TW200809406A - Light sensitive composition, light sensitive film, permanent pattern forming method and printing substrate - Google Patents

Abstract

The object of the invention is to provide a light sensitive composition and a light sensitive film both having good sensitivity and excellent properties of fresh storage and processing, as well as to provide a permanent pattern-forming method capable of forming a permanent pattern (such as a protect film, an interlayer insulate film, a solder resist pattern and so on) in high fineness and good efficiency, and a printing substrate having a permanent pattern formed by aforesaid light sensitive-forming method. Therefore, a light sensitive composition is provided, which comprises at least (A) a binder obtained by reacting a reactant between an epoxy compound (a) having bisphenol skeleton in a part of structure and a unsaturated group-containing mono carbonic acid (b) with a polybasic acid compound (c) having any one of a saturated group and an unsaturated group, (B) a polymerizable compound and (C) a photo-polymerization initiator using any one of an acyl phosphine oxide compound and an oxium derivate.

Description

[Technical Field] The present invention relates to a photosensitive composition which is excellent in sensitivity and excellent in storage stability and handleability, a photosensitive film, and a high-definition structure capable of forming a semiconductor field with good efficiency. A permanent pattern forming method of a permanent pattern (a protective film, an interlayer insulating film, a solder resist pattern, etc.), and a printed circuit board in which a permanent pattern is formed by the permanent pattern forming method. [Prior Art] Conventionally, when a permanent pattern such as a solder resist pattern is formed, a photosensitive film which is formed by applying a photosensitive composition on a support and drying it is used. In the method for producing the permanent pattern described above, for example, a photosensitive film may be laminated on a substrate such as a copper-clad laminate in which the permanent pattern is formed to form a laminate, and the photosensitive layer in the laminate may be exposed. After the exposure, the photosensitive layer is developed to form a pattern, and then the permanent pattern is formed by performing a curing treatment or the like. In order to efficiently obtain the high-precision aforementioned permanent pattern, it is required to increase the sensitivity. In addition, the present inventors have proposed a photosensitive film for the purpose of achieving improvement in sensitivity, which comprises using an α-aminoalkylphenone compound (Irgacure 907) as a photopolymerization initiator, and A photosensitive layer using a thioxanthone compound (Kachacure DETX-S) as a sensitizer (see Patent Document 1). However, since the aforementioned α-aminoalkylphenone compound has an amine group structure, in the case of using a thermal crosslinking agent, heat is slowly induced even when the temperature is attached to the room temperature at 200809406. The reaction of the crosslinking agent will inevitably lead to a decrease in the stability of the storage, such as the stability over time of the sensitivity. Therefore, when the photosensitive composition solution forming the photosensitive layer is directly applied onto the substrate (hereinafter referred to as "liquid photoresist type"), it is a dispersion which is prepared by dispersing a component other than the thermal crosslinking agent. And a so-called two-liquid type in which a liquid of a thermal crosslinking agent is dispersed or dissolved, and then the two are mixed and prepared. However, in a state of being laminated on the substrate after the mixing operation, the hardening reaction proceeds slowly. Therefore, there is a case where exposure or development cannot be performed with time, and it has been desired to improve the preservation stability of the laminated body state. In addition, a film in which a photosensitive layer composed of the above-described photosensitive composition is formed on a support and laminated on a substrate such as a printed circuit board (hereinafter referred to as "film type") is used. Since it is required to be easy to handle, it is difficult to adopt the aspect as the above-described liquid photoresist type. On the other hand, a photosensitive composition including an alkali-soluble binder of an unsaturated double bond, a photopolymerizable compound of an anthracene compound, a sensitizer of a thioxanthone compound, a polymerizable compound, and a product 2 have also been proposed. An epoxy compound having more than one epoxy group (see Patent Documents 2 and 3). However, even if the sensitivity is improved by using these, there is still a problem that the storage stability of the sensitivity such as the stability over time is lowered. In other respects, an epoxy acrylate compound or the like having an epoxy compound partially having a bisphenol skeleton is used for a binder as a solder resist pattern forming material which can be used as a binder for a photosensitive layer (see Patent Literature However, the material of Patent Document 4 has a problem of low sensitivity, especially in 4). 200809406 In the case of laser exposure, there will be a slow exposure (takt, German) problem. Further, there is no description as to how to achieve both stability and high sensitivity after application of the liquid solder resist. Therefore, the current state of the art is that a photosensitive composition having high sensitivity and excellent storage property of a laminate, a photosensitive film, a photosensitive film using the photosensitive composition described above, and a protective film can be formed with good efficiency. A permanent pattern forming method of a high-definition permanent pattern such as a film or an insulating film, and a printed substrate in which a permanent pattern is formed by the permanent pattern forming method; further development is desired. [Patent Document 1] JP-A-2000-232264 (Patent Document 2) JP-A-2002-5 1 9732 (Patent Document 3) JP-A-2005-1 82004 (Patent Document 4) International Publication No. 014/34147 OBJECTS OF THE INVENTION [Problems to be Solved by the Invention] The present invention has been made in order to solve the above-mentioned problems of the conventional use and achieve the following objects. In other words, an object of the present invention is to provide a photosensitive composition having high sensitivity and excellent storage stability of a laminate, a photosensitive film using the photosensitive composition, and a semiconductor field capable of forming a semiconductor with good efficiency. A permanent pattern forming method of a fine permanent pattern (a protective film, an interlayer insulating film, a solder resist pattern, etc.), and a printed substrate in which a permanent pattern is formed by the permanent pattern forming method. [Means for Solving the Problem] The means for solving the above problems are as follows. That is: 200809406 &lt; 1 &gt; A photosensitive composition comprising at least (A) a binder, (B) a polymerizable compound, and (c) a photopolymerization initiator, wherein (A) a binder system a reaction product of an epoxy compound (a) having a bisphenol skeleton and a monocarboxylic acid (b) having an unsaturated group, and a polybasic acid compound containing any one of a saturated group and an unsaturated group ( c) A binder obtained by the reaction. The photosensitive composition of the above-mentioned <1>, wherein the (A) binder is represented by any one of the following general formula (1) and general formula (2). Photocurability obtained by reacting an epoxy compound (a) with a reaction product of an unsaturated group-containing monocarboxylic acid (b) and a polybasic acid compound (c) containing either a saturated group or an unsaturated group Resin

〇——CH2—CH-CH〇—d

Ox

General formula (1) but in the above general formula (1), x represents any of a hydrogen atom and a glycidyl group; and R represents any of a methylene group and an isopropylidene group; Represents an integer greater than 1;

In the above general formula (2), R1 represents any one of a hydrogen atom and a methyl group 200809406; R2 and R 3 represent a stretching base; m and η represent m + n It is a positive integer of 2 to 50; the ρ system represents a positive integer. The photosensitive composition according to any one of the above-mentioned items, wherein the photosensitive composition has a sensitivity of 0.1 to 20 mJ/cm 2 . The photosensitive composition according to any one of the above-mentioned <1> to (3), further comprising (D) a thermal crosslinking agent. The photosensitive composition according to any one of the above-mentioned <1>, wherein the anthracene derivative has the following general formula (3) and the following general formula (4) Part of the structure represented by any one of them;

Ar-(c(Y1)=N-〇-Y2)m - general formula (3)

Ar-(〇〇-C(Y1)=N-〇-Y2) General Formula (4) However, in the above general formulas (3) and (4), the Ar system represents any of an aromatic group and a heterocyclic group. Y1 represents any one of a hydrogen atom and a monovalent substituent; Y2 represents any of an aliphatic group, an aromatic group, a heterocyclic group, COY3, C02Y3, and CONY4Y5; Y3, 丫4, and Y5 represent Any of an aliphatic group, an aromatic group and a heterocyclic group; m represents an integer of 1 or more. The photosensitive composition described in any one of the above-mentioned <4>, wherein (D) the crosslinking group of the thermal crosslinking agent and (A) the acidic group of the binder The ratio is crosslinkable / acidic base = 〇. 3~3.0. The photosensitive composition described in any one of the above-mentioned, wherein the (B) polymerizable compound includes -10- from the (meth)acrylic group. 200809406 At least one of the monomers selected. The photosensitive composition according to any one of the above-mentioned, wherein the (D) thermal crosslinking agent is an epoxy compound or an oxetane compound. At least one selected from the group consisting of a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a block agent, and a melamine derivative. The photosensitive composition according to any one of the above-mentioned <1> to (8), further comprising (E) an elastomer. The photosensitive composition according to any one of the above-mentioned items, wherein the photosensitive composition according to any one of the above-mentioned items, further comprising (F) a phenoxy resin. The photosensitive composition according to any one of the above-mentioned items, wherein the photosensitive composition according to any one of the above-mentioned items, further comprising (G) a sensitizer. The photosensitive composition according to the above-mentioned <1>, wherein the (G) sensitizer includes a heterocyclic ring compound. The photosensitive composition according to the above <1>, wherein the heterocyclic ring compound is a thioxanthone compound. &lt;14&gt; A photosensitive film comprising at least a support and a photosensitive composition according to any one of the above &lt;1&gt; to &lt;13&gt; The photosensitive layer of the photosensitive film described in the above &lt;14&gt; wherein the photosensitive layer has a thickness of 1 to 1 μm. The photosensitive film according to any one of the above-mentioned, wherein the support system contains a synthetic resin and is transparent. The film of the photosensitive thin -11-200809406 according to any one of the above-mentioned items, wherein the support system has a long shape. The film according to any one of the above-mentioned items, which has a long shape and is wound into a cylindrical shape. The film described in any one of the above-mentioned <1>, which has a protective film on the photosensitive layer; &lt;20&gt; The body is characterized in that it is a photosensitive layer composed of the feeling described in any one of the above &lt;1&gt; to &lt;1&gt;&gt;&lt;21&gt; The photosensitive laminate described in the above &lt;20&gt; is formed by any one of the films of <14> to <19>. &lt; 22 &gt; A pattern forming apparatus characterized in that at least the light irradiation means of the light and the modulation from the light irradiation are recorded in any one of the above &lt;20 &gt; to &lt; 2 1 &gt; In the pattern forming apparatus described in the optical modulator 22 for exposing the photosensitive layer in the body, the light modulation mechanism is irradiated to the light modulation mechanism. The aforementioned light modulation is modulated by the light received by the light irradiation means. The light system modulated by the modulation mechanism faces the photosensitive layer. For example, a fine pattern at the time of development of the aforementioned photosensitive layer is then performed. <23> The pattern forming apparatus according to the above <22>, which is composed of a pattern signal generating means having a pattern control signal formed by a light modulation mechanism, and having a photosensitive thin photosensitive film. The photosensitive structure is composed of, for example, a photosensitive composition, wherein the photosensitive layer described in the photosensitive layer is light-loaded by an illuminable mechanism. The &lt;light-illuminating mechanism changing mechanism is exposed by the light, and can be generated by generating higher information, and is modulated by the control signal generated by the signal generating means of FIG. 12-200809406. Light irradiated from a light irradiation mechanism. In the pattern forming apparatus described in the above [23], the light modulation mechanism described above is provided with the pattern signal generating means described above, and is adjusted in accordance with the control signal generated by the pattern signal generating means. The light irradiated from the light irradiation means is changed. The pattern forming apparatus according to any one of the above-mentioned <22>, wherein the light modulation mechanism is formed by having n pixel portions and capable of forming a pattern along with the pattern Information is used to control any of the aforementioned pixel portions that are less than n in a continuous arrangement among the n pixel portions. In the pattern forming apparatus according to the above <24>, by controlling the pattern elements to control any of the n pixel elements that are continuously arranged in the n pixel elements in the light modulation mechanism, The light irradiated from the light irradiation mechanism described above can be modulated at a high speed. The pattern forming device according to any one of the above-mentioned <22>, wherein the light modulation mechanism is a spatial light modulation element. The pattern forming device according to the above <25>, wherein the spatial light modulation element is a digital microlens device (DMD). The pattern forming device according to any one of the above-mentioned <24>, wherein the pixel portion is a microlens. The pattern forming apparatus according to any one of the above-mentioned items, wherein the light-irradiating means can illuminate by combining two or more lights. In the pattern forming apparatus described in <28>, the light irradiation mechanism of the 200809406, which can illuminate by combining two or more lights, is exposed to light having a deep exposure depth. . As a result, the exposure of the aforementioned photosensitive layer can be performed with extremely high definition. For example, when the above-mentioned photosensitive layer is imaged, an extremely fine pattern can be formed. The pattern forming apparatus according to any one of the above-mentioned <22>, wherein the light-irradiating mechanism has a plurality of lasers, a multimode optical fiber, and a plurality of lasers from the plurality of lasers The collective optical system in which the separately irradiated laser light is condensed to be combined with the aforementioned multimode optical fiber. In the pattern forming apparatus according to the above aspect, the light-emitting means is configured to collect laser light that is individually irradiated from the plurality of laser beams by the collective light system described above, and can combine the light beams. The above-mentioned multimode optical fiber is exposed to light having a deep exposure depth. As a result, the exposure of the aforementioned photosensitive layer can be performed with extremely high definition. For example, when the development of the photosensitive layer is performed, a very high-definition pattern 〇 &lt;30&gt; is formed as a permanent pattern forming method, which is characterized by including for &lt;20&gt; to &lt;21&gt; The photosensitive layer in the photosensitive laminate described in any one of the sheets is exposed. &lt;31&gt; The permanent pattern forming method according to the above <30>, wherein the exposure system uses laser light having a wavelength of 350 to 415 nm. The permanent pattern forming method according to any one of the above-mentioned, wherein the exposure is based on the formed pattern information to form an image pattern. The method of permanent formation as described in any one of the above-mentioned <30>, wherein the exposure system uses an exposure head, the attachment mechanism, and has received light from the foregoing a two-array pixel portion of the irradiation mechanism that emits n (however, η is a natural number of 2 or more), and an exposure head that can control the light modulation mechanism of the precursor portion in response to the pattern information, and is configured to The column direction of the pixel portion and the scanning direction of the exposure head are set to an inclination angle of 0, and the exposure head is used for the exposure head by using the pixel unit specified by the pixel specifying device. &lt; However, the above-mentioned pixel portion of 自然 is a natural number of 2 or more; for the above-mentioned exposure head, by the pixel control mechanism, only the prime part specified by the above-mentioned using the pixel specifying unit is involved in the exposure. In the manner of controlling the pixel portion, the exposure head is moved relative to the scanning direction to expose the front layer. In the permanent pattern method described in <33>, in the above-described exposure head, by using a pixel mechanism, a secondary exposure is specified among the available pixel portions (however, Ν is 2) The above-mentioned pixel number is controlled by the pixel control unit, and the pixel unit is controlled in such a manner that only the pixel portion specified by the pixel specifying unit is used. Exposing the photosensitive layer by moving the exposure in the scanning direction to prepare a light pattern for the long-term pattern of the mounting position and the mounting angle of the exposure head, and to make the front view a predetermined structure, by underexposure (The resolution of the aforementioned pattern formed on the exposed surface of the photosensitive layer is caused by the above-mentioned figure and the step of designating the photosensitive forming portion for the crotch portion to be opposed to the exposure head as described above. -15-200809406 The variation of the variation and the concentration unevenness are uniformized. As a result, the exposure of the photosensitive layer is performed with high precision. For example, a high-definition pattern is formed by performing development of the photosensitive layer. <34> As described above &lt;33&gt; The permanent pattern forming method described in which the exposure system can be performed by a plurality of exposure heads, and the pixel portion specifying means is used for repeated exposure from the exposed surface formed by the plurality of exposure heads. In the pixel part of the exposure area of the head of the genus, the N-exposure is specified in the aforementioned inter-header connection area. In the permanent pattern forming method described in <34>, the exposure is performed by a plurality of exposure heads, and the pixel specifying means is used from a plurality of the exposure heads. In the pixel portion participating in the exposure of the inter-head contact region of the repeatedly exposed exposure surface on the exposed surface, the pixel portion used in the inter-head contact region for realizing N exposure is designated, thereby The phenomenon of variation in resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to variations in the mounting position and the mounting angle of the exposure head are uniformized. As a result, the exposure of the photosensitive layer is obtained. The high-definition pattern is formed by, for example, forming a high-definition pattern by performing the development of the photosensitive layer. [35] The method of forming a permanent pattern as described in the above &lt;34&gt;, wherein the exposure system can be plural An exposure head is used, and the means for specifying the repeat exposure range of the exposed surface formed by the plurality of the aforementioned exposure heads is specified by the pixel portion designation-16-200809406 In the pixel portion participating in the exposure other than the inter-connected region, the pixel portion used for realizing N exposure in the region other than the inter-head contact region is specified. The &lt;35 &gt; In the permanent pattern forming method, the exposure system can be performed by a plurality of exposure heads, and the pixel portion specifying means is used to connect the inter-head contact regions of the repeated exposure range on the exposed surface formed by the plurality of the exposure heads. In the pixel portion participating in the exposure, the pixel portion used to realize the N exposure in the region other than the inter-head contact region may be specified, and the mounting position and the mounting angle of the exposure head may be used. The variation of the resolution of the pattern formed on the exposed surface of the photosensitive layer and the density unevenness are uniformized by the deviation. As a result, the exposure of the aforementioned photosensitive layer is performed with high precision, for example, and then a high-definition pattern is formed by performing development of the above-mentioned photosensitive layer. The permanent pattern forming method according to any one of the above-mentioned, wherein the setting of the inclination angle 0 is set to have a relationship conforming to 0 0 0 ideal, and the foregoing 0 ideal, the number N of N exposures, the number s of the direction of the pixel portion, the interval P of the direction of the pixel portion, and the orientation perpendicular to the exposure head when the exposure head is tilted The distance between the column directions of the pixel portions in the direction of the sweep direction is in accordance with the following formula: s psine idealg N 5 〇 &lt; 37 &gt; as described above &lt; 33 &gt; to &lt; 36 &gt; The permanent pattern -17· 200809406 described in the item is a method in which the N-time exposure N is a natural number of 3 or more. In the permanent pattern forming method described in &lt;3&gt;&gt;, the multi-drawing is performed by making N of the N exposures a natural number of 3 or more. As a result, due to the effect of the correction, the variation of the resolution and the density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to the variation in the mounting position and the mounting angle of the exposure head can be made more precise. The ground is uniform. The permanent pattern forming method according to any one of the above-mentioned, wherein the use of the pixel portion specifying means includes: a spot position detecting means, a mechanism for detecting a position of a spot on the exposed surface as a pixel unit constituting an exposure range on the exposed surface by the pixel portion; and a pixel selection mechanism based on the spot The result detected by the position detecting means selects the mechanism for realizing the pixel portion used for N exposures. The permanent pattern forming method according to any one of the above-mentioned <33>, wherein the pixel specifying means is used to specify the use of the N exposures in units of rows. Use the graphics section. The method of forming a permanent pattern according to any one of the above-mentioned items, wherein the spot position detecting means is defined based on the detected at least two spot positions. When the exposure head is tilted, the direction of the light spot on the exposed surface is substantially 0° with the scanning direction of the exposure head, and the pixel selection mechanism is configured to absorb the aforementioned substantial tilt. Angle 0, -1 8 - 200809406 Select the use of the pixel unit in a way that sets the error between the tilt angles of 0. The permanent pattern forming method according to the above <40>, wherein the substantial tilt angle Θ ' is a direction in which the light spots on the exposed surface are in a state in which the exposure head is tilted, and the exposure is as described above. Any one of a plurality of substantial tilt angles, a central 値, a maximum 値, and a minimum 形成 formed by the scanning direction of the head. The permanent pattern forming method according to any one of the above-mentioned <38>, wherein the pixel portion selecting mechanism derives based on the substantial tilt angle 0' to satisfy t tan 0, =N ( However, the N-line represents the natural number t' of the relationship of the number N of N exposures, and is selected from the first row of the pixel parts in which m rows (only m is a natural number of 2 or more) are arranged. The aforementioned pixel portion of the T-th row is used as the pixel portion. The permanent pattern forming method according to any one of the above-mentioned <38>, wherein the pixel portion selecting mechanism derives based on the substantial tilt angle 0' to satisfy tta η 0 ' = N ( However, the N number represents the number of times of N exposures Ν) is close to the natural number of t Τ 'will be ranked in the pixel part of m rows (except that m is a natural number of 2 or more) (T+ 1) The aforementioned pixel portion that is lined up to the mth line is defined as not using the pixel portion, and the above-described pixel portion other than the pixel portion is selected as the used pixel portion. The method of forming a permanent pattern according to any one of the above-mentioned <38>, wherein the pixel selection mechanism is at least included in the plurality of pixels by -19-200809406 (1) in the region of the repeated exposure range on the exposed surface to be formed, the mechanism for using the pixel portion is selected in such a manner as to minimize the total area of the exposure for the ideal N exposures and the area of the underexposed region. (2) Selecting the mechanism using the pixel part in such a manner that the number of pixel units of the overexposed area for the ideal N exposure is equal to the number of pixel units of the underexposed area, (3) according to the ideal N times Selecting the mechanism using the pixel portion in such a manner that the area of the exposed excessive exposure area is minimized and the underexposed area is not generated, and (4) minimizing the area of the underexposed area for the ideal N exposures, and not A method of generating an overexposed area to select any of the mechanisms using the pixel part. The method of forming a permanent pattern according to any one of the above-mentioned items, wherein the pixel portion selecting means is on an exposed surface formed by a plurality of pixel portions. (1) in the connection region between the heads of the repeated exposure range, in such a manner as to minimize the total area of the exposure for the ideal N exposures and the area of the underexposed regions, from the exposure regarding the aforementioned inter-head region The pixel part is defined to not use the pixel part, and the above-mentioned pixel part other than the pixel part is selected as the mechanism using the pixel part, -20- 200809406 (2) according to the ideal N times The number of pixel units of the exposed overexposed area is equal to the number of pixel units of the underexposed area, and the pixel portion is defined from the pixel portion of the exposure of the inter-head contact area, and the non-use map is selected. The pixel portion other than the element portion is used as a mechanism using the pixel portion, and (3) the method is such that the area of the excessive exposure region for the ideal N exposure is minimized, and the underexposure region is not generated. The pixel portion of the exposure in the inter-header connection region defines a non-use pixel portion, and selects the pixel portion other than the pixel portion as the mechanism for using the pixel portion, and (4) The method of defining the non-use of the pixel portion from the pixel portion of the exposure of the inter-head contact region is made such that the area of the underexposed region of the ideal N-time exposure is minimized and the overexposed region is not generated. The above-described pixel portion other than the pixel portion is not used as the mechanism for using the pixel portion. &lt; 46 &gt; The method of forming a permanent pattern as described in the above &lt;45&gt;, wherein the pixel portion is not defined in units of rows. The method of forming a permanent pattern according to any one of the above-mentioned items, wherein the pixel portion is used for specifying the use of the pixel portion specifying means. Among the above-described pixel portions, reference exposure is performed using only the aforementioned pixel portions constituting each of the (N-1) columns of the pixel portion - 21 - 200809406 with respect to N for N exposures. In the permanent pattern forming method described in the above-mentioned &lt;4&gt;&gt;, in order to designate the use of the pixel portion in the pixel specifying unit, among the aforementioned pixel portions that are usable, the N exposure is used. In the case of N, only the pixel portion constituting the pixel portion of each (N -1) column is used for reference exposure, and a simple pixel portion which is slightly drawn once can be obtained. As a result, the aforementioned pixel portion in the aforementioned inter-head contact region can be easily specified. The method of forming a permanent pattern according to any one of the above-mentioned items, wherein the use of the pixel portion in the pixel specifying unit is used as described above. In the pixel portion, reference light exposure is performed using only the pixel portion constituting the pixel portion line per 1/N row with respect to N of the N exposures. In the permanent pattern forming method according to the above [48], in order to specify the use of the pixel portion in the pixel specifying unit, among the pixel portions that are usable, the N exposure is used. N, only the pixel portion constituting the pixel portion of each 1/N row is used for reference exposure, and a simple pixel portion of the drawing is obtained once. As a result, the aforementioned pixel portion in the aforementioned inter-head contact region can be easily specified. The permanent pattern forming method according to any one of the above-mentioned, wherein the pixel specifying mechanism has slits and light as a spot position detecting mechanism. The detector and the calculation device connected to the photodetector as the pixel selection mechanism. The method of forming a permanent pattern according to any one of the above-mentioned items, wherein the N-time exposure is N-series 3 or more and 7 or less from -22 to 200809406. The permanent pattern forming method according to any one of the above-mentioned, wherein the light modulation mechanism further has pattern signal generation for generating a control signal based on the formed pattern information. The mechanism is configured to modulate the light irradiated from the light irradiation means in accordance with a control signal generated by the pattern signal generating means. In the permanent pattern forming method according to the above, the optical modulation means includes the pattern signal generating means described above so as to be modulated by a control signal generated by the pattern signal generating means. The light irradiated by the aforementioned light irradiation means. The permanent pattern forming method according to the above <51>, wherein the optical modulation mechanism is a spatial light modulation element. &lt;53&gt; The permanent pattern forming method according to the above <52>, wherein the spatial light modulation element is a digital microlens device (DMD). The method of forming a permanent pattern according to any one of the above-mentioned <33>, wherein the pixel portion is a microlens. The method of forming a permanent pattern according to any one of the above-mentioned <33>, which has a predetermined portion of a pattern indicating pattern information, and a The conversion means for converting the pattern information described above is used in such a manner that the size of the corresponding portion realized by the pixel portion is the same. The method of forming a permanent pattern according to any one of the above-mentioned <33>, wherein the light-irradiating means can illuminate by combining two or more lights. In the method of permanent pattern formation -23-200809406 described in the above-mentioned &lt;56&gt;, since the light irradiation mechanism can illuminate two or more light beams, exposure light having a deep depth of focus can be exposed for exposure. . As a result, the exposure of the photosensitive film is performed extremely finely, and thereafter, an extremely high-definition pattern is formed by performing development of the photosensitive layer. The method of forming a permanent pattern according to any one of the above-mentioned items, wherein the light-irradiating mechanism has a plurality of lasers, a multimode optical fiber, and a plurality of lasers from the plurality of lasers The laser light that is irradiated separately is collected to be combined with the aforementioned multimode fiber. In the method of forming a permanent pattern according to the above <57>, the laser light irradiated by the plurality of lasers can be condensed by the light irradiation means to be combined with the multimode described above. A combination optical system in which optical fibers are combined, and thus exposure light having a deep depth of focus can be exposed for exposure. As a result, the exposure of the photosensitive film is performed extremely finely, and then an extremely high-definition pattern is formed by performing development of the photosensitive layer. The method of forming a permanent pattern according to any one of the above-mentioned items, wherein the photosensitive layer is subjected to development processing after exposure. In the permanent pattern forming method described in &lt;58&gt;, after performing the above-described exposure, a developing process is performed on the photosensitive layer to form a high-definition pattern. The permanent pattern forming method according to the above <58>, wherein the permanent pattern is formed after the development. &lt;60&gt; A permanent pattern formed by the permanent pattern forming method as described in any one of the above-mentioned &lt;3&gt; to -24-200809406 &lt;5&gt; The permanent pattern described in the above <60> is formed by the above-described pattern forming method, and thus has excellent chemical resistance, surface hardness, heat resistance, and the like, and can be effectively used for high definition. High-density mounting of semiconductors, multilayer wiring boards, and stacked wiring boards. &lt;61&gt; The permanent pattern described in the above &lt;60&gt;, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. The permanent pattern described in <6 1 &gt; is formed of at least one of a protective film, an interlayer insulating film, and a solder resist pattern, so that the film can have insulation properties, heat resistance, and the like. Protect the wiring to avoid impact and bending from the outside. And a permanent pattern forming method according to any one of the above-mentioned <30> to <59>, wherein a permanent pattern is formed. [Effect of the Invention] When the present invention is utilized, the problem of the conventional use can be solved, and a permanent pattern formation such as solder resistance can be provided, and even in the form of the above-mentioned film, the sensitivity is good, and the storage is good. A photosensitive composition excellent in properties and handleability, a photosensitive film, and a permanent pattern forming method capable of forming a high-definition permanent pattern (a protective film, an interlayer insulating film, a solder resist pattern, etc.) in a semiconductor field with good efficiency, and A printed circuit board in which a permanent pattern is formed by the permanent pattern forming method. [Embodiment] -25-200809406 [Best form for carrying out the invention] (Photosensitive composition) The photosensitive composition of the present invention includes at least (A) a binder, (B) a polymerizable compound, and (C) The photopolymerization initiator optionally contains (D) a thermal crosslinking agent, (E) an elastomer, (F) a phenoxy resin, (G) a sensitizer, and (H) other components. The sensitivity of the photosensitive composition is such that when the photosensitive layer formed by using the photosensitive composition is subjected to exposure development, the photosensitive layer used in the exposure does not change the photosensitive layer after the exposure and development. The minimum energy of the light of the thickness of the medium exposed portion is 0.1 to 200 mJ/cm 2 , more preferably 0.2 to 100 mJ/cm 2 , and particularly preferably 0 to 5 to 50 mJ/cm 2 . When the minimum energy system is less than 0.1 mJ/cm2, whitening occurs in the processing step, and when it exceeds 200 mJ/cm2, the time required for exposure becomes longer and the processing speed becomes slower. As used herein, "the minimum energy of light used in the above exposure does not change the thickness of the exposed portion of the photosensitive layer after exposure and development" (hereinafter, simply referred to as "the minimum of light" The energy ") is a so-called development sensitivity, for example, the light energy (exposure amount) used in the exposure described above when the photosensitive layer is exposed, and the aforementioned development processing by the exposure described above. The resulting relationship between the thicknesses of the hardened layers (sensitivity curves) was obtained. The thickness of the hardened layer described above increases as the amount of exposure described above increases, and is then approximately the same as the thickness of the photosensitive layer before exposure, and is approximately constant. The above-mentioned development sensitivity is obtained by reading the aforementioned hardened layer thickness -26-200809406 which is approximately the exposure amount at the time of the fixed enthalpy. Here, when the difference between the thickness of the hardened layer and the thickness of the photosensitive layer before the exposure is within ±1 μm, it can be considered that the thickness of the hardened layer is not changed by exposure development. The method for measuring the thickness of the hardened layer and the thickness of the photosensitive layer before the exposure is not particularly limited, and may be appropriately selected depending on the purpose, and for example, may be a film thickness measuring device or a rough surface. A method of measuring by a measuring machine (for example, Safkheim 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)). The thickness of the photosensitive layer is not particularly limited and may be appropriately selected according to the purpose, and is, for example, preferably 1 to 100 μm, more preferably 2 to 50 μm, and particularly preferably 4 to 30 μm. &lt;Binder&gt; The binder used in the present invention is a reaction product of an epoxy compound (a) partially having a bisphenol skeleton and a monocarboxylic acid (b) having an unsaturated group, A compound obtained by reacting with a polybasic acid compound (c) containing either a saturated group or an unsaturated group. An epoxy compound (a) having a bisphenol skeleton as a part of the above-mentioned epoxy compound, preferably a compound represented by any one of the following general formula (1) and general formula (2) .

General formula (1) -27- 200809406 However, in the above general formula (1), X represents either a hydrogen atom or a glycidyl group; and R represents a methylene group and an isopropylidene group. One; the η system represents an integer of 1 or more. The above-mentioned X represented by the general formula (1) is a glycidyl-based bisphenol fluorene-type epoxy resin or a bisphenol F-type epoxy resin represented by the following structural formula, and may be, for example, The hydroxyl group of the bisphenol A type epoxy resin or the bisphenol F type epoxy resin represented by the formula (5) is obtained by reacting with epichlorohydrin. In order to promote the reaction of a hydroxyl group with epichlorohydrin, it is preferably at 50 to 12 (the reaction temperature of TC, in the presence of an alkali metal hydroxide, in dimethylformamide, dimethylacetamide, dimethylene). The reaction is carried out in a polar organic solvent such as hydrazine. When the above reaction temperature is less than 50 ° C, the reaction becomes slow; when the reaction temperature exceeds 1200 ° C, a side reaction often occurs; They are not ideal. -CH 2_C HC Η 9 \〇/ 2

-28- 200809406 However, in the above general formula (5), R represents any one of a hydrogen atom and a methyl group; and η represents an integer of 1 or more.

In the above general formula (2), R1 represents either a hydrogen atom or a methyl group. 'R2 and R3 represent an alkylene group; m and η represent m + η A positive integer of 2 to 50; the ρ system represents a positive integer. Further, the above m + n is preferably a positive integer of 2 to 30, and more preferably a positive integer of 2 to 20. Further, the above ρ is preferably an integer of 1 to 25, more preferably an integer of 1 to 15, and particularly preferably an integer of 1 to 1 Å. The compound (polymer) represented by the general formula (2) described above is composed of the following repeating unit (1a) and unit (1b). Further, the terminal of the polymer may be any one of units (1 a) and units (1 b); in the case of a terminal unit (1 a), the hydroxyl group in the bisphenol may be substituted with a glycidyl group. . In the unit (1a) and the unit (1b), R1 represents any one of a hydrogen atom and a methyl group; and R2 and R3 represent an alkylene group.

(1b) -29- 200809406 A (b) monocarboxylic acid containing an unsaturated group - the above monocarboxylic acid containing an unsaturated group, for example, it may be acrylic acid, dimer of acrylic acid, methyl group a vinyl-containing monocarboxylic acid such as acrylic acid, furan methacrylic acid, /3-styrylacrylic acid, cinnamic acid, crotonic acid or α-cyano cinnamic acid; and, for example,, for example, a hydroxy group-containing acrylate a half ester compound of a reaction product with a saturated or unsaturated dibasic acid anhydride, a monoglycidyl ether containing a vinyl group or a monoglycidyl ester containing a vinyl group, and a reaction product with a saturated or unsaturated dibasic acid anhydride Ester compound. These semi-ester compounds can be obtained by using a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester, and a saturated or unsaturated dibasic acid anhydride in an equimolar ratio. Obtained by reaction. These monocarboxylic acids containing a vinyl group may be used singly or in combination of two or more. The foregoing may be used for the synthesis of a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether, a vinyl group-containing monoglycidyl ester, and the like, for example, of a vinyl group-containing monocarboxylic acid, for example, for example, It may be hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylic acid Ester, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol pentamethyl acrylate, glycidyl acrylate, glycidyl methacrylate, and the like. The above-mentioned saturated or unsaturated binary -30-200809406 acid anhydride which can be used for the synthesis of a half ester compound, for example, it may be succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrogen Anthracene anhydride, ethyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, ethyl hexahydrophthalic anhydride, and itaconic anhydride, etc., in the foregoing epoxy resin and the aforementioned vinyl-containing monocarboxylic acid In the reaction, it is preferred to carry out the reaction in an amount of from 0.8 to 1.05 equivalents per 1 equivalent of the epoxy group of the epoxy resin, and it is more preferably 0.9. ~1.0 equivalents. The above epoxy resin and the above-mentioned monocarboxylic acid containing a vinyl group may be dissolved in an organic solvent to carry out a reaction; and the organic solvent may, for example, be methyl ethyl ketone or cyclohexanone. Ketones; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; methyl cellosolve, ethyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, a glycol ether such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether or triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate Esters such as esters; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum gas oil, hydrogenated petroleum gas oil, solvent light oil, and the like. Further, in order to promote the aforementioned reaction, it is preferred to use a catalyst. The aforementioned catalyst may be, for example, triethylamine, benzylmethylamine, methyltriethylchlorohydrin, benzyltrimethylammonium chloride or benzyltrimethylammonium bromide, for example. Benzyltrimethylmethylammonium chloride, triphenylphosphine, and the like. The amount of the catalyst to be used is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total of the epoxy resin and the vinyl group-containing monocarboxylic acid. -31- 200809406 Further, in order to prevent the purpose of polymerization in the reaction, it is preferred to use a polymerization inhibitor. The polymerization inhibiting agent may, for example, be hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol or the like. The amount of the polymerization inhibiting agent to be used is preferably 0.01 to 1 part by mass based on 100 parts by mass of the total amount of the epoxy resin and the above-mentioned vinyl group-containing monocarboxylic acid. The above reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 1 20 ° C. The above-mentioned vinyl group-containing monocarboxylic acid may be used together with a polybasic acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride or biphenyltetracarboxylic anhydride, as the case requires. (c) a polybasic acid compound containing a saturated group or an unsaturated group - the above-mentioned polybasic acid anhydride containing a saturated group or an unsaturated group, for example, it may be succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, Anthracene anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, and the like. In the reaction of the above reaction product with the above-mentioned polybasic acid anhydride containing a saturated group or an unsaturated group, by saturating the hydroxyl group in one equivalent of the reaction product with respect to the above-mentioned oxime equivalent of 0.1 to 1. The reaction is carried out by using a polybasic acid anhydride having a base or an unsaturated group, that is, the acid value of the aforementioned binder can be adjusted. The acid value of the above binder is preferably from 30 to 150 mg KOH/g, more preferably from 50 to 120 mg KOH/g. When the acid value is less than 30 mg KOH/g, the solubility of the photocurable resin composition for a dilute alkali solution is lowered; and when it exceeds 150 mg KOH/g, the electrical properties of the cured film are The situation of decline. The reaction temperature between the above reaction product and the above-mentioned saturated or unsaturated group-containing polybasic acid anhydride -32 to 200809406 is preferably 60 to 120 °C. A further adhesive, a binder which can be used together with the above-mentioned binder, is preferably a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain. For example, the acid group may be a carboxyl group, a phosphoric acid group, a sulfonic acid group or the like. However, it is preferably a carboxyl group from the viewpoint of obtaining a raw material or the like. The above-mentioned binder is preferably a compound which is insoluble in water and which is swollen or dissolved by an aqueous alkaline solution. Further, as the binder, at least one polymerizable double bond may be used in the molecule. For example, an acrylic group such as (meth) acrylate or (meth) acrylamide or a vinyl ester of a carboxylic acid may be used. Various polymerizable double bonds such as vinyl ether and allyl ether. More specifically, for example, it may be a compound obtained by adding a cyclic ether group-containing polymerizable compound to an acrylic resin containing a carboxyl group as an acidic group, and the like, for example, glycidol acrylate may be added. a glycidyl ester of an unsaturated acid such as an ester, glycidyl methacrylate or cinnamic acid, or an alicyclic epoxy group (for example, an epoxy group having a cyclohexene oxide or the like in the same molecule) and (a) An epoxy group-containing polymerizable compound or the like which is a compound of an acrylonitrile group. Further, for example, it may be a compound obtained by adding a polyisocyanate group-containing polymerizable compound such as (meth)acrylic acid polyisocyanate ethyl ester to an acrylic resin containing an acidic group and a hydroxyl group, and containing an anhydride. A compound obtained by adding a hydroxyl group-containing polymerizable compound such as a hydroxyalkyl (meth)acrylate to the acrylic resin is added to the base resin. Further, a vinyl ether-containing polymerizable compound such as glycidyl methacrylate or a vinyl monomer such as (meth) propylene decyl alkyl ester is copolymerized with -33 - 200809406 and (meth)acrylic acid A compound obtained by addition to an epoxy group of a side chain. Examples of such an example include, for example, Japanese Patent Publication No. 2,763,075, Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. &lt;(B) Polymerizable compound&gt; The above-mentioned polymerizable compound is not particularly limited, and may be appropriately selected according to the purpose, but it is preferred to have at least one polymerizable group in the molecule, and The compound having a boiling point of at most 100 ° C is, for example, at least one selected from the group having a (meth)acryl group. The aforementioned monomer having a (meth)acryl group is not particularly limited and may be appropriately selected according to the purpose of the object; for example, it may be polyethylene glycol mono(meth)acrylate or polypropylene glycol alone. Monofunctional acrylate or monofunctional methacrylate such as (meth) acrylate or phenoxyethyl (meth) acrylate; polyethylene glycol di(meth) acrylate, polypropylene glycol bis (A) Acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trihydrocarbyl propane diacrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tetra(methyl) Acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di(meth) acrylate, trimethylolpropane Tris(propylene methoxypropyl)ether, tris(propylene decyloxyethyl)isocyanate, tris(propylene decyloxyethyl) cyanurate, tris(meth)acrylate Trimethylol Propylene, glycerin, bisphenol, etc., which are subjected to an addition reaction of an oxirane group or a propylene oxide on a polyfunctional alcohol, followed by a (meth) acrylate-ester-34-200809406; in Japanese Patent Publication No. 48-41708 No. pp. 50-6034, and JP-A-51-37193, etc., and the urethane acrylates described in each of the publications: JP-A-48-641 83, JP-A-49-431 91, and JP-A 52 A polyfunctional acrylate such as an epoxy acrylate described in each of the publications such as No. 30490; an epoxy acrylate such as an epoxy acrylate of a reaction product of an epoxy resin and (meth)acrylic acid, or a methacrylate. Among these, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate is particularly preferred. In the solid content of the photosensitive composition described above, the solid content of the polymerizable compound is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. When the content of the solid content is less than 5% by mass, problems such as deterioration in developability and deterioration in exposure sensitivity occur, and when it exceeds 50% by mass, adhesion of the photosensitive layer becomes excessively strong. . &lt;(C) Photopolymerization initiator> The photopolymerization initiator is preferably a compound selected from the group consisting of a mercaptophosphine oxide compound and an anthracene derivative, and particularly preferably an anthracene derivative. Further, other photopolymerization initiators may be contained as occasion demands. An fluorenylphosphine oxide compound-'mercaptophosphine oxide compound, for example, may be a monodecylphosphine oxide, a bis-indenylphosphine oxide or a tridecylphosphine oxide compound. The above-mentioned fluorenylphosphine oxide compound is, for example, a compound represented by the following general formula (6) as suitable. 0 0 II II ... R11 — P — c — R13 — (6) R12 -35- 200809406 However, in the above general formula (6), R11 and R1 2 each independently represent a carbon number of 1 a phenyl group of -12, a sulfhydryl group, an amino atom, a halogen atom, a phenyl group substituted 1 to 4 times via an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms; Any of phenyl group, cyclohexyl group, and a group represented by COR13 in the following formula (i), and r11 may also represent an OR14 group and a group represented by the following formula (i) Either. R1 3 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, and 1 to 4 times by halogen atom substitution. Any one of a phenyl group and a group represented by the following formula (M); and R14 represents any one of an alkyl group having 1 to 8 carbon atoms, a phenyl group and a benzyl group. The γ-ray represents a phenyl group, an alkenyl group having 1 to 12 carbon atoms, and a cycloalkenyl group, and x represents an alkenyl group having 1 to 8 carbon atoms, and is represented by the following formula (hi) Any of the bases. 〇 0

II II Formula (i) X — P — c — R13 R11 〇 0 Formula (ii) II || Y — C — P — R11

I R12 Formula (iii) is a specific compound represented by the general formula (6), for example, 'which may be bis(2,6-dimethoxybenzyl) phenylphosphine oxide, Bis(2,6-monomethoxyloxy)(2,4,4-trimethylpentyl)phosphine oxide, bis(2,6_-36 - 200809406 dimethoxybenzylidene)-η - Butyl phosphine oxide, bis(2,6-dimethoxybenzyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzyl)-( 1-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzyl) ring Hexyl phosphine oxide, bis(2,6-dimethoxybenzyl) octyl phosphine oxide, bis(2-dimethoxybenzyl) (2-methylpropan-1-yl) phosphine oxide, double (2-dimethoxybenzyl) (1-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzyl)-(2-methylpropan-1-yl) Phosphine oxide, bis(2,6-diethoxybenzyl) (1-methylpropan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzyl) (2-methyl) Propane-1-yl)phosphine oxide, bis(2,4-dimethoxy (benzylidene)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzylidene)(2,4-dipentyloxyphenyl)phosphine oxide, double 2,6-dimethoxybenzylidene)benzylphosphine oxide, bis(2,6-dimethoxybenzyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxy Benzylidene-2-(phenylethylphosphine oxide), bis(2,6-dimethoxybenzylidene)benzylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2 -Phenylpropylphosphine oxide, bis(2,6-dimethoxybenzyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzyloxybenzylphosphonium butylphosphine oxide , 2,6-dimethoxybenzylphosphonylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-2,5-diisopropylphenylphosphine oxide, double (2, 4,6-trimethylbenzylidene)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-4-methylphenylphosphine oxide, double (2, 4,6-trimethylbenzylidene)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-2,3,5,6-tetramethyl Phenyl phenylphosphine oxide, bis(2,4,6-trimethylbenzylindenyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzylidene two Phosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzylidene)isobutyl Phenyl phenylphosphine oxide, 2,6-dimethoxybenzyl-37- 200809406 fluorenyl-2,4,6-trimethylbenzylidene-η·butylphosphine oxide, bis(2,4,6· Trimethyl benzhydryl)phenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[double (2 , 4,6-trimethylbenzylidene)phosphine oxide ruthenium, tris(2-methylthionyl)phosphine oxide, and the like. Among these, bis(2,4,6-trimethylsulfonyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-2,4-di- is preferred. N-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzylphosphonium diphenylphosphine oxide, bis(2,6-dimethoxybenzylidene 2,4,4_trimethyl A fluorenylphosphine oxide. The monoterpene derivative is not particularly limited, and may be appropriately selected depending on the purpose, and is preferably a compound having at least an aromatic group, and more preferably has the following general A compound having a partial structure represented by any one of the formula (3) and the following general formula (4). The above-mentioned anthracene derivative may be used in combination of two or more kinds.

Ar~(c(Y1)= Ν-〇-Y2)m General (3) Ar-(c〇-C(Y1)=N~〇-Y2) General formula (4) \ / m However, in the foregoing In the general formulae (3) and (4), the Ar system represents any one of an aromatic group and a heterocyclic group; Y 1 represents a hydrogen atom and a monovalent substituent; and the Y 2 represents an aliphatic group. Any one of an aromatic group, a heterocyclic group, COY3, C02Y3 and CONY4Y5; Y3, Y4 and 丫5 represent any of an aliphatic group, an aromatic group and a heterocyclic group; m represents an integer of 1 or more . The above Y1 is preferably any one of a hydrogen atom, an aliphatic group and an aromatic group. -38- 200809406 The aforementioned Y2 is preferably any of an aliphatic group, COY6, and C02Y6. Y6 represents any of an aliphatic group, an aromatic group, and a heterocyclic group. 〇 Y3 and Y4 are preferably any of an aliphatic group and an aromatic group. The above-mentioned general formula (3) and the structure represented by the above general formula (4), which are the above-mentioned anthracene derivatives, may be a compound which is bonded by a plurality of linking groups. Further, in the above general formula (3) and the above general formula (4), the above aliphatic group represents an alkyl group, an alkenyl group or an alkynyl group which may have an individual substituent, and the above aromatic group may have individual The substituent aryl group, heterocyclic ring group, the above monovalent substituent represents a halogen atom, an amine group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a sulfur An ether group, a decyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have an individual substituent. The above aromatic group may be, for example, one to three benzene rings to form a condensed ring, a benzene ring, and a 5-membered unsaturated ring to form a condensed ring; and the like; for example, for example, for example It may be a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, a dihydroindenyl group, a fluorenyl group or the like; among these, it is preferably a group having a phenyl group and a naphthyl group, and more preferably It is preferably a group having a naphthyl group. Further, these aromatic groups may have a substituent such as a substituent. For example, it may be a group composed of a monovalent non-metal atom group other than a hydrogen atom. For example, it may be an alkyl group, a substituted alkyl group, or a substituent as a substituent in the substituted alkyl group, which will be described later. Further, the above (hetro ring) group, pyrrole ring group, furan ring group, thiophene-39 - 200809406 ring group, benzopyrrole group, benzofuran ring group, benzothiophene ring group, pyrazole ring group, different Oxazole ring group, isothiazole ring group, carbazole ring group, benzoisoxazole ring group, benzisothiazole ring group, imidazole ring group, indazole ring group, thiazole ring group, benzimidazole ring group, benzene And oxazolyl ring group, benzothiazole ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, hydrazine ring group, pyrimidine ring group, pyr trap ring group, anthracene ring group, quinazoline ring , quinoxaline ring group, oxaziridine ring group, phenanthridine ring group, carbazole ring group, porphyrin ring group, piper ring group, piperidine ring group, piperazine ring group, morpholin ring a group, an anthracene ring group, an anthracene ring group, a chromene ring group, a porphyrin ring group, an acridine ring group, a morpholidine group, a tetrazole ring group, a triple well ring group, etc.; Preferably, it is a furanyl group, a thiophene ring group, an imidazole ring group, a thiazole ring group, a benzothiazole ring group, a pyridine ring group, an anthracene ring group, an acridine ring group. Further, the heterocyclic group may have a substituent. Such a substituent may be, for example, a group composed of a monovalent non-metal atom other than a hydrogen atom. For example, it may be an alkyl group, a substituted alkyl group, or a substituent as a substituent in the substituted alkyl group, which will be described later. The above monovalent substituent is preferably a halogen atom, an amine group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group, a decyl group, a nitro group, a cyano group, or the like. An alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group having an individual substituent. Further, the above-mentioned monovalent substituent composed of a non-metal atomic group is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have an individual substituent. The above-mentioned alkyl group which may have a substituent, for example, may be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Its -40 - 200809406 specific examples, for example, may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, eleven Twelve, thirteen, hexadecyl, octadecyl, icosyl, isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, 1-methyl Butyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-mercaptocarbonyl. Among these, an alkyl group having a linear chain of 1 to 12 carbon atoms, a branched form having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms is more preferable. The substituent of the above-mentioned alkyl group which may have a substituent, for example, it may be a substituent composed of a monovalent non-metal atom group other than a hydrogen atom; preferably, for example, it may be a halogen Atom (a F, a Br, a CI, an I), a thiol, an alkoxy group, an aryloxy group, a thiol group, a thiol group, an arylthio group, an alkyldithio group, an aryldithio group, Amino, N-alkylamino, N,N-dialkylamino, N-arylamino, hydrazine, hydrazine, diarylamino, N-alkyl-N-arylamino, decyloxy, amine Alkoxy, Ν-alkylamine methyl methoxy, Ν-arylamine methyl methoxy, hydrazine, hydrazine-dialkylamine methyl methoxy, hydrazine, fluorene-diarylamine methyl methoxy, Ν-Alkyl-fluorenyl-arylamine methyl methoxy, alkyl sulfonyloxy, aryl sulfonyloxy, decylthio, decylamino, fluorenyl-alkyl sulfhydryl, hydrazine Aryl mercaptoamine, ureido, Ν'-ureido, Ν', Ν'-dialkylureido, Ν'-arylureido, Ν', Ν'-diarylureido, Ν' -alkyl-Ν'-arylureido, Ν-alkylureido, Ν-arylureido, Ν'-alkyl-oxime-alkylurea, Ν' -alkyl-fluorene-arylureido, Ν', Ν'-dialkyl- phenylalkylurea, 1^', Q'-dialkyl-bualkylurea, ^, 『-dioxane Benzyl-arylurea, Ν'-aryl-hydrazine-alkylureido, Ν'-alkyl-oxime-arylureido, N',N'-diaryl-N-alkylureido, N ', N'-diaryl-N-arylureido, N'-alkyl-N'-aryl-N-alkylureido, etc., N'-alkyl-N'-aryl-N- Arylureido, alkoxy-41 - 200809406, carbonylamino, aryloxycarbonylamino, N-alkyl-N-alkoxycarbonyl, N-alkyl-N-aryloxy Amine, N-aryl-N-alkoxycarbonylamino, N-aryl-N-aryloxycarbonylamino, decyl, decyl, carboxy, alkoxycarbonyl, aryloxy Carbonyl, amine methyl sulfhydryl, N-alkylamine methyl sulfhydryl, N,N-dialkylamine methyl fluorenyl, N-arylamine carbhydryl, anthracene, fluorene-diarylamine carbhydryl, N -alkyl-N-arylaminecarbamyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonate (-S03H) and their conjugation Base (referred to as sulfonate), alkoxysulfonyl, amine sulfinyl, N-alkylamine sulfin N,N-dialkylamine sulfinyl, N-arylamine sulfinyl, N,N-diarylamine sulfinyl, N-alkyl-N-arylamine sulfin Sulfhydryl, amine sulfonyl, N-alkylamine sulfonyl, anthracene, fluorenyl-dialkylamine sulfonyl, N-arylamine sulfonyl, N,N-diarylamine sulfonyl, N-alkyl-N-arylamine sulfonyl, phosphonic acid (-P〇3H2) and its conjugated base (referred to as phosphonate), dialkylphosphonic acid group (a P03 (alkyl) 2 "Alkyl = decentral, the same as below", diarylphosphonic acid group (a P03 (aryl) 2) "aryl = aryl, the same as below", alkyl arylphosphonic acid group (a P03 (alkyl) (aryl )), a monoalkylphosphonic acid group (a P〇3 (alkyl)) and its conjugated base (referred to as an alkylphosphonate group), a monoarylphosphonic acid group (-P03H (aryl)) and A conjugate base (referred to as an arylphosphonate group), a phosphonic acidoxy group (a 〇ρ〇3η2) and a conjugated base thereof (referred to as a phosphonateoxy group), a dialkylphosphonic acid oxy group (“0P03H ( Alkyl) 2), diarylphosphonic acidoxy (mono OP03 (aryl) 2), alkyl aryl phosphonic acid oxy (a OP 〇 3 (a | ky |) (aryl)), monoalkyl phosphonic acid Oxygen (—0卩0chuan (3丨1&lt;71 )) and its conjugated base (referred to as alkylphosphonateoxy), monoarylphosphonate ("PO03H (aryl)) and its conjugated base (referred to as arylphosphonateoxy), cyanide Base, nitro, aryl, alkenyl, alkynyl, heterocyclic, decyl and the like. -42- 200809406 Specific examples of the alkyl group in the substituents, for example, may be the aforementioned alkyl group. Specific examples of the aryl group in the above substituent may be, for example, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a cumyl group, a chlorophenyl group, or the like. Bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, ethoxylated phenyl, benzhydryloxyphenyl, methylsulfide Phenyl, phenylthiophenyl, methylaminophenyl, dimethylaminophenyl, ethionylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, phenoxy Phenylcarbonylphenyl, N-phenylamine-nonylphenyl, cyanophenyl, sulfophenyl, sulfonylphenyl, phosphonicphenyl, phosphonatephenyl, and the like. Further, specific examples of the alkenyl group in the above substituent may, for example, be a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, a 2-chloro-1-ether group, etc.; Specific examples of the alkynyl group in the substituent may, for example, be ethynyl, 1-propynyl, 1-butynyl, trimethyldecylethynyl and the like. The heterocyclic group in the above substituent may, for example, be a pyridyl group, a piperidinyl group or the like. The decyl group in the above substituent may, for example, be a trimethyl decyl group or the like. In the above substituent, a fluorenyl group (RQ1CO -) may be contained; for example, it may be, for example, a hydrogen atom, a pharmaceutically acceptable group, an aryl group or the like. RQ1 of a mercapto group (RQ1CO-), for example, may be a hydrogen atom, and the aforementioned alkyl group, aryl group or the like. Among these substituents, it is more reasonable that -43 - 200809406 is a dentate atom (-F, -B", -C丨, -丨), alkoxy, aryloxy, alkylthio, Arylthio, N-alkylamino, hydrazine, hydrazine-dialkylamino, decyloxy, hydrazine-alkylamine methyl methoxy, fluorene-arylamine methyl methoxy, decylamino, formazan Base, fluorenyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, amine carbaryl, fluorenyl-alkylamine, fluorene, hydrazine, hydrazine-dialkylamine, hydrazino, hydrazine Base, fluorenyl-alkyl-fluorene-arylamine, mercapto group, sulfonate group, sulfonate group, fluorenyl-alkylamine sulfonyl group, anthracene, fluorenyl-dialkylamine sulfonyl group, Anthracene-arylsulfonyl, anthracene, fluorene-diarylamine sulfonyl, phosphonic acid, phosphonate, dialkylphosphonic acid, diarylphosphonic acid, monoalkylphosphonic acid, An alkylphosphonate group, a monoarylphosphonate group, an arylphosphonate group, a phosphonic acidoxy group, a phosphonateoxy group, an aryl group, an alkenyl group, etc. On the other hand, an alkylene group in the above substituted alkyl group For example, it may be, for example, 2 of any one of the hydrogen atoms removed from the aforementioned alkyl group having 1 to 20 carbon atoms. The organic residue; for example, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a carbon number of 5 to 10; A preferred specific example of the substituted alkyl group obtained by combining a substituent with an alkylene group, for example, may be, for example, a chloromethyl group, a bromomethyl group or a 2-chloroethyl group. Base, trifluoromethyl, methoxymethyl, isopropoxymethyl, butoxymethyl, s-butoxybutyl, methoxyethoxyethyl, allyloxymethyl, Phenoxymethyl, methylthiomethyl, tolylthiomethyl, pyridylmethyl, tetramethylpiperidinylmethyl, indole-ethenyltetramethylpiperidinylmethyl, trimethyldecane Methyl, methoxyethyl, ethylaminoethyl, diethylaminopropyl, morpholinylpropyl, ethoxymethyloxy, benzhydryloxymethyl, fluorene-cyclohexylamine Methoxyethyl, Ν-phenylamine methyl methoxyethyl, ethionylaminoethyl, Ν-methylbenzhydrylaminopropyl, 2-oxoethoxy-44 - 200809406 , 2-sided oxypropyl, decylpropyl, methoxyethyl, propylene Alkyl butyl, chlorophenoxycarbonylmethyl, amine mercaptomethyl, N-methylamine, decylethyl, N,N-dipropylamine, decylmethyl, N-(A Oxyphenyl) amine methyl decyl ethyl, N-methyl-N-(phosphonophenyl) amine methyl decyl methyl, sulfonic acid butyl, sulfonyl butyl, sulfonyl butyl , N-ethylamine sulfonylmethyl, hydrazine, hydrazine-dipropylamine sulfonyl sulfonyl, hydrazino-anilinosulfonyl propyl, hydrazine-methyl-hydrazine-(phosphonophenyl)amine Sulfosyloctyl, phosphonic acid butyl, phosphonic acid hexyl, diethylphosphonic butyl, diphenylphosphonic propyl, methylphosphonic butyl, methylphosphonic butyl , tolylphosphonylhexyl, fluorenylphenylphosphonate hexyl, phosphonooxypropyl, phosphonitoxypropyl, benzyl, phenethyl, a-methylbenzyl, 1-methyl-1 -phenylethyl, ρ-methylbenzyl, cinnamyl, allyl, 1-propenylmethyl, 2-butenyl, 2-methylallyl, 2-methylpropenylmethyl, 2-propynyl, 2-butynyl, 3-butynyl and the like. The aforementioned aryl group, for example, may be a substance which forms a condensed ring from 1 to 3 benzene rings, a condensed ring formed of a benzene ring and a 5-membered unsaturated ring; specific examples, for example, for example It may be a phenyl group, a naphthyl group, an onion group, a phenanthryl group, an anthracenyl group, an indanyl group, a fluorenyl group or the like. Among these, a phenyl group and a naphthyl group are more preferable. The above substituted aryl group may have a group composed of a monovalent non-metal atom group other than a hydrogen atom as a substituent on the ring-forming carbon atom of the above-mentioned aryl group. Examples of preferred substituents, for example, may be the aforementioned alkyl group, substituted alkyl group, and exemplified as the substituent in the aforementioned substituted alkyl group. Preferred specific examples of the above substituted aryl group, for example, may be -45-200809406 to be biphenyl, tolyl, xylyl, trimethylphenyl, cumyl, chlorophenyl, bromobenzene , fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl , methylthiophenyl, tolylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinylphenyl, ethoxylated phenyl, benzhydryloxyphenyl, N- Cyclohexylamine methyl methoxy phenyl, N-phenylamine methyl methoxy phenyl, ethyl hydrazino phenyl, N -methyl benzyl phenyl phenyl, carboxy phenyl, methoxy Carbonylphenyl, allyloxycarbonylphenyl, chlorophenoxycarbonylphenyl, amine methyloxyphenyl, N-methylamine methyloxyphenyl, N,N-dipropylamine formazan Oxyphenyl, N-(methoxyphenyl)amine, methoxyphenyl, N-methyl-N-(sulfonylphenyl)amine, methoxyphenyl, sulfonylphenyl, Sulfonic acid phenyl, acesulfonyl phenyl, N-ethylamine sulfonyl phenyl, hydrazine, -dipropylaminesulfonylphenyl, fluorenyl-tolylaminesulfonylphenyl, fluorenyl-methyl-hydrazine-(sulfonylphenyl)amine sulfonylphenyl, phosphophenyl phenyl, phosphine Acid-based phenyl, diethylphosphonic phenyl, diphenylphosphonic phenyl, methylphosphonic phenyl, methylphosphonic phenyl, tolylphosphonic phenyl, tolyl phosphine Acid-based phenyl, allylphenyl, 1-propenylmethylphenyl, 2-butenylphenyl, 2-methylallylphenyl, 2-methylpropenylphenyl, 2-propenyl Alkynylphenyl, 2-butynylphenyl, 3-butynylphenyl, and the like. The above alkenyl group, the aforementioned substituted alkenyl group, the aforementioned alkynyl group and the above substituted alkynyl group (a C(R02) = C(R03)(R〇4, 〇, n05, , ) and a Ce C(R05) For example, it may be, for example, RQ2, RQ3, R〇4 and R5 which are radicals composed of monovalent non-metal radicals. The aforementioned RQ2, RQ3, and R. 4 and r〇5 , for example, may be a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituent. Specific examples of such, for example, may be exemplified by the examples described. Among these, a specific example is a hydrogen atom, a halogen atom, a linear alkyl group having a number of 1 to 10, a branched alkyl group, or a cyclic alkyl group. For example, it may be ethylene. Base, group, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-octenyl, 1-E propenyl, 2-methyl-1-propenyl, 2-methyl-1 a butenyl group, a 2-phenyl 3 alkenyl group, a 2-chloro-1-vinyl group, an ethynyl group, a 1-propynyl group, a 1-butynyl ethynyl group or the like. The heterocyclic group, for example, may be, for example, a pyridyl group or the like which is exemplified as a substituent. The aforementioned oxy group (R^O-), for example, may be a desired substituted oxy group of a group consisting of a monovalent non-metal atomic group other than a hydrogen atom, for example, it may be an alkane Oxy, decyloxy, carbamoyloxy, N-alkylamine, decyloxy, N-methylindolyloxy, N,N-di-systemylamine, fluorenyloxy, ν, Ν-Diaryloxy, Ν-alkyl-Ν-arylamine, fluorenyloxy, alkylsulfonic acid arylsulfonyloxy, phosphonic acidoxy, phosphonic acidoxy, etc. . The alkyl group and the aryl group, for example, may be exemplified as an alkyl group, a substituted alkyl group, and an aryl group and a substituted aryl group. Further, a mercapto group (RQ7CO-) in the prooxy group, for example, r〇7 can be used as the alkyl group, the substituted alkyl group, and the aryl group and the object of the previous examples. Among these substituents, an alkoxy group, an aryloxy group or an arylsulfonic acid group is preferred. A specific example of a preferred substituted oxy group, a aryl group or the like is used as a procarbocarbon atom 〇 1-propene P-yl-1-S-1-ethyl or phenylalkyl R06. The aryloxyarylamine amine methyl methoxy group, and the like described above are aryl, methoxyoxy, -47-200809406 ethoxy, propoxy, isopropoxy, butyl Oxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, carboxyethyloxy, methoxycarbonyloxy, ethoxycarbonyl Oxy, methoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, morpholinylethoxy, morpholinylpropoxy, allyloxy Ethoxyethoxy, phenoxy, tolyloxy, xylyloxy, tricyloxy, tricyloxy, isopropyloxy, methoxyphenyloxy, ethoxy Phenyloxy, chlorophenyloxy, bromophenyloxy, acetyloxy, benzhydryloxy, naphthyloxy, phenylsulfonyloxy, phenylsulfonylbenzene A group, a phosphonic acidoxy group, a phosphonate group oxy group, and the like. Also substituted with a mercapto substituted amine group (RG8NH-, (R^MR^^N-), for example, F^8, F^9, and a non-metal other than a hydrogen atom may be used. Further, F^9 and R151 may be linked to form a ring. Preferred examples of the substituted amine group may, for example, be an N-alkylamine group, N, N. a dialkylamino group, an N-arylamino group, an N,N-diarylamino group, an N-alkyl-N-arylamino group, a decylamino group, an N-alkyldecylamino group, N-aryldecylamino, ureido, Ν'-alkylureido, Ν', Ν'-dialkylureido, Ν'-arylureido, Ν', Ν'-diarylurea Base, Ν'-alkyl-Ν'-arylureido, Ν-alkylureido, Ν-arylureido, Ν'-alkyl-oxime-alkylureido, Ν'-alkyl-oxime -Arylureido, Ν', Ν'-dialkyl-oxime-alkylureido, Ν'-alkyl-1^-arylureido, 1^,1^'-dialkyl-cycloalkane Urea group, 1^', Q'-dialkyl-^-arylureido, Ν'-aryl-hydrazine-alkylureido, Ν'-aryl-fluorene-arylurea, Ν' ,Ν'-diaryl-fluorenyl-alkylurea, Ν', Ν'- Aryl-fluorene-arylureido, Ν'-alkyl-Ν'-aryl-hydrazine-alkylureido, Ν'-alkyl-Ν'-aryl-Ν-arylureido, alkoxy Carbonyl-48- 200809406 Amino, aryloxycarbonylamine, N-alkyl-hydrazine alkoxycarbonylamino, N-alkyl-N-aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamine a base, an N-aryl-N-aryloxyamino group, etc. The alkyl group and the aryl group among these, for example, may be exemplified as the aforementioned alkyl group, substituted alkyl group, and The aryl group and the substituted aryl group; the fluorenyl group of the mercaptoamine group, the N-alkyldecylamino group, and the N-aryl fluorenylamino group (R07CO-) are as described above. Among them, More desirable examples are, for example, an N-alkylamino group, an N,N-dialkylamino group, an N-arylamino group, a mercaptoamine group, a specific example of a preferred substituted amine group, For example, 'methylamino, ethylamino, diethylamino, morpholinol, piperidinyl, pyridinyl, phenylamino, benzhydrylamino, ethyl fluorenyl Amine group, etc. Substituted sulfonyl group (RQ11 - S02 -), for example, RG11 can be used as a More preferably, for example, it may be an alkylsulfonyl group or an arylsulfonyl group. Among them, an alkyl group and an aryl group, for example, For example, it may be exemplified as the aforementioned alkyl group, substituted alkyl group, and aryl group and substituted aryl group. Specific examples of the substituted sulfonyl group such as, for example, it may be butyl sulfonate. Sulfhydryl, phenylsulfonyl, chlorophenylsulfonyl, etc. Sulfonate (a so3-), as mentioned above, means the conjugated base anion of a sulfonic acid group (-S03H), usually more suitable It is used together with the cation. Such a cationic system can be suitably selected by using a generally known object, for example, for example, it may be a key (for example, ammonium, sulfur, scaly, anthraquinone, acridine, etc.), Metal ions (for example, Na+, K+, Ca2+, Zn2+, etc.). Instead of a carbonyl group (RQ13 - CO-), for example, -49 - 200809406 rQ13 can be used as a group consisting of monovalent non-metal atomic groups. A preferred example of the substituted carbonyl group may, for example, be a fluorenyl group, a fluorenyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxy group, an amine carbaryl group, an N-mercaptoamine fluorenyl group, N, N-Secondary amine carbamyl, N-aryl amide, hydrazine, hydrazine-diarylamine carbhydryl, hydrazine-alkyl- Ν'-arylamine carbaryl. The alkyl group and the aryl group among these are, for example, exemplified as the above-mentioned alkyl group, substituted alkyl group, aryl group and substituted aryl group. Among these, a preferred substituted carbonyl group is, for example, a decyl group, a fluorenyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, a fluorenyl-alkylamine carbaryl group, an anthracene group, Anthracene-dialkylaminecarbamyl, fluorene-arylaminecarbamyl; more desirable examples, for example, it may be a decyl group, a fluorenyl group, an alkoxycarbonyl group or the like, and an aryloxycarbonyl group. Specific examples of the preferred substituted carbonyl group may, for example, be a methyl group, an ethyl fluorenyl group, a benzamidine group, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an allyloxycarbonyl group or a dimethylamino group. Phenyl ether carbonyl, methoxycarbonylmethoxycarbonyl, hydrazine-methylaminecarbamyl, anthracene-phenylaminecarbamyl, anthracene, fluorene-diethylamine methyl hydrazino, phenolyl carbonyl, and the like. Instead of the sulfinyl group (RQ14-SO-), for example, RQ14 may be used as a group composed of a monovalent non-metal atomic group. A preferred example, for example, may be an alkylsulfinyl group, an arylsulfinyl group, an amine sulfinyl group, an N-alkylamine sulfinyl group, an N,N-dialkyl group. Amine subunit, N-arylamine sulfinylene, anthracene, fluorenyl-diarylamine sulfinylene, N-homo-indole-arylamine sulfinyl group, and the like. The alkyl group and the aryl group among these are, for example, exemplified as the above-mentioned alkyl group, substituted alkyl group, aryl group and substituted aryl group. Among these, a more desirable example is an alkylsulfinyl group or an arylsulfinyl group. Specific examples of the substituted sulfinyl group like this, -50-200809406 For example, a suitable one is a hexylsulfinyl group, a benzylsulfinyl group, a tolylsulfinyl group or the like. The term "substituted phosphonic acid group" means that one or two hydroxyl groups on the phosphonic acid group are substituted by other organic side oxy groups; preferably, for example, it may be the aforementioned A dialkylphosphonic acid group, a diarylphosphonic acid group, an alkylarylphosphonic acid group, a monoalkylphosphonic acid group, a monoarylphosphonic acid group or the like. Among these, a dialkylphosphonic acid group or a diarylphosphonic acid group is more preferable. As a specific example of this, for example, it may be diethylphosphonic acid group, dibutylphosphonic acid group, diphenylphosphonic acid group or the like. The so-called phosphonate radical (-P〇3H2-, a po3h-), as described above, refers to the conjugated base anion derived from the first dissociation of the acid of the phosphonic acid group (-P03H2) or the second dissociation of the acid. the meaning of. Generally, it is preferred to use it together with a cation. Such a cationic system may be suitably selected from those generally used, for example, for example, it may be an anthracene (for example, ammonium, sulfur, scaly, anthraquinone, acridine, etc.), Metal ions (for example, Na+, K+, Ca2+, Zn2+, etc.). The so-called substituted phosphonate group may be a conjugated base anion group in which a hydroxyl group within a phosphonic acid group is substituted into an organic pendant oxy group; for example, for example, it may be a monoalkyl group as described above Phosphonic acid group (mono P 〇 3H (alkyl)), monoarylphosphonic acid group (mono P 〇 3H (aryl)). Other specific examples of the above-described anthracene derivative, for example, may be a compound disclosed in JP-A-2001-233842, JP-A-2004-534797, and JP-A-2002-51 9732, and the like. A compound represented by the following structural formula or the like. 3200809406

〇 N-O-C-CH

〇 N-〇-ϋ - CH3

-52 - 200809406 In the above structural formula, R represents any of η - C 3 Η 7 ' η - C8H17, rod brain, and Ρ - CH3C6H4. 0 〇 II Μ

In the above structural formula, R represents any of n-C3H7 and p-CH3C6H4. 0

Cogh3 I 0

XN

-53 - 3200809406 ο

3 Ν force-C〇C3H7

-54 200809406

H3x.N-0-C0CH3 ch3v.no-coch3 Λ Λ υ V - I OC12H25 s-^^-ch3 NO-off 3 c2h5v^no-coch3 Λ Λ v V och3 och3 ch3_n-o-coc2h5 ch3v.no-coc3h7 Ch3,^no-co2ch3 ch3x^no-co2c2h5 Λ Λ X Λ VV u V och3 och3 Xh3 och3

CH3vN - 0-C0N(C2H5)2 OCH3 The content of the neutral radical generator in the photosensitive composition is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, still more preferably 0.5 to 1%. 5 mass%, particularly preferably 1 to 10 parts by mass. Other photopolymerization initiators -55 - 200809406 The other photopolymerization initiators described above are not particularly limited as long as they have the ability to initiate polymerization of the above polymerizable compound, although known light can be used. The polymerization initiator is appropriately selected, however, for example, it is preferably a photosensitive material for ultraviolet light to visible light, and may be an active agent which generates any active radical with any action of a photoexcited sensitizer, or may be The initiator of cationic polymerization is initiated by the type of monomer. Further, the photopolymerization initiator is preferably a component containing at least one molecular absorption coefficient of at least about 50 in the range of about 300 to 800 nm (more preferably 330 to 500 nm). The other photopolymerization initiators mentioned above may be, for example, halogenated hydrocarbon derivatives (for example, those having a three-till skeleton, having an oxadiazole skeleton, etc.), hexaarylbiimidazole, ketone condensation An alcohol compound, a hydroxyalkyl ketone compound, an organic peroxide, a sulfur compound, a ketone compound, an acridine compound, a metallocene or the like. Among these, it is preferred to have a ketone compound and an acridine compound from the viewpoints of the sensitivity of the photosensitive layer, the preservability, and the adhesion between the photosensitive layer and the substrate. The other photopolymerization initiators described above, for example, may be, for example, those of [0288] to [02 99] and [0305] to [03 07] of JP-A-2005-258431. The compound or the like described. The ketal compound described above may, for example, be Irgacure 651 of a benzyl methyl ketal or the like. The aforementioned hydroxyalkyl ketone compound may, for example, be a hydroxyalkylphenone such as Irgacure 184, Darocure 1173, Irgacure 2959, Irgacure 127 or the like. The above organic peroxide may, for example, be 3,3',4,4'-fluorene (t-butylperoxycarbonyl)benzophenone or the like. The aforementioned sulfur compound may be, for example, 2-benzylidenemethylene-3-methylnaphthylthiazoline or the like. In the above-mentioned photosensitive layer, the total content of the photopolymerization initiator containing the above-mentioned mercaptophosphine oxide compound and rhodium derivative is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass. /〇, especially good for 0.5~15 quality. /〇. &lt;(D) Thermal crosslinking agent> The above-mentioned thermal crosslinking agent is not particularly limited, and may be appropriately selected according to the purpose, and for the purpose of improving the film strength after curing of the photosensitive layer formed using the photosensitive film described above, In the range which does not adversely affect the developing property, for example, an epoxy compound having at least 2 ethylene oxide groups in one molecule and oxygen having at least 2 oxetane groups in one molecule can be used. Heterocyclobutane compound. The above epoxy compound having at least two ethylene oxide groups in one molecule, for example, it may be a dimethicone or a biphenol type epoxy resin ("YX40 00, manufactured by Nippon Epoxy Co., Ltd. </ RTI> or a mixture of these; a heterocyclic epoxy resin having a different isocyanate skeleton ("TEPIC, manufactured by Nissan Chemical Industries, Ltd.", "Ala Louise PT810, manufactured by Ciba Specialty Chemicals Co., Ltd." ), bisphenol A epoxy resin, novolac epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, Cresol novolak type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, highly halogenated epoxy resin, brominated phenol novolak type epoxy resin, etc.), aryl group-containing bisphenol A type ring Oxygen resin, -57- 200809406 trisphenol methane type epoxy resin, diphenyl dimethylol type epoxy resin, diphenyl double stretch phenyl type epoxy resin, dicyclopentadiene type epoxy resin ( "HP-7200, HP-7200H, Otsuka Ink Chemical Industry Co., Ltd. , etc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidyl aniline, triglycidylamino phenol, etc.), glycidyl ether type epoxy resin (Glycidyl citrate, diglycidyl adipate, diglycidyl hexahydrophthalate, diglycidyl dimer acid, etc.), hindered amine type epoxy resin, alicyclic epoxy resin ( 3,4-Ethoxycycloheptylmethyl-3',4'-epoxycycloheptanecarboxylate, bis(3,4-epoxycycloheptylmethyl)adipate, bicyclo Pentadiene epoxide, "GT-300, GT-400, ZEHPE3150; made by Daisy Chemical Industry", bismuth imine type alicyclic epoxy resin, trishydroxyphenylmethane type epoxy resin, double Phenol A novolac type epoxy resin, tetraphenylethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenol ethane resin, naphthyl group-containing epoxy resin (naphthol aralkyl group) Type epoxy resin, naphthol novolac type epoxy resin, 4-functional naphthalene type epoxy resin, and commercial products include "ESN-190, ESN-360, Nippon Steel Chemical Co., Ltd., "HP-4032, EXA-4750 and EXA-4700, manufactured by Dainippon Ink Chemical Industry Co., Ltd.", phenol compounds and diolefins such as divinylbenzene or dicyclopentadiene a polyphenol compound obtained by an addition reaction between compounds, a reaction product with epichlorohydrin, or a ring-opening polymer of 4-vinylcycloheptane-1-oxide with peracetic acid or the like, having Epoxy resin with linear phosphorus-containing structure, epoxy resin with cyclic phosphorus-containing structure, α 'methyl fluorene type liquid crystal epoxy resin, benzophenoxy phenyl liquid crystal epoxy resin, azobenzene Base type liquid crystal epoxy resin, azomethylene phenyl type liquid crystal epoxy resin, -58- 200809406 Binaphthyl type liquid crystal epoxy resin, 吖 well type epoxy resin, glycidyl methacrylate copolymer epoxy Resin ("CP-50S and CP-50M, manufactured by Sakamoto Oil Co., Ltd."); epoxy resin copolymer of cyclohexylmaleimide and glycidyl methacrylate, bis(glycidyloxyphenyl)莽 type epoxy resin, bis(glycidyloxyphenyl) adamantane ring Resin. These epoxy resins may be used singly or in combination of two or more. Further, in addition to the above-mentioned epoxy compound having at least two ethylene oxide groups in one molecule, an epoxy group containing at least one epoxy group having an alkyl group at the /3 position in at least one molecule may be used. The compound is particularly preferably a compound containing an alkyl group-substituted epoxy group (more specifically, a fluorenyl-substituted glycidyl group). The epoxy compound containing an epoxy group having an alkyl group at least in the above-mentioned position may be one or more of the epoxy groups contained in one molecule, all of which are fluorene-alkyl substituted glycidyl groups, or At least one epoxy group is a /3-alkyl substituted glycidyl group. The above epoxy compound containing an epoxy group having an alkyl group at the oxime, and the total amount of the epoxy compound contained in the photosensitive composition is from the viewpoint of the stability of storage stability at room temperature. Among them, the proportion of the /3-alkyl group-substituted glycidyl group in all the epoxy groups is preferably at least 30%, more preferably 40% or more, and particularly preferably 50% or more. The aforementioned /3-alkyl substituted glycidyl group is not particularly limited' and may be appropriately selected depending on the purpose, for example, it may be Θ-methyl glycidyl group, ethyl glycidyl group, /5- Propyl glycidyl group, /3 - butyl glycidyl group, etc.; among these, from the viewpoint of enhancing the storage stability of the photosensitive resin-59-200809406 composition and the easiness of synthesis, It is not -methyl glycidyl. The foregoing epoxy compound containing an epoxy group having an alkyl group at the θ position, for example, is preferably an epoxy compound derived from a polyvalent phenol compound and a /3-alkylepihalool. The above-mentioned fluorene-alkyl epihalohydrin is not particularly limited and may be appropriately selected according to the purpose, and for example, it may be /3 -methylepichlorohydrin, cold-methylepibromohydrin, hydrazine - 0-methylepihalol such as methyl epifluorohydrin; /3-ethylepichlorohydrin, /3-ethylepichlorohydrin, stone-ethylepifluoroalcohol, etc. Θ-propyl epichlorohydrin, Θ-propyl epibromohydrin, /3-propylepiphenol, etc. /3-propylepihalohydrin; /3 - butyl epichlorohydrin, /3 - butyl /3-butyl epihalohydrin, such as epibromohydrin, hydrazine-butylperfluoroalcohol, and the like. Among these, Θ-methylepichlorohydrin is preferably used from the viewpoint of reactivity with the polyvalent phenol and fluidity. The polyvalent phenol compound is not particularly limited as long as it is a compound having 2 or more aromatic hydroxyl groups in one molecule, and may be appropriately selected according to the purpose. For example, it may be bisphenol. A, a bisphenol compound such as bisphenol F or bisphenol S; a biphenolic compound such as a biphenol or a tetramethylphenol; a naphthol compound such as a dihydronaphthalene or a binaphthol; a novolac such as a phenol-formaldehyde polycondensate; a monoalkyl-substituted phenol-formaldehyde polycondensate having a carbon number of 1 to 1 Å, a phenol-formaldehyde polycondensate or the like; a dialkyl-substituted phenol having a carbon number of 1 to 10, such as a xylenol-formaldehyde polycondensate. Formaldehyde polycondensate; phenol-formaldehyde polycondensate of bisphenol A-formaldehyde polycondensate; phenol and a monoalkyl-substituted benzene with a carbon number of 1~ and a copolycondensate of formaldehyde; and the weight of a phenol compound and divinylbenzene加-60 - 200809406 成成等. Among these, for example, when it is selected for the purpose of improving fluidity and preserving stability, it is preferred to use the aforementioned bisphenol compound. The foregoing epoxy compound having an epoxy group having a pendant group at the /3 position, for example, it may be a di-fluorene-glycidyl ether of bisphenol A or a bis-/3 of bisphenol F. a dialkyl glycidyl ether of a bisphenol compound such as an alkyl glycidyl ether or a di-alkyl glycidyl ether of bisphenol S; a di-hydrazine-alkyl glycidyl ether of bisphenol, and a tetramethyl bisphenol Di-indolyl-glycidyl ether of bisphenol compound such as bis-/3-alkyl glycidyl ether; di-cold-alkyl glycidyl ether of dihydronaphthalene, di-/3-alkane of bisnaphthol Di-non-alkyl glycidyl ether of a naphthol compound such as glycidyl ether; bis-/3-alkyl glycidyl ether of a phenol-formaldehyde polycondensate; di-anthracene-alkyl of a cresol-formaldehyde polycondensate a di-s-alkyl glycidyl ether of a monoalkylphenol-formaldehyde polycondensate having a carbon number of 1 to 1 Å, such as glycidyl ether; a di- fluorene-glycidyl ether of a xylenol-formaldehyde polycondensate; a di-O-alkyl glycidyl ether having a carbon number of 1 to 10 dialkylphenol-formaldehyde polycondensate; a phenol-formaldehyde such as a di-/3-alkyl glycidyl ether of a bisphenol A-formaldehyde polycondensate Polycondensate Two - / 3-alkyl ether; and poly -Θ two phenol compounds and divinylbenzene adducts - alkyl glycidyl ether. Among these, it is preferred to use a bisphenol compound represented by the following structure (I), a fluorene-alkyl glycidyl ether derived from a polymer obtained from an epihalohydrin or the like, and a structure (Π) A poly-/3-alkyl glycidyl ether represented by a phenol compound-formaldehyde polycondensate. Ch3 ch3 •ch2 ch3 -〇—CH2rCH-CH2 OH . CH, Structural formula (I) -61- 200809406

However, in the above structure (I), R represents any one of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and η represents an integer of 0 to 20. However, in the above structure (R), R represents any one of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and R" represents either a hydrogen atom or CH3. The η system represents 0. The epoxy compound having an epoxy group having an alkyl group may be used singly or in combination of two or more kinds. Alternatively, it may have at least 2 in one molecule. An epoxy compound having an oxirane group and an epoxy compound containing an epoxy group having an alkyl group at the /3 position are used together. The skeleton of the above epoxy compound is preferably a bisphenol type epoxy resin. At least one selected from the group consisting of a novolak type epoxy resin, an alicyclic base type epoxy resin, and a poorly soluble epoxy resin. The aforementioned oxetane compound 'for example, for example, it may be double [(3-Methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1 , 4-bis[(3-methyl-3-oxetanyloxy)methyl]benzene, 1,4-bis[(3_ethyl_3_oxetanylmethoxy) Methyl]benzene, (3- Methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetanyl)methacrylate, (3-mercapto-3-oxetane a polyfunctional oxetane-62 such as methyl methacrylate, (3-ethyl-3 oxetanyl) methyl methacrylate, or an oligomer or copolymer thereof - 200809406 Oxetane other than alkanes, novolac resin, poly(p-hydroxystyrene), bulky bisphenols, calixarenes, cup-resorcinol aromatics, and sesquiterpene An ether compound between a resin having a hydroxyl group such as oxane or the like; a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate, etc. Thermal hardening of the epoxy compound with the aforementioned oxetane compound, for example, an amine compound (for example, cyanogen, benzyldimethylamine, 4-(dimethylamino)-N,N-di can be used. Methylbenzylamine, 4-methoxy-hydrazine, hydrazine-dimethylbenzylamine, 4-methyl-hydrazine, hydrazine-dimethylbenzylamine, etc.), quaternary ammonium salt compound (for example, triethyl chloride) Base benzyl ammonium a blocked isocyanate compound (for example, dimethylamine, etc.), an imidazole derivative bicyclic hydrazine compound and a salt thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4- Methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole Etc.), a phosphorus compound (for example, triphenylphosphine, etc.), a guanamine compound (for example, melamine, guanamine, acetamide, benzoguanamine, etc.), an S-triazine derivative (for example, 2,4- Diamino-6-methacryloxyethyl _S-triazine, 2-vinyl-2,4-diamino-S-trin, 2-vinyl-4,6-diamino -S - triple well isomeric cyanuric acid adduct, 2,4-diamino-6-methylpropenyloxyethyl-S-three-pronged isocyanuric acid adduct, etc.) . These may be used singly or in combination of two or more. In addition, as long as it is a curing catalyst of the epoxy compound and the oxetane compound, or a reaction with the carboxyl group can be promoted, it is not particularly limited, and heat other than the above can be used. Hardened compound. The above-mentioned epoxy compound, the above-mentioned oxetane-63-200809406 compound, and the compound which is thermally hardened with the carboxylic acid, which are solids in the solid content of the photosensitive composition The content of the component is usually from 0.01 to 15% by mass. Further, the above-mentioned thermal crosslinking agent may be a polyisocyanate compound described in JP-A-5-9407, and the polyisocyanate compound may be an aliphatic compound or a cyclic aliphatic compound containing at least two isocyanate groups. Or derived from an aromatic-substituted aliphatic compound. Specifically, for example, it may be a bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene) Diisocyanate, 1,3- and 1,4-xylene diisocyanate, bis(4-isocyanatophenyl)methane, bis(4-isocyanatoethylcyclohexyl)methane, isophorone Diisocyanate, hexyl diisocyanate, trimethylhexyl diisocyanate, etc.), the bifunctional isocyanate, polyfunctional alcohol with trimethylolpropane, pentaerythritol, glycerin, etc., addition of alkylene oxide of the polyfunctional alcohol And an adduct of the above-mentioned bifunctional isocyanate; a cyclic trimer of exohexyl diisocyanate, exohexyl-1,6-diisocyanate and derivatives thereof, and the like. Further, in order to achieve the purpose of improving the preservability of the photosensitive film of the present invention, a compound obtained by reacting the isocyanate group of the above polyisocyanate and its derivative with a block agent may be used. The above-mentioned isocyanato blocker may, for example, be an alcohol (for example, isopropanol, tert-butanol, etc.), an intrinsic amine (for example, ε-caprolactam, etc.), Terpenoids (for example, hydrazine, formazan, p-tert-butyl hydrazine, p-sec-butyl hydrazine, p-sec-aminophenol, p-octyl phenol, p-nonyl phenol, etc.), heterocyclic ring a hydroxy compound (for example, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), an active methylene compound (for example, -64-200809406 dialkyl malonate, methyl ethyl ketone oxime, acetamidine acetone, alkyl group) Acetyl acetate oxime, acetone oxime, cyclohexanone oxime, etc.). In addition, a compound having at least one polymerizable double bond and at least one block isocyanate group in the molecule described in JP-A-6-209506 can be used. Wait. Further, a melamine derivative can be used as the aforementioned thermal crosslinking agent. The melamine derivative may, for example, be methylol melamine or alkylated methylol melamine (a compound which etherifies a hydroxymethyl group such as a methyl group, an ethyl group or a butyl group). These may be used alone or in combination of two or more. Among these, from the viewpoint of good storage stability, effective improvement of the surface hardness of the photosensitive layer or film strength of the cured film itself, it is preferred to use alkylated methylol melamine, particularly preferably hexamethylated. Hydroxymethyl melamine. In the solid content of the photosensitive composition, the solid content of the thermal crosslinking agent is preferably from 1 to 50% by mass, more preferably from 3 to 30% by mass. When the solid content is less than 1 mass 7 . When the film strength of the cured film is not confirmed to be increased, when it exceeds 50% by mass, the developability is lowered and the exposure sensitivity is lowered. Further, from the viewpoint of reactivity, the above-mentioned thermal crosslinking agent is preferably an epoxy compound. &lt;(E) Elastomer&gt; The above-mentioned elastomer is not particularly limited and may be appropriately selected according to the purpose, and for example, it may be used in (0061) to [0073] of International Publication No. 04/34147. The compounds described, etc. -65 - 200809406 &lt; (F) phenoxy resin&gt; The phenoxy resin described above is not particularly limited and may be appropriately selected according to the purpose, and for example, it may be used in [0074] to [0078] of the International Publication No. 04/34147. The compound described above and the like. &lt; (G) Sensitizer> The above-mentioned sensitizer is particularly excellent in terms of improving the minimum energy (sensitivity) of the above-mentioned light which 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, the sensitizer may be appropriately selected in accordance with the above-described light irradiation means (for example, visible light, ultraviolet light, visible light laser, or the like). The sensitizer described above can be excited by an active energy ray, and interacts with other substances (for example, a radical generator, an acid generator, etc.) (for example, energy movement, electron movement, etc.). A useful group that generates a radical or an acid or the like. The aforementioned sensitizer includes a condensed ring compound, an aminophenyl ketone compound, a polynuclear aromatic compound, an acid core, a base having a core, and a fluorescent whitening agent core. At least one selected one may contain other sensitizers as the case requires. The sensitizer is more preferably a heterocyclic ring compound or an aminobenzophenone compound, and particularly preferably a heterocyclic ring compound, from the viewpoint of enhancing sensitivity. Monocyclic ring-forming compound 1 Among the compounds exemplified above, the aromatic ring and the heterocyclic ring compound (condensed ring compound) are preferably a heterocyclic ring compound. The aforementioned -66-200809406 heterocyclic ring compound means a polycyclic compound having a hetero element in the ring; it is preferred to contain a nitrogen atom in the aforementioned ring. The aforementioned heterocyclic ring compound may, for example, be a heterocyclic ketone compound. Among the above heterocyclic ketone compounds, 'are more preferably an acridone compound and a thioxanthone compound; and among them, a thioxanthone compound is particularly preferred. Specific examples of the aforementioned heterocyclic ketone compound 'for example, it may be acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl- An acridone compound such as chloroacridone; thioxanthone, isopropyl thioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioacetate, etc. Tons of ketone compounds; 3-(2-benzofurancarbenyl)-7-diethylamino coumarin, 3-(2-benzofuranylmethyl)-7-(1-pyrrolidinyl) Coumarin, 3-benzylidinyl-7-diethylamine coumarin, 3-(2-methoxybenzimidyl)-7-diethylamino coumarin, 3-( 4-dimethylaminobenzimidyl)-7-diethylamino coumarin, 3,3'-carbonylbis(5,7-di-n-propoxycoumarin), 3, 3'-Carbonyl bis(7-diethylaminocoumarin), 3-benzylidene-7-methoxycoumarin, 3-(2-furylmercapto)-7-diethyl Amino coumarin, 3-(4-diethylaminocinnamoyl)-7-diethylamino coumarin, 7-methoxy-3-(3 pyrrolidinylcarbonyl) coumarin, 3-benzylidenyl-5,7-dipropoxycoumarin, 7-benzotriazole-2 - coumarin, 7-diethylamino-4-methylcoumarin, and also in Japanese Patent Laid-Open No. 5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207 Coumarins such as coumarin compounds described in JP-A-2002-363208, and JP-A-2002-363209. Further, for example, it may be a well-known polynuclear aromatic compound (-67-200809406, for example, ruthenium, osmium, tri-o-phenylene), xanthene (for example, luciferin, eosin, erythromycin). , Rhodamine B, Bengal Rose Red), Cyanine (for example, quinoxaline carbocyanine, thioquinoline carbocyanine, quinoxaline carbocyanine), merocyanine (for example, merocyanine) , carbonyl merocyanine), thiophene (for example, Lloyd's violet, methylene blue, toluidine blue), steroids (for example, 蒽醌), square key (for example, square key), and the like. The content of the sensitizer is preferably 〇 〇 1 to 4 by mass based on the total composition of the photosensitive composition for the photosensitive film. /. More preferably, it is 〇. 02~2% by mass, especially good for 〇. 〇 5~1% by mass. When the content is less than 〇.〇1% by mass, the sensitivity decreases; when it exceeds 4% by mass, the pattern shape deteriorates. The mass ratio of the sensitizer and the photopolymerization initiator in the photosensitive composition is preferably [(sensitizer) / (photopolymerization initiator)] = 1 / 〇 · 1 〜 1 / 1 00, more preferably 1 / 1 ~ 1 / 50. When the mass ratio of the content of the sensitizer and the content of the photopolymerization initiator is outside the above range, the sensitivity may be lowered, and the change with time of the sensitivity may be deteriorated. The combination of the aforementioned sensitizer and the aforementioned photopolymerization initiator is particularly preferably a combination of a thioxanthone compound and an anthracene derivative from the viewpoint of high sensitivity. Further, the above-mentioned anthracene derivative may be a photopolymerization initiator compound which contains a small amount of an aminoalkyl group and an aminophenyl group in combination with other neutral radical generators and a partial structure. &lt;(Η) Other components> The other components mentioned above, for example, may be a thermal polymerization inhibiting agent-68-200809406 agent, a plasticizer, a coloring agent (coloring pigment or dye), an anthraquinone pigment, etc.; It can also be used as an adhesion promoter and other auxiliary agents on the surface of the substrate (for example, conductive particles, a charging agent, an antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, a fragrance, and a surface tension adjuster). , chain mover, etc.). By appropriately containing these components, the properties of the photosensitive film such as stability, film quality, and film properties can be adjusted. A thermal polymerization inhibiting agent - The above thermal polymerization inhibiting agent may be added for the purpose of preventing thermal polymerization or polymerization over time of the above polymerizable compound. The aforementioned thermal polymerization inhibitor may, for example, be 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, benzenetriol, 2- Hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, benzothiazepine, chloranil, naphthylamine, β-naphthol, 2,6-dibutyl-4 -cresol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper A reaction product with an organic chelating agent, methyl urate and a benzothiazide, a nitroso compound, a chelating compound of a nitroso compound and AI, and the like. The content of the above-mentioned thermal polymerization inhibitor is preferably from 1 to 5 mass%, more preferably from 0.005 to 2 mass, based on the polymerizable compound. /°' is particularly preferably 0.0 1 to 1% by mass 〇 When the aforementioned content is less than 0·0 01 mass. /. At the time of 'there is a case where the stability of the storage is lowered, and when it exceeds 5% by mass, the sensitivity to the active energy ray is lowered. A plasticizer-69-200809406 The aforementioned plasticizer' may be added for the purpose of controlling the film properties (flexibility) of the aforementioned photosensitive layer. The aforementioned plasticizer, for example, may be, for example, dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, Cyclohexyl phthalate, decyl decanoate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl decanoate, octyl decyl Phthalate esters such as phthalic acid esters, triethylene glycol diacetate, tetraethylene glycol diacetate 'dimethyl gluconate decanoate, ethyl decyl butyl glycolate, ethyl decyl Glycol esters such as ethyl glycolate, methyl decyl ethyl glycolate, butyl decyl butyl glycolate, triethylene glycol dicaprylate; tricresyl phosphate, triphenyl phosphate Phosphate esters such as 4-toluenesulfonamide, benzenesulfonamide, N-n-butylbenzenesulfonamide, Nn-butylacetamide, etc.; diisobutyl adipate, adipic acid Aliphatic dibasic acid esters of dioctyl ester, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, dioctyl sebacate, dibutyl maleate, etc.; lemon Triethyl citrate, tributyl citrate, C Three acetyl alcohol ester, butyl laurate, 4,5-epoxy-cyclohexane-1,2-dicarboxylic acid dioctyl ester, polyethylene glycol, polypropylene glycol, etc. glycols. The content of the aforementioned plasticizer is preferably from 1 to 50 by mass based on the total composition of the photosensitive layer. /〇, more preferably 0.5 to 40% by mass, particularly preferably 1 to 30% by mass. - Coloring Pigment - The coloring pigment is not particularly limited and may be appropriately selected depending on the purpose; for example, it may be, for example, Victoria Pure Blue (C_丨_ 4259 5) or gold amine (CI 41000). , Fat Black HB (C·I. 2615 0), -70- 200809406 Single Pigment Yellow GT (C. I·Pig Yellow 12), Permanent Yellow GR (C. I·Pig Yellow 17), Permanent Yellow HR ( CI Pigment Yellow 83), Permanent Magenta FBB (C. I·Pigment Red 146), Horst Plaque Red ESB (CI Pigment Violet 19), Permanent Gem Red FBH (CI Pigment Red 11), Fixation Super Pink B (C·I·Pigment Red 81), Single Star Fast Blue (CI Pigment Blue 15), Single Pigment Fast Black (Β-ΐ·Pigment Black 1), Carbon Black, C_I·Pigment Red 97, C·I·Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Blue 15:1, C·I·Pigment Blue 15:4, C·丨·Pigment Blue 15:6, C.丨·Pigment Blue 22, C·I·Pigment Blue 60, and C·I. Pigment Blue Pigment Blue 64. These may be used alone or in combination of two or more. Further, as appropriate, a dye suitably selected from known dyes can be used. The solid content of the coloring pigment in the solid content of the photosensitive composition can be determined in consideration of the exposure sensitivity and the resolution of the photosensitive layer at the time of permanent pattern formation, although it may vary depending on the type of the color pigment. Different, however, generally more preferably 〇.〇1~1〇% by mass, more preferably 〇·〇5~5% by mass. An enamel pigment may be added to the photosensitive composition as described above to increase the surface hardness of the permanent pattern, or to suppress a decrease in the coefficient of linear expansion, or to suppress the decrease in the dielectric constant and dielectric tangent of the cured film itself. Inorganic pigments and organic particles for the purpose. The above-mentioned inorganic pigment is not particularly limited and may be selected locally from the known material, for example, kaolin, barium sulfate, barium titanate, cerium oxide powder, fine powdered cerium oxide, Gas phase magnesia, amorphous vermiculite, crystalline vermiculite, molten vermiculite, globular vermiculite, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, mica, and the like. The above inorganic pigment preferably has an average particle diameter of less than 1 〇 micrometer, more preferably 3 micrometers or less. When the average particle diameter is 10 μm or more, the resolution may be deteriorated due to light scattering. The above-mentioned organic fine particles are not particularly limited and may be appropriately selected according to the purpose, and may be, for example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin or the like. Further, spherical porous fine particles formed of vermiculite having an average particle diameter of 0.01 to 5 μm and an oil absorption of about 100 to 200 m 2 /g or a crosslinked resin can be used. The amount of the above-mentioned stilbene pigment added is preferably from 1 to 60% by mass. When the amount added is less than 1% by mass, there is a case where the coefficient of linear expansion cannot be sufficiently lowered; and when it exceeds 60% by mass, in the case where a cured film is formed on the surface of the photosensitive layer, the film of the cured film is It becomes brittle; in the case where wiring is formed using a permanent pattern, there is a function of impairing the protective film as a wiring. One adhesion promoter 1 A known so-called adhesion promoter can be used for each layer in order to improve the adhesion between the layers or the adhesion between the photosensitive layer and the substrate. For example, the adhesion promoter described in the above-mentioned Japanese Patent Application Laid-Open No. Hei No. Hei 5- No. Hei. Specific examples, for example, may be benzimidazole, benzoxazole, benzothiazole, 2-mercapto-72-200809406 benzimidazole, 2-mercaptobenzoxazole, 2_fluorenyl Benzothiazole, 3-morpholinylmethyl-1-phenyl-triazol-2-one, 3-morpholinylmethyl-5-phenyl-oxadiazol-2-one, 5-amino- 3- morpholinylmethyl-thiadiazole-2-one, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amine Benzotriazole, and decane coupling agent. The content of the adhesion promoter described above is preferably 0.001 to 2 Å by mass based on the total composition of the photosensitive layer. /〇, more preferably 〇_〇1~10% by mass, particularly preferably 0.1 to 5% by mass. (Photosensitive film) The photosensitive film of the present invention preferably has at least a support and a photosensitive layer formed of the photosensitive composition of the present invention formed on the support, and is preferably appropriately provided as occasion demands It is formed by other layers such as a thermoplastic resin layer. &lt;Photosensitive layer&gt; The photosensitive layer described above is formed using the photosensitive composition of the present invention. In the photosensitive film described above, the position at which the photosensitive layer is disposed is not particularly limited, and may be appropriately selected according to the purpose. However, it is usually laminated on the above-mentioned support. The sensitivity of the photosensitive layer, as described above, is 〇1 to 200 mJ/cm2, more preferably 0.2 to 100 mJ/cm2, and particularly preferably 〇5 to 50 mJ/cm2. The thickness of the photosensitive layer, as described above, is preferably from 1 to 10 μm, more preferably from 2 to 50 μm, particularly preferably from 4 to 30 μm. -73- 200809406 &lt;Support and Protective Film&gt; The above-mentioned support is not particularly limited, and may be appropriately selected depending on the purpose. However, it is preferable that the above-mentioned photosensitive layer can be peeled off and the light transmittance is good; A material with good surface smoothness. The support and the protective film are specifically described in, for example, [0342] to [0348] of JP-A-2005-25843. &lt;Other Layers&gt; The other layers in the photosensitive film are not particularly limited, and may be appropriately selected according to the purpose, and may, for example, have a buffer layer, an oxygen barrier layer (pc layer), and a peeling layer. a layer of a layer, an adhesive layer, a light absorbing layer, a surface protective layer, or the like. One of these layers may be provided alone or in combination of two or more. Further, a protective film may be provided on the photosensitive layer described above. A buffer layer The above-mentioned buffer layer is not particularly limited and may be appropriately selected according to the purpose; it may be swellable or soluble in an alkaline liquid, or may be insoluble. In the case where the aforementioned buffer layer is swellable or soluble to the alkaline liquid, the aforementioned thermoplastic resin may, for example, be a saponified product of ethylene and an acrylate copolymer, ethylene and (meth) acrylate. Saponification of copolymer, saponification of vinyl toluene and (meth) acrylate copolymer, poly(meth) acrylate, butyl (meth) acrylate and vinyl acetate copolymerization of (meth) acrylate a saponified product such as a saponified product, a copolymer of (meth) acrylate and (meth) acrylate, a copolymer of styrene and (meth) acrylate and (meth) acrylic acid, and the like. -74- 200809406 The softening point (Vicat) of the thermoplastic resin in this case is not particularly limited, and may be appropriately selected according to the purpose of the object; for example, it is preferably 80 ° C or lower. The above-mentioned thermoplastic resin having a softening point of 80 ° C or less, for example, in addition to the above-mentioned thermoplastic resin, may be a "plastic property note" (edited by the Japan Plastics Industry Federation, the All Japan Plastic Forming Industry Federation, industrial The softening point of the investigation will be issued on October 25, 1968, which is soluble in alkaline liquids in organic polymers below about 80 °C. Further, even in the organic polymer material having a softening point of 80 ° C or higher, various plasticizers having compatibility with the organic polymer material can be added to the organic polymer material. The softening point is substantially reduced below 80 °C. Further, when the buffer layer is swellable or soluble to the alkaline liquid, the interlayer bonding strength of the photosensitive film is not particularly limited, and may be appropriately selected according to the purpose; for example, it is preferably Among the interlayer bonding forces of the respective layers, the interlayer bonding force between the support and the buffer layer is minimized. By causing the interlayer bonding force to be such that only the support is peeled off from the photosensitive film, the photosensitive layer is exposed through the buffer layer, and then the photosensitive layer is exposed using an alkaline developing solution. Visualization. Further, after the remaining support is exposed to the photosensitive layer as it is, the support may be peeled off from the photosensitive film, and the photosensitive layer may be formed using an alkaline developing solution. Give it a picture. The method for adjusting the interlaminar bonding force is not particularly limited, and it can be changed from -75 to 200809406, and the quality is as good as the material, but the cold is said to be '' The various types of the selected agents are added, and the medium is required to be viscous, and the plasticizer is not particularly limited, and may be used according to the purpose. Suitably selected; for example, it may be polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate An alcohol or an ether such as an ester or a biphenyldiphenyl phosphate; an amide such as toluenesulfonamide or the like. In the case where the buffer layer is insoluble to the alkaline liquid, the thermoplastic resin is, for example, a copolymer in which the main component is ethylene as a necessary copolymerization component. The copolymer having ethylene as an essential copolymerization component is not particularly limited and may be appropriately selected according to the purpose; for example, it may be ethylene-vinyl acetate copolymer (EVA), ethylene- Ethyl acrylate copolymer (EEA) and the like. In the case where the buffer layer is insoluble to the alkaline liquid, the interlayer bonding strength of the photosensitive film is not particularly limited, and may be appropriately selected according to the purpose; for example, it is preferably a bonding force between layers of each layer. In the middle, the interlayer bonding force between the support body and the buffer layer is minimized. By bringing the interlayer bonding force into this manner, the support and the buffer layer can be peeled off from the photosensitive film, and the photosensitive layer can be exposed, and then the photosensitive layer can be developed using an alkaline developing solution. Further, after the exposed support layer is exposed to the photosensitive layer as it is, the support and the buffer layer may be peeled off from the photosensitive film - 76 - 200809406, and alkaline is used. The developing layer develops the photosensitive layer. The method for adjusting the interlaminar bonding force is not particularly limited, and may be appropriately selected according to the purpose. For example, a known polymer, a supercooling substance, a adhesion improving agent, or the like may be added to the thermoplastic resin. A method of a surfactant, a release agent or the like; for example, it may be, for example, a method of adjusting an ethylene copolymerization ratio described below or the like. The ethylene copolymerization ratio in the copolymer of ethylene as an essential copolymerization component is not particularly limited and may be appropriately selected according to the purpose; for example, it is preferably 60 to 90% by mass, more preferably 60 to 60%. 80% by mass, particularly preferably 6 5 to 80% by mass. When the copolymerization ratio of ethylene described above becomes less than 60% by mass, the interlayer bonding force between the buffer layer and the photosensitive layer becomes high, and peeling at the interface between the buffer layer and the photosensitive layer becomes Difficult; and when it exceeds 90% by mass, since the interlayer bonding force between the buffer layer and the photosensitive layer is small, the buffer layer and the photosensitive layer are easily peeled off so that the photosensitive layer containing the buffer layer is photosensitive. The manufacture of thin films becomes difficult. The thickness of the aforementioned buffer layer is not particularly limited and may be appropriately selected according to the purpose; for example, it is preferably 5 to 50 μm, more preferably 10 to 50 μm, and particularly preferably 15 to 40 μm. When the aforementioned thickness becomes less than 5 μm, the unevenness of the unevenness and the bubbles in the surface of the substrate is lowered, so that a high-definition permanent pattern cannot be formed; and when it exceeds 50 μm, there is It is not suitable for the production to increase the drying load and the like. -77 - 200809406 An oxygen barrier layer (PC layer) ~ - The oxygen barrier layer is preferably formed by using a general polyvinyl alcohol as a main component to form a film having a thickness of about 0.5 to 5 μm. [Method for Producing Photosensitive Film] The above-mentioned photosensitive film can be produced, for example, by the following method. First, the material contained in the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive resin composition solution. The solvent is not particularly limited and may be appropriately selected according to the purpose of the object; for example, it may be methanol, ethanol, η-propanol, isopropanol, η-butanol, sec-butanol, η Alcohols such as hexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; ethyl acetate, butyl acetate, and η-amyl acetate , esters of methyl sulfate, ethyl propionate, dimethyl decanoate, ethyl benzoate and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; Halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, trichloroethane, dichloromethane, monochlorobenzene, etc.; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1 An ether such as methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl hydrazine, cyclobutyl hydrazine or the like. These may be used alone or in combination of two or more. Further, a known surfactant may be added. Then, a photosensitive film can be produced by applying the above-mentioned photosensitive resin composition solution onto the above-mentioned support and drying it to form a photosensitive layer. The coating method of the photosensitive composition solution is not particularly limited -78 - 200809406, and may be appropriately selected according to the purpose, and for example, it may be a spray method, a roll coating method, a rotary coating method, or a slit coating method. Various coating methods such as a method, an extrusion coating method, a curtain coating method, a die coating method, a gravure coating method, a bar coating method, and a knife coating method. Although the drying conditions vary depending on the components, the type of the solvent, the ratio of use, and the like, it is usually carried out at a temperature of 60 to 110 ° C for about 30 seconds to 15 minutes. The photosensitive film described above is, for example, a core wound in a cylindrical shape, and is preferably stored in a roll shape having a roll-shaped shape. The length of the long-length photosensitive film described above is not particularly limited, and for example, it can be appropriately selected from the range of 10 to 20,000 m. Further, in order to make it easy for the user to use, it is also possible to perform a slit process to form a long-length body having a roll shape of 100 to 1,000 meters. Further, in this case, it is preferable to wind the aforementioned support body to the outermost side. Further, the above-mentioned roll-shaped photosensitive film may be subdivided into a sheet shape. When storing, from the viewpoint of end face protection and prevention of end face melting, it is preferable to provide a separator (especially a moisture-proof substance and a desiccant) on the end surface, and it is also preferable to use the bag and the bag. Low wet material. (Photosensitive laminated body) The photosensitive laminated system of the present invention has at least a photosensitive layer formed of the photosensitive composition of the present invention on the substrate, and other layers which are appropriately selected as needed. &lt;Substrate&gt; The above-mentioned substrate is not particularly limited as long as it is a substrate to be processed to form a photosensitive layer or a transferable body of at least a photosensitive layer of the photosensitive film described in the above-mentioned publication No. 79-200809406. It can be suitably selected according to the purpose, for example, it can be arbitrarily selected from the surface smoothness to the surface having the uneven surface. It is preferably a plate-like substrate, that is, a so-called substrate is used. Specifically, for example, it may be a known printed wiring manufacturing substrate (printing substrate), a glass plate (such as an alkali glass plate), a synthetic resin resin film, paper, a metal plate, or the like. [Manufacturing Method of Photosensitive Laminate] The method for producing the photosensitive laminate described above is, for example, a method of applying the photosensitive composition onto the surface of a substrate and drying the first aspect, and In the second aspect, at least one of heating and pressurization of the photosensitive layer in the photosensitive film of the present invention is carried out by transferring the photosensitive layer. In the method for producing a photosensitive laminate according to the first aspect described above, the photosensitive composition is applied and dried on the substrate, and dried to form a photosensitive layer. The method of coating and drying described above is not particularly limited, and may be appropriately selected depending on the purpose; for example, the photosensitive composition may be dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive film. The composition solution is applied directly to the surface of the above-mentioned substrate, and dried and laminated. The solvent of the photosensitive composition solution is not particularly limited and may be appropriately selected according to the purpose. For example, a solvent similar to that used in the photosensitive film may be used. These may be used alone or in combination of two or more. Further, a surfactant known in the form of -80-200809406 may be added. The coating method and drying conditions described above are not particularly limited, and may be appropriately selected depending on the purpose. For example, it can be carried out, for example, by using the same methods and conditions as those of the above-mentioned photosensitive film. In the method for producing a photosensitive laminate of the second aspect described above, it is preferred that at least one of heating and pressurization is carried out, and the photosensitive film of the present invention is laminated on the surface of the substrate. Further, in the case where the photosensitive film described above has the protective film, it is preferred to peel off the protective film and laminate the above-mentioned photosensitive layer on the above-mentioned substrate in a superposed manner. The heating temperature is not particularly limited and may be appropriately selected according to the purpose, however, for example, it is preferably 15 to 180 ° C, more preferably 60 to 140 ° C. The pressure of the above-mentioned pressurization is not particularly The definition can be appropriately selected according to the purpose of the object, however, for example, it is preferably 0.1 to 1.0 MPa, more preferably 0 to 0.8 MPa. The apparatus for performing at least any of the above-described heating is not particularly limited, and may be appropriately selected according to the needs of the object. However, for example, a suitable laminator (for example, VP-丨丨 manufactured by Dacheng Laminator Co., Ltd., Nike Qimeng Co., Ltd. VP130) and so on. Since the photosensitive film of the present invention and the above-mentioned photosensitive layered product are formed by using the photosensitive composition of the present invention, it is possible to form a permanent pattern having excellent sensitivity and excellent storage stability with high precision, and thus it is suitable. Liquid crystal for use in various pattern formation, color filters, pillars, ribs, spacers, partition walls, etc., such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern. -81 - 200809406 Manufacture of structural components For permanent pattern forming applications such as holography, micromachining, and verification, in particular, it can be suitably used for permanent pattern forming applications of printed substrates. In particular, in the photosensitive film of the present invention, since the thickness of the film is uniform, even when a permanent pattern is formed, even a permanent pattern (a protective film, an interlayer insulating film, a solder resist pattern, etc.) is thinned. In the high acceleration test (HAST), a high-definition permanent pattern excellent in ion migration, heat resistance, and moisture resistance can be obtained, so that the deposition on the substrate can be performed more finely. (Pattern Forming Apparatus and Permanent Pattern Forming Method) The pattern forming apparatus of the present invention includes the above-described photosensitive layer, and has at least a light irradiation mechanism and a light modulation mechanism. The permanent pattern forming method of the present invention includes at least an exposure step and includes other steps of a developing step, a hardening step, and the like. Further, the above-described pattern forming apparatus of the present invention will be apparent from the description of the above-described pattern forming method of the present invention. &lt;Exposure Step&gt; The above-described exposure step is a step of exposing the photosensitive layer in the photosensitive film of the present invention. The materials of the photosensitive film and the substrate of the present invention described above are as described above. The object to be exposed is preferably a photosensitive layer in the photosensitive film. Although it is not particularly limited, it may be appropriately selected according to the purpose. However, for example, as described above, it is preferably It is carried out by laminating a layer formed on the substrate by one of -82 to 200809406 by heating and pressurizing the photosensitive film. The above-mentioned exposure is not particularly limited and may be appropriately selected depending on the purpose, however, for example, it is preferably a digital exposure, an analog exposure, or the like; among these, digital exposure is preferred. The aforementioned analog exposure is not particularly limited, and may be appropriately selected according to the needs of the object. For example, for example, it may be exposed through a negative mask having a predetermined pattern, using a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or the like. The method. The aforementioned digital exposure is not particularly limited and may be appropriately selected according to the needs of the object, for example, using light generated based on the formed pattern forming information and modulated with the control signal; for example, It is preferable to use an exposure head for the photosensitive layer described above, which is provided with a light irradiation means and a quaternary element having η (however, η is a natural number of 2 or more) that receives light from the light irradiation means and emits it. The aligned pixel portion, the exposure head capable of controlling the light modulation mechanism of the pixel portion in response to the pattern information, and configured to cause the column direction of the pixel portion to form a predetermined direction with the scanning direction of the exposure head The tilt angle β is set. For the above-described exposure head, by using the pixel portion specifying means, the aforementioned use of the above-mentioned pixel portion is used for the first exposure (however, the natural number of 2 or more) In the above-mentioned exposure head, by the pixel control mechanism, the aforementioned pixel portion specified by the above-mentioned use of the pixel designation mechanism is involved The way to control the picture element portion; and so that the exposure head is moved with respect to the method for exposing the photosensitive layer with respect to the scanning direction. In the present invention, "Ν exposure" means a line parallel to the scanning direction of the exposure head in approximately the entire area of the -83 - 200809406 surface exposed on the photosensitive layer, and the surface to be exposed on the exposed surface The N spot columns (pixel columns) are set to be crossed and exposed. In the present disclosure, the "spot array" is a direction which is smaller than the angle of the scanning direction of the exposure head among the pixel (pixel) columns of the pixel unit generated by the pixel portion. The list. Further, the arrangement of the aforementioned pixel portions does not have to be a rectangular lattice shape, and for example, it may be a configuration of a parallelogram shape or the like. The "about all regions" described herein, in terms of the both side edges of the respective pixel portions, reduce the use of pixels that intersect the scanning direction parallel to the exposure head by tilting the pixel portion. The number of pixels in the part, so in this case, even if a plurality of exposure heads are connected for use, a straight line parallel to the scanning direction is caused by an error in the mounting angle and arrangement of the exposure head. In the case of using the number of pixels in the pixel portion, the number of pixels in the pixel portion is slightly increased or decreased, and the resolution of each of the pixel portions in the pixel portion is divided into a minimum of the following, due to the mounting angle and the arrangement of the pixel portion. The error is such that the pitch of the pixel portion along the direction perpendicular to the scanning direction cannot be strictly coincident with the pitch of the pixel portion of the other portion, and thus the pixel portion intersecting with the straight line parallel to the scanning direction is used. The number of pixels in the figure is increased or decreased within the range of ± 1. Further, in the following description, the N-time exposure in which the natural number of N is 2 or more is referred to as "multiple exposure". Furthermore, in the following description, the exposure apparatus and the exposure method of the present invention are implemented as a drawing apparatus and a drawing method, and the terms "N times drawing" and "multiple drawing" are used. It is a term corresponding to "N exposure" and "multiple exposure". -84- 200809406 The N of the N-th exposure described above is not particularly limited as long as it is a natural number of 2 or more, and may be appropriately selected according to the purpose. However, it is preferably a natural number of 3 or more, and more preferably 3 or more natural numbers below 7. As an example of the pattern forming apparatus of the permanent pattern forming method of the present invention, for example, [0028] to [0139] and [0185] to [0191] in JP-A-2006- 284842 can be used. The means of recording, etc. &lt;Exposure Step&gt; The above-described development is performed by removing the unexposed portion of the photosensitive layer described above. The method for removing the uncured region is not particularly limited, and may be appropriately selected according to the purpose, for example, a method in which it can be removed using a developing solution. The developing solution is not particularly limited, and may be appropriately selected according to the purpose. However, for example, it may be an alkaline liquid, a water-based developing liquid, an organic solvent, or the like; among them, It is preferably a weakly alkaline aqueous solution. The alkali component of the weakly alkaline liquid may be, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate or potassium hydrogencarbonate. Sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, borax, and the like. The p Η値 of the aforementioned weakly basic aqueous solution is, for example, preferably about 8 to 12, more preferably about 9 to 11. The aforementioned weakly alkaline aqueous solution may be, for example, 0.1 to 5 mass, for example. / 〇 sodium carbonate aqueous solution or potassium carbonate aqueous solution. -85-200809406 The temperature of the above-mentioned developing liquid can be appropriately selected in view of the development of the photosensitive layer. However, for example, it is preferably about 25 ° C to 4 0 X:. The above-mentioned developing solution may also use a surfactant, an antifoaming agent, or an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diamethylenetriamine, triethyleneamine, morpholine, triethanolamine, etc.). Or an organic solvent (for example, an alcohol, a ketone, an ester, an ether, a guanamine, a lactone, etc.) for promoting development. Further, the developing solution may be a water-based developing solution obtained by mixing water or an aqueous alkali solution with an organic solvent, or may be a single organic solvent. In the formation of the aforementioned pattern, for example, a hardening treatment step, an etching step, a plating step, or the like may be contained. These may be used alone or in combination of two or more. &lt;Hardening treatment step&gt; In the case where the pattern forming method described above is a permanent pattern forming method of forming a permanent pattern of a protective film, an interlayer insulating film, a solder resist pattern, or the like, and a color furnace sheet, the aforementioned hardening treatment step It is preferred to have a step of hardening the photosensitive layer in the formed pattern after performing the above-described developing step. The hardening treatment described above is not particularly limited and may be appropriately selected according to the purpose of the object. For example, a suitable exposure treatment, a full-surface heat treatment, or the like is suitable. The above-described overall exposure treatment method is, for example, a method of exposing the entire surface of the laminate in which the permanent pattern is formed after the development step. By this full exposure, the hardening of the resin in the photosensitive composition forming the above-mentioned photosensitive layer can be promoted, and the surface of the above-mentioned permanent drawing -86-200809406 can be hardened. The apparatus for performing the above-described overall exposure is not particularly limited, and may be appropriately selected according to the purpose, and for example, a UV exposure machine such as an ultrahigh pressure mercury lamp, an exposure machine using a xenon lamp, a laser exposure machine, or the like is suitable. The exposure is usually 10 to 2,000 mJ/cm2. The above-described overall heating treatment method may be, for example, a method of performing overall heating on the above-mentioned laminated body in which the aforementioned permanent pattern is formed. By this overall heating, the film strength of the surface of the aforementioned permanent pattern can be improved. The heating temperature for the above comprehensive heating is preferably 120 to 250 ° C, more preferably 1 2 0 to 2 0 ° C. When the heating temperature is less than 120 ° C, the effect of increasing the film strength by heat treatment is not obtained; and when it exceeds 250 ° C, the resin in the photosensitive composition is decomposed. And make the membrane weak and brittle. The heating time of the above overall heating is preferably from 10 to 120 minutes, more preferably from 1 5 to 60 minutes. The apparatus for performing the above overall heating is not particularly limited. For example, it may be appropriately selected from conventional devices according to the purpose, such as a drying oven, a hot plate, an I R heater, or the like. The pattern forming method described above can be used to prevent formation of various patterns necessary for the sensitivity of the photosensitive layer due to oxygen when directly drawing with a 405 nm laser exposure, and can be suitably used for high. Pattern formation with both density and high production. In the above-described permanent pattern forming method, when the permanent pattern formed by the above-described permanent pattern forming method is the aforementioned protective film and the above-mentioned interlayer-87-200809406 edge film, the wiring can be protected from external impact. And the bending, in particular, in the case of the above-mentioned interlayer insulating film, for example, it can be effectively used for mounting on a high-density semiconductor or a component such as a multilayer wiring substrate or a stacked wiring substrate. In the above-described permanent pattern forming method of the present invention, since the photosensitive composition of the present invention is used, it can be suitably used for forming various patterns such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern. The manufacture of liquid crystal structural components such as color filters, pillars, ribs, spacers, partition walls, etc., manufacturing of holograms, micromachines, verification, etc., can be suitably used for permanent pattern formation of printed substrates. [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited thereto. (Example 1) Preparation of a photosensitive composition - Each component was blended in the following amounts to prepare an aqueous photosensitive composition solution. [Amount of each component of the photosensitive composition solution] • KAYARAD ZFR-1492H (bisphenol F type epoxy acrylate, concentration 66%, manufactured by Nippon Chemical Co., Ltd.)....46·8 Parts by mass • Dipentaerythritol hexaacrylate (polymerizable compound) · · · · 9 parts by mass • Irgacure 819 (I -1, photopolymerization initiator).....6 parts by mass • The following structural formula (1) Sensitizer (S-1)·································································· ΥΡ-50 (phenoxy resin, manufactured by Dongdu Chemical Co., Ltd.) · · 4 parts by mass • Thermal hardening accelerator (cyanide)..........0.77 parts by mass • Fluoride-based surfactant (Mega method) Library F-176, manufactured by Dainippon Ink Chemical Industry Co., Ltd., 30% by mass of 2-butanone solution) 0.2 parts by mass • Barium sulfate dispersion (manufactured by Dai Chemical Industry Co., Ltd., Β-30) · · · · 80 parts by weight • Methyl ethyl ketone......... 30 parts by mass In addition, the above barium sulfate dispersion is 28.5 parts by mass of barium sulfate (堺Chemical Industry) (share) company system, Β 30), 15.6 quality KAYARAD ZFR — 1492 Η (bisphenol F epoxy acrylate, 66%, manufactured by Nippon Kayaku Co., Ltd.), 28.2 parts by mass of n-propyl acetate, and 〇 2 parts by mass of cyanine green After pre-mixing, it was prepared by using a motor honing machine 200-200 (manufactured by Aga Co., Ltd.), using a chrome oxide bead having a diameter of 1.0 mm, and dispersing at a peripheral speed of 9 m/sec for 3 hours. The ratio of the crosslinking group of the thermal crosslinking agent in Example 1 to the acidity of the binder: thermal crosslinking group / acidic group = 0.5 / 1.0 = 0.5.

Ο CI

Structural Formula (1) 〇C3H7 Preparation of a photosensitive laminate First, a chemical honing treatment is performed on the surface of the copper clad laminate (without through holes and having a copper thickness of 12 μm) which is formed as a wiring of the above-mentioned substrate. modulation. On the copper clad laminate, the above-mentioned photosensitivity is applied by a screen printing method using a Teflon mesh screen of 120-89 - 200809406, and the film thickness after drying is 30 μm. The composition was dried at 80 ° C for 15 minutes in a hot air circulation dryer to form a photosensitive layer, and a photosensitive laminate in which the copper-clad laminate and the photosensitive layer were laminated in this order was prepared. The photosensitive laminates described above were evaluated for sensitivity, resolution, storage stability, and edge roughness in accordance with the following methods. The results other than the shortest development time are shown in Table 1. &lt;Evaluation of Shortest Developing Time&gt; For the entire photosensitive layer on the copper clad laminate described above, 30 ° C, 1% by mass of sodium carbonate as an alkaline developing solution was sprayed at a pressure of 0.15 MPa. The aqueous solution was measured for the time required from the spraying of the aqueous sodium carbonate solution until the photosensitive layer on the copper clad laminate was dissolved and removed, thereby taking the shortest development time. In addition, the shortest development time is 20 seconds. &lt;Evaluation of Sensitivity&gt; The photosensitive layer in the photosensitive laminate described above was irradiated from 0.1 mJ/cm 2 to 100 mJ/cm 2 at intervals of 21/2 times using the pattern forming apparatus described below. The light of different light energies is subjected to two exposures to harden a part of the photosensitive layer. After standing at room temperature for 10 minutes, 30 ° C, 1% by mass aqueous sodium carbonate solution was sprayed on the copper-clad laminate at a spray pressure of 0.15 MPa at twice the shortest development time as described above. The photosensitive layer on the plate was entirely removed to dissolve and remove the unhardened region, and the thickness of the remaining hardened region was measured. Next, the relationship between the amount of irradiation of light and the thickness of the hardened layer is plotted to obtain a sensitivity curve. From the sensitivity curve thus obtained, the thickness of the hardened region was determined to be -90 - 200809406 light energy at the same thickness of 30 μm as that of the photosensitive layer before exposure, and was taken as the necessary exposure energy for hardening the photosensitive layer. &lt;&lt;Pattern forming apparatus&gt;&gt; A pattern forming apparatus 10 including an exposure head 30 having a composite wave laser light source as disclosed in Japanese Laid-Open Patent Publication No. 2005-258431 And as the above-mentioned optical modulation mechanism, it is controllable to drive only the microlens array of 1,024 microlenses 58 arranged in the main scanning direction as shown in the schematic diagram of FIG. 2, and 768 groups arranged in the sub-scanning direction. 1 024 256 columns of DMDs 36 in the microlens array, and an optical system as shown in FIGS. 1A and 1B in which light is imaged on the photosensitive film. For each of the exposure heads 30, i.e., the set tilt angle of each of the DM D36, the available microlens 58 of 1 024 trains χ 2 56 rows can be used at an angle slightly larger than the angle 0 id eal of exactly 2 exposures. The angle 0 idea i is the number N of N exposures, the number s of the direction of the microlenses 58 that can be used, the interval p of the available microlenses 58 in the column direction, and the exposure head 30 are inclined. In the meantime, the scanning line pitch δ formed by the microlens has a relationship of the following formula 1: sp sin 0 Ideal ^ Ν δ (Formula 1) DM D36 in the present embodiment, as described above, because In the case where the plurality of microlenses 58 having the same vertical and horizontal arrangement intervals are arranged in a rectangular lattice shape, pcos0ideai=5 (Expression 2), and thus the above formula 1 becomes: s tan 0 ideal = N (Expression 3) -91 - 200809406 Since s = 2 5 6 and N = 2, the angle 0 jdea! is about ο. 4 5 degrees. Thus, the inclination angle 0' can be set, for example, 〇.50 degrees. First, in order to correct the variation of the resolution and the unevenness of the exposure in the two exposures, the state of the exposure pattern of the exposed surface is adjusted. The result is shown in Figure 3. In Fig. 3, a microlens 58 is provided which is projected onto the exposed surface of the photosensitive film 12 while the stage 14 is stationary, and has a DMD 36 of the exposure heads 30! 2 and 3021. The pattern of the light spot group. Further, in a state where the pattern of the spot group shown in the lower half and the upper half appears, when the moving stage 14 performs continuous exposure, the exposure pattern formed on the exposed surface is displayed for the exposed areas 3212 and 3221. status. In addition, in FIG. 3, for the sake of convenience of explanation, the exposure patterns of the microlenses 58 which are available for use are separated into the exposure patterns of the pixel group A and the exposure patterns of the pixel group B. In addition, the actual pattern on the exposed surface is formed by superimposing two kinds of exposure patterns. As shown in FIG. 3, it can be understood that since the relative position between the exposure heads 3012 and 3021 deviates from the ideal state, both the exposure pattern of the pixel group A and the exposure pattern of the pixel group B are in the exposure region 3212. And the repeated exposure range on the coordinate axis perpendicular to the scanning direction of the aforementioned exposure head of 3221, both of which generate more exposure than the ideal two exposure states, using a combination of slits 28 and photodetectors. For the aforementioned spot position detecting mechanism, the positions of the spots P(1, 1) and P(256, 1) in the exposure region 3 2 1 2 are detected for the exposure heads 3 0 1 2 and 3 0 2 i, and exposure is performed. The positions of the spots P (1, 1 024) and P (2 56, 1 024) in the region 3212, and the angle formed between the -92-200809406 tilt angle of the line connecting the lines and the scanning direction of the exposure head are measured. Using the substantial tilt angle 0', the natural number T of 値t closest to the exposure heads 30! 2 and 3 021 that satisfies the relationship 4: t tan 0 ' = N (Expression 4) is obtained. The results are respectively derived as follows: for exposure head 3 (T = 2 54 for ^ 2; T = 255 for exposure head 3021. As a result, the microlens system constituting portions 78 and 80 covered with oblique lines in Fig. 4 is defined A microlens that is not used in the present exposure. Then, the microlens corresponding to the light spot other than the light spot constituting the range of 7 8 and 80 covered with oblique lines in Fig. 4 is defined and constructed in the same manner. The microlens corresponding to the spot 82 covered by the oblique line and the spot 84 covered by the halftone dot in Fig. 4 is added as a microlens which is not used in the present exposure. It is defined not for use in such exposure. The microlens, by means of the pixel control mechanism, sends a signal of an angle that is normally set to the OFF state, to control the microlenses to be substantially independent of the exposure. Thereby, the exposure regions 3212 and 3221 can be made. In each of the ranges other than the connection region between the heads of the repeated exposure ranges formed on the exposed surface formed by the plurality of exposure heads, the area is excessively exposed and becomes Exposure not The sum of the areas of the areas is minimized. <Evaluation of resolution> The photosensitive layered body described above was produced in the same manner and conditions as the evaluation method of the shortest development time described above at room temperature (23 ° C, 55% RH). The lower standing -93- 200809406 1 〇 min. From the photosensitive layer of the obtained photosensitive laminate, using the above-described pattern forming device, the line width is 10 μm in a column size/space =1 /1 on a 1 μm scale. The exposure of each line width up to 100 micrometers. The exposure amount at this time is the light energy required to harden the photosensitive layer. After standing at room temperature for 10 minutes, the photosensitive layer on the copper clad laminate is comprehensively applied. Spraying a 30 ° C, 1% by mass aqueous solution of sodium carbonate at a spray pressure of 0.15 MPa and twice the shortest development time to dissolve and remove the uncured region. Observing the hardened lens with an optical microlens The surface of the copper-clad laminate of the resin pattern is measured for the minimum column width which is free from abnormalities such as clogging, wavy, etc., and which can form a space, and is regarded as the resolution. The resolution coefficient is smaller. <Evaluation of Preservation Stability 1> The photosensitive laminate was stored under a condition of promoting drying at 40 ° C (relative humidity: 50%) for one day. After one day, the same as described above. In the measurement, the sensitivity and the resolution were measured, and the stability was evaluated according to the following criteria. [Evaluation criteria] 〇: The sensitivity and the resolution were almost unchanged, and the stability over time was excellent. △: The sensitivity and resolution were lowered, and the image was developed. Difficulty, poor stability over time. X: Sensitivity and resolution are significantly reduced, and evaluation of stability over time is extremely poor, or cannot be preserved. &lt;Evaluation of edge roughness&gt; For the above-mentioned photosensitive laminate, the above-mentioned The pattern forming apparatus is irradiated for two exposures so as to form a pattern of a horizontal line -94 - 200809406 in a direction perpendicular to the scanning direction of the exposure head, and is similar to the measurement of the resolution of a part of the photosensitive layer. Practice to form a pattern. For each of the five arbitrary positions of the column having a width of 50 μm in the obtained pattern, a laser microscope (VK-9500, manufactured by Keynes Co., Ltd., 50 times of the objective lens) was observed to obtain a field of view. In the inner edge position, the absolute difference between the most expanded position (the top of the mountain) and the lowest position (the bottom of the valley), and the average 値 of the five positions observed is calculated as the edge roughness. The smaller the roughness of the edge, the better the performance, and thus the better. (Example 2) Production of a photosensitive film A photosensitive composition solution obtained in Example 1 was applied to a PET of 16 μm thick, 300 mm wide, and 200 m long as a support (poly) The film of ethylene terephthalate) was dried in a hot air circulating dryer at 80 ° C to form a photosensitive layer having a thickness of 30 μm. Next, on the photosensitive layer, a polypropylene film of 20 μm thick, 310 mm wide and 210 m long which was laminated as a protective film was used to produce the above-mentioned photosensitive film. First, the preparation of the photosensitive layered layered body is followed by the use of a vacuum laminator while peeling off the protective film in the photosensitive film on the same copper-clad laminate as in the first embodiment.制 股 公司 VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP And a layered body in which the above-mentioned polyethylene monoester film (support) is laminated in this order. -95- 200809406 The pressing conditions are: vacuum suction time is 40 seconds, and pressing temperature is 70. (:, the pressure of the press is 〇. 2 MP a, and the pressurization time is 1 〇. The sensitivity, the resolution, the storage stability, and the edge roughness are evaluated in the same manner as in the first embodiment of the photosensitive laminate] The results are shown in Table 1. In addition, the stability with respect to the resolution and the storage stability (the evaluation 1 of the above-mentioned storage stability) and the edge roughness were evaluated in the same manner as in Example 1. The evaluation was carried out in accordance with the following procedure. The storage stability was evaluated in accordance with the following method in addition to the aforementioned stability over time. The results are shown in Table 1. &lt;Evaluation of Sensitivity&gt; The photosensitive layer of the photosensitive film in the photosensitive laminate was prepared, and a part of the photosensitive layer was cured in the same manner as in Example 1 from the support side by the pattern forming apparatus described in Example 1. After standing at room temperature for 1 minute, the above-mentioned support was peeled off from the above-mentioned photosensitive laminate, and the light energy required for curing the photosensitive layer was measured in the same manner as in Example 1. &lt;Evaluation of Preservation Stability 2 &gt; The above-mentioned photosensitive film was crimped by a wrapping machine to produce an initial roll (cylinder) of the photosensitive film. The initial cylinder of the obtained photosensitive film obtained, It is made into a thin film by a coaxial roller, and is formed into a photosensitive film on a cylindrical core of ABS resin having a length of 30 mm and an inner diameter of 76 mm and wound up to 150 m in a width of 250 mm. The photosensitive film cylinder thus obtained is packaged in a tubular bag made of black polyethylene-96-200809406 (film thickness: 80 μm, water vapor-passing square, 24 hours or less), The polypropylene was brushed into the cylindrical sample of the above-mentioned two-stage cylindrical sample, and the end surface was melted, and the storage stability was evaluated. The laminated body is at a good price Δ: a part of the end face is shiny, and causes a certain amount of state (use limit). X: the end face is completely dull, and a large amount of face welding occurs (Example 3) In Embodiment 1, except Sensitive The Irgacure 819 (1, 1, photopolymerization initiator) of the composition was changed to the same manner as in Example 1 except that the anthracene derivative (I-2, 3) represented by the following structure (2) was used. The photosensitive composition solution was used in the same manner as in Example 2 to prepare a photosensitive laminate.

C2h5 For the above-mentioned photosensitive laminate, both the sensitivity, the resolution, the storage stability 1 and 2, and the permeability: 25 g/flat both ends of the core were carried out. Stored at 25 ° C, based on the following benchmarks. The state in which the end face is melted is melted. 6 parts by mass and 2 parts by mass of the polymerization initiator in the solution are used as a composition solution. The sense of the formation of the sense of the structure (2) column 2 the same approach edge roughness evaluation -97- 200809406 price. The results are shown in Table 2. (Example 4) In Example 1, except that 6 parts by mass of Irg a cure 8 1 9 (I-1, photopolymerization initiator) in the photosensitive composition solution was changed to 1 part by mass, the following structure was used. (3) The photosensitive composition solution was prepared in the same manner as in Example 1 except that the compound (I-3, photopolymerization initiator) and 0.5 part by mass of N-phenylglycine (additive) were used. . Using the photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2, and a photosensitive laminate was prepared.

The sensitivity, resolution, storage stability 1 and 2, and edge roughness were evaluated in the same manner as in Example 2 for the photosensitive laminate described above. The results are shown in Table 2. (Example 5) In Example 1, except that 6 parts by mass of 丨rg a cure 81 9 (I-1, photopolymerization initiator) in the photosensitive composition solution was changed to 2 parts by mass, the following structure was used. The photosensitive composition solution was prepared in the same manner as in Example 1 except for the compound (I-4, photopolymerization initiator) represented by the above. Using the photosensitive composition solution, a gastric light film was formed in the same manner as in Example 2, and a photosensitive laminate was prepared. -98- 200809406

^x〇-C02CH3 Structural formula (4) With respect to the above-mentioned photosensitive laminate, sensitivity, resolution, storage stability 1 and 2, and edge rough quotation were carried out in the same manner as in Example 2. The results are shown in Table 2. (Example 6) In the example 1, the Irgacure 819 (1, 1, photopolymerization initiator) in the photosensitive composition solution was changed to a compound represented by the following structure (5) ( In the same manner as in Example 1, the photosensitive composition was prepared in the same manner as in Example 1 except that the photosensitive film solution was used, and a photosensitive film was prepared in the same manner as in Example 2, and a photosensitive laminate was prepared. The degree of practice is evaluated by 6 mass parts of the tanning agent). Make sense of formation

Structural Formula (5) In the same manner as in Example 2, the photosensitive laminate was subjected to sensitivity, resolution, storage stability 1 and 2, and edge roughness. The results are shown in Table 2. (Example 7) In the example 1, Irgacure 819 (1, 1, photopolymerization initiator) in the photosensitive composition solution was changed to a compound represented by the following structure (6) ( 1 _6, photopolymerization; evaluation of the degree of practice 6 parts by mass of 5 parts), in the same manner as in the implementation of Μ 1 except for -99-200809406, the photosensitive composition is dissolved, and the photosensitive composition is dissolved. The photosensitive film is prepared by using a liquid film and a photosensitive film. The structural layer (6) is obtained. The sensitivity, resolution, and storage stability of the photosensitive laminate described above are the same as in the case of the first embodiment. And 2, and the edge of the rough cake price. The results are shown in Table 2. (Example 8) In the example 1, the Irgacure 819 (1, 1, photopolymerization initiator) in the photosensitive composition solution was changed to a compound represented by the following structure (7) ( In the same manner as in Example 1, except that the photosensitive composition was used for the photopolymerization, the photosensitive composition solution was used, and a photo-sensitive film was prepared in the same manner as in Example 2, and a photosensitive laminate was prepared. Body.

The degree of treatment of the 6 mass parts of the tincture) to the liquid. Make sense of formation

N-Ο-COCH3 Structural Formula (7) With respect to the above-mentioned photosensitive laminate, sensitivity, resolution, storage stability 1 and 2, and edge roughness were carried out in the same manner as in Example 2. The results are shown in Table 2. Evaluation of the degree of practice-100-200809406 (Embodiment 9) In Embodiment 3, in addition to the production of a negative glass made of glass having the same pattern as that in place of the above-described pattern forming device 'and the negative glass is contacted The photosensitive laminate was exposed to light at 40 mJ/cm 2 by an ultrahigh pressure mercury lamp. Evaluations of sensitivity, resolution, storage stability 1 and 2, and edge roughness were carried out in the same manner as in Example 2 except that the above-described exposure method was used. The results are shown in Table 1. (Embodiment 10) In the second embodiment, the set inclination angle Θ of N = 1 is calculated based on the above Equation 3, and the natural number closest to the ttan (9' = 1 relationship 値t) is derived based on the above Equation 4. In the same manner as in Example 2, the sensitivity, the resolution, the storage stability 1 and 2, and the edge roughness were evaluated in the same manner as in Example 2. The results are shown in Table 1. (Example 11) In Example 3, In addition to KAYARAD ZFR-1492H (bisphenol F epoxy acrylate) and KAYARAD ZFR-1492H in the photosensitive composition solution, KAYARAD ZAR-1413H (bisphenol A epoxy acrylate, 66% concentration, Japan) A photosensitive composition solution was prepared in the same manner as in Example 3 except that the photosensitive composition solution was used, and a photosensitive film was formed in the same manner as in Example 2, and the photosensitivity was prepared. In the same manner as in Example 2, the photosensitivity, the resolution, the storage stability 1 and 2, and the edge roughness were evaluated in the same manner as in Example 2. The results are shown in Table 1. Example 1 heat in 1 The ratio of the crosslinking group of the crosslinking agent to the acidity of the binder: thermal crosslinking group / acidic group = 0.5 / 1. 0 = 0.5. (Example 12) In Example 3, except in the photosensitive composition solution The KAYARAD ZFR-1492H (bisphenol F type epoxy acrylate) was changed to the following adhesive (the binder represented by the above-mentioned general formula (2) as a raw material), and Example 3 In the same manner, a photosensitive composition solution was prepared. Using the photosensitive composition solution, a photosensitive film was formed in the same manner as in Example 2, and a photosensitive laminate was prepared. The photosensitive laminate described above and examples 2 The same procedure was used to evaluate the sensitivity, resolution, preservation stability 1 and 2, and edge roughness. The results are shown in Table 1. A binder preparation of 200 parts by mass of Epter YDPF-1 000 (East 36 parts by mass of acrylic acid, 0.2 parts by mass of methylhydroquinone, and 60 parts by mass of propylene glycol monomethyl ether monoacetate were placed in a reaction vessel, and the reaction was carried out by stirring at 90 ° C. , the internal temperature is cooled to 60 °C, plus 1 part by mass of triphenylphosphine, stirred at 1 ° C for 3 hours, then, 50 parts by mass of tetrahydrophthalic anhydride, and 94 parts by mass of propylene glycol monomethyl ether monoacetate at 85 ° The mixture was stirred for 6 hours to obtain a binder having a concentration of 65%. (Comparative Example 1) In Example 1, except for 6 parts by mass of Irgacure 819 (1 -1, photopolymerization initiator) in the photosensitive composition solution ) changed to 3 parts by mass

The composition of the photosensitive -10 2 - 200809406 composition was prepared in the same manner as in Example 1 except for Irgacu re 9 07, and a photosensitive laminate was prepared. The sensitivity, resolution, storage stability 1 and 2, and edge roughness were evaluated in the same manner as in Example 1 for the photosensitive laminate described above. The results are shown in Table 1. (Comparative Example 2) The same procedure as in Example 2 was carried out, except that the photosensitive composition solution of Comparative Example 1 was used (6 parts by mass of Irgacu re 81 9 was changed to 3 parts by mass of 丨rg a cure 9 07). The photosensitive composition solution was prepared, and a photosensitive laminate was prepared. The sensitivity, resolution, storage stability 1 and 2, and edge roughness were evaluated in the same manner as in Example 2 for the photosensitive laminate described above. The results are shown in Table 1. (Comparative Example 3) In Example 1, except that KAYARAD ZFR-1 492H (bisphenol F type epoxy acrylate) in the photosensitive composition solution was changed to RIPOXY PR-300 (catechol novolac type epoxy) The photosensitive composition solution was prepared in the same manner as in Example 1 except that the glycerin was changed to a concentration of 65 %, and the concentration was changed to 65% by the product of Showa Co., Ltd., and a photosensitive laminate was prepared. The sensitivity, resolution, storage stability 1 and 2, and edge roughness were evaluated in the same manner as in Example 1 for the photosensitive laminate described above. The results are shown in Table 1. (Comparative Example 4) A photosensitive composition solution was prepared in the same manner as in Example 2-103-200809406 except that the photosensitive composition solution of Comparative Example 3 (changed KAYARAD ZFR-1492H to RIPOXY PR-300) was used. And modulating the photosensitive laminate. The sensitivity, the resolution, the storage stability 1 and 2, and the edge roughness were evaluated in the same manner as in Example 2 for the photosensitive laminate described above. The results are shown in Table 1. Table 1 Sensitivity (mJ/cm2) Resolution (μm) Preservation Stability 1 Preservation Stability 2 Edge Roughness ~ Example 1 98 45 〇 - 1.6 Example 2 54 35 〇〇 1.4 Example 3 49 35 〇〇 1.4 Example 4 41 35 〇〇 1.4 Example 5 43 35 〇〇 1.4 Example 6 44 35 〇〇 1.4 Example 7 43 35 〇〇 1.4 Example 8 45 35 〇〇 1.4 Example 9 A 35 〇〇 1.5 Example 10 54 35 〇〇 2.1 Example 11 47 35 〇〇 1.4 Example 12 48 35 1 〇〇 1.4 Comparative Example 1 ~?30 _ 45 X - Ti Comparative Example 2 70 35 X 〇 1.4 Comparative Example 3 110 50 Δ .- 1.6 Comparison Example 4 65 40 Δ Δ 1.4 From the results of Table 1, it can be judged that in Examples 1 to 12 using the photosensitive composition of the present invention and the photosensitive film of the present invention, a high sensitivity and excellent storage stability can be formed. High resolution pattern. [Industrial Applicability] The photosensitive composition of the present invention can form a high-definition pattern excellent in high sensitivity, storage stability, and handleability, and can be widely used to form a printed wiring substrate suitable for containing an encapsulating substrate. Or the like, or the permanent pattern (interlayer insulating film, protective film, and solder resist pattern, etc.) in the high-definition permanent pattern in the semiconductor field' and can be very suitably used for forming the photosensitivity of the present invention. The film is used for forming a permanent pattern and forming a printed substrate. The photosensitive film of the present invention can form a high-definition pattern excellent in high sensitivity, good storage stability, and handleability by using the photosensitive composition of the present invention, and can be widely used to form a substrate suitable for inclusion. a pattern on the manufacture of a printed wiring board or the like, or a permanent pattern (interlayer insulating film, protective film, solder resist pattern, etc.) in a high-definition permanent pattern in the semiconductor field, and can be suitably used for forming the photosensitivity of the present invention. The film and the method for forming a permanent pattern and the formation of a printed substrate. Since the permanent pattern forming method of the present invention is formed by using the photosensitive composition or the photosensitive film of the present invention, it is possible to form a high-definition pattern excellent in high sensitivity, storage stability, and handleability. Further, it is effective to form a pattern suitable for manufacturing a printed wiring board or the like including an encapsulating substrate, or a permanent pattern (interlayer insulating film, protective film, solder resist pattern, etc.) in a high-definition permanent pattern in the semiconductor field, and thus It can be used to form the formation of various patterns requiring high-definition exposure, and is particularly well suited for use in the formation of the printed substrate of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A is a top view showing an example of a detailed configuration of an exposure head. Fig. 1B is a side view showing an example of a detailed configuration of an exposure head. Fig. 2 is a partially enlarged view showing an example of a DMD of the pattern forming apparatus. -105- 200809406 Fig. 3 is an explanatory view showing an example in which the pattern on the surface to be exposed is deviated when there is a deviation in the relative position between the adjacent exposure heads and an error in the mounting angle. Fig. 4 is an explanatory view showing the exposure using only the selected pixel portion in Fig. 3. [Description of component symbols] 12 Photosensitive material, photosensitive layer 36 Digital microlens device (DMD) 38 Fiber array light source 40 Lens system 42 Lens 44, 46 Combined lens 48 Concentrating lens 50 Lens system 52, 54 Lens 56 SRAM unit ( Memory) -106-

Claims (1)

200809406 X. Patent Application Range: 1. A photosensitive composition characterized by comprising at least (A) a binder, (B) a polymerizable compound and (C) a photopolymerization initiator, wherein (A) a binder system a reaction product of an epoxy compound (a) having a bisphenol skeleton and a monocarboxylic acid (b) having an unsaturated group, and a polybasic acid compound containing any one of a saturated group and an unsaturated group ( c) A binder obtained by the reaction. 2. The photosensitive composition of claim 1, wherein the (A) binder is an epoxy compound represented by any one of the following general formula (1) and general formula (2) (a) a photocurable resin obtained by reacting a reaction product of an unsaturated group-containing monocarboxylic acid (b) with a polybasic acid compound (c) containing either a saturated group or an unsaturated group; However, in the above general formula (1), 'x represents a hydrogen atom and a glycidyl group; R represents any of a methylene group and an isopropylidene group; and the η system represents 1 or more. Integer General formula (2) -107- 200809406 However, in the above general formula (2), R1 represents any one of a hydrogen atom and a methyl group; R2 and R3 represent an alkylene group; m and η represent m + n is a positive integer from 2 to 50; p is a positive integer. 3. For the photosensitive composition of claim 1, the sensitivity is 〇 · 1 ～ 2 〇 mJ/cm 2 . 4 The photosensitive composition of claim 1, further comprising (D) a thermal crosslinking agent. 5. The photosensitive composition of claim 1, wherein the anthracene derivative has a partial structure represented by any one of the following general formula (3) and the following general formula (4); Ar such as (Y ”= N-〇-Y2) m - General formula (3) Ar-(c〇-C(Y1)=N-〇-Y2)m General formula (4) However, in the above general formula (3) and In 4), the Ar system represents any one of an aromatic group and a heterocyclic group; Y1 represents any one of a hydrogen atom and a monovalent substituent; and Y2 represents an aliphatic group, an aromatic group, a heterocyclic group, Any one of COY3, C02Y3 and CONY4Y5; Y3, Y4 and Y5 represent any of an aliphatic group, an aromatic group and a heterocyclic group; m represents an integer of 1 or more. 6. If the patent application is the fourth item a photosensitive composition in which (D) a crosslinking group of a thermal crosslinking agent and (A) a ratio of an acidic group of a binder are a crosslinking group/acid group = 0.3 to 3.0. 7· a photosensitive film, And a photosensitive layer composed of at least a support and a photosensitive composition of the photosensitive-108-200809406 composition as recited in claim 1 of the support, and the photosensitive layer 8. The photosensitive film of claim 7, wherein the photosensitive film is formed into a long shape and rolled into a cylindrical shape. 9. A photosensitive laminated body characterized by having a substrate A photosensitive layer comprising the photosensitive composition according to the first aspect of the invention. The photosensitive layer according to claim 9 wherein the photosensitive layer is as described in claim 7 A method for forming a permanent pattern, comprising: exposing a photosensitive layer in a photosensitive laminate as described in claim 9 of the patent application. 12. Patent Application No. 1 The permanent pattern forming method, wherein the exposure system uses laser light having a wavelength of 350 to 415 nm. 13. A printed circuit board characterized by: forming a permanent pattern by a permanent pattern forming method as described in claim 11 Pattern. -109-