGS. 3A and 3B, each of the exposure heads 30 in each row arranged in a line so that each of the strip-shaped exposed regions 34 partially overlaps the adjacent exposed region 34 is In the arrangement direction, they are shifted by a predetermined interval (a natural number times the long side of the exposure area, twice in this embodiment). Therefore, can not be exposed portion between the exposure area _{32 11} in the first row and the exposure area _{32 12,} it can be exposed by the second row of the exposure area _{32 21.}

  As shown in FIGS. 4, 5A, and 5B, each of the exposure heads 30 includes a light modulation unit that modulates incident light for each pixel part according to image data (spatial light that modulates each pixel part). As a modulation element, a DMD 36 (manufactured by Texas Instruments Inc., USA) is provided. The DMD 36 is connected to a controller serving as a pixel part control unit including a data processing unit and a mirror drive control unit. The data processing unit of this controller generates a control signal for driving and controlling each micromirror in the use area on the DMD 36 for each exposure head 30 based on the input image data. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 36 for each exposure head 30 based on the control signal generated by the image data processing unit.

  As shown in FIG. 4, on the light incident side of the DMD 36, there is provided a laser emission portion in which the emission end portion (light emission point) of the optical fiber is arranged in a line along the direction that coincides with the long side direction of the exposure area 32. The fiber array light source 38, the lens system 40 for correcting the laser light emitted from the fiber array light source 38 and condensing it on the DMD, and the mirror 42 for reflecting the laser light transmitted through the lens system 40 toward the DMD 36 Arranged in order. In FIG. 4, the lens system 40 is schematically shown.

  As shown in detail in FIGS. 5A and 5B, the lens system 40 includes a pair of combination lenses 44 that convert the laser light emitted from the fiber array light source 38 into parallel light, and a light quantity distribution of the parallel laser light. A pair of combination lenses 46 that are corrected so as to be uniform, and a condensing lens 48 that condenses the laser light whose light quantity distribution has been corrected on the DMD 36 are configured.

  Further, on the light reflection side of the DMD 36, a lens system 50 that images the laser light reflected by the DMD 36 on the exposed surface of the photosensitive layer 12 is disposed. The lens system 50 includes two lenses 52 and 54 arranged so that the DMD 36 and the exposed surface of the photosensitive layer 12 have a conjugate relationship.

  In the present embodiment, the laser light emitted from the fiber array light source 38 is substantially magnified five times, and then the light from each micromirror on the DMD 36 is reduced to about 5 μm by the lens system 50. Is set to

-Light modulation means-
As the light modulation means, there are n (where n is a natural number of 2 or more) two-dimensionally arranged image elements, and the image elements can be controlled according to the pattern information. If it is, there will be no restriction | limiting in particular, According to the objective, it can select suitably, 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. 6, the DMD 36 is a mirror device in which a large number of micromirrors 58 are arranged in a lattice pattern on a SRAM cell (memory cell) 56 as a pixel portion constituting each pixel (pixel). . In this embodiment, a DMD 36 in which 1024 columns × 768 rows of micromirrors 58 are arranged is used. Among these, the micromirrors 58 that can be driven by a controller connected to the DMD 36, that is, usable, are 1024 columns × 256 rows. Suppose only. The data processing speed of the DMD 36 is limited, and the modulation speed per line is determined in proportion to the number of micromirrors to be used. Thus, by using only some of the micromirrors in this way, Modulation speed increases. Each micromirror 58 is supported by a support column, and a material having high reflectivity such as aluminum is deposited on the surface thereof. In the present embodiment, the reflectance of each micromirror 58 is 90% or more, and the arrangement pitch thereof is 13.7 μm in both the vertical direction and the horizontal direction. The SRAM cell 56 is of a silicon gate CMOS manufactured in a normal semiconductor memory manufacturing line via a support including a hinge and a yoke, and the whole is configured monolithically (integrated).

  When an image signal representing the density of each point constituting a desired two-dimensional pattern in binary is written in the SRAM cell (memory cell) 56 of the DMD 36, each micromirror 58 supported by the column is centered on the diagonal line. As shown in FIG. 1, the inclination is inclined to ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 36 is disposed. FIG. 7A shows a state in which the micromirror 58 is tilted to + α degrees in the on state, and FIG. 7B shows a state in which the micromirror 58 is tilted to −α degrees in the off state. In this way, by controlling the inclination of the micromirror 58 in each pixel of the DMD 36 as shown in FIG. 6 in accordance with the image signal, the laser light B incident on the DMD 36 moves in the inclination direction of each micromirror 58. Reflected.

  FIG. 6 shows an example of a state in which a part of the DMD 36 is enlarged and each micromirror 58 is controlled to + α degrees or α degrees. The on / off control of each micromirror 58 is performed by the controller connected to the DMD 36. Further, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 58 travels.

-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 means capable of synthesizing and irradiating two or more lights. Among these, means capable of synthesizing and irradiating two or more lights are 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 ultraviolet to visible light is preferably, for example, 300 to 1,500 nm, more preferably 320 to 800 nm, and particularly preferably 330 to 650 nm.
As a wavelength of the said laser beam, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330-500 nm is still more preferable, 400-450 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 the laser beams respectively emitted from the plurality of lasers and coupling them 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. 8, the fiber array light source 38 includes a plurality of (for example, 14) laser modules 60, and one end of a multimode optical fiber 62 is coupled to each laser module 60. An optical fiber 64 having a cladding diameter smaller than that of the multimode optical fiber 62 is coupled to the other end of the multimode optical fiber 62. As shown in detail in FIG. 9, seven ends of the optical fiber 64 opposite to the multimode optical fiber 62 are arranged along the direction orthogonal to the scanning direction, and these are arranged in two rows to form the laser emitting unit 66. Is configured.

  As shown in FIG. 9, the laser emitting portion 66 constituted by the end portion of the optical fiber 64 is sandwiched and fixed between two support plates 68 having a flat surface. Moreover, it is desirable that a transparent protective plate such as glass is disposed on the light emitting end face of the optical fiber 64 for protection. The light exit end face of the optical fiber 64 has a high light density and is likely to collect dust and easily deteriorate. However, by arranging the protective plate as described above, it is possible to prevent the dust from adhering to the end face and to delay the deterioration. Can do.

  For example, as shown in FIG. 25, such an optical fiber is formed by coaxially connecting an optical fiber 64 having a length of 1 to 30 cm with a small cladding diameter at the tip portion on the laser light emission side of a multimode optical fiber 62 having a large cladding diameter. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 64 is fused and joined to the outgoing end face of the multimode optical fiber 62 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 64 a of the optical fiber 64 is the same as the diameter of the core 62 a of the multimode optical fiber 62.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused with an optical fiber having a small cladding diameter may be coupled to the output end of the multimode optical fiber 62 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 64 may be referred to as an emission end portion of the multimode optical fiber 62.

  The multimode optical fiber 62 and the optical fiber 64 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 62 and the optical fiber 64 are step index type optical fibers, and the multimode optical fiber 62 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 64 has a clad 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 is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber array light source is 125 μm. However, the smaller the clad diameter, the deeper the focal depth, so the clad diameter of the optical fiber is preferably 80 μm or less, more preferably 60 μm or less. 40 μm or less is more preferable. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 64 is preferably 10 μm or more.

  The laser module 60 is composed of 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 arranged on the heat block 110, And LD7, collimator lenses L1, L2, L3, L4, L5, L6, and L7 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 200, and one multimode. And an optical fiber 62. 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. Moreover, 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 semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above-described 405 nm in a wavelength range of 350 to 450 nm may be used.

  As shown in FIGS. 27 and 28, the combined laser light source is housed in a box-shaped package 400 having an upper opening together with other optical elements. The package 400 includes a package lid 410 created so as to close the opening. After the degassing process, a sealing gas is introduced, and the package 400 and the package lid are closed by closing the opening of the package 400 with the package lid 410. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by the reference numeral 410.

  A base plate 420 is fixed to the bottom surface of the package 400, and the heat block 110, a condensing lens holder 450 that holds the condensing lens 200, and the multimode optical fiber 62 are disposed on the top surface of the base plate 420. A fiber holder 460 that holds the incident end is attached. The exit end of the multimode optical fiber 62 is drawn out of the package from an opening formed in the wall surface of the package 400.

  A collimator lens holder 440 is attached to the side surface of the heat block 110, and the collimator lenses L1 to L7 are held. An opening is formed in the lateral wall surface of the package 400, and a wiring 470 for supplying a driving current to the GaN semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 28, in order to avoid complication of the drawing, only the GaN semiconductor laser LD7 is numbered among the plurality of GaN semiconductor lasers, and only the collimator lens L7 is numbered among the plurality of collimator lenses. is doing.

  FIG. 29 shows a front shape of a mounting portion of the collimator lenses L1 to L7. Each of the collimator lenses L <b> 1 to L <b> 7 is formed in a shape in which a region including the optical axis of a circular lens having an aspherical surface is cut out in a parallel plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses L1 to L7 are closely arranged in the light emitting point arrangement direction so that the length direction is orthogonal to the light emitting point arrangement direction of the GaN-based semiconductor lasers LD1 to LD7 (left-right direction in FIG. 29).

  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 has a divergence angle in a direction parallel to or perpendicular to the active layer, for example, 10 ° or 30 °. Lasers that emit beams B1 to B7 are 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 L1 to L7 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 L1 to L7 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. In addition, each of the collimator lenses L1 to L7 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 200 is formed by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane in parallel planes, and is long in the arrangement direction of the collimator lenses L1 to L7, that is, in the horizontal direction and short in the direction perpendicular thereto. Is formed. The condenser lens 200 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 200 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.

  Further, since the cladding diameter of the output end of the optical fiber is smaller than the cladding diameter of the incident 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.

  Moreover, as a light irradiation means provided with a plurality of light emitting points, for example, as shown in FIG. 30, a laser in which a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 are arranged on a heat block 110. An array can be used. Further, a chip-shaped multi-cavity laser 110 shown in FIG. 31A in which a plurality of (for example, five) light emitting points 111a are arranged in a predetermined direction is known. Since the multicavity laser 111 can arrange the light emitting points with higher positional accuracy than 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, as the number of light emitting points increases, the multi-cavity laser 111 is likely to be bent at the time of laser manufacture. Therefore, the number of light emitting points 111a is preferably 5 or less.

  As the light irradiation means, as shown in FIG. 31B, a plurality of multi-cavity lasers 111 are arranged on the heat block 110 in the same direction as the arrangement direction of the light emitting points 111a of each chip. A 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. 32, a combined laser light source including a chip-shaped multicavity laser 111 having a plurality of (for example, three) light emitting points 111a can be used. The combined laser light source includes a multi-cavity laser 111, a single multi-mode optical fiber 62, and a condenser lens 200. The multicavity laser 111 can be composed of, for example, a GaN laser diode having an oscillation wavelength of 405 nm.

  In the above-described configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111 a of the multicavity laser 111 is collected by the condenser lens 200 and enters the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  A plurality of light emitting points 111 a of the multicavity laser 111 are arranged in parallel within a width substantially equal to the core diameter of the multimode optical fiber 62, and a focal point substantially equal to the core diameter of the multimode optical fiber 62 is formed as the condenser lens 200. By using a convex lens of a distance or a rod lens that collimates the outgoing beam from the multicavity laser 111 only in a plane perpendicular to the active layer, the coupling efficiency of the laser beam B to the multimode optical fiber 62 can be increased. it can.

  As shown in FIG. 33, a multi-cavity laser 111 having a plurality of (for example, three) emission points is used, and a plurality of (for example, nine) multi-cavity lasers 111 are equidistant from each other on the heat block 110. A combined laser light source including the laser array 140 arranged in (1) can be used. The plurality of multi-cavity lasers 111 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 111a 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 111, 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 111 a of the plurality of multi-cavity lasers 111 is condensed 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 collected by the condenser lens 200 and enters the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  Still another example of the combined laser light source will be described. As shown in FIGS. 34A and 34B, this combined laser light source has a heat block 182 having an L-shaped cross section in the optical axis direction mounted on a substantially rectangular heat block 180, and is housed between two heat blocks. A space is formed. On the upper surface of the L-shaped heat block 182, a plurality of (for example, two) multi-cavity lasers 111 in which a plurality of light emitting points (for example, five) are arranged in an array form the light emitting points 111a 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 111, a collimator lens array 184 in which collimator lenses are arranged corresponding to the light emission points 111a 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 divergence angle of the laser beam 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 beam emitting side of the collimating lens array 184, there is one multimode optical fiber 62 and a condensing lens 200 that condenses and couples the laser beam to the incident end of the multimode optical fiber 62. Has been placed.

  In the above configuration, each of the laser beams B emitted from each of the plurality of emission points 111a of the plurality of multi-cavity lasers 111 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and collected. The light is collected by the optical lens 200 and is incident on the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a 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.

  A laser module in which each of the combined laser light sources is housed in a casing and the emission end portion of the multimode optical fiber 62 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.

<< Used pixel part designation means >>
The used pixel part specifying means includes a light spot position detecting means for detecting the position of a light spot on a surface to be exposed as a pixel unit, and N-fold exposure based on a detection result by the light spot position detecting means. It is preferable to include at least a pixel part selection unit that selects a pixel part to be used for the realization.
Hereinafter, an example of a method for designating a pixel part used for N-exposure by the used pixel part specifying unit will be described.

(1) Method for Specifying Picture Element Portions Used in Single Exposure Head In the present embodiment (1), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and each exposure head 30. A description will be given of a method for designating a used pixel part for reducing the variation in resolution and density unevenness caused by the mounting angle error and realizing ideal double exposure.

The set inclination angle θ in the column direction of the image element (micromirror 58) with respect to the scanning direction of the exposure head 30 can be used as long as there is no mounting angle error of the exposure head 30 and the like. It is assumed that an angle slightly larger than the angle θ _ideal, which is a double exposure using 256 lines of pixel parts, is adopted.
This angle θ _ideal is equal to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p of usable micromirrors 58 in the column direction, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsinθ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcosθ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
It becomes. In the present embodiment (1), since s = 256 and N = 2 as described above, the angle θ _ideal is about 0.45 degrees according to the equation 3. Therefore, for example, an angle of about 0.50 degrees may be employed as the set inclination angle θ. The pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

  FIG. 10 illustrates an example of unevenness in a pattern on an exposed surface due to the influence of an attachment angle error of one exposure head 30 and pattern distortion in the pattern forming apparatus 10 that is initially adjusted as described above. FIG. In the following drawings and description, the light spot in the m-th row is represented by r (m) with respect to the light spot generated by each pixel part (micromirror) and constituting the exposure area on the exposed surface. ), The light spot in the nth column is denoted as c (n), and the light spot in the mth row and the nth column is denoted as P (m, n).

The upper part of FIG. 10 shows a pattern of light spots from the usable micromirror 58 projected onto the exposed surface of the photosensitive material 12 with the stage 14 being stationary, and the lower part is the upper part. 2 shows the state of the exposure pattern formed on the surface to be exposed when the stage 14 is moved and continuous exposure is performed in the state where the pattern of light spots as shown in FIG.
In FIG. 10, for convenience of explanation, the exposure pattern by the odd-numbered columns and the exposure pattern by the even-numbered columns of the micromirrors 58 that can be used are shown separately. Two exposure patterns are superimposed.

In the example of FIG. 10, as a result of adopting the set inclination angle θ slightly larger than the above angle θ _ideal , and because it is difficult to finely adjust the mounting angle of the exposure head 30, the actual mounting angle and the above As a result of the error in the set inclination angle θ, density unevenness occurs in any region on the exposed surface. Specifically, in the overlapped exposure region on the exposed surface, which is formed by a plurality of pixel part rows in both the exposure pattern by the odd-numbered micromirrors and the exposure pattern by the even-numbered micromirrors, it is ideal. Overexposure occurs with respect to double exposure, resulting in a redundant drawing area and uneven density.

Furthermore, the example of FIG. 10 is an example of pattern distortion appearing on the surface to be exposed, and “angular distortion” occurs in which the inclination angle of each pixel row projected on the surface to be exposed is not uniform. Causes of such angular distortion include various aberrations and alignment deviations of the optical system between the DMD 36 and the exposed surface, distortion of the DMD 36 itself, micromirror placement errors, and the like.
The angular distortion appearing in the example of FIG. 10 is a distortion in which the inclination angle with respect to the scanning direction is smaller in the left column of the figure and larger in the right column of the figure. As a result of this angular distortion, the overexposed area is smaller on the exposed surface shown on the left side of the figure and larger on the exposed surface shown on the right side of the figure.

In order to reduce the density unevenness in the overlapped exposure area on the exposed surface formed by a plurality of pixel part rows as described above, a set of the slit 28 and the photodetector is used as the light spot position detecting means. The actual inclination angle θ ′ is specified for each exposure head 30, and based on the actual inclination angle θ ′, the calculation device connected to the photodetector as the pixel portion selection unit is used for actual exposure. A process of selecting a micromirror to be used is performed.
The actual tilt angle θ ′ is based on at least two light spot positions detected by the light spot position detecting means, and the column direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted. It is specified by the angle formed by.
Hereinafter, the specification of the actual inclination angle θ ′ and the used pixel selection process will be described with reference to FIGS.

-Specification of actual inclination angle θ'-
FIG. 11 is a top view showing the positional relationship between the exposure area 32 by one DMD 36 and the corresponding slit 28. The size of the slit 28 is set to sufficiently cover the width of the exposure area 32.
In the example of the present embodiment (1), the angle formed by the 512th light spot row positioned substantially at the center of the exposure area 32 and the scanning direction of the exposure head 30 is measured as the actual inclination angle θ ′. . Specifically, the micromirrors 58 in the first row and the 512th column on the DMD 36 and the micromirrors 58 in the 256th row and the 512th column are turned on, and the light spots on the exposure surface corresponding to each of the micromirrors 58 are turned on. The positions of P (1,512) and P (256,512) are detected, and the angle formed by the straight line connecting them and the scanning direction of the exposure head is specified as the actual inclination angle θ ′.

FIG. 12 is a top view illustrating a method for detecting the position of the light spot P (256, 512).
First, in a state where the micromirror 58 in the 256th row and the 512th column is turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 512) is changed. The slit 28 is positioned at an arbitrary position between the upstream slit 28a and the downstream slit 28b. The coordinates of the intersection of the slit 28a and the slit 28b at this time are (X0, Y0). The value of this coordinate (X0, Y0) is determined and recorded from the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved to the right in FIG. 12 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 12, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 12 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 12, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 512) on the surface to be exposed are X = X0 + (Y1-Y2) / 2, Y = (Y1 + Y2) / 2. Determine by calculation. By the same measurement, coordinates indicating the position of P (1,512) are also determined, an inclination angle formed by a straight line connecting the respective coordinates and the scanning direction of the exposure head 30 is derived, and this is obtained as an actual inclination angle θ ′. As specified.

-Selection of used pixel part-
The arithmetic unit connected to the photodetector using the actual inclination angle θ ′ specified in this way is
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived, and a process of selecting the micromirrors in the first to Tth rows on the DMD 36 as micromirrors that are actually used during the main exposure is performed. As a result, in the exposure region near the 512th column, a micromirror that minimizes the total area of the overexposed region and the underexposed region with respect to the ideal double exposure is actually obtained. Can be selected as a micromirror to be used in

Here, instead of deriving the natural number closest to the above value t, the minimum natural number equal to or greater than the value t may be derived. In that case, in the exposure region near the 512th column, a micromirror that minimizes the area of the overexposed region and does not produce an underexposed region with respect to ideal double exposure. It can be selected as a micromirror to be actually used.
It is also possible to derive the maximum natural number equal to or less than the value t. In that case, in the exposure region near the 512th row, a micromirror that minimizes the area of the underexposed region and does not produce an overexposed region with respect to ideal double exposure, It can be selected as a micromirror to be actually used.

FIG. 13 shows how the unevenness on the exposed surface shown in FIG. 10 is improved in the exposure performed using only the light spot generated by the micromirror selected as the micromirror actually used as described above. It is explanatory drawing which showed what was done.
In this example, it is assumed that T = 253 is derived as the natural number T and the micromirrors in the first row to the 253rd row are selected. For the micromirrors in the 254th to 256th lines that are not selected, the pixel part control means sends a signal for setting the angle to the always-off state. Not involved in exposure. As shown in FIG. 13, overexposure and underexposure are almost completely eliminated in the exposure region near the 512th column, and uniform exposure very close to ideal double exposure is realized.

On the other hand, in the left region of FIG. 13 (near c (1) in the figure), the inclination angle of the light spot sequence on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. It is smaller than the inclination angle of the light beam row in the region. Therefore, in the exposure using only the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, an ideal double is applied to each of the exposure pattern of the even-numbered column and the exposure pattern of the odd-numbered column. An area that is underexposed with respect to the exposure is slightly generated.
However, in the actual exposure pattern formed by overlaying the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the regions where the exposure amount is insufficient are complemented with each other, and the exposure unevenness due to the angular distortion is double-exposed. The effect of offsetting can be minimized.

Further, in the region on the right side of FIG. 13 (near c (1024) in the figure), the inclination angle of the light beam on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. It is larger than the inclination angle of the light beam row in the region. Therefore, in the exposure with the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, as shown in the figure, there is an overexposed region with respect to the ideal double exposure. It will occur slightly.
However, in the actual exposure pattern formed by superimposing the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the overexposed regions are complemented with each other, and the density unevenness due to the angular distortion is caused by the double exposure. The effect of offsetting can be minimized.

In the present embodiment (1), as described above, the actual inclination angle θ ′ of the 512th ray array is measured, and based on T derived from the equation (4) using the actual inclination angle θ ′. The micro-mirror 58 to be used is selected. However, as the method of specifying the actual inclination angle θ ′, a plurality of actual directions formed by the column direction (light spot column) of the plurality of image elements and the scanning direction of the exposure head are used. Each of the tilt angles is measured, and any one of the average value, the median value, the maximum value, and the minimum value is specified as the actual tilt angle θ ′. It is good also as a form to select.
When the average value or the median value is set to the actual inclination angle θ ′, it is possible to realize exposure with a good balance between an overexposed area and an underexposed area with respect to an ideal N-fold exposure. For example, the total area of the overexposed region and the underexposed region is minimized, and the number of pixel units (number of light spots) in the overexposed region and the underexposed region are drawn. It is possible to realize exposure such that the number of prime units (number of light spots) is equal.
Further, if the maximum value is set to the actual inclination angle θ ′, it is possible to realize an exposure that places more importance on eliminating an overexposed region with respect to an ideal N double exposure, for example, an underexposure. It is possible to realize exposure that minimizes the area of the region and does not generate an overexposed region.
Further, if the minimum value is set to the actual inclination angle θ ′, it is possible to realize exposure that places more importance on eliminating underexposed areas with respect to ideal N-fold exposure, for example, overexposure. It is possible to realize exposure that minimizes the area of the region and does not cause a region that is underexposed.

On the other hand, the specification of the actual inclination angle θ ′ is not limited to the method based on the positions of at least two light spots in the same pixel part row (light spot row). For example, the angle obtained from the position of one or more light spots in the same pixel part sequence c (n) and the position of one or more light spots in a row near the c (n), The actual inclination angle θ ′ may be specified.
Specifically, one light spot position in c (n) and one or a plurality of light spot positions included in a light spot row on a straight line and in the vicinity along the scanning direction of the exposure head are detected. The actual inclination angle θ ′ can be obtained from the position information. Further, the angle obtained based on the positions of at least two light spots (for example, two light spots arranged so as to straddle c (n)) in the light spot array in the vicinity of the c (n) line is an actual inclination. The angle θ ′ may be specified.

  As described above, according to the specification method of the used picture element portion of the present embodiment (1) using the pattern forming apparatus 10, resolution variation and density unevenness due to the influence of the mounting angle error of each exposure head and pattern distortion are eliminated. It is possible to reduce and realize an ideal N double exposure.

(2) Method for designating used pixel parts between a plurality of exposure heads <1>
In the present embodiment (2), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12 and is a head that is an overlapped exposure region on the exposed surface formed by the plurality of exposure heads 30. In the intermittent region, resolution variations and density unevenness due to deviation from the ideal state of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction are reduced, A description will be given of a method for designating a used pixel portion for realizing ideal double exposure.

As the set inclination angle θ of each exposure head 30, that is, each DMD 36, the usable pixel portion micromirror 58 of 1024 columns × 256 rows is used if there is no ideal mounting angle error of the exposure head 30. Then, it is assumed that an angle θ _ideal that is exactly double exposure is adopted.
This angle θ _ideal is obtained from the above equations 1 to 3 in the same manner as in the above embodiment (1). In the present embodiment (2), it is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 becomes this angle θ _ideal .

FIG. 14 shows how the relative positions of the two exposure heads (for example, the exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction in the pattern forming apparatus 10 initially adjusted as described above are shifted from an ideal state. It is explanatory drawing which showed the example of the density nonuniformity which arises in the pattern on a to-be-exposed surface by the influence. The relative position shift in the X-axis direction of each exposure head can occur because it is difficult to finely adjust the relative position between the exposure heads.

14 is projected onto the exposed surface of the photosensitive material 12 in a state where the stage 14 is stationary, the light spot group from the usable micromirror 58 of the DMD 36 of the exposure heads 30 ₁₂ and 30 _21. It is the figure which showed these patterns. The lower part of FIG. 14 shows the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing. The state is shown for exposure areas 32 ₁₂ and 32 ₂₁ .
In FIG. 14, for convenience of explanation, every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

In the example of FIG. 14, as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ in the X-axis direction from the ideal state, the exposure pattern by the pixel column group A and the pixel column group B In both of the above exposure patterns, a portion where the exposure amount is larger than the ideal double exposure state occurs in the connection area between the heads in the exposure areas 32 ₁₂ and 32 ₂₁ .

In order to reduce density unevenness appearing in the inter-head connecting region formed on the exposed surface by the plurality of exposure heads as described above, in this embodiment (2), a slit is used as the light spot position detecting means. 28 and a pair of photodetectors, the positions of some of the light spots constituting the connecting area between the heads formed on the exposed surface among the light spot groups from the exposure heads 30 ₁₂ and 30 _21. Detect (coordinates). Based on the position (coordinates), processing for selecting a micromirror to be used for actual exposure is performed using an arithmetic unit connected to the photodetector as the pixel portion selection means.

-Detection of position (coordinates)-
FIG. 15 is a top view showing the positional relationship between the exposure areas 32 ₁₂ and 32 ₂₁ similar to those in FIG. 14 and the corresponding slits 28. The size of the slit 28 is large enough to cover the width of the overlapping portion between the exposed areas 34 by the exposure heads 30 ₁₂ and 30 ₂₁ , that is, the slit 28 is formed on the exposed surface by the exposure heads 30 ₁₂ and 30 _21. The size is sufficient to cover the connection area between the heads.

Figure 16 is a top view for explaining a detection method of detecting the position of a point P of the exposure area _{32 21} as an example (256, 1024).
First, with the micromirror in the 256th row and the 1024th column turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 1024) is upstream. The slit 28 is positioned at an arbitrary position so as to be between the slit 28a on the side and the slit 28b on the downstream side. The coordinates of the intersection of the slit 28a and the slit 28b at this time are (X0, Y0). The value of this coordinate (X0, Y0) is determined and recorded from the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved to the right in FIG. 16 along the Y axis. Then, as indicated by the two-dot chain line in FIG. 16, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 1024).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 16 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 16, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the light spot P (256, 1024).

  From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 1024) on the exposed surface are calculated as X = X0 + (Y1−Y2) / 2, Y = (Y1 + Y2) / 2. Determined by

-Identification of unused pixel parts-
In the example of FIG. 14, first, the position of the point P of the exposure area _{32 12} (256,1) is detected by a set of slits 28 and a photodetector as the light spot position detecting unit. Subsequently, the position of each light spot on the 256 line of light spots row r of the exposure area _{32 21 (256), P (} 256,1024), to detect the P (256,1023) ··· and order periodically, where the exposure area _{32 21} of point P indicating the exposure area _{32 12} point P (256,1) larger X coordinate than the (256, n) is detected, and terminates the detecting operation. Then, the micro mirrors corresponding to light spots constituting the c (1024) from the light spot column c of the exposure area 32 ₂₁ (n + 1), specifies as a micro-mirror is not used during the exposure (unused pixel parts).
For example, in FIG. 14, the exposure area _{32 21} point P (256,1020) is shows a larger X coordinate than the point P of the exposure area _{32 12} (256,1) of the exposure area _{32 21} spot If P (256,1020) is that the detection operation at the detected ended, the light spots constituting the first 1024 lines from the 1021 line of exposure area _{32 21,} corresponding to the portion 70 covered with hatched in FIG. 17 The corresponding micromirror is identified as a micromirror that is not used during the main exposure.

Next, the number N of the N multiple exposure, the position of the point P of the exposure area _{32 12} (256, N) is detected. In this embodiment (2), since N = 2, the position of the light spot P (256, 2) is detected.
Then, among the light spot columns of the exposure area 32 _21, except those identified as light spots string corresponding to the micromirrors is not used during the exposure in the above, the position of the light spot constituting the rightmost 1020 column a, P (1,1020) in order from P (1,1020), P (2,1020 ) ··· and continue to detection, greater than the point P of the exposure area _{32 12} (256,2) X When the light spot P (m, 1020) indicating the coordinates is detected, the detection operation is terminated.
Thereafter, the connected operational devices to said light detector, and X-coordinate of the exposure area _{32 12} of the light spot P (256, two), point P of the exposure area _{32 21} (m, 1020) and P (m- and X-coordinate of 1,1020) are compared, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m, 1020) is closer to the X coordinate of the point P in the exposure area _{32 12} (256, 2) a micro mirror corresponding to P (m-1,1020) from point P of the exposure area _{32 21} (1,1020) is identified as a micro-mirror is not used during the exposure.
Also, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m-1,1020) is close to the X-coordinate of the point P in the exposure area _{32 12} (256, 2), the light of the exposure area _{32 21} Micromirrors corresponding to points P (1, 1020) to P (m−2, 1020) are specified as micromirrors that are not used for the main exposure.
Furthermore, the position of the point P of the exposure area _{32 12 (256, N-1} ) That point P (256,1), the position of each point constituting the first 1019 column is the next row of the exposure area _{32 21} The same detection process and identification of micromirrors that are not used are also performed.

  As a result, for example, micromirrors corresponding to the light spots that form the shaded area 72 in FIG. 17 are added as micromirrors that are not used during actual exposure. These micromirrors are always signaled to set the micromirror angle to the off-state angle, and these micromirrors are substantially not used for exposure.

As described above, the micromirrors that are not used at the time of actual exposure are identified, and the micromirrors that are not used at the time of actual exposure are selected as the micromirrors that are used at the time of actual exposure, whereby the exposure areas 32 ₁₂ and 32 ₂₁ In the connection area between the heads, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure can be minimized. As shown in the lower part of FIG. Uniform exposure extremely close to double exposure can be realized.

In the above example, upon the particular light spots constituting the regions 72 covered with hatched in FIG. 17, the X coordinate of the point P in the exposure area _{32 12} (256, 2), the exposure area _{32 21} of the light spot P (m, 1020) and P (m-1,1020) without comparison of the X-coordinate of the immediately, P from point P of the exposure area _{32 21 (1,1020) (m-} 2 , 1020) may be specified as a micromirror that is not used during the main exposure. In that case, in the connecting area between the heads, a micromirror is actually used that minimizes the area of an overexposed area with respect to an ideal double exposure and does not cause an underexposed area. It can be selected as a micromirror.
Further, the micro-mirrors corresponding to P (m-1,1020) from point P of the exposure area _{32 21} (1,1020), it may be specified as micro mirrors not used in this exposure. In that case, in the connecting region between the heads, a micromirror is actually used in which the area of the region that is underexposed with respect to the ideal double exposure is minimized and the region that is not overexposed does not occur. It can be selected as a micromirror.
Further, in the connecting area between the heads, the number of pixel units (the number of light spots) in an area that is overexposed with respect to an ideal double drawing and the number of pixel units (the number of light spots) in an area that is underexposed. It is good also as selecting the micromirror actually used so that it may become equal.

  As described above, according to the specification method of the used pixel part of the present embodiment (2) using the pattern forming apparatus 10, the resolution variation caused by the relative position shift in the X-axis direction of the plurality of exposure heads Density unevenness can be reduced, and ideal N-fold exposure can be realized.

(3) Specification method of used pixel parts between a plurality of exposure heads <2>
In this embodiment (3), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12 and is a head that is an overlapping exposure region on the exposed surface formed by a plurality of exposure heads 30. In the connection region, the relative position of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) from the ideal state in the X-axis direction, the mounting angle error of each exposure head, and the two exposure heads A description will be given of a method for designating a used pixel portion for reducing the variation in resolution and density unevenness due to the relative mounting angle error between them and realizing ideal double exposure.

As the set tilt angle of each exposure head 30, that is, each DMD 36, in an ideal state where there is no mounting angle error of the exposure head 30, a usable 1024 column × 256 row pixel element (micromirror 58) is provided. It is assumed that an angle slightly larger than the angle θ _ideal that is used for exactly double exposure is adopted.
This angle θ _ideal is a value obtained in the same manner as in the above embodiment (1) using the above equations 1 to 3. In this embodiment, s = 256 and N = 2 as described above. The angle θ _ideal is about 0.45 degrees. Therefore, for example, an angle of about 0.50 degrees may be employed as the set inclination angle θ. The pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

FIG. 18 shows a mounting angle error of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the pattern forming apparatus 10 in which the mounting angle of each exposure head 30, that is, each DMD 36 is initially adjusted as described above, the influence of the deviation of the relative mounting angle error and the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ is an explanatory view showing an example of unevenness that occurs in the pattern on the exposed surface.

In the example of FIG. 18, as in the example of FIG. 14, as a result of the shift of the relative positions of the exposure heads 30 ₁₂ and 30 _{21 in} the X-axis direction, exposure by every other light spot group (pixel column groups A and B) is performed. In both exposure patterns 32 ₁₂ and 32 ₂₁ , the exposure amount overlaps on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface of the exposure areas 32 ₁₂ and 32 ₂₁ , which is more than the ideal double exposure state. A region 74 is generated, which causes uneven density.
Furthermore, in the example of FIG. 18, it is difficult to finely adjust the result of setting the tilt angle θ of each exposure head to be slightly larger than the angle θ _ideal satisfying the formula (1) and the mounting angle of each exposure head. Therefore, as a result of the actual mounting angle deviating from the set inclination angle θ, even in regions other than the exposure region overlapping on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface, In the connection region between the pixel part columns, which is an overlapped exposure region on the exposed surface, formed by a plurality of pixel part columns, both in the exposure pattern by every other light spot group (pixel column group A and B). A region 76 that is overexposed than the ideal double exposure state is generated, and this causes further density unevenness.

In this embodiment (3), first, the use pixel selection process for reducing the uneven density due to the influence of the deviation of the mounting angle error and relative mounting angle of the exposure heads 30 ₁₂ and 30 _21.
Specifically, a set of a slit 28 and a photodetector is used as the light spot position detecting means, and an actual inclination angle θ ′ is specified for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the actual inclination angle θ ′ is determined. Based on this, it is assumed that processing for selecting a micromirror to be used for actual exposure is performed using an arithmetic unit connected to a photodetector as the pixel part selection means.

-Specification of actual inclination angle θ'-
The actual inclination angle θ ′ is specified with respect to the positions of the light spots P (1, 1) and P (256, 1) in the exposure area 32 ₁₂ for the exposure head 30 _{12 and in the} exposure area 32 ₂₁ for the exposure head 30 ₂₁ . The positions of the light spots P (1,1024) and P (256,1024) are detected by the combination of the slit 28 and the photodetector used in the above-described embodiment (2), and the inclination angle of the straight line connecting them. And the angle formed by the scanning direction of the exposure head.

-Identification of unused pixel parts-
The arithmetic device connected to the photodetector using the actual inclination angle θ ′ thus specified is similar to the following equation 4 similar to the arithmetic device in the embodiment (1) described above.
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the micromirrors in the (T + 1) th to 256th rows on the DMD 36 are not used for the main exposure. Processing to identify as a micromirror is performed.
For example, T = 254 for the exposure head _{30 12,} when T = 255 was derived for the exposure head _3O21, micro mirrors corresponding to light spots constituting the parts 78 and 80 covered with hatched in FIG. 19 These are specified as micromirrors that are not used for the main exposure. Thus, in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure is minimized. be able to.

Here, instead of deriving the natural number closest to the above value t, the minimum natural number equal to or greater than the value t may be derived. In that case, exposure is performed for ideal double exposure in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads. It is possible to minimize the area where the amount is excessive and to prevent an area where the exposure amount is insufficient.
Or it is good also as deriving the maximum natural number below value t. In that case, exposure is performed for ideal double exposure in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads. It is possible to minimize the area of the insufficient region and prevent the region from being overexposed.
In each area other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads, the number of pixel units (light It is also possible to specify micromirrors that are not used during the main exposure so that the number of pixel units (the number of light spots) in the underexposed area is equal to the number of points.

Thereafter, with respect to the micromirror corresponding to the light spot other than the light spots constituting the regions 78 and 80 covered with diagonal lines in FIG. 19, the same processing as that of the present embodiment (3) described with reference to FIGS. In FIG. 19, micromirrors corresponding to the light spots constituting the shaded area 82 and the shaded area 84 are identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors specified as not used at the time of exposure, the pixel element control means sends a signal for setting the angle to the always-off state, and these micromirrors are substantially exposed. Not involved.

  As described above, according to the method for designating the used picture element portion of the present embodiment (3) using the pattern forming apparatus 10, the relative position shift in the X-axis direction of the plurality of exposure heads and the attachment of each exposure head Variations in resolution and density unevenness due to angle errors and relative mounting angle errors between exposure heads can be reduced, and ideal N-fold exposure can be realized.

  As described above, the method for designating the used pixel portion by the pattern forming apparatus 10 has been described in detail. However, the above-described embodiments (1) to (3) are merely examples, and various modifications can be made without departing from the scope of the present invention. It is.

  In the above embodiments (1) to (3), as a means for detecting the position of the light spot on the exposed surface, a set of the slit 28 and the single cell type photodetector is used. The present invention is not limited to this, and any form may be used. For example, a two-dimensional detector may be used.

  Further, in the above embodiments (1) to (3), the actual inclination angle θ ′ is obtained from the position detection result of the light spot on the exposed surface by the combination of the slit 28 and the photodetector, and the actual inclination angle θ ′ is obtained. The micromirrors to be used are selected based on the above, but a usable micromirror may be selected without the derivation of the actual inclination angle θ ′. Furthermore, for example, the reference exposure using all available micromirrors is performed, and the micromirror used by the operator is manually specified by checking the resolution and density unevenness by visual observation of the reference exposure results. It is included in the scope of the invention.

There are various forms of pattern distortion that can occur on the exposed surface, in addition to the angular distortion described in the above example.
As an example, as shown in FIG. 20A, there is a form of magnification distortion in which light rays from each micromirror 58 on the DMD 36 reach the exposure area 32 on the exposure surface at different magnifications.
As another example, as shown in FIG. 20B, there is a form of beam diameter distortion in which the light from each micromirror 58 on the DMD 36 reaches the exposure area 32 on the exposed surface with a different beam diameter. . These magnification distortion and beam diameter distortion are mainly caused by various aberrations and alignment deviation of the optical system between the DMD 36 and the exposed surface.
As yet another example, there is a form of light amount distortion in which light beams from the micromirrors 58 on the DMD 36 reach the exposure area 32 on the exposed surface with different light amounts. In addition to various aberrations and misalignment, the light amount distortion includes the positional dependency of the transmittance of the optical element between the DMD 36 and the exposed surface (for example, the lenses 52 and 54 in FIGS. 5A and 5B which are single lenses) This is caused by unevenness in the amount of light caused by the DMD 36 itself. These forms of pattern distortion also cause unevenness in resolution and density in the pattern formed on the exposed surface.

  According to the above embodiments (1) to (3), the residual elements of pattern distortion in these forms after selecting the micromirrors actually used for the main exposure are the same as the residual elements of angular distortion described above. It is possible to level out by the effect of filling by multiple exposure, and the unevenness of resolution and density can be reduced over the entire exposure area of each exposure head.

<< Reference exposure >>
As a modified example of the above embodiments (1) to (3), among available micromirrors, it corresponds to (N-1) every micromirror column or 1 / N rows of all light spot rows. A reference exposure is performed using only a group of micromirrors constituting an adjacent row, and among the micromirrors used for the reference exposure, micromirrors that are not used at the time of actual exposure are specified so that uniform exposure can be realized. It is good as well.
The result of the reference exposure by the reference exposure means is output as a sample, and the output reference exposure result is analyzed to confirm resolution variation and density unevenness and to estimate the actual inclination angle. The analysis of the result of the reference exposure may be a visual analysis by an operator.

FIG. 21A and FIG. 21B are explanatory views showing an example of a form in which reference exposure is performed using only (N-1) rows of micromirrors using a single exposure head.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only the micromirrors corresponding to the odd-numbered light spot arrays indicated by the solid lines in FIG. 21A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, it is possible to specify a micromirror to be used in the main exposure by confirming variations in resolution and density unevenness, or estimating an actual inclination angle.
For example, micromirrors other than the micromirror corresponding to the light spot array shown by hatching in FIG. 21B are designated as actually used in the main exposure among the micromirrors constituting the odd light spot array. . For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and the micromirror used during the main exposure may be designated, or the same pattern as that for the odd-numbered light spot arrays may be applied. Good.
By specifying the micromirrors used in the main exposure as described above, in the main exposure using both the odd-numbered and even-numbered micromirrors, a state close to ideal double exposure can be realized.

FIG. 22 is an explanatory diagram showing an example of a form in which reference exposure is performed using only a plurality of (N-1) rows of micromirrors using a plurality of exposure heads.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference is made using only the micromirrors corresponding to the odd-numbered light spot rows of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction, which are indicated by solid lines in FIG. Exposure is performed, and a reference exposure result is output as a sample. Based on the output reference exposure result, the variation in resolution and density unevenness in the area other than the joint area between the heads formed on the exposed surface by the two exposure heads are confirmed, or the actual inclination angle is estimated. Thus, the micromirror to be used at the time of the main exposure can be designated.
For example, the micromirrors other than the micromirrors corresponding to the light spot rows in the region 86 shown by hatching in FIG. Specified as actually used. For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and a micromirror used in the main exposure may be designated, or the same pattern as that for the odd-numbered pixel columns may be applied. Good.
In this way, in the main exposure using both the odd-numbered and even-numbered micromirrors by designating the micromirrors that are actually used during the main exposure, the two exposure heads form the surface to be exposed. A state close to ideal double exposure can be realized in a region other than the head-to-head connection region.

FIG. 23A and FIG. 23B show an example of a mode in which a single exposure head is used and reference exposure is performed using only micromirror groups constituting adjacent rows corresponding to 1 / N rows of the total number of light spot rows. FIG.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only micromirrors corresponding to the light spots in the first to 128 (= 256/2) rows indicated by the solid line in FIG. 23A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, a micromirror to be used in the main exposure can be designated.
For example, a micromirror other than the micromirror corresponding to the light spot group indicated by hatching in FIG. 23B is designated as actually used in the main exposure among the micromirrors in the first to 128th rows. Can be done. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used in the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
By designating the micromirror to be used at the time of the main exposure in this way, a state close to an ideal double exposure can be realized in the main exposure using the entire micromirror.

FIG. 24 uses a plurality of exposure heads and two adjacent exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction are adjacent to each other corresponding to 1 / N rows of the total number of light spots. It is explanatory drawing which showed an example of the form which performs reference exposure using only the micromirror group which comprises a line.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only the micromirrors corresponding to the light spots in the first to 128th (= 256/2) rows indicated by solid lines in FIG. 24, and the reference exposure results are output as samples. . Based on the reference exposure result outputted from the sample, it is possible to realize the main exposure in which the variation in resolution and the density unevenness in the region other than the joint region between the heads formed on the exposed surface by the two exposure heads are minimized. In addition, it is possible to designate a micromirror to be used during the main exposure.
For example, micromirrors other than the micromirrors corresponding to the light spot arrays in the region 90 shown by hatching in FIG. 24 and the region 92 shown by shading are included in the micromirrors in the first to 128th rows. Designated as actually used at the time of exposure. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used for the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
In this way, by specifying the micromirror to be used during the main exposure, a state close to ideal double exposure is realized in an area other than the inter-head connecting area formed on the exposed surface by two exposure heads. it can.

  In the above embodiments (1) to (3) and the modified examples, the case where the main exposure is the double exposure has been described. However, the present invention is not limited to this, and any multiple exposure more than the double exposure may be used. . In particular, by setting the exposure to about 3 to 7 exposures, high resolution can be secured, and exposure with reduced variations in resolution and density unevenness can be realized.

  Further, in the exposure apparatus according to the embodiment and the modified example, the dimension of the predetermined part of the two-dimensional pattern represented by the image data is matched with the dimension of the corresponding part that can be realized by the selected use pixel. A mechanism for converting image data is preferably provided. By converting the image data in this way, a high-definition pattern according to a desired two-dimensional pattern can be formed on the exposed surface.

[Development process]
The development is performed by removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, alkaline aqueous 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 aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

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

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

  In the formation of the pattern, for example, a curing process, an etching process, a plating process, and the like may be included. These may be used alone or in combination of two or more.

-Curing process-
When the pattern forming method is a pattern forming method for forming a permanent pattern such as a protective film, an interlayer insulating film, a solder resist pattern, or a color filter, the photosensitive layer is cured after the developing step. It is preferable to provide a curing treatment step for performing.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the development. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the development. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
As heating time in the said whole surface heating, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

-Etching process-
The etching step can be performed by a method appropriately selected from known etching methods.
There is no restriction | limiting in particular as an etching liquid used for the said etching process, 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 in terms of an etching factor. Moreover, a well-known sandblasting method can be used.
A wiring pattern can be formed on the surface of the substrate by removing the pattern after performing the etching process in the etching step.

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

  The pattern forming method can be used for forming various patterns that require prevention of sensitivity reduction of the photosensitive layer by oxygen in direct writing by laser exposure of 405 nm, and has high density and high productivity. It can be suitably used for forming a compatible pattern.

-Protective film, interlayer insulating film, solder resist pattern formation method-
When the pattern forming method is a pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern using a so-called solder resist photosensitive layer, the pattern is formed on a printed wiring board. A permanent pattern can be formed by the forming method, and soldering can be performed as follows.
That is, by the development, a hardened layer that is the permanent pattern is formed, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.

  In the pattern forming method, when the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from external impact and bending, and in particular, In the case of an interlayer insulating film, it is useful for high-density mounting of semiconductors and components on, for example, a multilayer wiring board and a build-up wiring board.

-Printed wiring pattern formation method-
When the pattern forming method is a pattern forming method for forming a printed wiring pattern using a photosensitive layer for an etching resist, the pattern can be formed at a high speed and can be widely used for forming various patterns. In particular, it can be suitably used for the production of a printed wiring board, particularly for the production of a printed wiring board having a hole portion such as a through hole or a via hole.

  As a method for producing a printed wiring board having a hole portion such as the through hole or via hole by the pattern forming method, (1) a hole filling ink is formed on a printed wiring board forming substrate having a hole portion as the base material. And (2) forming the photosensitive layer, laminating a photosensitive layer cover film on the photosensitive layer to form a laminate, and (3) the base material of the laminate and From the opposite side, the wiring pattern formation region and the hole portion formation region are irradiated with light under reduced pressure to cure the photosensitive layer, and (4) develop the photosensitive layer to remove the uncured portion of the photosensitive layer. A pattern can be formed by removing.

  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)). 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.

-Color filter manufacturing method-
When the photosensitive layer of the pattern forming material of the present invention is bonded onto a substrate such as a glass substrate and the support is peeled off from the pattern forming material, the charged support (film) and the human body are uncomfortable. There is a problem that a shock may occur or dust adheres 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 opposite to the photosensitive 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 similarly performed 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, The photosensitive layer and the support may be laminated on the glass substrate by drying. Further, when three types of pixels of red, green, and blue are arranged, 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 on 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.

  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 composition solution having the following composition was applied onto a 16 μm thick polyethylene terephthalate film (Toray Co., Ltd., 16QS52) as the support, and dried to form a 20 μm thick photosensitive layer on the support. The pattern forming material was manufactured.

[Composition of photosensitive resin composition solution]
・ The following monocarboxylic acid compound (1)
(Corresponding to A-78 in the exemplified compound, molecular weight 284.31) 0.08 parts by mass. Methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio):
29/19/52, mass average molecular weight: 60,000, acid value 189, 30 mass% concentration product methyl ethyl ketone / propylene glycol monomethyl ether solvent) 84.4 parts by mass / polymerizable monomer represented by the following structural formula (75) 8.2 parts by mass-1/2 molar ratio adduct of decamethylene diisocyanate and tetraethylene oxide monomethacrylate 8.2 parts by mass-4.3 parts by weight of dodecapropylene glycol diacrylate-2,2-bis (o-chlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole 3.4 parts by mass, 10-butyl-2-chloroacridone 0.18 parts by mass, malachite green oxalic acid 0.03 parts by mass, leuco crystal violet 2 parts by mass • Phenoxazine 0.006 parts by mass • Methyl ethyl ketone 30 parts by mass Propylene glycol monomethyl ether 40 parts by weight Fluorine-based surfactant (manufactured by DAINIPPON INK AND CHEMICALS, F780F 30 wt% concentration product methyl
Ethyl ketone solvent) 0.14 parts by mass The glass transition temperature (Tg) of the binder (methacrylic acid / methyl methacrylate / styrene copolymer) was 131 ° C.

However, m + n represents 10 in Structural Formula (75).
On the photosensitive layer of the pattern forming material, a polypropylene film having a thickness of 12 μm (Alfane E-501, manufactured by Oji Paper Co., Ltd.) was laminated as the protective film.
Next, a laminator (MODEL8B-720-PH) was used as the substrate while peeling the protective film of the pattern forming material on the surface of a copper clad laminate (no through-hole, copper thickness 12 μm) polished, washed with water and dried. , Manufactured by Taisei Laminator Co., Ltd.) to prepare a laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were a pressure roll temperature of 105 ° C., a pressure roll pressure of 0.3 MPa, and a laminating speed of 1 m / min.

  The laminate was evaluated for sensitivity, resolution, aspect ratio, resist pattern shape, edge roughness, and number of tent film tears. The results are shown in Table 1.

<Resolution>
(1) Measuring method of shortest development time The polyethylene terephthalate film (support) is peeled off from the laminate, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. is added to the entire surface of the photosensitive layer on the copper clad laminate at 0.15 MPa. Spraying was performed under pressure, and the time required from the start of spraying of the aqueous sodium carbonate 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 15 seconds.

(2) Measurement of sensitivity With respect to the photosensitive layer of the pattern forming material in the prepared laminate, from the support side, a pattern forming apparatus described below is used, and an interval of 0.1 mJ / cm ² to 2 ^1/2 times. Were irradiated with light having different light energy amounts up to 100 mJ / cm ² and double-exposed to harden a part of the photosensitive layer. After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was applied to the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa. Spraying was performed twice as long as 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. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve, the amount of light energy when the thickness of the cured region was the same as that of the photosensitive layer before exposure was 20 μm was determined as the amount of light energy necessary for curing the photosensitive layer.
As a result, the amount of light energy necessary for curing the photosensitive layer was 4.5 mJ / cm ² .

<< Pattern Forming Apparatus >>
The combined laser light source shown in FIGS. 8 to 9 and 25 to 29 as the light irradiating means, and 1024 micromirrors 58 arranged in the main scanning direction schematically shown in FIG. 6 as the light modulating means. DMD 36 controlled to drive only 1024 × 256 rows out of 768 pairs of mirror rows arranged in the sub-scanning direction, and optical for imaging the light shown in FIGS. 5A and 5B on the pattern forming material A pattern forming apparatus 10 including an exposure head 30 having a system was used.

As the set inclination angle of each exposure head 30, that is, each DMD 36, an angle slightly larger than the angle θ _{ideal at} which double exposure is performed using 1024 columns × 256 rows of usable micromirrors 58 was adopted. This angle θ _ideal is equal to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p of usable micromirrors 58 in the column direction, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsinθ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcosθ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
Since s = 256 and N = 2, the angle θ _ideal is about 0.45 degrees. Therefore, for example, 0.50 degrees is adopted as the set inclination angle θ.

First, the state of the exposure pattern on the exposed surface was examined in order to correct the variation in resolution and uneven exposure in double exposure. The results are shown in FIG. In FIG. 18, the light spot group from the micromirror 58 that can be used for the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the pattern forming material 12 with the stage 14 being stationary. Showed the pattern. The state of the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part. Are shown for exposure areas 32 ₁₂ and 32 ₂₁ . In FIG. 18, for convenience of explanation, every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

As shown in FIG. 18, as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ from the ideal state, both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B are both. Thus, it can be seen that, in the exposure areas overlapping on the coordinate axes orthogonal to the scanning direction of the exposure head in the exposure areas 32 ₁₂ and 32 ₂₁ , an overexposed area is generated as compared with the ideal double exposure state.

The use of a set of slits 28 and a photodetector as a light spot position detection means, the position of the point P of the exposure head _{30 12} For the exposure area _{32 12} (1,1) and P (256,1), the exposure head For 30 ₂₁ , the positions of the light spots P (1,1024) and P (256, 1024) in the exposure area 32 ₂₁ are detected, and the angle formed by the inclination angle of the straight line connecting them and the scanning direction of the exposure head is determined. It was measured.

Using the actual inclination angle θ ′, the following equation 4
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ . T = 254 for the exposure head _{30 12,} the exposure head _{30 21} T = 255 was derived respectively. As a result, the micromirrors constituting the portions 78 and 80 covered with diagonal lines in FIG. 19 were identified as micromirrors that are not used during the main exposure.

Thereafter, the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered with the oblique lines in FIG. 19 were similarly covered with the shaded areas 82 and the shaded areas in FIG. Micromirrors corresponding to the light spots constituting the region 84 were identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. It was controlled not to be involved.
As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ , an ideal double exposure is performed in each area other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. Thus, the total area of the overexposed region and the underexposed region can be minimized.

(3) Measurement of resolution The laminate was prepared by the same method and conditions as the evaluation method for the shortest development time in (1), 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 is performed for each line width in increments of 1 μm from line / space = 1/1 to a line width of 10 to 50 μm using the pattern forming apparatus. The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the pattern forming material measured in (2). After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate. A 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed over the entire surface of the photosensitive layer on the copper-clad laminate at a spray pressure of 0.15 MPa for twice the shortest development time determined in (1) above, and uncured areas are sprayed. Dissolve and remove. The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, and the cured resin pattern line is free of irregularities such as lumps and twists, and the minimum line width that allows space formation is measured. This is the resolution. The smaller the numerical value, the better the resolution. The results are shown in Table 1.

<Calculation of aspect ratio>
From the line width (L; μm) of the obtained resist pattern and the resist film thickness (d; μm), it was determined by the following equation, aspect ratio = d / L. The results are shown in Table 1.

<Evaluation of resist pattern shape>
The shape of the resist pattern after development was observed with a scanning electron microscope (SEM) (manufactured by Hitachi, Ltd., S-900), and evaluated according to the following four evaluation criteria. The results are shown in Table 1.
-Evaluation criteria-
◎ ・ ・ ・ Resist is rectangular and there is no resist residue between patterns ○ ・ ・ ・ Resist is a slightly rounded rectangle, but there is no resist residue between patterns △ ・・ ・ The resist is approximately semicircular (kamaboko), but there is no resist residue between the patterns. × ・ ・ ・ The resist is approximately semicircular (kamaboko) and between the patterns. Residue residue (resist skirting)

<Edge roughness>
Using the pattern forming apparatus, the laminated body is irradiated with double exposure so that a horizontal line pattern in a direction perpendicular to the scanning direction of the exposure head is formed, and a partial region of the photosensitive layer is A pattern was formed in the same manner as in the resolution measurement (3). Among the obtained patterns, any five points of a line having a line width of 30 μm were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×), and among the edge positions in the field of view Then, the difference between the most swollen portion (mountain peak portion) and the most constricted portion (valley bottom portion) was obtained as an absolute value, and an average value of five observed positions was calculated, and this was defined as edge roughness. The edge roughness is preferably as the value is small because it exhibits good performance. The results are shown in Table 1.

<Number of tent film tears>
As the substrate, a copper-clad laminate having 200 through-holes with a diameter of 2 mm was used, and the pattern forming material was laminated on both sides of the copper-clad laminate simultaneously. A laminated body is manufactured in the same manner, and the entire surface of the photosensitive layer is produced with the energy amount of light twice as large as the sensitivity value (9 mJ / cm ² ) using the pattern forming apparatus for the laminated body. Was exposed. Similarly, the entire surface of the photosensitive layer was exposed from the opposite side.
After standing at room temperature for 15 minutes, the polyethylene terephthalate (support) is peeled off from the laminate, and sprayed from above and below at a spray pressure of 0.15 MPa for twice the shortest development time determined in (1) above. Thus, a cured resin pattern was formed.
Further, this developing operation was repeated, and the number of tent film breaks after a total of 3 passes was counted. As the number of tent film tears is smaller, the tent property is better. The results are shown in Table 1.

(Example 2)
A pattern was obtained in the same manner as in Example 1 except that the monocarboxylic acid compound (1) in the photosensitive composition solution was replaced with the following monocarboxylic acid compound (2) (molecular weight 351.44) in Example 1. Forming materials and laminates were produced.
Further, the sensitivity, resolution, aspect ratio, resist pattern shape, edge roughness, and number of tent film tears were evaluated for the laminate as in Example 1. The results are shown in Table 1. The shortest development time was 15 seconds.

(Example 3)
In Example 1, the same procedure as in Example 1 was performed except that the monocarboxylic acid compound (1) in the photosensitive composition solution was replaced with a high molecular weight product of phenylglycine (molecular weight 193.24) shown below. Thus, a pattern forming material and a laminate were manufactured.
Further, the sensitivity, resolution, aspect ratio, resist pattern shape, edge roughness, and number of tent film tears were evaluated for the laminate as in Example 1. The results are shown in Table 1. The shortest development time was 15 seconds.

Example 4
In Example 1, the same procedure as in Example 1 was conducted except that the monocarboxylic acid compound (1) in the photosensitive composition solution was replaced with a high molecular weight product of phenylglycine (molecular weight 207.27) shown below. Thus, a pattern forming material and a laminate were manufactured.
Further, the sensitivity, resolution, aspect ratio, resist pattern shape, edge roughness, and number of tent film tears were evaluated for the laminate as in Example 1. The results are shown in Table 1. The shortest development time was 15 seconds.

(Example 5)
-Preparation of photosensitive composition-
A photosensitive composition solution was prepared based on the following composition.
[Composition of photosensitive composition solution]
・ The monocarboxylic acid compound (1)
(Corresponding to A-78 in the exemplified compound, molecular weight 284.31) 0.8 parts by mass Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30) Dispersion 63 parts by mass Epoxy acrylate compound: binder (PR-300, concentration) 67%, Showa Polymer Co., Ltd.) 24.5 parts by mass. Vinyl copolymer having (meth) acryloyl group and carboxyl group in side chain: binder (SPC-2X, concentration 60%, Showa Polymer Co., Ltd.) 13.8 parts by mass / epoxy compound represented by the following structural formula (76): 16.7 parts by mass / dipentaerythritol hexaacrylate / polymerizable compound 5.5 parts by mass / IRGACURE819 (Ciba) Specialty Chemicals Co., Ltd.) 4.1 parts by mass, hydroquinone monomethyl ether 0.056 parts by mass, dicyandiamide 0.4 parts by mass, 2 A-OK (Shikoku Chemicals Co., Ltd.) 0.3 parts by weight phthalocyanine green 0.42 parts by mass · F780F (30% strength by weight product methyl ethyl ketone solution of Dainippon Ink Co., Ltd.)
0.066 parts by mass
-Methyl ethyl ketone 60.0 parts by mass The above barium sulfate dispersion is composed of 22 parts by mass of barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30), 12 parts by mass of a 67% by mass solution of diethylene glycol monomethyl ether acetate of PR-300, and methyl ethyl ketone. 29 parts by mass was mixed in advance, and then dispersed with a motor mill M-200 (manufactured by Eiger) using zirconia beads having a diameter of 1.0 mm at a peripheral speed of 9 m / s for 3.5 hours.

-Production of pattern forming material-
The obtained photosensitive composition solution was applied onto a PET (polyethylene terephthalate) film having a thickness of 16 μm as the support and dried to form a photosensitive layer having a thickness of 35 μm. Next, a 20 μm-thick polypropylene film was laminated as a protective film on the photosensitive layer to produce the pattern forming material.

-Formation of permanent pattern-
-Preparation of laminate-
Next, the surface of a copper-clad laminate (no through hole, copper thickness 12 μm) on which wiring was formed was prepared as the base material by subjecting it to a chemical polishing treatment. A vacuum laminator (MVLP500, manufactured by Meiki Seisakusho Co., Ltd.) was used on the copper-clad laminate while peeling off the protective film from the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. Lamination was performed to prepare a laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were a pressure bonding temperature of 90 ° C., a pressure bonding pressure of 0.4 MPa, and a laminating speed of 1 m / min.

  The laminated body was evaluated in the same manner as in Example 1 for sensitivity, resolution, aspect ratio, resist pattern shape, and edge roughness. The results are shown in Table 1. The shortest development time was 20 seconds.

(Example 6)
In Example 5, the same procedure as in Example 1 was conducted except that the monocarboxylic acid compound (1) in the photosensitive composition solution was replaced with the monocarboxylic acid compound (2) (molecular weight 351.44). A pattern forming material and a laminate were produced.
Further, the sensitivity, resolution, aspect ratio, resist pattern shape, and edge roughness of the laminate were evaluated in the same manner as in Example 5. The results are shown in Table 1. The shortest development time was 20 seconds.

(Example 7)
In Example 5, the same procedure as in Example 5 was conducted except that the monocarboxylic acid compound (1) in the photosensitive composition solution was replaced with the high molecular weight product of phenylglycine (molecular weight 193.24) shown below. Thus, a pattern forming material and a laminate were manufactured.
Further, the sensitivity, resolution, aspect ratio, resist pattern shape, and edge roughness of the laminate were evaluated in the same manner as in Example 5. The results are shown in Table 1. The shortest development time was 20 seconds.

(Example 8)
In Example 5, the same procedure as in Example 5 was performed except that the monocarboxylic acid compound (1) in the photosensitive composition solution was replaced with a high molecular weight product of phenylglycine (molecular weight 207.27) shown below. Thus, a pattern forming material and a laminate were manufactured.
Further, the sensitivity, resolution, aspect ratio, resist pattern shape, and edge roughness of the laminate were evaluated in the same manner as in Example 5. The results are shown in Table 1. The shortest development time was 20 seconds.

Example 9
In the first embodiment, the set inclination angle θ is calculated with N = 1 based on the equation 3, the natural number T closest to the value t satisfying the relationship of t tan θ ′ = 1 is derived based on the equation 4, and the N multiple exposure ( The sensitivity, resolution, aspect ratio, resist pattern shape, edge roughness, and number of tent film tears were evaluated in the same manner as in Example 1 except that N = 1). The results are shown in Table 1. The shortest development time was 15 seconds.

(Comparative Example 1)
In Example 1, a pattern forming material was produced in the same manner as in Example 1 except that the monocarboxylic acid compound (1) in the photosensitive composition solution was replaced with phenylglycine (molecular weight 151) shown below. did.
Further, the sensitivity, resolution, aspect ratio, resist pattern shape, edge roughness, and number of tent film tears were evaluated for the laminate as in Example 1. The results are shown in Table 1. The shortest development time was 15 seconds.

(Comparative Example 2)
A pattern was obtained in the same manner as in Example 1 except that the monocarboxylic acid compound (1) in the photosensitive composition solution was replaced with the monocarboxylic acid compound (molecular weight 165.19) shown below in Example 1. Forming materials and laminates were produced.
Further, the sensitivity, resolution, aspect ratio, resist pattern shape, edge roughness, and number of tent film tears were evaluated for the laminate as in Example 1. The results are shown in Table 1. The shortest development time was 15 seconds.

(Comparative Example 3)
A pattern was obtained in the same manner as in Example 1 except that the monocarboxylic acid compound (1) in the photosensitive composition solution was replaced with the polycarboxylic acid compound (molecular weight 209.20) shown below in Example 1. Forming materials and laminates were produced.
Further, the sensitivity, resolution, aspect ratio, resist pattern shape, edge roughness, and number of tent film tears were evaluated for the laminate as in Example 1. The results are shown in Table 1. The shortest development time was 15 seconds.

(Comparative Example 4)
A pattern was obtained in the same manner as in Example 5 except that the monocarboxylic acid compound (1) in the photosensitive composition solution was replaced with a normal molecular weight product of phenylglycine (molecular weight 151) shown below in Example 5. A forming material was produced.
Further, the sensitivity, resolution, aspect ratio, resist pattern shape, and edge roughness of the laminate were evaluated in the same manner as in Example 5. The results are shown in Table 1. The shortest development time was 20 seconds.

(Comparative Example 5)
In Example 5, a pattern was obtained in the same manner as in Example 5 except that the monocarboxylic acid compound (1) in the photosensitive composition solution was replaced with the monocarboxylic acid compound (molecular weight 165.19) shown below. Forming materials and laminates were produced.
Further, the sensitivity, resolution, aspect ratio, resist pattern shape, and edge roughness of the laminate were evaluated in the same manner as in Example 5. The results are shown in Table 1. The shortest development time was 20 seconds.

(Comparative Example 6)
A pattern was obtained in the same manner as in Example 1 except that the monocarboxylic acid compound (1) in the photosensitive composition solution was replaced with the polycarboxylic acid compound (molecular weight 209.20) shown below in Example 1. Forming materials and laminates were produced.
Further, the sensitivity, resolution, aspect ratio, resist pattern shape, and edge roughness of the laminate were evaluated in the same manner as in Example 1. The results are shown in Table 1. The shortest development time was 20 seconds.

From the results shown in Table 1, the pattern forming materials of Examples 1 to 9 containing a monocarboxylic acid compound having a molecular weight of 180 or more in the photosensitive layer are excellent in sensitivity and resolution, and the resist pattern having an aspect ratio of 1 is obtained. It was confirmed that it was possible to form a high-definition pattern because it was in the range of 0.0 to 5.0 and the shape was good. Moreover, it was confirmed that the pattern formation material of Examples 1-4 of this invention of Example 1-4 and Example 9 is excellent in the value of a tent film | membrane tear number.
Furthermore, in the pattern formation method of this invention, it turned out that the pattern of Examples 1-8 which correct | amended the dispersion | variation in the resolution and exposure nonuniformity in double exposure is high definition, and especially edge roughness is also small.

Since the pattern forming material of the present invention has high sensitivity, a good resist pattern shape is obtained, and the tent film strength is strong, and a high-definition and high aspect ratio pattern can be formed. It can be suitably used for the formation of permanent patterns such as patterns, the manufacture of liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, and proofs. It can use suitably for formation of.
Since the pattern forming apparatus and pattern forming method of the present invention use the pattern forming material of the present invention, formation of 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 liquid crystal structural members, holograms, micromachines, proofs, etc., and can be particularly suitably used for the formation of high-definition wiring patterns.

FIG. 1 is a perspective view showing an appearance of an example of a pattern forming apparatus. FIG. 2 is a perspective view showing an example of the configuration of the scanner of the pattern forming apparatus. FIG. 3A is a plan view showing an exposed region formed on the exposed surface of the photosensitive layer. FIG. 3B is a plan view showing an arrangement of exposure areas by each exposure head. FIG. 4 is a perspective view showing an example of a schematic configuration of the exposure head. FIG. 5A is a top view showing an example of a detailed configuration of the exposure head. FIG. 5B is a side view showing an example of a detailed configuration of the exposure head. FIG. 6 is a partially enlarged view showing an example of the DMD of the pattern forming apparatus of FIG. FIG. 7A is a perspective view for explaining the operation of the DMD. FIG. 7B is a perspective view for explaining the operation of the DMD. FIG. 8 is a perspective view showing an example of the configuration of the fiber array light source. FIG. 9 is a front view showing an example of the arrangement of light emitting points in the laser emitting section of the fiber array light source. FIG. 10 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is an exposure head mounting angle error and pattern distortion. FIG. 11 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit. FIG. 12 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 13 is an explanatory diagram showing a state in which unevenness generated in a pattern on an exposed surface is improved as a result of using only selected micromirrors for exposure. FIG. 14 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift between adjacent exposure heads. FIG. 15 is a top view showing the positional relationship between the exposure areas by two adjacent exposure heads and the corresponding slits. FIG. 16 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 17 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 14 are actually moved and the unevenness in the pattern on the exposed surface is improved. FIG. 18 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift and a mounting angle error between adjacent exposure heads. FIG. 19 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG. FIG. 20A is an explanatory diagram showing an example of magnification distortion. FIG. 20B is an explanatory diagram showing an example of beam diameter distortion. FIG. 21A is an explanatory view showing a first example of reference exposure using a single exposure head. FIG. 21B is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 22 is an explanatory diagram showing a first example of reference exposure using a plurality of exposure heads. FIG. 23A is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 23B is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 24 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads. FIG. 25 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 26 is an example of a plan view showing the configuration of the combined laser light source. FIG. 27 is an example of a plan view showing the configuration of the laser module. FIG. 28 is an example of a side view showing the configuration of the laser module shown in FIG. FIG. 29 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 30 is an example of a perspective view showing a configuration of a laser array. FIG. 31A is an example of a perspective view showing a configuration of a multi-cavity laser. FIG. 31B is an example of a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. 31A are arranged in an array. FIG. 32 is an example of a plan view showing another configuration of the combined laser light source. FIG. 33 is an example of a plan view showing another configuration of the combined laser light source. FIG. 34A is an example of a plan view showing another configuration of the combined laser light source. FIG. 34B is an example of a cross-sectional view along the optical axis of FIG. 34A.

Explanation of symbols

B1 to B7 Laser beam L1 to L7 Collimator lens LD1 to LD7 GaN-based semiconductor laser 10 Pattern forming device 12 Photosensitive layer (photosensitive material)
DESCRIPTION OF SYMBOLS 14 Moving stage 18 Installation stand 20 Guide 22 Gate 24 Scanner 26 Sensor 28 Slit 30 Exposure head 32 Exposure area 36 Digital micromirror device (DMD)
38 Fiber array light source 58 Micro mirror (picture element)
60 laser module 62 multimode optical fiber 64 optical fiber 66 laser emitting section 110 heat block 111 multicavity laser 113 rod lens 114 lens array 140 laser array 200 condenser lens

Claims (21)

It has a photosensitive layer formed using a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, and a monocarboxylic acid compound having a molecular weight of 180 to 2,000, and the photosensitive composition is heated. A crosslinking agent, wherein the binder includes at least one epoxy acrylate compound, a (meth) acryloyl group in the side chain, and at least one vinyl copolymer having an acidic group,
When the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 50 mJ / cm ^2. A pattern forming material characterized by The pattern forming material according to claim 1, wherein the monocarboxylic acid compound contains a group represented by the following structural formula (1).
In the structural formula (1), X is a divalent linking group selected from —O—, —S—, —SO ₂ —, —NH—, —N (R ³ ) —, and —CO—. R ³ represents a hydrogen atom or a monovalent substituent. R ¹ and R ² each independently represents a hydrogen atom or a monovalent substituent. Note that the ^{R 1} and ^R 2, ^{R 1} and at least one and ^{R 3} of ^{R 2,} may be bonded to form a ring structure. The pattern forming material according to claim 1, wherein the monocarboxylic acid compound is a compound represented by the following structural formula (2).
However, in said structural formula (2), A represents an aromatic group or a heterocyclic group. R ¹ and R ² each independently represents a hydrogen atom or a monovalent substituent. Note that at least one of R ¹ and R ² , R ¹ and R ² and at least one of X ¹ , R ¹ and R ² and A, A and X may be bonded to each other to form a ring structure. X ¹ represents a divalent linking group selected from —O—, —S—, —SO ₂ —, —NH—, —N (R ³ ) —, and —CO—, and R ³ represents hydrogen. Represents an atom or a monovalent substituent.   The aspect ratio (d / L) between the line width (L; μm) of the pattern after exposure and development and the film thickness (d; μm) of the pattern is 1.0 to 5.0. The pattern forming material according to any one of the above.   The pattern forming material according to claim 1, wherein the binder contains 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 polymerizable compound contains a monomer having at least one of a urethane group and an aryl group.   The photopolymerization initiator is at least one selected from halogenated hydrocarbon derivatives, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, metallocenes, and acylphosphine oxide compounds. The pattern formation material in any one of Claim 1 to 6 containing a seed | species. The thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. The pattern forming material as described. The pattern forming material according to claim 1, comprising at least a support and a photosensitive layer formed on the support. The pattern formation material of Claim 9 which has a thermoplastic resin layer and a photosensitive layer in this order on a support body. 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. The photosensitive layer in the pattern forming material according to claim 1 is laminated on the surface of the substrate under at least one of heating and pressurization, and then the photosensitive layer is exposed. A pattern forming method comprising at least a pattern forming method. The pattern forming method according to claim 12, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm. The exposure has light irradiation means, and n (where n is a natural number of 2 or more) two-dimensionally arranged pixel elements that receive and emit light from the light irradiation means. An exposure head provided with a light modulation means capable of controlling the picture element portion in response to the scanning direction of the exposure head, wherein the column direction of the picture element part forms a predetermined set inclination angle θ. Using the exposed exposure head,
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
The pattern forming method according to claim 12, wherein the exposure head is moved relative to the photosensitive layer in a scanning direction. The light modulation means further includes pattern signal generation means for generating a control signal based on the pattern information to be formed, and the light emitted from the light irradiation means is generated according to the control signal generated by the pattern signal generation means. The pattern forming method according to claim 14, wherein the pattern is modulated. The conversion means for converting the pattern information so that the dimension of the predetermined part of the pattern represented by the pattern information matches the dimension of the corresponding part that can be realized by the designated used pixel part. The pattern formation method as described. The light irradiating means includes a plurality of lasers, a multimode optical fiber, and a collective optical system for condensing and coupling the laser beams respectively emitted from the plurality of lasers to the multimode optical fiber. The pattern formation method according to any one of 16. The pattern forming method according to claim 12, wherein the photosensitive layer is developed after the exposure. The pattern forming method according to claim 18, wherein a permanent pattern is formed after the development. The pattern formation method according to claim 19, 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. The pattern forming method according to claim 19, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.