JP4711886B2 - Photosensitive composition, photosensitive film and printed circuit board - Google Patents

Description

  The present invention provides a photosensitive composition, a photosensitive film, which is excellent in sensitivity, resolution, and storage stability, and can efficiently form a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern). The present invention relates to a printed board on which a permanent pattern is formed by the photosensitive composition.

  The solder resist is used for the purpose of preventing a solder bridge and protecting a circuit when soldering a component to a printed wiring board, and requires various characteristics such as adhesion, chemical resistance, and electrical characteristics. In recent years, in the printed wiring board manufacturing industry, there has been a demand for weight reduction of printed wiring boards and higher density of conductor circuits, and in response to this, development can be performed with a photosensitive composition for forming a photographic development type solder resist, particularly an alkaline aqueous solution. Photosensitive compositions have been developed and used (see, for example, Patent Document 1).

However, in the case of the photosensitive composition for forming a solder resist that has been used so far, the coating film may be peeled off during development because of insufficient photocuring of the coating film at the time of exposure during image formation. In other words, this is a major factor that prevents high-resolution images from being obtained. For this reason, there is an increasing demand for the development of a photosensitive composition for forming a solder resist having excellent deep-curing properties at the time of exposure, but no material that has been fully satisfied has been found so far.
In addition, formation of a photosensitive layer using such a photographic development type solder resist-forming photosensitive composition can be performed by screen printing, curtain coating, spray coating, roll coating, or the like. Application process for coating the entire surface of the composition on the substrate, temporary drying process for volatilizing the organic solvent to enable contact exposure, exposure process for cooling and contact exposure, development process for removing unexposed areas by development, sufficient coating film Requires a thermosetting step to obtain properties. Among these processes, the exposure process is an extremely sensible process in which the negative film is exchanged depending on the type of the printed wiring board, aligned, vacuumed and exposed. Therefore, the shortening of the exposure process is a major factor for improving the productivity and reducing the price, and the high sensitivity of the photosensitive composition for forming a solder resist greatly contributes to the shortening of the exposure process. For these reasons, there is a growing demand for higher sensitivity for the photosensitive composition for forming a solder resist used in general-purpose electronic devices.
In order to realize such a demand for higher sensitivity, it is generally considered that a large amount of a polyfunctional (meth) acrylate compound is added to the composition. However, when a large amount of a low molecular weight polyfunctional (meth) acrylate compound is added, the sensitivity increases, but the touch drying property (tack-free property) required for contact exposure is remarkably lowered, and the cured coating film properties are also lowered. There's a problem.

  Furthermore, in the formation of a photosensitive layer using such a photographic development type solder resist forming photosensitive composition, in the preliminary drying step with heating, the exposure step, the thermosetting step, and the soldering step, a hot air circulation type Volatile components (mist) generated from the photosensitive composition for forming a solder resist adhere to a drying furnace or an exposure machine, which causes a mounting abnormality in a subsequent soldering process or a subsequent gold plating process. . Therefore, in the preliminary drying process, the exposure process, the thermosetting process, and the soldering process, there is an increasing demand for the development of a photosensitive composition for forming a solder resist with less component (mist) volatilized from the composition. No material has been found that is satisfactory.

On the other hand, a multilayer press method has been conventionally known as a method for producing a multilayer printed wiring board, but this method requires a large amount of production equipment, increases costs, and causes plating on the outer layer during through-hole plating. As a result, the copper thickness increases, and it is difficult to form a fine pattern. In order to overcome such problems, in recent years, development of a multilayer printed wiring board in which resin insulating layers are alternately built up on a conductor layer has been actively promoted (build-up method).
As one of such build-up methods, for example, there is a method for producing a multilayer printed wiring board in which a resin insulating layer is formed using a photographic development type photosensitive composition. In this method, first, a liquid photosensitive composition is applied to the entire surface of a wiring board on which a conductor circuit is formed by an arbitrary method such as screen printing, curtain coating, spray coating or the like so as to fill the conductor circuit, and then dried. Then, a negative film having a predetermined exposure pattern is superimposed on the dried coating film and exposed by irradiating with ultraviolet rays, and after removing the negative film, development processing is performed to form a cured resin insulating layer having a predetermined pattern, After performing a roughening treatment with a roughening agent, a conductor layer is formed by electroless plating, electrolytic plating, or the like.

  In the manufacturing process of the multilayer printed wiring board in which the conductor layer and the resin insulating layer are alternately built up in this way, the photosensitive composition to be used has a sufficient depth of light curing at the time of exposure, and the interlayer to be formed. The resin insulation layer is required to be excellent in various properties such as adhesion to the conductor layer, electrical insulation, heat resistance, and chemical resistance. In addition, in the heating process after forming a conductor layer by electroless plating, electroplating, etc., volatile components generated from the interlayer resin insulation layer have been a cause of poor adhesion of the conductor layer. No material has been found that can sufficiently solve this problem.

  In addition, with regard to the manufacture of printed wiring boards used in low-volume production models such as analytical instruments and the production of prototype printed wiring boards, images are directly printed on printed wiring boards using CAD (Computer Aided Design) data from computers. There is a need for a photosensitive composition for forming a solder resist corresponding to a direct imaging method. As a light source used for such direct imaging, a laser light source is mainly used. Ultraviolet light having a wavelength of 300 to 450 nm is used in combination with a single wavelength or a plurality of wavelengths, and a beam diameter is 5 to 15 μm. Yes, the output is about several watts. In order to draw an image by scanning with a width of 5 to 15 μm while turning on and off such laser light, the time for forming a resist pattern on one printed wiring board depends on the sensitivity of the photosensitive composition for forming a solder resist. Depends heavily on Therefore, the photosensitive composition for forming a solder resist corresponding to laser direct imaging (LDI) is required to have higher sensitivity than the photosensitive composition for forming a developing solder resist by general-purpose contact exposure.

In order to solve such a problem, there is provided a photosensitive composition in which a compound having an oxime bond is used as a photopolymerization initiator that initiates polymerization of a monomer (polymerizable compound) by generating an active radical by the action of light. It has been proposed (see Patent Documents 2 and 3). These photosensitive compositions are compared to the conventional photosensitive compositions using photopolymerization initiators such as acetophenone-based, benzophenone-based, benzoin-based, and aminoketone-based active energy rays irradiated during exposure. It reacts with high sensitivity, increases the photopolymerization rate of the monomer, increases resolution, and stably forms a cured film with excellent properties such as adhesion, solder heat resistance, and electroless plating resistance. It becomes possible to do.
However, at present, no sufficiently satisfactory photosensitive composition has yet been provided as a photosensitive composition that is sensitive enough to be compatible with LDI, and has excellent resolution and storage stability.

JP-A-1-141904 WO2004 / 048434 JP 2002-107926 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 photosensitive composition excellent in sensitivity, resolution, and storage stability, a photosensitive film, and a print on which a permanent pattern is formed by the photosensitive composition for the purpose of forming a permanent pattern such as a solder resist. An object is to provide a substrate.

Means for solving the problems are as follows. That is,
<1> (A) a carboxyl group-containing resin having one or more carboxyl groups in one molecule, (B) a polymerizable compound, (C) a photopolymerization initiator represented by the following general formula (1), and ( D) A photosensitive composition containing a thermal crosslinking agent.
However, in the general formula (1), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and these substituents may further have a substituent. m represents any integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heteroaromatic ring. A represents any of 4, 5, 6, and 7-membered rings, and each of these rings may contain a hetero atom.
<2> (A) The carboxyl group-containing resin having one or more carboxyl groups in one molecule further has one or more polymerizable unsaturated double bonds in one molecule. It is a photosensitive composition.
<3> (A) The above-mentioned <1> to <2>, wherein the (A) carboxyl group-containing resin has a carboxyl group, an aromatic group that may include a heterocycle, and an ethylenically unsaturated double bond in the side chain. It is the photosensitive composition in any one.
<4> The photosensitive composition according to <3>, wherein the content of the ethylenically unsaturated double bond in the (A) carboxyl group-containing resin is 0.5 to 3.0 meq / g.
<5> The photosensitive composition according to any one of <1> to <4>, wherein a content of the carboxyl group (A) in the carboxyl group-containing resin is 1.0 to 4.0 meq / g.
<6> (A) The photosensitive composition according to any one of <1> to <5>, wherein the carboxyl group-containing resin has a mass average molecular weight of 10,000 or more and less than 100,000.
<7> (A) The photosensitive composition according to any one of <1> to <6>, wherein the carboxyl group-containing resin contains 20 mol% or more of a structural unit represented by the following general formula (A-3). It is.
However, in said general formula (A-3), R < ₁ >, R < ₂ > and R < ₃ > represent a hydrogen atom or monovalent organic group. L represents either an organic group or a single bond. Ar represents an aromatic group.
<8> (C) The photosensitive property according to any one of <1> to <7>, wherein the photopolymerization initiator represented by the general formula (1) is a compound represented by the following general formula (2). It is a composition.
However, in the general formula (2), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and these substituents may further have a substituent. m represents any integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heteroaromatic ring. X represents either O or S. A represents either a 5- or 6-membered ring.
<9> The photosensitive composition according to <8>, wherein the photopolymerization initiator represented by the general formula (2) is a compound represented by any one of the following general formulas (3) and (4). is there.
However, in the general formulas (3) and (4), R ³ represents an alkyl group, and the alkyl group may further have a substituent. l represents an integer of 0 to 6. R ⁴ represents an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, or an acyloxy group. When l is 2 or more, the R ^{4 s} may be the same or different. May be. X represents either O or S. A represents either a 5- or 6-membered ring.
<10> Further, (CI) other photopolymerization initiator (however, (C) excluding the photopolymerization initiator represented by the general formula (1)) and (C-II) sensitizer. It is the photosensitive composition in any one of said <1> to <9> containing these.
<11> (C-II) The photosensitive composition according to <10>, wherein the sensitizer includes a hetero-fused ring compound.
<12> The photosensitive composition according to <11>, wherein the hetero-fused ring compound is a thioxanthone compound.
<13> The polymerizable compound (B) includes a compound having one or more unsaturated double bonds in one molecule, and the content of the polymerizable compound (B) is (A) a carboxyl group-containing resin 100. It is a photosensitive composition in any one of said <1> to <12> which is 2-50 mass parts with respect to a mass part.
<14> The photosensitive composition according to any one of <1> to <13>, wherein the polymerizable compound (B) includes at least one selected from monomers having a (meth) acryl group.
<15> The photosensitive composition according to any one of <1> to <14>, wherein (D) the thermal crosslinking agent is an epoxy compound having two or more epoxy groups in one molecule.
<16> At least one epoxy compound having two or more epoxy groups in one molecule is selected from a bisphenol type epoxy resin, a novolac type epoxy resin, an alicyclic group-containing type epoxy resin, and a hardly soluble epoxy resin It is the photosensitive composition as described in said <15>.
<17> The photosensitive composition according to any one of <1> to <16>, further including (E) at least one of an inorganic filler and an organic filler.

<18> A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive composition according to any one of <1> to <17> on the support. .
<19> The photosensitive film according to <18>, wherein the photosensitive layer has a thickness of 1 to 100 μm.
<20> The photosensitive film according to any one of <18> to <19>, wherein the support includes a synthetic resin and is transparent.
<21> The photosensitive film according to any one of <18> to <20>, wherein the support has a long shape.
<22> The photosensitive film according to any one of <18> to <21>, which is long and wound in a roll shape.
<23> The photosensitive film according to any one of <18> to <22>, which has a protective film on the photosensitive layer.

<24> Light irradiating means capable of irradiating light, and a photosensitive layer formed of the photosensitive composition according to any one of <1> to <17>, wherein light from the light irradiating means is modulated. And a light modulation means for performing exposure. In the pattern forming apparatus according to <24>, 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.
<25> The light modulation unit further includes a pattern signal generation unit that generates a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation unit generates light emitted from the light irradiation unit. It is a pattern formation apparatus as described in said <24> modulated according to. In the pattern forming apparatus according to <25>, 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.
<26> The light modulation means has 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 <24> to <25>, which is controllable according to pattern information. In the pattern forming apparatus according to <26>, any less than n pixel parts arranged continuously from 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.
<27> The pattern forming apparatus according to any one of <24> to <26>, wherein the light modulation unit is a spatial light modulation element.
<28> The pattern forming apparatus according to <27>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<29> The pattern forming apparatus according to any one of <26> to <28>, wherein the picture element portion is a micromirror.
<30> The pattern forming apparatus according to any one of <24> to <29>, wherein the light irradiation unit is capable of combining and irradiating two or more lights. In the pattern forming apparatus according to <30>, 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.
<31> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser light emitted from each of the plurality of lasers and couples the laser light to the multimode optical fiber. The pattern forming apparatus according to any one of <24> to <30>. In the pattern forming apparatus according to <31>, 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.

<32> A method for forming a permanent pattern, comprising at least a step of exposing a photosensitive layer formed of the photosensitive composition according to any one of <1> to <17>.
<33> After the photosensitive layer in the photosensitive film according to any one of <18> to <23> is laminated on the surface of the substrate under at least one of heating and pressurization, It is a permanent pattern formation method as described in <32> which performs exposure.
<34> The permanent pattern forming method according to any one of <32> to <33>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
<35> The method for forming a permanent pattern according to any one of <32> to <34>, wherein the exposure is performed imagewise based on pattern information to be formed.
<36> Exposure includes 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 permanent pattern forming method according to any one of <32> to <35>, wherein the exposure head is moved relative to the photosensitive layer in a scanning direction. In the method for forming a permanent pattern according to <36>, the exposure head is subjected to N multiple exposures (where N is a natural number of 2 or more) among the usable pixel parts by the used pixel part specifying means. 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.
<37> The exposure is performed by a plurality of exposure heads, and the drawing element specifying means is related to the exposure of the joint area between the heads which is the overlapping exposure area on the exposed surface formed by the plurality of exposure heads. The permanent pattern forming method according to <36>, 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 method for forming a permanent pattern according to <37>, the exposure is performed by a plurality of exposure heads, and the used image element 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 of the connection area between the heads, by specifying the picture element part used for realizing the N-fold exposure in the connection area between the heads, the mounting position of the exposure head, Variations in the 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 mounting angle deviation 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.
<38> 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 permanent pattern forming method according to <37>, wherein the drawing element portion used to realize N double exposure in an area other than the inter-head connection area among the drawing element parts is designated. In the method for forming a permanent pattern according to <38>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating means is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. Mounting of the exposure head by designating the picture element part used for realizing N double exposure in areas other than the inter-head connection area among the image element parts related to exposure other than the inter-head connection area Variations in the resolution and density unevenness of the pattern formed in areas other than the joint area between the heads on the exposed surface of the photosensitive layer due to a shift in position and mounting angle 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.
<39> When the set inclination angle θ is N, the number of N exposures, the number s of pixel parts in the column direction, the interval p in the column direction of the pixel parts, 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 <36> The method for forming a permanent pattern according to any one of <38>.
<40> The method for forming a permanent pattern according to any one of <36> to <39>, wherein N in N-exposure exposure is a natural number of 3 or more. In the permanent pattern forming method according to <40>, multiple drawing is performed when N in N-fold 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.
<41> 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;
<36> to <40>, 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 permanent pattern forming method.
<42> The permanent pattern forming method according to any one of <36> to <41>, wherein the used pixel part specifying unit specifies, in line units, the used pixel part used to realize N double exposure. It is.
<43> The fact that the light spot position detector detects the column direction of the light spot on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted based on the detected at least two light spot positions. 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 permanent pattern forming method according to any one of the above.
<44> The average 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 permanent pattern forming method according to <43>, wherein the permanent pattern forming method is one of a maximum value and a minimum value.
<45> The pixel part selection means derives a natural number T close to t that satisfies the relationship of t tan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <43> to <44> for selecting the pixel part from the first line to the T-th line in a line element (where m represents a natural number of 2 or more) arranged as a used pixel part The permanent pattern forming method according to any one of the above.
<46> The pixel part selection means derives a natural number T close to t that satisfies the relationship of t tan 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 permanent pattern forming method according to any one of <43> to <45>, wherein the pixel part excluding the element part is selected as a use pixel part.
<47> 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 <41>, which is one of means for selecting a used pixel portion so that an area of an underexposed region is minimized and an overexposed region is not generated with respect to a typical N double exposure. It is the permanent pattern formation method as described in <46>.
<48> In the connecting 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 method for forming a permanent pattern according to any one of <41> to <47>.
<49> The permanent pattern forming method according to <48>, wherein the unused pixel parts are specified in units of rows.
<50> In order to specify the used pixel part in the used pixel part specifying unit, among the usable pixel elements, N (n-1) pixel element columns for N multiple exposures The permanent pattern forming method according to any one of <36> to <49>, wherein the reference exposure is performed using only the image element portion constituting the. In the permanent pattern forming method according to <50>, in order to specify a used pixel part in the used pixel part specifying unit, among the usable pixel parts, 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.
<51> In order to specify a used pixel part in the used pixel part specifying means, among the usable pixel parts, a N / N line pixel part row is configured for N of N multiple exposures. The permanent pattern forming method according to any one of <36> to <50>, wherein the reference exposure is performed using only the picture element portion. In the permanent pattern forming method according to <51>, in order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, N is set to 1 for N double exposure. / 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.
<52> From the above <36> to <51>, 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 permanent pattern forming method according to any one of the above.
<53> The method for forming a permanent pattern according to any one of <36> to <52>, wherein N of N-exposure is a natural number of 3 or more and 7 or less.
<54> 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. The method for forming a permanent pattern according to any one of <36> to <53>, wherein the modulation is performed according to the method. In the pattern forming apparatus according to <54>, 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.
<55> The permanent pattern forming method according to any one of <36> to <54>, wherein the light modulation unit is a spatial light modulation element.
<56> The method for forming a permanent pattern according to <55>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<57> The permanent pattern forming method according to any one of <36> to <56>, wherein the picture element portion is a micromirror.
<58> From the above <36> to <36> 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 57>. The method for forming a permanent pattern according to any one of the above.
<59> The permanent pattern forming method according to any one of <36> to <58>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the method for forming a permanent pattern according to <59>, the light irradiation means can synthesize and irradiate two or more lights, so that exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<60> 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 permanent pattern forming method according to any one of <36> to <59>. In the method for forming a permanent pattern according to <60>, the light irradiating means can collect the laser light respectively emitted from the plurality of lasers by the collective optical system and be coupled to the multimode optical fiber. As a result, exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<61> The permanent pattern forming method according to any one of <32> to <60>, wherein the photosensitive layer is developed after the exposure. In the method for forming a permanent pattern described in <61>, a high-definition pattern is formed by developing the photosensitive layer after the exposure.
<62> The method for forming a permanent pattern according to <61>, wherein a permanent pattern is formed after development.
<63> The method for forming a permanent pattern according to <62>, wherein after the development, the photosensitive layer is cured.
<64> The method for forming a permanent pattern according to <63>, wherein the curing treatment is at least one of a whole surface exposure treatment and a whole surface heat treatment performed at 120 to 200 ° C.
<65> The permanent pattern formation method according to any one of <63> to <64>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed. In the permanent pattern forming method according to <65>, at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed. Protected from impact and bending.

<66> A printed circuit board having a permanent pattern formed using the photosensitive composition according to any one of <1> to <17>.
<67> The printed circuit board according to <66>, wherein the permanent pattern is formed by the permanent pattern forming method according to any one of <32> to <65>.

  According to the present invention, there are provided a photosensitive composition, a photosensitive film, and a printed board on which a permanent pattern can be formed by the photosensitive composition, which can solve conventional problems and is excellent in sensitivity, resolution, and storage stability. can do.

(Photosensitive composition)
The photosensitive composition of the present invention comprises (A) a carboxyl group-containing resin having one or more carboxyl groups in one molecule, (B) a polymerizable compound, and (C) a photopolymerization represented by the general formula (1). An initiator, and (D) a thermal crosslinking agent, preferably (CI) other photopolymerization initiator, (C-II) sensitizer, (E) inorganic filler and organic filler Or, if necessary, other components.

<(A) Carboxyl group-containing resin (binder) having one or more carboxyl groups in one molecule>
The carboxyl group-containing resin (A) having one or more carboxyl groups in one molecule (hereinafter sometimes simply referred to as “carboxyl group-containing resin (A)”) is insoluble in water and is alkaline. A compound that swells or dissolves in an aqueous solution is preferred.
The carboxyl group-containing resin (A) is not particularly limited as long as it has one or more carboxyl groups in one molecule. However, the carboxyl group and the polymerizable unsaturated double can be contained in one molecule. It is preferable to have at least one bond. Examples of the unsaturated double bond include various polymerizable double bonds such as acrylic group (for example, (meth) acrylate group, (meth) acrylamide group), vinyl ester of carboxylic acid, vinyl ether, allyl ether and the like. It is done. As such a carboxyl group-containing resin having at least one carboxyl group and polymerizable unsaturated double bond in one molecule, more specifically, an acrylic resin containing a carboxyl group, Cyclic ether group-containing polymerizable compounds (for example, glycidyl acrylate; glycidyl methacrylate; glycidyl esters of unsaturated fatty acids such as cinnamic acid; compounds having an alicyclic epoxy group (for example, cyclohexene oxide) and a (meth) acryloyl group; And the like). In addition, compounds obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing a carboxyl group and a hydroxyl group are also included.
Examples of these compounds include compounds described in Japanese Patent No. 2763775, Japanese Patent Application Laid-Open No. 3-172301, Japanese Patent Application Laid-Open No. 2000-232264, and the like.

Among these compounds, as the carboxyl group-containing resin (A), among the above-mentioned compounds, a cyclic ether group (for example, a group having an epoxy group or an oxetane group in a partial structure) is contained in a part of the carboxyl group. It is more preferable that the polymer is selected from any of those obtained by adding a compound and those obtained by adding a carboxyl group-containing polymerizable compound to a part or all of the cyclic ether group. At this time, the addition reaction between the carboxyl group and the compound having a cyclic ether group is preferably carried out in the presence of a catalyst. In particular, the catalyst is preferably selected from an acidic compound and a neutral compound.
Among these, from the viewpoint of the development stability of the photosensitive composition over time, the carboxyl group-containing resin (A) includes, as the side chain, a carboxyl group, an aromatic group that may contain a heterocyclic ring, and an ethylenic group. Those containing a saturated bond are preferred.

-Carboxyl group-
The carboxyl group can be produced by a normal radical polymerization method using at least one radical polymerizable compound having an acid group and, if necessary, at least one other radical polymerizable compound as a copolymerization component. Examples of the polymerization method include suspension polymerization method and solution polymerization method.
Examples of the acid group possessed by such a radical polymerizable compound include carboxylic acid, sulfonic acid, and phosphoric acid group, and carboxylic acid is particularly preferable.
The radical polymerizable compound having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p -Carboxylstyrene etc. are mentioned, Among these, acrylic acid, methacrylic acid, and p-carboxylstyrene are preferable. These may be used individually by 1 type and may use 2 or more types together.

The carboxyl group content in the carboxyl group-containing resin (A) is 1.0 to 4.0 meq / g, preferably 1.5 to 3.0 meq / g. If the content is less than 1.0 meq / g, the developability may be insufficient, and if it exceeds 4.0 meq / g, the image strength may be easily damaged by alkaline water development.
Here, the carboxyl group content (meq / g) can be measured by neutralization titration using sodium hydroxide.

-Aromatic group which may contain a heterocycle-
Examples of the aromatic group that may contain a heterocycle (hereinafter, also simply referred to as “aromatic group”) include, for example, a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, benzene And those in which a ring and a 5-membered unsaturated ring form a condensed ring.
Specific examples of the aromatic group include phenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, fluorenyl group, benzopyrrole ring group, benzofuran ring group, benzothiophene ring group, pyrazole ring group, isoxazole. Ring group, isothiazole ring group, indazole ring group, benzisoxazole ring group, benzisothiazole 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, acylidine ring group, phenanthridine ring group, carbazole ring Group, purine ring group, pyran ring group, Lysine ring group, a piperazine ring group, an indole ring group, an indolizine ring group, a chromene ring group, a cinnoline ring group, an acridine ring group, a phenothiazine ring group, a tetrazole ring group, such as a triazine ring group. Among these, a hydrocarbon aromatic group is preferable, and a phenyl group and a naphthyl group are more preferable.

  The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, 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 aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, and the like, each of which may have a substituent, may be mentioned.

Examples of the alkyl group include linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups, and cyclic alkyl groups.
Specific examples of the alkyl group include 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, 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 preferable.

Examples of the substituent that the alkyl group may have include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. Specific examples of such substituents include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, and alkyldithio groups. , 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, carbamoyl Oxy group, N-alkylcarbamoyloxy 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 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 ', 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, 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, carboxyl 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, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo Group (—SO ₃ H) and its conjugate base group (referred to as sulfonate 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-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (referred to as phosphonato group) ), A dialkylphosphono group (—PO ₃ (alkyl) ₂ ) (hereinafter “alkyl” is an alkyl group) Means. ), A diarylphosphono group (—PO ₃ (aryl) ₂ ) (hereinafter “aryl” means an aryl group), an alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphone 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) ), A phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as a phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (aryl)) ) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphonates Oxy group _(-OPO 3 H (alkyl)) and its conjugated base group (referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugate base (aryl phosphite Hona preparative oxy Group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

  Specific examples of the alkyl group as a substituent that the alkyl group may have include the aforementioned alkyl groups.

  Specific examples of the aryl group as the substituent which the alkyl group may have 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 chlorophenyl group, Methylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetyl Aminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulfonatof Group, phosphono phenyl group, such as phosphate Hona preparative phenyl group.

  Specific examples of the alkenyl group as a substituent that the alkyl group may have include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, and a 2-chloro-1-ethenyl group.

  Specific examples of the alkynyl group as a substituent that the alkyl group may have include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group.

Examples of the acyl group (R ⁰¹ CO—) as a substituent that the alkyl group may have include those in which R ⁰¹ is any one of a hydrogen atom, the aforementioned alkyl group, and an aryl group. It is done.

  Specific examples of the heterocyclic group as a substituent that the alkyl group may have include a pyridyl group, a piperidinyl group, and the silyl group in the substituent includes a trimethylsilyl group.

Examples of the oxy group (R ⁰² O—) as a substituent that the alkyl group may have include those in which R ⁰² is a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. .
Examples of such oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N- A diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, phosphonooxy group, phosphonatoxy group and the like are preferable.
Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Further, examples of the acyl group (R ⁰³ CO—) in the acyloxy group include those in which R ⁰³ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group mentioned as the previous example. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable.
Specific examples of more preferred oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, 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, chlorophenyl Alkoxy group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, a phosphonatooxy group.

Examples of the sulfonyl group (R ⁰⁴ —SO ₂ —) as a substituent that the alkyl group may have include a group in which R ⁰⁴ is a monovalent nonmetallic atomic group.
As such a sulfonyl group, for example, an alkylsulfonyl group, an arylsulfonyl group, and the like are preferable. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
Specific examples of the sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, and a chlorophenylsulfonyl group.

The sulfonate group (—SO ₃ —) as a substituent that the alkyl group may have means a conjugate base anion group of the sulfo group (—SO ₃ H) as described above, and is usually a counter cation. It is preferably used with.
As such counter cations, generally known ones can be appropriately selected and used. For example, oniums (for example, ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), metal ions (For example, Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^{2+ and the} like).

Examples of the carbonyl group (R ⁰⁵ —CO—) as a substituent that the alkyl group may have include those in which R ⁰⁵ is a group composed of a monovalent nonmetallic atomic group.
Examples of such carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, and N-arylcarbamoyl group. N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group and the like. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
As the carbonyl group, a formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, and N-arylcarbamoyl group are preferable. A group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group are more preferable.
Specific examples of the carbonyl group include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, aryloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N- A methylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-diethylcarbamoyl group, a morpholinocarbonyl group and the like are preferable.

Examples of the sulfinyl group (R ⁰⁶ —SO—) as a substituent that the alkyl group may have include those in which R ⁰⁶ is 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 -Diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, etc. are mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, an alkylsulfinyl group and an arylsulfinyl group are preferable.
Specific examples of the substituted sulfinyl group include hexylsulfinyl group, benzylsulfinyl group, tolylsulfinyl group and the like.

The phosphono group as a substituent that the alkyl group may have means one in which one or two hydroxyl groups on the phosphono group are substituted with another organic oxo group. Group, diarylphosphono group, alkylarylphosphono group, monoalkylphosphono group, monoarylphosphono group and the like are preferable. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred.
More preferred specific examples of the phosphono group include a diethylphosphono group, a dibutylphosphono group, a diphenylphosphono group, and the like.

The phosphonate group (—PO ₃ H ₂ —, —PO ₃ H—) as a substituent that the alkyl group may have is, as described above, the acid first of the phosphono group (—PO ₃ H ₂ ). It means a conjugated base anion group derived from dissociation or acid second dissociation. Usually, it is preferable to use it with a counter cation. As such counter cations, generally known ones can be appropriately selected. For example, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).
The phosphonato group may be a conjugated base anion group obtained by substituting one organic oxo group in the phosphono group. Specific examples thereof include the monoalkylphosphono group (—PO ₃ H (alkyl)) and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

  Among these 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, carboxyl 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-aryls Famoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphospho A nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, an alkenyl group and the like are preferable.

  Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkyl 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 N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxy Carbonylmethyl 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- (phosphonophene) L) Sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples include propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

On the other hand, examples of the aryl group as a substituent that the aromatic group may have include, for example, a benzene ring, a ring in which 2 to 3 benzene rings form a condensed ring, a benzene ring and a 5-membered unsaturated group. Examples include those in which a ring forms a condensed ring.
Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. In these, a phenyl group and a naphthyl group are preferable.
The aryl group may have a substituent. Examples of the aryl group having such a substituent (hereinafter sometimes referred to as “substituted aryl group”) include, for example, the ring-forming carbon of the aforementioned aryl group. The thing which has group which consists of monovalent nonmetallic atomic groups other than a hydrogen atom as a substituent on an atom is mentioned.
As the substituent that the aryl group may have, for example, the above-described alkyl group, substituted alkyl group, and the substituents that the alkyl group may have are preferable.

  Preferred 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, Nyl group, methoxycarbonylphenyl 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-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methyl Phosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

Examples of the alkenyl group or alkynyl group as a substituent that the aromatic group may have include, for example, any one or two hydrogen atoms on the alkyl group having 1 to 20 carbon atoms described above. And a divalent or trivalent organic residue, for example, a straight-chain alkenyl group or alkynyl group having 1 to 12 carbon atoms, or a branched structure having 3 to 12 carbon atoms. Are preferably an alkenyl group or alkynyl group, a cyclic alkenyl group or alkynyl group having 5 to 10 carbon atoms.
Examples of the alkenyl group (—C (R ⁰⁷ ) ═C (R ⁰⁸ ) (R ⁰⁹ )) and the alkynyl group (—C≡C (R ⁰¹⁰ )) include, for example, R ⁰⁷ , R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ is a group composed of a monovalent nonmetallic atomic group.
Examples of R ⁰⁷ , R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Specific examples thereof include those shown as the above examples. 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 the alkenyl group and alkynyl group include a vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 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, phenyl Examples include an ethynyl group.
As said heterocyclic group, the pyridyl group illustrated as a substituent of a substituted alkyl group etc. are mentioned, for example.

Examples of the amino group (R ⁰¹¹ NH—, (R ⁰¹² ) (R ⁰¹³ ) N—) that may contain a substituent as the substituent that the aromatic group may have include, for example, R ⁰¹¹ , R ⁰¹² and R ⁰¹³ may be a group consisting of a monovalent nonmetallic atomic group excluding a hydrogen atom. R ⁰¹² and R ⁰¹³ may be bonded to form a ring.
Examples of the amino group include N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, 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 ', N'- Alkyl-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, aryloxycarbonylamino Group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group and the like. It is done. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Also, ^{R 03} acylamino group, N- alkylacylamino group, N- arylacylamino group definitive acyl group ^(R 03 CO-) are as defined above. Of these, an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group are more preferable.
Specific examples of preferred amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

The method for introducing the aromatic group into the side chain is not particularly limited. For example, the polymer containing a carboxyl group in the side chain described above and one or more radically polymerizable compounds containing an aromatic group, As needed, it can manufacture by the normal radical polymerization method with 1 or more types of other radically polymerizable compounds as a copolymerization component.
Examples of the radical polymerization method generally include a suspension polymerization method and a solution polymerization method.

As the radically polymerizable compound containing an aromatic group, for example, a compound represented by the general formula (A-1) and a compound represented by the general formula (A-2) are preferable.
However, in said general formula (A-1), R < ₁ >, R < ₂ > and R < ₃ > represent a hydrogen atom or monovalent organic group. L represents either an organic group or a single bond. Ar represents an aromatic group that may include a heterocycle.
However, in said general formula (A-2), R < ₁ >, R < ₂ >, R < ₃ > and Ar represent the same meaning as the said general formula (A-1).

The organic group of L is, for example, a polyvalent organic group composed of non-metallic atoms, and includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 oxygen atoms. Those consisting of atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms.
More specifically, examples of the organic group of L include those formed by combining the following structural units, polyvalent naphthalene, and polyvalent anthracene.

  The L linking group may have a substituent, and examples of the substituent include the aforementioned halogen atom, hydroxyl group, carboxyl group, sulfonate group, nitro group, cyano group, amide group, amino group, alkyl group, Examples include alkenyl groups, alkynyl groups, aryl groups, substituted oxy groups, substituted sulfonyl groups, substituted carbonyl groups, substituted sulfinyl groups, sulfo groups, phosphono groups, phosphonato groups, silyl groups, and heterocyclic groups.

In the compound represented by the general formula (A-1) and the compound represented by the general formula (A-2), the general formula (A-1) is preferable in terms of sensitivity. Of the general formula (A-1), those having a linking group are preferable from the viewpoint of stability, and the organic group of L is an alkylene group having 1 to 4 carbon atoms in the non-image area. It is preferable in terms of removability (developability).
When the compound represented by the general formula (A-1) is polymerized, it becomes a polymer including a structural unit represented by the following general formula (A-3). Moreover, the compound represented by the said general formula (A-2) becomes a polymer containing the structural unit of the following general formula (A-4). Among these, the polymer containing the structural unit of the general formula (A-4) is preferable from the viewpoint of storage stability.

However, in the general formulas (A-3) and (A-4), R ₁ , R ₂ , R ₃ , L, and Ar have the same meanings as the general formulas (A-1) and (A-2). Represents.
In the general formulas (A-3) and (A-4), R ₁ and R ₂ are preferably a hydrogen atom, and R ₃ is preferably a methyl group, from the viewpoint of removability (developability) of a non-image area.
Further, L in the general formula (A-3) is preferably an alkylene group having 1 to 4 carbon atoms in terms of removability (developability) of non-image areas.

  The compound represented by the general formula (A-1) or the compound represented by the general formula (A-2) is not particularly limited, and examples thereof include the following exemplary compounds (1) to (30). It is done.

  Among the exemplary compounds (1) to (30), (5), (6), (11), (14), and (28) are preferable, and among these, (5) and (6) are storage stable. Is more preferable from the viewpoints of colorability and developability.

  The content of the aromatic group that may contain a heterocycle in the carboxyl group-containing resin (A) is not particularly limited, but when the total structural unit of the carboxyl group-containing resin (A) is 100 mol%, It is preferable to contain 20 mol% or more of the structural unit represented by the general formula (A-3), and it is more preferable to contain 30 to 45 mol%. When the content is less than 20 mol, storage stability may be lowered, and when it exceeds 45 mol%, developability may be lowered.

-Ethylenically unsaturated bond-
There is no restriction | limiting in particular as said ethylenically unsaturated bond, Although it can select suitably according to the objective, For example, what is represented by either of the following general formula (A-5)-(A-7) Is preferred.

In the general formula (A-5) ~ (A -7), R 1 ~R 11 independently represents a hydrogen atom, a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R ₄ . Z represents an oxygen atom, a sulfur atom, —N—R ₄ , or a phenylene group. R ₄ represents a hydrogen atom or a monovalent organic group.

In the general formula (A-5), as R ₁ , for example, a hydrogen atom or an optionally substituted alkyl group is preferable, and the hydrogen atom or methyl group has high radical reactivity. This is more preferable.
R ₂ and R ₃ are each independently, for example, a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl which may have a substituent. Group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like, such as a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent An alkyl group that may have a substituent and an aryl group that may have a substituent are more preferable because of high radical reactivity.
As R ₄ , for example, a hydrogen atom, an alkyl group which may have a substituent, and the like are preferable, and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are more preferable because of high radical reactivity.
Here, examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group, an arylamino group, a carboxyl group, and an alkoxy group. Examples include carbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group and the like.

In the general formula (A-6), R _{4 to} R ₈ are each independently, for example, a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, or a nitro group. , A cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, substituted An alkylamino group which may have a group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like are preferable, A hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.
Examples of the substituent that can be introduced include those listed in the general formula (A-5).

In the general formula (A-7), as R ₉ , for example, a hydrogen atom, an alkyl group which may have a substituent, and the like are preferable, and a hydrogen atom and a methyl group are more preferable because of high radical reactivity.
R ₁₀ and R ₁₁ each independently have, for example, a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or a substituent. An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino which may have a substituent Group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like are preferable, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable because of high radical reactivity.
Here, as the substituent which can be introduced, those exemplified in the general formula (A-5) are exemplified.
Z represents an oxygen atom, a sulfur atom, —NR ₁₃ —, or a phenylene group which may have a substituent. R ₁₃ represents an alkyl group which may have a substituent, and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

Among the ethylenically unsaturated bonds represented by the general formulas (A-5) to (A-7), the ethylenically unsaturated bond represented by the general formula (A-5) has high polymerization reactivity. Sensitivity is increased, which is more preferable.
The content of the ethylenically unsaturated bond in the carboxyl group-containing resin (A) is not particularly limited, but is preferably 0.5 to 3.0 meq / g, more preferably 1.0 to 3.0 meq / g. 1.5 to 2.8 meq / g is particularly preferable. When the content is less than 0.5 meq / g, the curing reaction amount is small, so that the sensitivity may be low. When the content is more than 3.0 meq / g, the storage stability may be deteriorated.
Here, the content (meq / g) can be measured by, for example, iodine value titration.

  The method for introducing the ethylenically unsaturated bond represented by the general formula (A-5) into the side chain is not particularly limited. For example, the polymer containing a carboxyl group in the side chain described above and the ethylenically unsaturated bond are not limited. It can be obtained by addition reaction with a compound having a saturated bond and an epoxy group.

The compound having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these, but for example, a compound represented by any one of the following general formulas (A-8) and (A-9) Compounds are preferred.
However, in said general formula (A-8), R < ₁ > represents a hydrogen atom or a methyl group. L ₁ represents an organic group.
In the general formula (A-9), _{R 2} represents a hydrogen atom or a methyl group. L ₂ represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.
Of the compound represented by the general formula (A-8) and the compound represented by the general formula (A-9), the compound represented by the general formula (A-8) is preferable, and the general formula (A- In 8), L ₁ is more preferably an alkylene group having 1 to 4 carbon atoms.

The compound represented by the general formula (A-8) or the compound represented by the general formula (A-9) is not particularly limited, and examples thereof include the following exemplary compounds (31) to (40). It is done.

  Specific examples of the introduction reaction to the side chain include tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, and tetraethylammonium chloride, pyridine, and triphenyl. The reaction can be performed by reacting phosphine or the like in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours.

Although there is no restriction | limiting in particular as a structural unit which has an ethylenically unsaturated bond in the said side chain, For example, the structural unit represented by the following general formula (A-10), represented by general formula (A-11) Structural units and structural units synthesized by mixing these are preferred.
However, in said general formula (A-10) and (A-11), Ra-Rc represents a hydrogen atom or monovalent organic group. R ₁ represents a hydrogen atom or a methyl group. L ₁ represents an organic group that may have a linking group.

  Although there is no restriction | limiting in particular as content of the structural unit represented by the structure thru | or the general formula (A-11) represented by the said general formula (A-10), All the structural units of carboxyl group-containing resin (A) Is preferably 20 mol% or more, more preferably 20 to 50 mol%, particularly preferably 25 to 45 mol%. When the content is less than 20 mol%, the curing reaction amount is small, so that the sensitivity may be low. When the content is more than 50 mol%, the storage stability may be deteriorated.

The carboxyl group-containing resin (A) of the present invention is preferably further copolymerized with another radical polymerizable compound in addition to the above-mentioned radical polymerizable compound for the purpose of improving various performances such as image strength.
Examples of the other radical polymerizable compounds include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.

Specific examples include acrylic acid esters such as alkyl acrylate, methacrylic acid esters such as aryl acrylate and alkyl methacrylate, styrenes such as aryl methacrylate, styrene and alkyl styrene, alkoxy styrene, and halogen styrene.
As the acrylate esters, alkyl groups having 1 to 20 carbon atoms are preferable. For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate Octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl Examples thereof include acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like.
Examples of the aryl acrylate include phenyl acrylate.

As the methacrylic acid esters, those having 1 to 20 carbon atoms in the alkyl group are preferable. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl. Methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydro And furfuryl methacrylate.
Examples of the aryl methacrylate include phenyl methacrylate, cresyl methacrylate, and naphthyl methacrylate.

Examples of the styrenes include methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, and trifluoromethyl. Examples thereof include styrene, ethoxymethyl styrene, acetoxymethyl styrene and the like.
Examples of the alkoxystyrene include methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene and the like.
Examples of the halogen styrene include chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, and 2-bromo-4-. Examples include trifluoromethyl styrene and 4-fluoro-3-trifluoromethyl styrene.
These radically polymerizable compounds may be used individually by 1 type, and may use 2 or more types together.

  There is no restriction | limiting in particular as a solvent used when synthesize | combining the carboxyl group-containing resin (A) of this invention, According to the objective, it can select suitably, For example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, Ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N -Dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate and the like. These may be used alone or in combination of two or more.

The molecular weight of the carboxyl group-containing resin (A) of the present invention is preferably 10,000 or more and less than 100,000, and more preferably 10,000 to 50,000 in terms of mass average molecular weight. If the mass average molecular weight is less than 10,000, the cured film strength may be insufficient, and if it is less than 100,000, developability tends to be lowered.
Further, the carboxyl group-containing resin (A) of the present invention may contain an unreacted monomer. In this case, the content of the monomer in the carboxyl group-containing resin (A) is preferably 15% by mass or less.

The carboxyl group-containing resin (A) according to the present invention may be used alone or in combination of two or more.
As content of the said carboxyl group containing resin (A), 5-80 mass% is preferable with respect to the total solid in a photosensitive composition, and 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 80% by mass, the exposure sensitivity is increased. May decrease.

<(B) Polymerizable compound>
There is no restriction | limiting in particular as said polymeric compound (B), Although it can select suitably according to the objective, It is preferable that it has at least 1 unsaturated double bond in 1 molecule, for example, Suitable examples include at least one selected from monomers having a (meth) acrylic group. Moreover, the compound whose boiling point is 100 degreeC or more at normal pressure is preferable.

  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.

  As content of the said polymeric compound (B), 2-50 mass parts is preferable when content of the said carboxyl group-containing resin (A) is 100 mass parts, and 10-35 mass parts is more preferable. When the content is less than 2 parts by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and when it exceeds 50 parts by mass, the adhesiveness of the photosensitive layer may become too strong. It is not preferable.

<(C) Photopolymerization initiator>
The photopolymerization initiator (C) is an oxime compound represented by the following general formula (1).
However, in the general formula (1), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and these substituents may further have a substituent. m represents any integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heteroaromatic ring. A represents any of 4, 5, 6, and 7-membered rings, and each of these rings may contain a hetero atom.

Among the oxime compounds represented by the general formula (1), a compound represented by the following general formula (2) is more preferable, and a compound represented by any one of the following general formulas (3) and (4) is particularly preferable. preferable.
However, in the general formula (2), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and these substituents may further have a substituent. m represents any integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heteroaromatic ring. X represents either O or S. A represents either a 5- or 6-membered ring.
However, in the general formulas (3) and (4), R ³ represents an alkyl group, and the alkyl group may further have a substituent. l represents an integer of 0 to 6. R ⁴ represents an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, or an acyloxy group. When l is 2 or more, the R ^{4 s} may be the same or different. May be. X represents either O or S. A represents either a 5- or 6-membered ring.

In the general formulas (1) and (2), the acyl group represented by R ¹ may be aliphatic, aromatic or heterocyclic, and may further have a substituent.
Examples of the aliphatic acyl group include an acetyl group, a propanoyl group, a butanoyl group, a hexanoyl group, a decanoyl group, a phenoxyacetyl group, and a chloroacetyl group. Examples of the aromatic acyl group include a benzoyl group, a naphthoyl group, a methoxybenzoyl group, and a nitrobenzoyl group. Examples of the heterocyclic acyl group include a furanoyl group and a thiophenoyl group. As the substituent, any of an alkoxy group, an aryloxy group, and a halogen atom is preferable.
As said acyl group, a C2-C30 thing is preferable, A C2-C20 thing is more preferable, A C2-C16 thing is especially preferable. Examples of the acyl group include acetyl group, propanoyl group, methylpropanoyl group, butanoyl group, pivaloyl group, hexanoyl group, cyclohexanecarbonyl group, octanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, benzylcarbonyl Group, phenoxyacetyl group, 2-ethylhexanoyl group, chloroacetyl group, benzoyl group, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, pyridylcarbonyl group, furanoyl group, A thiophenoyl group, a methacryloyl group, an acryloyl group, and the like can be given.

In the general formulas (1) and (2), the alkyloxycarbonyl group represented by R ¹ may have a substituent, and is preferably an alkoxycarbonyl group having 2 to 30 carbon atoms in total. Those having 2 to 20 carbon atoms are more preferable, and those having 2 to 16 carbon atoms are particularly preferable. Examples of such alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, aryloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, ethoxyethoxycarbonyl group. , Etc.

In the general formulas (1) and (2), the aryloxycarbonyl group represented by R ¹ may have a substituent, and is preferably an alkoxycarbonyl group having 7 to 30 carbon atoms in total. Those having a number of 7 to 20 are more preferable, and those having a total carbon number of 7 to 16 are particularly preferable. Examples of such aryloxycarbonyl groups include phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5-diethoxyphenoxycarbonyl group, parachlorophenoxycarbonyl group, paranitrophenoxycarbonyl group. And paracyanophenoxycarbonyl group.

In the general formulas (1) and (2), the substituent represented by R ² is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, an acyloxy group, and a nitro group. Group, acylamino group, and the like. Among these, any of an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, and an acyloxy group is preferable.

Here, specific examples of the oxime compound represented by the general formula (1) include compounds represented by the following structural formulas (1) to (54). However, the present invention is not limited to these. It is not something.
However, in the structural formulas (1) to (54), Me represents a methyl group. Ph represents a phenyl group. Ac represents an acetyl group.

The said photoinitiator (C) may be used individually by 1 type, and may use 2 or more types together.
As content of the said photoinitiator (C), 0.001-30 mass% is preferable with respect to the total solid in the said photosensitive composition, 0.01-20 mass% is more preferable, 0 5 to 10% by mass is particularly preferable. When the content is less than 0.01% by mass, sufficient curing sensitivity may not be obtained, and when it exceeds 30% by mass, developability and storage stability may be adversely affected.

  When the photopolymerization initiator (C) uses an alkali development type photosensitive composition containing the same on a copper foil, a copper ion, which is a strong Lewis acid, is generated by carboxyl groups and moisture at the copper foil interface. There are things to do. Such a Lewis acid may decompose the photopolymerization initiator (C) and cause an undercut in the coated film after exposure and development. Therefore, the photosensitive composition of the present invention comprises the photopolymerization initiator (C) and other photopolymerization initiators (CI) and sensitizers (C) other than the photopolymerization initiator (C) described later. -II) is preferably used together.

-(CI) Other photopolymerization initiators-
The other photopolymerization initiator (CI) 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, those having photosensitivity to visible light from the ultraviolet region are preferable, and may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, depending on the type of monomer. It may be an initiator that initiates cationic polymerization.
The other photopolymerization initiator (CI) 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). It is preferable.

Examples of the other photopolymerization initiator (CI) include, for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, and organic peroxides. , Thio compounds, ketone compounds, acridine compounds, metallocenes, and the like. Specific examples include compounds described in JP-A-2005-258431. Among these, ketone compounds and acridine compounds are preferable from the viewpoints of the sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the substrate.
These compounds may be used alone or in combination of two or more.

  As content of the said other photoinitiator (CI), 0.1-30 mass% is preferable with respect to the total solid in a photosensitive composition, and 0.5-20 mass% is more. 0.5 to 15% by mass is preferable.

-(C-II) sensitizer-
The sensitizer (C-II) improves 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 when the photosensitive layer is exposed and developed. Have the effect of
The sensitizer (C-II) can be appropriately selected according to the light irradiation means (for example, visible light, ultraviolet light, and visible light laser).
The sensitizer (C-II) is excited by active energy rays and interacts (eg, energy transfer, electron transfer, etc.) with other substances (eg, radical generator, acid generator, etc.). It is possible to generate useful groups such as radicals and acids.
Examples of the sensitizer (C-II) include condensed ring compounds, aminophenyl ketone compounds, polynuclear aromatics, those having an acidic nucleus, those having a basic nucleus, those having a fluorescent brightener nucleus. It contains at least one selected, and may contain other sensitizers as necessary. Among these, a hetero-fused compound and an aminobenzophenone compound are preferable in terms of improving sensitivity, and a hetero-fused compound is particularly preferable.

-Heterocyclic ring compound-
The hetero-fused ring compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. Examples of the hetero-fused ring compound include a hetero-fused ring ketone compound. Of the hetero-fused ketone compounds, acridone compounds and thioxanthone compounds are more preferred, and among these, thioxanthone compounds are particularly preferred.
Specific examples of the hetero-fused ketone compound include an acridone compound such as acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone; thioxanthone, Thioxanthone compounds such as isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, QuantacureQTX; 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′-carboni Rubis (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, 7-diethylamino-4-methylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-2002 Coumarins such as coumarin compounds described in Japanese Patent No. 363209; Can be mentioned.
Also known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, thiacarbocyanine, oxacarbanine) Cyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), anthraquinones (for example, anthraquinone), squalium (for example, squalium), and the like.

As content of the said sensitizer (C-II), 0.01-4 mass% is preferable with respect to all the components of a photosensitive composition, 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.

The mass ratio of the content of the sensitizer (C-II) and the content of the photopolymerization initiator (C) in the photosensitive composition is [sensitizer (C-II) / photopolymerization initiator]. (C)] = 1 / 0.1 to 1/100, preferably 1/1 to 1/50.
If the mass ratio between the content of the sensitizer (C-II) and the content of the photopolymerization initiator (C) is outside the above range, the sensitivity is lowered and the sensitivity changes with time. May get worse.

<(D) Thermal crosslinking agent>
The thermal cross-linking agent (D) is not particularly limited as long as it is a compound that causes a cross-linking reaction upon heating, and can be appropriately selected according to the purpose. Photosensitivity formed using the photosensitive composition In order to improve the film strength after curing of the layer, for example, an epoxy compound having at least two epoxy groups (oxirane ring) in one molecule (oxirane compound), one molecule within a range that does not adversely affect developability and the like An oxetane compound having at least two oxetane rings can be used. Among these, an epoxy compound having at least two epoxy groups in one molecule is particularly preferable.

  Examples of the epoxy compound having at least two epoxy 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 resins, novolac type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenols 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, odor Phenol novolac type epoxy resin), 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 resins (diaminodiphenylmethane type epoxy resins, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resins (phthalic acid diglycidyl ester) Adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) hydantoin type epoxy resin, alicyclic epoxy resin (3,4 Poxycyclohexylmethyl-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.”), a polyphenol compound obtained by an addition reaction between a phenol compound and a diolefin compound such as divinylbenzene or dicyclopentadiene, Reaction product with epichlorohydrin, ring-opening polymer of 4-vinylcyclohexene-1-oxide epoxidized with peracetic acid, epoxy resin having linear phosphorus-containing structure, epoxy resin having cyclic phosphorus-containing structure, α- Methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type 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.

The epoxy group in the epoxy compound having at least two epoxy groups in one molecule may have an alkyl group at the β-position, and an epoxy group in which the β-position is substituted with an alkyl group (more specifically, Are particularly preferably β-alkyl-substituted glycidyl group and 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 preferable from the viewpoint of improving the storage stability of the photosensitive composition and the viewpoint of 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 Carbon number of 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 C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate such as 1-10 monoalkyl-substituted phenol-formaldehyde polycondensate, xylenol-formaldehyde polycondensate, bisphenol A-formal Hydrate 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 general formula (C-1), a β-alkyl glycidyl ether derived from a polymer obtained from this compound and epichlorohydrin, and the following general formula (C-2) Poly-β-alkyl glycidyl ether of a phenol compound-formaldehyde polycondensate represented by
However, in said general formula (C-1), R represents either a hydrogen atom and a C1-C6 alkyl group. n represents an integer of 0 to 20.
However, in said general formula (C-2), R represents either a hydrogen atom and a C1-C6 alkyl group. R ″ represents either a hydrogen atom or CH ₃ , and n represents an integer of 0 to 20.
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 epoxy groups (oxirane ring) in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

  The skeleton of the epoxy compound is preferably at least one selected from a bisphenol type epoxy resin, a novolac type epoxy resin, an alicyclic group-containing type epoxy resin, and a hardly soluble epoxy resin.

  Examples of the epoxy compound having at least two oxetane rings in one molecule include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether and 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) Multifunctionals such as methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof In addition to oxetanes, compounds having an oxetane group and novola Resin, poly (p-hydroxystyrene), cardo type bisphenols, calixarenes, calixresorcinarenes, silsesquioxanes and other ether compounds, and other ether compounds. And a copolymer of an unsaturated monomer having an alkyl group and an alkyl (meth) acrylate.

  As content of the said thermal crosslinking agent (D), 1-50 mass% is preferable with respect to the total solid in a photosensitive composition, and 3-30 mass% is more preferable. When the 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, the developability and the exposure sensitivity may be decreased.

<(E) At least one of inorganic filler and organic filler (extreme pigment)>
If necessary, the photosensitive composition may be inorganic for the purpose of improving the surface hardness of the permanent pattern or keeping the linear expansion coefficient low, or keeping the dielectric constant or dielectric loss tangent of the cured film itself low. At least one of a filler and an organic filler (E) can be added.
The inorganic filler is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor phase method silica, amorphous Examples thereof include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.
The average particle size of the inorganic filler is preferably less than 10 μm, and more preferably 3 μm or less. When the average particle size is 10 μm or more, resolution may be deteriorated due to light scattering.
There is no restriction | limiting in particular as said organic filler, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. Further, silica having an average particle diameter of 0.01 to 5 μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  As content of at least any one of the said inorganic filler and an organic filler (E), 1-60 mass% is preferable with respect to the total solid of the said photosensitive composition. When the content is less than 1% by mass, the linear expansion coefficient may not be sufficiently reduced. When the content exceeds 60% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

<Other ingredients>
Examples of the other components include epoxy curing accelerators, thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), extender pigments, and further adhesion promoters to the substrate surface and others. Auxiliary agents (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. . By appropriately containing these, properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.

-Epoxy curing accelerator-
Since the photosensitive composition of the present invention accelerates the thermal curing of the thermal crosslinking agent (D), a known epoxy curing accelerator can be used. Examples of the epoxy curing accelerator include amine compounds (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 derivative bicyclic amidine compounds and salts thereof (eg , Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl)- -Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino- 6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric 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 curing accelerator is not particularly limited as long as it can accelerate the reaction between the thermal crosslinking agent (D) or these and a carboxyl group, and accelerates thermal curing other than the above. Possible compounds may be used.
Solid content in the said photosensitive composition solid content of the said epoxy hardening accelerator is 0.01-15 mass% normally.

-Thermal polymerization inhibitor-
The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound (B) in the photosensitive composition.
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 with respect to the polymerizable compound (B) in the photosensitive composition. 0.01 to 1% by mass is particularly preferable.
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 formed by the photosensitive composition.
Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, and the like. Phthalic acid esters: Triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters of tricresyl phosphate, triphenyl phosphate, etc. Acid esters; Amides such as 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl Aliphatic dibasic acid esters such as sepacate, dioctyl azelate, dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid Examples include glycols such as dioctyl acid, polyethylene glycol, and polypropylene glycol.

  As content of the said plasticizer, 0.1-50 mass% is preferable with respect to the total solid of the said photosensitive composition, 0.5-40 mass% is more preferable, 1-30 mass% is especially preferable. preferable.

-Color pigment-
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (CI. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow HR). Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral Fa Strike Blue (C.I. Pigment Blue 15), mono Light Fast Black B (C.I. Pigment Black 1), carbon, C. 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. And CI Pigment Blue 64. These may be used alone or in combination of two or more. Moreover, the dye suitably selected from well-known dye can be used as needed.

  The content of the color pigment can be determined in consideration of the exposure sensitivity and resolution of the photosensitive layer at the time of forming a permanent pattern, and varies depending on the type of the color pigment. 0.01-10 mass% is preferable with respect to the total solid of an adhesive composition, and 0.05-5 mass% is more preferable.

-Adhesion promoter-
In order to improve the adhesion between the layers, or the adhesion between the photosensitive layer composed of the photosensitive composition and the photosensitive film using the photosensitive composition, the layers are known. So-called adhesion promoters can be used.

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

  As content of the said adhesion promoter, 0.001 mass%-20 mass% are preferable with respect to the total solid of the said photosensitive composition, 0.01-10 mass% is more preferable, 0.1 mass % To 5% by mass is particularly preferable.

  The photosensitive composition of the present invention is excellent in sensitivity, resolution, and storage stability, and can efficiently form a high-definition permanent pattern. For this reason, it can be widely used for forming permanent patterns such as printed wiring boards, display members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc. It can be suitably used for forming.

(Photosensitive film)
The photosensitive film of the present invention has at least a support and a photosensitive layer made of the photosensitive composition of the present invention on the support, and preferably has a protective film on the photosensitive layer. Furthermore, it has another layer selected suitably, such as a thermoplastic resin layer, as needed.

<Support>
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 in the 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. The support may be a single layer or may have a multilayer structure.

  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 in the length of the said elongate support body, For example, the thing of 10-20,000m length is mentioned.

<Photosensitive layer>
The photosensitive layer is formed using the photosensitive composition of the present invention.
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 200 mJ / cm ² . Preferably, it is 0.2 to 100 mJ / cm ² , more preferably 0.5 to 50 mJ / cm ² , and particularly preferably 1 to 30 mJ / cm ² .
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs, it exceeds 200 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.

  There is no restriction | limiting in particular in the 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.

<Protective film>
The photosensitive film 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 in the 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, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
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.

  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. for 1 to 30 minutes. The drying temperature is particularly preferably 50 to 120 ° C.

<Other layers>
The other layers in the photosensitive film are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a cushion layer, an oxygen barrier layer (PC layer), a release layer, an adhesive layer, a light absorption layer, You may have layers, such as a surface protective layer. These layers may be used alone or in combination of two or more.

−Cushion layer−
There is no restriction | limiting in particular as said cushion layer, According to the objective, it can select suitably, Swelling thru | or soluble with respect to alkaline liquid may be sufficient, and it may be insoluble.

  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 can be appropriately selected according to the purpose. For example, 80 ° C. or lower is preferable.
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.

  Further, when the cushion layer is swellable or soluble in an alkaline liquid, the interlayer adhesive force of the photosensitive film 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. By setting such an interlayer adhesive force, only the support is peeled off from the photosensitive film, the photosensitive layer is exposed through the cushion layer, and then the photosensitive layer is developed using an alkaline developer. can do. In addition, after exposing the photosensitive layer while leaving the support, only the support is peeled off from the photosensitive film, 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 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 force of the photosensitive film is not particularly limited and may be appropriately selected depending on the intended purpose. Of the adhesive strength, it is preferable that the adhesive force between the photosensitive layer and the cushion layer is the smallest. With such an interlayer adhesive strength, the support and the cushion layer are peeled off from the photosensitive film, and after the photosensitive layer is exposed, 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 are peeled off from the photosensitive film, 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.

The ethylene copolymerization ratio in the copolymer containing ethylene as an essential copolymerization component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 60 to 90% by mass is preferable, and 60 to 80 is preferable. % 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. Production of the photosensitive film may be difficult.

There is no restriction | limiting in particular in the thickness of the said cushion layer, Although it can select suitably according to the objective, 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.

-Oxygen barrier layer (PC layer)-
The oxygen barrier layer is preferably formed usually with polyvinyl alcohol as a main component, and is preferably a film having a thickness of about 0.5 to 5 μm.

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

  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 composition solution is applied on the support and dried to form a photosensitive layer, whereby a photosensitive film can be produced.

The method for applying the photosensitive 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.

The photosensitive film is preferably stored, for example, wound around a cylindrical core, wound in a long roll shape.
There is no restriction | limiting in particular in the length of the said elongate photosensitive film, 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. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. When storing, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof and containing a desiccant) on the end face, and use a low moisture-permeable material for packaging. Is preferred.

The photosensitive film of the present invention has a photosensitive layer made of the photosensitive composition of the present invention, which is excellent in sensitivity, resolution, and storage stability and can form a high-definition permanent pattern. For this reason, it can be widely used for the formation of permanent patterns such as printed circuit boards, display members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc. It can be suitably used for use.
In particular, since the photosensitive film of the present invention has a uniform thickness, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned, the high acceleration test is performed. In (HAST), there is no occurrence of ion migration, and a high-definition permanent pattern excellent in heat resistance and moisture resistance can be obtained.

(Pattern forming apparatus and permanent pattern forming method)
The pattern forming apparatus of the present invention includes the photosensitive layer and includes at least light irradiation means and light modulation means.

The permanent pattern forming method of the present invention includes at least an exposure process for exposing the photosensitive layer made of the photosensitive composition of the present invention, and includes other processes such as a development process and a curing process that are appropriately selected.
In addition, the said pattern formation apparatus of this invention is clarified through description of the said permanent pattern formation method of this invention.

(Formation of laminate)
When pattern formation is performed using the permanent pattern forming method of the present invention, the photosensitive layer is preferably laminated on a substrate to form a laminate.

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed or a member to be transferred onto which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited and may be appropriately selected according to the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having an uneven surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.

  As a manufacturing method of the said photosensitive laminated body, the method of apply | coating the said photosensitive composition to the surface of the said base | substrate and drying as a 1st aspect is mentioned, In the photosensitive film of this invention as a 2nd aspect. Examples include a method of transferring and laminating at least one of the photosensitive layer while performing at least one of heating and pressurization.

In the method for producing a photosensitive laminate of the first aspect, a photosensitive layer is formed by applying and drying the photosensitive composition on the substrate.
The method for applying and drying is not particularly limited and can be appropriately selected depending on the purpose. For example, the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent on the surface of the substrate. And a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, The same solvent as what was used for the said photosensitive film is mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  There is no restriction | limiting in particular as said coating method and drying conditions, According to the objective, it can select suitably, It carries out by the same method and conditions as what was used for the said photosensitive film.

In the method for producing a photosensitive laminate according to the second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular in the pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator VP-II, Nichigo Morton VP130) Etc. are preferable.

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

  The subject of the exposure is not particularly limited as long as it is a photosensitive layer in the photosensitive film, and can be appropriately selected according to the purpose. For example, as described above, the photosensitive film 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 analog exposure is not particularly limited and may be appropriately selected depending on the purpose.For example, a method of performing exposure with a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or the like through a negative mask having a predetermined pattern. Can be mentioned.

The digital exposure includes, for example, a light irradiating 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 irradiating means. An exposure head provided with a light modulation means capable of controlling the picture element portion according to pattern information, wherein the column direction of the picture element portion is a predetermined set inclination angle θ with respect to the scanning direction of the exposure head. Using an exposure head arranged to form
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,
A method of performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction is preferable.

The “N-double exposure” means N lines irradiated on the exposed surface 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. The exposure by setting that intersects the light spot array (pixel array). 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. .

<Pattern forming device>
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 flatbed type exposure apparatus, and as shown in FIG. A flat plate-like moving stage 14 is provided that adsorbs and holds the photosensitive layer 12 on 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 and 5, each of the exposure heads 30 includes a light modulation unit (spatial light modulation element that modulates each pixel unit) that modulates incident light for each pixel unit according to image data. DMD36 (manufactured by Texas Instruments, USA). 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 FIG. 5, the lens system 40 has a pair of combination lenses 44 that collimate the laser light emitted from the fiber array light source 38, and the light quantity distribution of the collimated laser light becomes uniform. A pair of combination lenses 46 to be corrected in this way, and a condensing lens 48 that condenses the laser light whose light quantity distribution has been corrected on the DMD 36.

  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.

As a wavelength of the ultraviolet to visible light, for example, 300 to 1500 nm is preferable, 320 to 800 nm is more preferable, and 330 nm to 650 nm is particularly preferable.
As a wavelength of the laser beam, for example, 200 to 1500 nm is preferable, 300 to 800 nm is more preferable, 330 nm to 500 nm is further preferable, and 400 nm to 450 nm is particularly 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.

  As means (fiber array light source) capable of irradiating the combined laser, means described in JP-A-2005-258431 can be used.

<< 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 exactly double exposure using 256 lines of pixel parts is adopted.
This angle θ _ideal corresponds to the number N of N exposures, the number s of usable micromirrors 58 in the column direction, the interval p in the column direction of the usable micromirrors 58, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsin θ _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.
pcos θ _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. 8 illustrates an example of unevenness that occurs in the pattern on the exposed surface due to the influence of the mounting 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. 8 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 a state where the light spot group pattern as shown in FIG.
In FIG. 8, 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. 8, as a result of adopting the set inclination angle θ slightly larger than the angle θ _ideal as described above, and because it is difficult to finely adjust the mounting angle of the exposure head 30, 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.

Further, the example of FIG. 8 is an example of pattern distortion appearing on the exposed surface, and “angular distortion” is generated in which the inclination angle of each pixel row projected on the exposed surface 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. 8 is a distortion in which the tilt 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. 9 and 10.

-Specification of actual inclination angle θ'-
FIG. 9 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 micromirror 58 in the first row and the 512th column and the micromirror 58 in the 256th row and the 512th column on the DMD 36 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. 10 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 along the Y axis to the right in FIG. Then, as indicated by a two-dot chain line in FIG. 10, 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. 10 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 10, 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
t tan θ ′ = 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. 11 shows how the unevenness on the exposed surface shown in FIG. 8 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. 11, in the exposure region near the 512th column, overexposure and underexposure are almost completely eliminated, and uniform exposure very close to ideal double exposure is realized.

On the other hand, in the left region of FIG. 11 (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. This 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 right region of FIG. 11 (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, 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 this 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. 12 shows the deviation of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction from the ideal state in the pattern forming apparatus 10 initially adjusted as described above. 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.

The upper part of FIG. 12 is a light spot group from the micromirror 58 usable for the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ that is projected onto the exposed surface of the photosensitive material 12 with the stage 14 being stationary. It is the figure which showed these patterns. The lower part of FIG. 12 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. 12, 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. 12, 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. 13 is a top view showing the positional relationship between the exposure areas 32 ₁₂ and 32 ₂₁ similar to those in FIG. 12 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 14 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 along the Y axis to the right in FIG. Then, as indicated by a two-dot chain line in FIG. 14, 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. 14 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 14, 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. 12, 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, to identify the micro mirrors corresponding to light spots constituting the c (1024) from the point light spot column c of the exposure area 32 ₂₁ (n + 1), as a micro-mirror is not used during the exposure (unused pixel parts) .
For example, in FIG. 12, 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. 15 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. 15 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.

Thus, to identify the micro-mirror is not used during the actual exposure, the minus micromirrors without the use, by selecting as micro mirrors to be used in actual exposure, the exposure area 32 ₁₂ 32 ₂₁ In the joint 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, when the light spot of a specific constituting the regions 72 covered with hatched in FIG. 15, the X-coordinate of the exposure area _{32 12} of the light spot P (256, two), 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 formulas 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. 16 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 angles of the exposure heads 30, that is, the DMDs 36 are 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. 16, exposure by every other light spot group (pixel column groups A and B) as a result of the relative position shift of the exposure heads 30 ₁₂ and 30 _{21 in} the X-axis direction is the same as the example of FIG. 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.
Further, in the example of FIG. 16, it is difficult to finely adjust the result of setting the tilt angle θ of each exposure head slightly larger than the angle θ _ideal satisfying the above equation (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.
t tan θ ′ = 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. 17 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 by the oblique lines in FIG. 17, the same processing as that of the present embodiment (3) described with reference to FIGS. In FIG. 17, the 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. 18A, 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. 18B, 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, this light amount distortion is caused by the positional dependence of the transmittance of the optical element between the DMD 36 and the exposed surface (for example, the lenses 52 and 54 in FIG. 5 which is a single lens) and the light amount by the DMD 36 itself. Caused by unevenness. 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.

19A and 19B are explanatory diagrams showing an example of a form in which reference exposure is performed by using only a single (N-1) row 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 micromirrors corresponding to the odd-numbered light spot rows shown by the solid lines in FIG. 19A, 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, a micromirror other than the micromirror corresponding to the light spot array shown by hatching in FIG. 19B is 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. 20 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 micromirrors corresponding to odd-numbered light spot rows of two exposure heads adjacent to each other in the X-axis direction (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) shown by a solid line 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 area 86 shown by hatching in FIG. 20 and the shaded area 88 are among the micromirrors constituting the odd-numbered light spots during the main exposure. 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. 21 is an explanatory diagram showing an example of a form in which reference exposure is performed using a single exposure head and using only micromirror groups constituting adjacent rows corresponding to 1 / N rows of the total number of light spots. It is.
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. 21A, 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. 21B 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.

In FIG. 22, a plurality of exposure heads are used, 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 spot rows. 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 micromirrors corresponding to the light spots in the first to 128th (= 256/2) rows shown by the solid line in FIG. 22, 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. 22 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.

For example, the pH of the weakly alkaline aqueous solution is 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.

[Curing process]
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
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.
An apparatus for performing the entire surface exposure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a UV exposure machine such as an ultra-high pressure mercury lamp, an exposure machine using a xenon lamp, a laser exposure machine and the like are preferable. It is mentioned in. The exposure amount is usually 10 to 2,000 mJ / cm ² .

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.
120-250 degreeC is preferable and the heating temperature in the said whole surface heating has more preferable 120-200 degreeC. 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.
The heating time in the entire surface heating is preferably 10 to 120 minutes, and more preferably 15 to 60 minutes.
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.

-Protective film, interlayer insulating film, solder resist pattern formation method-
When the pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, a permanent pattern is formed on a printed wiring board by the permanent pattern forming method. Then, 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 permanent pattern forming method of the present invention, it is preferable to form at least one of a protective film and an interlayer insulating film. 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, particularly when the interlayer insulating film is the interlayer insulating film. Is useful for high-density mounting of semiconductors and components on, for example, multilayer wiring boards and build-up wiring boards.

  Since the permanent pattern forming method of the present invention uses the photosensitive composition of the present invention, it is used for forming various patterns such as a protective film, an interlayer insulating film, a solder resist pattern, a printed circuit board, a color filter, a pillar material, a rib material, It can be widely used for forming permanent patterns such as display members such as spacers and partition walls, holograms, micromachines, and proofs, and can be particularly suitably used for forming permanent patterns on printed boards.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

(Synthesis Example 1)
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was placed and heated to 85 ° C. under a nitrogen stream. To this, a solution of 159 g of 1-methoxy-2-propanol containing 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 2 hours. After completion of the dropwise addition, the reaction was continued by heating for 5 hours. Subsequently, the heating was stopped to obtain a copolymer of benzyl methacrylate / methacrylic acid (ratio of 30/70 mol%).
Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and stirred to dissolve. After dissolution, 3.0 g of triphenylphosphine was added and heated to 100 ° C. to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 1-Methoxy-2-propanol was added to prepare a 1-methoxy-2-propanol solution of polymer compound 1 shown in Table 1 below with a solid content of 30% by mass.
It was 15,000 as a result of measuring the mass mean molecular weight (Mw) of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used the polystyrene as a reference material.
Further, from the titration using sodium hydroxide, the content (acid value) of the carboxyl group per solid content was 2.2 meq / g.
Furthermore, the content of ethylenically unsaturated bonds per solid (C = C value) determined by iodine value titration was 2.1 meq / g.

(Synthesis Examples 2 to 5)
Polymers shown in Table 1 were obtained in the same manner as in Synthesis Example 1 except that benzyl methacrylate, methacrylic acid, and glycidyl methacrylate in Synthesis Example 1 were appropriately changed to arbitrary monomers in order to obtain the target polymer compound. 1-methoxy-2-propanol solutions of compounds 2-5 were prepared respectively.
For the obtained polymer compounds 2 to 5, the mass average molecular weight (Mw), the acid value, and the C = C value were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

(Synthesis Example 6)
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was placed and heated to 85 ° C. under a nitrogen stream. To this was added dropwise a solution of 159 g of 1-methoxy-2-propanol containing 36 g of methyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) over 2 hours. After completion of the dropwise addition, the reaction was continued by heating for 5 hours. Subsequently, the heating was stopped to obtain a copolymer of methyl methacrylate / methacrylic acid (molar ratio: 30/70).
Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and stirred to dissolve. After dissolution, 2.4 g of triphenylphosphine was added and heated to 100 ° C. to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 1-Methoxy-2-propanol was added to prepare a 1-methoxy-2-propanol solution of polymer compound 6 represented by Table 1 below having a solid content of 30% by mass.
Moreover, when it measured similarly to the synthesis example 1 about the obtained high molecular compounds 2-5, a mass mean molecular weight (Mw) is 15,000, an acid value is 2.3 meq / g, C = The C value was 2.6 meq / g.

In Table 1, * 1 represents the mixing of the structure represented by the following structural formula (a) and the structure represented by (b) (mixing ratio is unknown).

Example 1
-Preparation of photosensitive composition-
A photosensitive composition was prepared based on the following composition.
―――――――――――――――――――――――――――――――――――――――
Polymer compound 1 solution (30% by mass 1-methoxy-2-propanol solution): 87 parts by mass Pigment dispersion: 30 parts by mass Dipentaerythritol hexaacrylate (DPHA, manufactured by UCB Chemicals, solid Concentration 76%; polymerizable compound) ... 13 parts by mass / photopolymerization initiator represented by the following structural formula (26) ... 2.6 parts by mass / SPEEDCURE CPTX (manufactured by Lambson Fine Chemical, sensitizer) ) ... 0.5 parts by mass-Epototo YD-8125 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 170 g / eq., Epoxy compound) ... 8 parts by mass-Dicyandiamide (thermosetting agent) ... 0.77 parts by mass -Fluorosurfactant (Megafac F-176, manufactured by Dainippon Ink & Chemicals, Inc., 30% 2-butanone solution) ... 0.2 parts by mass, methyl ethyl ketone (solvent) ... 15 parts by mass ―――――――――――――――――――――――――――――――――― ―――――
In the above composition, the pigment dispersion is composed of 30 parts by mass of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30) and 61% by mass of diethylene glycol monomethyl ether acetate of PCR-1157H (manufactured by Nippon Kayaku Co., Ltd.). After 34 parts by mass of the solution and 36 parts by mass of normal propyl acetate were mixed in advance, a motor mill M-200 (manufactured by Eiger) was used for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 1.0 mm. Prepared by dispersing.

The oxime compound represented by the structural formula (26) was synthesized by the method shown in Synthesis Example 7 below. Moreover, content in the photosensitive composition of the oxime compound represented by the said Structural formula (26) is 1.2 mass%.
(Synthesis Example 7)
A mixed solution of naphthofuran-1-one (10 g), hydroxylamine monohydrate (13 g), acetic acid (12 g), and methanol 30 mL was heated under reflux for 3 hours. The reaction solution was cooled to room temperature, and the precipitated naphthofuran-1-one oxime was collected by filtration. Next, 10 mL of acetone, triethylamine (8 g), and acetic anhydride (8 g) were sequentially added to the obtained oxime compound. The reaction solution was poured into water (30 ml), and the precipitated crystals were collected by filtration, washed with water, and then washed with methanol to obtain an oxime compound represented by the structural formula (26).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of the oxime compound represented by the structural formula (26) is δ: 1.6 (m, 2H), 1.8 (m, 2H), 2.1 ( s, 3H), 2.8 (m, 4H), 7.1 (d, 1H), 7.2 (t, 1H), 7.4 (t, 1H), 7.5 (d, 1H) there were.

-Production of photosensitive film-
The obtained photosensitive composition solution was applied with a bar coater onto a PET (polyethylene terephthalate) film (manufactured by Toray Industries, Inc., 16FB50) having a thickness of 16 μm, a width of 300 mm, and a length of 200 m as the support, and hot air at 80 ° C. It dried in the circulation type dryer, and formed the 30-micrometer-thick photosensitive layer. Next, a polypropylene film (E-200, manufactured by Oji Paper Co., Ltd.) having a thickness of 20 μm, a width of 310 mm, and a length of 210 m was laminated as a protective film on the photosensitive layer by lamination to produce a photosensitive film.

-Formation of permanent pattern-
--- Preparation of photosensitive laminate--
Next, the substrate was prepared by subjecting a surface of a copper-clad laminate (no through hole, copper thickness 12 μm) on which a wiring was formed as a printed board to a chemical polishing treatment. A vacuum laminator (VP130, manufactured by Nichigo Morton Co., Ltd.) was peeled off on the copper-clad laminate while peeling the protective film from the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. The photosensitive laminate was prepared by laminating the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) in this order.
The pressure bonding conditions were a vacuum drawing time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure application time of 10 seconds.

--Exposure process--
The photosensitive layer in the laminate prepared above, from the support side, a patterning apparatus described below, the light energy amount from 0.1 mJ / cm ² to 100 mJ / cm ² at ^{2 1/2} times the interval Double exposure was performed by irradiating different light, and a part of the photosensitive layer was cured.

<< Pattern Forming Apparatus >>
A combined laser light source described in JP-A-2005-258431 as the light irradiating means, and a micromirror array in which 1024 micromirrors 58 are arranged in the main scanning direction schematically shown in FIG. 6 as the light modulating means. However, among the 768 sets arranged in the sub-scanning direction, DMD 36 controlled to drive only 1024 × 256 rows, and an optical system for imaging the light shown in FIGS. 5A and 5B on the photosensitive film, The pattern forming apparatus 10 including the exposure head 30 having the above is 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 a usable 1024 columns × 256 rows micromirror 58 is adopted. This angle θ _ideal corresponds to the number N of N exposures, the number s of usable micromirrors 58 in the column direction, the interval p in the column direction of the usable micromirrors 58, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsin θ _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.
pcos θ _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 usable micromirror 58 of the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the photosensitive film 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
t tan θ ′ = 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.

--Development process--
After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and a 1% by weight aqueous sodium carbonate solution was used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate at 30 ° C. Shower development was performed for a time twice as short as the shortest development time described later, and the uncured region was dissolved and removed.
Thereafter, it was washed with water and dried to form a permanent pattern.

-Curing process-
The entire surface of the laminate on which the permanent pattern was formed was heated at 150 ° C. for 60 minutes to cure the surface of the permanent pattern and increase the film strength.

<Evaluation>
Next, with respect to the obtained photosensitive laminate and permanent pattern, developability (shortest development time), sensitivity, resolution, storage stability (sensitivity after time), and resist performance after effect (adhesion, solder heat resistance) , And electroless plating resistance). The results are shown in Table 2.

<< Evaluation of developability (shortest development time) >>
The polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate. The time required from the start of spraying of the aqueous sodium 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. The shorter the shortest development time, the better the developability.

<< Evaluation of sensitivity >>
In the permanent pattern obtained by pattern exposure / development / washing as described above, the thickness of the cured region of the remaining photosensitive layer was measured. Subsequently, a sensitivity curve is obtained by plotting the relationship between the irradiation amount of the laser beam and the thickness of the cured layer. From the sensitivity curve thus obtained, the thickness of the cured region on the wiring is 30 μm, and the amount of light energy when the surface of the cured region is a glossy surface is set as the amount of light energy necessary for curing the photosensitive layer. The sensitivity was evaluated. The smaller the value of the amount of light energy required for curing the photosensitive layer, the higher the sensitivity, indicating that the photosensitive layer can be cured in a short time.

<< Evaluation of resolution >>
The laminate was prepared under the same method and conditions as the evaluation method for the shortest development time, and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate film (support) of the laminate, exposure is performed for each line width in increments of 1 μm from line / space = 1/1 to a line width of 10 to 100 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 photosensitive film in the sensitivity evaluation. 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 minimum development time to dissolve and remove uncured areas. 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.

<< Evaluation of storage stability (sensitivity after aging) >>
The prepared photosensitive laminate is sealed in a moisture-proof bag (black polyethylene cylindrical bag, film thickness: 80 μm, water vapor transmission rate: 25 g / m ² · 24 hr or less) at 24 ° C. and 60% RH. After storage at 40 ° C. for 3 days, the sensitivity was measured by the same method as the sensitivity evaluation.

<< Evaluation of adhesion >>
According to the test method of JIS (Japanese Industrial Standards) D-0202, 100 1 mm grids were prepared on the cured permanent pattern, a peel test was performed using a cellophane tape, and the number of peeled pieces was measured visually.

<< Evaluation of solder heat resistance >>
After the cured permanent pattern was immersed in a solder bath at 260 ° C. for 10 seconds in accordance with the test method of JIS C-6481, the test for peeling with a cellophane tape was defined as 1 cycle, and the coating state after 3 cycles in total was obtained. Evaluation was made according to the following criteria.
-Evaluation criteria-
○: No change in the coating film after 3 cycles ×: Separation after 3 cycles

<< Evaluation of electroless plating resistance >>
The cured permanent pattern is plated using a commercially available electroless nickel plating bath and electroless gold plating bath under the conditions of nickel: 0.5 μm, gold: 0.03 μm, and then peeled off using a cellophane tape. The test was performed, the state of the coating film was observed, and the following criteria were evaluated.
-Evaluation criteria-
○: No peeling at all △: Only slight peeling ×: The cured coating has peeling

(Example 2 to Example 6)
In Example 1, except that the 1-methoxy-2-propanol solution of the polymer compound 1 was replaced with the 1-methoxy-2-propanol solution of the polymer compounds 2 to 6 obtained in Synthesis Examples 2 to 6 above. Prepared the photosensitive composition like Example 1, and manufactured the photosensitive film, the photosensitive laminated body, and the permanent pattern.
The photosensitive laminate and permanent pattern were evaluated in the same manner as in Example 1 for developability, sensitivity, resolution, storage stability, and resist performance after curing. The results are shown in Table 2.

(Comparative Example 1)
In Example 1, the 1-methoxy-2-propanol solution of the polymer compound 1 was mixed with glycidyl methacrylate (equivalent to 33 mol) of benzyl methacrylate / methyl methacrylate / methacrylic acid (molar ratio: 34/33/33) copolymer. ) A photosensitive composition was prepared in the same manner as in Example 1 except for changing to an adduct (no carboxylic acid remaining), and a photosensitive film, a photosensitive laminate, and a permanent pattern were produced.
The photosensitive laminate and permanent pattern were evaluated in the same manner as in Example 1 for developability, sensitivity, resolution, storage stability, and resist performance after curing. The results are shown in Table 2.

(Example 7)
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1, except that the oxime compound represented by Structural Formula (26) was changed to the oxime compound represented by Structural Formula (24) below. A photosensitive film, a photosensitive laminate, and a permanent pattern were produced.
The photosensitive laminate and permanent pattern were evaluated in the same manner as in Example 1 for developability, sensitivity, resolution, storage stability, and resist performance after curing. The results are shown in Table 2.

The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of the oxime compound represented by the structural formula (24) is δ: 2.3 (s, 3H), 3.2 (m, 4H), 3.9 ( s, 3H), 7.2 (s, 1H), 7.3 (d, 1H), 7.4 (d, 1H), 7.8 (d, 1H), 9.0 (d, 1H) there were.

(Example 8)
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that the oxime compound represented by the structural formula (26) was changed to the oxime compound represented by the following structural formula (53). A photosensitive film, a photosensitive laminate, and a permanent pattern were produced.
The photosensitive laminate and permanent pattern were evaluated in the same manner as in Example 1 for developability, sensitivity, resolution, storage stability, and resist performance after curing. The results are shown in Table 2.

The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of the oxime compound represented by the structural formula (53) is δ: 2.3 (s, 3H), 5.4 (s, 2H), 7.2 ( d, 1H), 7.7 (d, 1H), 7.8 (d, 1H), 8.0 (s, 1H), 8.4 (d, 1H).

Example 9
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that the oxime compound represented by the structural formula (26) was changed to the oxime compound represented by the following structural formula (52). A photosensitive film, a photosensitive laminate, and a permanent pattern were produced.
The photosensitive laminate and permanent pattern were evaluated in the same manner as in Example 1 for developability, sensitivity, resolution, storage stability, and resist performance after curing. The results are shown in Table 2.

The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of the oxime compound represented by the structural formula (52) is δ: 2.2 (s, 3H), 5.4 (s, 2H), 7.45 ( d, 1H), 7.50 (t, 1H), 7.6 (t, 1H), 7.7 (d, 1H), 7.8 (d, 1H), 8.1 (d, 1H) there were.

(Example 10)
In Example 1, a photosensitive composition was prepared in the same manner as in Example 1 except that the oxime compound represented by Structural Formula (26) was changed to the oxime compound represented by Structural Formula (54) below. A photosensitive film, a photosensitive laminate, and a permanent pattern were produced.
The photosensitive laminate and permanent pattern were evaluated in the same manner as in Example 1 for developability, sensitivity, resolution, storage stability, and resist performance after curing. The results are shown in Table 2.

The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of the oxime compound represented by the structural formula (54) is δ: 2.4 (s, 3H), 4.4 (s, 2H), 7.4 ( d, 1H), 7.5 (t, 1H), 7.7 (t, 1H), 7.8 (d, 1H), 7.85 (d, 1H), 9.2 (d, 1H) there were.

(Comparative Example 2)
In Example 1, except that the oxime compound represented by the structural formula (26) was changed to CGI-325 (manufactured by Ciba Specialty Chemicals) represented by the following structural formula (55). The photosensitive composition was prepared like 1 and the photosensitive film, the photosensitive laminated body, and the permanent pattern were manufactured. In addition,
The photosensitive laminate and permanent pattern were evaluated in the same manner as in Example 1 for developability, sensitivity, resolution, storage stability, and resist performance after curing. The results are shown in Table 2.

(Example 11)
In Example 1, instead of the pattern forming apparatus, a glass negative mask having the same pattern as this was separately prepared, and this negative mask was brought into contact with the photosensitive laminate, and exposure was performed at 40 mJ / cm ² with an ultrahigh pressure mercury lamp. A permanent pattern was obtained by performing development and curing treatment in the same manner as in Example 1 except that the exposure was carried out in an amount.
The photosensitive laminate and permanent pattern were evaluated in the same manner as in Example 1 for developability, sensitivity, resolution, storage stability, and resist performance after curing. The results are shown in Table 2.

From the results of Table 2, it was found that the photosensitive compositions of Examples 1 to 11 were excellent in sensitivity, resolution, and storage stability (sensitivity after time), and could form a high-definition pattern. .
On the other hand, the photosensitive composition of Comparative Example 1 that did not use a carboxyl group-containing resin having one or more carboxyl groups in one molecule, in addition to the sensitivity, resolution, and storage stability described above, It was found that developability and resist performance after curing (adhesion, solder heat resistance, and electroless plating resistance) were inferior. Moreover, the photosensitive composition of Comparative Example 2 in which the oxime compound represented by the general formula (1) was not used as a photopolymerization initiator had the developability and resist performance after curing in Examples 1 to 11. However, sensitivity, resolution, and storage stability were found to be inferior.

  Since the photosensitive composition and photosensitive film of the present invention are excellent in sensitivity, resolution, and storage stability, and can efficiently form high-definition patterns, various kinds of protective films, interlayer insulating films, solder resist patterns, etc. It can be widely used for pattern formation, printed circuit boards, color filters, pillar materials, rib materials, spacers, display members such as spacers, partition walls, holograms, micromachines, proofs, and other permanent patterns. It can be suitably used for forming.

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 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. 9 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit. FIG. 10 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 11 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. 12 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. 13 is a top view showing a positional relationship between an exposure area by two adjacent exposure heads and a corresponding slit. FIG. 14 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 15 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 12 are actually moved and the unevenness in the pattern on the exposed surface is improved. FIG. 16 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. 17 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG. FIG. 18A is an explanatory diagram showing an example of magnification distortion. FIG. 18B is an explanatory diagram showing an example of beam diameter distortion. FIG. 19A is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 19B is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 20 is an explanatory diagram showing a first example of reference exposure using a plurality of exposure heads. FIG. 21A is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 21B is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 22 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads.

Explanation of symbols

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)
113 Rod lens 200 Condensing lens 310 Film roll 320 Core unit support means 330 Holding means

Claims (10)

(A) a carboxyl group-containing resin having one or more carboxyl groups in one molecule, (B) a polymerizable compound, (C) a photopolymerization initiator represented by the following general formula (1), and (D) heat A photosensitive composition comprising a crosslinking agent.
However, in the general formula (1), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and these substituents may further have a substituent. m represents any integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heteroaromatic ring. A represents any of 4, 5, 6, and 7-membered rings, and each of these rings may contain a hetero atom.   (A) The photosensitive composition according to claim 1, wherein the carboxyl group-containing resin having one or more carboxyl groups in one molecule further has one or more polymerizable unsaturated double bonds in one molecule. . (C) The photosensitive composition in any one of Claim 1 to 2 whose photoinitiator represented by General formula (1) is a compound represented by following General formula (2).
However, in the general formula (2), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and these substituents may further have a substituent. m represents any integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heteroaromatic ring. X represents either O or S. A represents either a 5- or 6-membered ring. The photosensitive composition of Claim 3 whose photoinitiator represented by General formula (2) is a compound represented by either of the following general formula (3) and (4).
However, in the general formulas (3) and (4), R ³ represents an alkyl group, and the alkyl group may further have a substituent. l represents an integer of 0 to 6. R ⁴ represents an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, or an acyloxy group. When l is 2 or more, the R ^{4 s} may be the same or different. May be. X represents either O or S. A represents either a 5- or 6-membered ring.   Further, it contains at least one of (CI) other photopolymerization initiator (except for (C) the photopolymerization initiator represented by formula (1)) and (C-II) sensitizer. The photosensitive composition according to any one of claims 1 to 4.   (B) The polymerizable compound contains a compound having one or more unsaturated double bonds in one molecule, and the content of the polymerizable compound (B) is (A) 100 parts by mass of the carboxyl group-containing resin. It is 2-50 mass parts with respect to the photosensitive composition in any one of Claim 1 to 5.   The photosensitive composition according to any one of claims 1 to 6, wherein (D) the thermal crosslinking agent is an epoxy compound having two or more epoxy groups in one molecule.   The photosensitive composition according to any one of claims 1 to 7, further comprising (E) at least one of an inorganic filler and an organic filler.   A photosensitive film comprising a support and a photosensitive layer made of the photosensitive composition according to claim 1 on the support.   A printed circuit board having a permanent pattern formed using the photosensitive composition according to claim 1.