JP4620700B2 - Photosensitive composition, photosensitive film, method for forming permanent pattern, and printed circuit board - Google Patents

Description

  The present invention relates to a photosensitive composition suitable for a blue-violet laser exposure system, forming a solder resist as an insulating film or protective film covering a printed wiring board or the like, a photosensitive film, and a permanent pattern using the photosensitive composition. And a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method.

  In the field of printed wiring boards, components such as semiconductors, capacitors and resistors are soldered onto the printed wiring board. In this case, for example, in a soldering process such as IR reflow, a permanent pattern corresponding to the unnecessary portion of soldering is used as a protective film and an insulating film in order to prevent solder from adhering to the unnecessary portion of soldering. The forming method is adopted. A solder resist is preferably used as the permanent pattern of the protective film.

As a method for forming the permanent pattern, a method for forming a permanent pattern using a liquid resist in which a photosensitive composition solution is applied to the printed wiring board and a photosensitive layer is laminated has been generally used. In order to be easy and excellent in film thickness uniformity, it is desired to make the liquid resist into a dry film.
On the other hand, as the exposure to the photosensitive layer, conventionally, it was common to perform exposure using a photomask, but in recent years, in order to pursue high productivity of printed boards and a reduction in defective rate, Maskless laser exposure systems are attracting attention.

Here, it has been found that a compound containing a halogen atom generates a harmful substance such as dioxin when incinerated, and there is an increasing demand for a printed circuit board containing no halogen atom.
Up to now, among the materials containing halogen atoms, phthalocyanine greens such as green pigments (CI Pigment Green 7 and CI Pigment Green) have occupied a large portion of the halogen atom content in the permanent resist. Green 36) is known.

  Therefore, as a photosensitive composition having a reduced halogen content, a technique of mixing a blue pigment containing no halogen atom and a yellow or orange pigment containing no halogen atom in place of the aforementioned phthalocyanine green is disclosed. (See Patent Documents 1 to 5).

  Patent Document 1 discloses a technique relating to a photosensitive resin composition using a cyanine green-based green and a yellow pigment in combination.

  In Patent Document 2, C.I. I. It is described that the halogen content of the solder resist cured film containing 1.9% by mass of Pigment Green 7 is 8,767 ppm.

  Patent Document 3 describes that an epoxy resin usually synthesized in a solder resist and synthesized via an epichlorohydrin intermediate contains several hundred ppm of halogen as an impurity. It is disclosed that the production method can be changed from 10 ppm to 50 ppm or less by changing to a peracid oxidation method or by chlorine reduction treatment.

  Patent Document 4 discloses a technique related to a resist ink composition using a halogen-free blue and yellow pigment in combination.

  Patent Document 5 discloses a technique relating to a solder resist ink using a halogen-free blue and orange pigment.

In these photosensitive compositions disclosed in Patent Documents 1 to 5, in place of the phthalocyanine greens, a blue pigment containing no halogen atom in one molecule, a yellow pigment containing no halogen atom in one molecule, and / or The object is to contain a colorant mixed with an orange pigment.
Besides these Patent Documents 1 to 5, a solder containing a copper phthalocyanine pigment containing one halogen atom in one molecule and having a halogen content of 25% or less in the molecular weight instead of the phthalocyanine greens. A technique relating to a resist ink is disclosed (see Patent Document 6).
However, the photosensitive compositions disclosed in these Patent Documents 1 to 5 are (1) inferior in dispersibility of the pigment constituting the colorant, and it is difficult to ensure a stable pigment dispersion, thereby obtaining a smooth photosensitive layer. However, the patent document 6 has a problem in storage stability (change in developability with time), although the stable pigment dispersion is ensured. .
Moreover, in patent documents 1-6, it was difficult to show the high sensitivity which is calculated | required with respect to (2) blue-violet laser beam (wavelength = 405 +/- 5nm).

  Therefore, although various resist materials have been developed in consideration of the environmental impact at the time of disposal, it has a smooth photosensitive layer, good storage stability, and high sensitivity when using a blue-violet laser exposure system. The present invention has not yet provided a photosensitive composition, a photosensitive film, a method for forming a permanent pattern using the photosensitive composition, and a printed circuit board on which a permanent pattern is formed by the method for forming a permanent pattern. is there.

JP-A-9-136942 JP 2000-7974 A JP 2000-232264 A JP 2000-290564 A International Publication No. WO01 / 67178 Pamphlet International Publication No. WO02 / 48794 Pamphlet

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention provides a photosensitive composition, a photosensitive film, and the photosensitive composition that form a smooth photosensitive layer, have good storage stability, and exhibit high sensitivity when using a blue-violet laser exposure system. It is an object of the present invention to provide a permanent pattern forming method used and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method.

  In view of the above problems, the present inventors have made extensive studies and obtained the following knowledge. That is, as a photosensitive composition that forms a smooth photosensitive layer and exhibits high sensitivity to blue-violet laser light, a colorant (pigment), an alkali-soluble photosensitive resin, a polymerizable compound, and a photopolymerization initiator. Alternatively, it is a photosensitive composition containing at least a photoinitiator compound and a thermally crosslinkable resin, wherein the colorant (pigment) contains 5 to 50% by mass of halogen atoms in one molecule, and has a yellow color. The pigment present and the pigment which does not contain a halogen atom in one molecule and exhibits a blue color are contained in a mixing ratio (mass ratio) of 1: 1 to 1: 4, and green color is exhibited by blending these pigments. The present inventors have found that a photosensitive composition having a halogen content in the total solid content of 900 ppm or less fulfills the purpose, and has reached the present invention.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> An alkali-soluble photosensitive resin, a polymerizable compound, a photopolymerization initiator, a photoinitiator compound, a thermally crosslinkable resin, and a colorant, wherein the colorant is in one molecule. 5 to 50% by mass of a halogen atom and a yellow pigment and a blue pigment which does not contain a halogen atom in one molecule and which has a blue color, have a mixing ratio of 1: 1 to 1: 4. It is contained in (mass ratio), exhibits a green color by blending these pigments, and has a halogen content in the total solid content of 900 ppm or less.
<2> The blue pigment is a phthalocyanine pigment,
Yellow pigments include monoazo compounds, disazo compounds, diarylide non-rake compounds and lake compounds, bisacetoacetalide compounds, benzimidazolone compounds, metal complex compounds, The pigment contains a halogen atom selected from any of an anthraquinone compound and a heterocyclic anthraquinone pigment among the quinophthalone compound, isoindoline compound, and condensed polycyclic compound in the molecule. It is the photosensitive composition as described in said <1>.
<3> The phthalocyanine pigment is C.I. I. It is a photosensitive composition as described in said <2> which is pigment blue 15: 3.
<4> A pigment exhibiting a yellow color is C.I. I. Pigment yellow 2, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 6, C.I. I. Pigment yellow 49, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 75, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 10, C.I. I. Pigment yellow 60, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 63, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 87, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 121, C.I. I. Pigment yellow 124, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 136, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 170, C.I. I. Pigment yellow 171, C.I. I. Pigment yellow 172, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 188, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 173, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 166, and C.I. I. The photosensitive composition according to <2>, selected from any one of CI Pigment Yellow 138.
<5> The photosensitive composition according to any one of <1> to <4>, wherein the halogen component contained in the photosensitive composition is 500 ppm or less.
<6> The photosensitive composition according to any one of <1> to <4>, wherein a halogen component contained in the photosensitive composition is 250 ppm to 800 ppm.
<7> The photosensitive composition according to any one of <1> to <6>, wherein the yellow pigment has an average particle diameter of 100 nm to 500 nm.

<8> A photosensitive film having a photosensitive layer obtained by coating the photosensitive composition according to any one of <1> to <7> on a support, and then drying.
<9> A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive composition according to any one of <1> to <7> on the support. .
<10> The photosensitive film according to any one of <8> to <9>, wherein the support has a thermoplastic resin layer and a photosensitive layer in this order.
<11> The photosensitive film according to any one of <8> to <10> is a photosensitive film that is long and wound in a roll shape.
<12> The photosensitive film according to any one of <8> to <11>, wherein the photosensitive layer has a thickness of 1 μm to 100 μm.
<13> The photosensitive film according to any one of <8> to <12>, wherein the support includes a synthetic resin and is transparent.
<14> The photosensitive film according to any one of <8> to <13>, which has a protective film on the photosensitive layer.

<15> A light irradiation means capable of irradiating light, and modulating the light from the light irradiation means, and applying the photosensitive composition according to any one of <1> to <7> to the surface of the substrate. A pattern forming apparatus comprising at least light modulating means for exposing a photosensitive layer formed by drying. In the pattern forming apparatus according to <15>, the light irradiation unit irradiates light toward the light modulation unit. The light modulation unit modulates light received from the light irradiation unit. The light modulated by the light modulator is exposed to the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed. It is a permanent pattern formation method characterized by exposing and developing.
<16> The photosensitive film according to any one of <8> to <14>, wherein the photosensitive film is capable of irradiating light, and modulates light from the light irradiating means. And a light modulation means for exposing the photosensitive layer. In the pattern forming apparatus according to <16>, the light irradiation unit irradiates light toward the light modulation unit. The light modulation unit modulates light received from the light irradiation unit. The light modulated by the light modulator is exposed to the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
<17> The light modulation means further includes pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation means is emitted from the light irradiation means. The pattern forming apparatus according to any one of <15> to <16>, wherein modulation is performed according to the above. In the pattern forming apparatus according to <17>, since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit corresponds to the control signal generated by the pattern signal generation unit. Modulated.
<18> The light modulation means has n pixel parts, and forms any less than n pixel parts arranged continuously from the n pixel parts. The pattern forming apparatus according to any one of <15> to <17>, which can be controlled according to pattern information. In the pattern forming apparatus according to <18>, an arbitrary less than n number of pixel parts continuously arranged from among the n number of picture element parts in the light modulation unit is controlled according to pattern information. Thereby, the light from the light irradiation means is modulated at high speed.
<19> The pattern forming apparatus according to any one of <15> to <18>, wherein the light modulation unit is a spatial light modulation element.
<20> The pattern forming apparatus according to <19>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<21> The pattern forming apparatus according to any one of <18> to <20>, wherein the picture element portion is a micromirror.
<22> The pattern forming apparatus according to any one of <15> to <21>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the pattern forming apparatus according to <22>, since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<23> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects laser beams irradiated from the plurality of lasers and couples them to the multimode optical fiber. The pattern forming apparatus according to any one of <15> to <22>. In the pattern forming apparatus according to <23>, the light irradiation unit can collect the laser beams irradiated from the plurality of lasers by the collective optical system and couple the laser beams to the multimode optical fiber. Thus, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<24> A permanent pattern forming method, wherein the photosensitive layer formed of the photosensitive composition according to any one of <1> to <7> is exposed and developed.
<25> After laminating the photosensitive layer in the photosensitive film according to any one of <8> to <14> on the surface of the substrate under at least one of heating and pressurization, It is the pattern formation method as described in said <24> including at least performing exposure.
<26> The method for forming a permanent pattern according to <24> to <25>, wherein the substrate is a printed wiring board on which wiring is formed.
<27> The permanent pattern forming method according to any one of <24> to <26>, wherein the exposure is performed using a laser beam having a wavelength of 350 nm to 415 nm.
<28> The permanent pattern forming method according to any one of <24> to <27>, wherein the exposure is performed imagewise based on pattern information to be formed.
<29> The photosensitive layer has light irradiation means and n (where n is a natural number of 2 or more) two-dimensionally arranged pixel parts that receive and emit light from the light irradiation means. An exposure head provided with a light modulation means capable of controlling the picture element unit according to pattern information, wherein the column direction of the picture element part is a predetermined set inclination angle θ with respect to the scanning direction of the exposure head. The exposure head is used for N-exposure (where N is a natural number of 2 or more) of the usable pixel parts by the use pixel part designation means. The pixel part of the pixel part is specified so that only the pixel part specified by the used pixel part specifying unit is involved in exposure by the pixel part control unit for the exposure head. Control and scan the exposure head for the photosensitive layer A permanent pattern forming method according to any one of <28> is relatively moved from said <24> performed in countercurrent. In the method for forming a permanent pattern according to <29>, the exposure head is subjected to N multiple exposures (where N is a natural number of 2 or more) among the usable pixel parts by the used pixel part specifying means. The pixel part to be used is specified, and the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in exposure. . By performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction, the exposure head is formed on the exposed surface of the photosensitive layer due to a shift in the mounting position or mounting angle of the exposure head. Variations in the resolution of the pattern and unevenness in density are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<30> The exposure is performed by a plurality of exposure heads, and the used drawing element specifying means is related to the exposure of the joint area between the heads which is the overlapping exposure area on the exposed surface formed by the plurality of exposure heads. The permanent pattern forming method according to the item <29>, wherein, among the element parts, the image element part used for realizing N double exposure in the inter-head connection region is designated. In the method for forming a permanent pattern according to <30>, the exposure is performed by a plurality of exposure heads, and the used image element designating unit is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. Of the picture element parts involved in the exposure of the connection area between the heads, by specifying the picture element part used for realizing the N-fold exposure in the connection area between the heads, the mounting position of the exposure head, Variations in the resolution and density unevenness of the pattern formed in the connecting area between the heads on the exposed surface of the photosensitive layer due to the mounting angle deviation are leveled. As a result, the photosensitive layer is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<31> The exposure is performed by a plurality of exposure heads, and the used picture element specifying means is involved in exposure other than the inter-head connection region that is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The permanent pattern forming method according to <29>, wherein the image element portion used for realizing N double exposure in an area other than the inter-head connection area among the image element parts is designated. In the method for forming a permanent pattern according to <31>, the exposure is performed by a plurality of exposure heads, and the used image element designating unit is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. Mounting of the exposure head by designating the picture element part used for realizing N double exposure in areas other than the inter-head connection area among the image element parts related to exposure other than the inter-head connection area Variations in the resolution and density unevenness of the pattern formed in areas other than the joint area between the heads on the exposed surface of the photosensitive layer due to a shift in position and mounting angle are leveled. As a result, the photosensitive layer is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<32> When the set inclination angle θ is N, the number N of the multiple exposures, the number s of the pixel portions in the column direction, the interval p in the column direction of the pixel portions, and the exposure head tilted. the relative row direction pitch δ of pixel parts in the direction perpendicular to the scanning direction, the following equation with respect to theta _ideal satisfying spsinθ _ideal ≧ Nδ, which is set so as to satisfy the relation of θ ≧ θ _ideal <29> to <31>.
<33> The method for forming a permanent pattern according to any one of <29> to <32>, wherein N in N-fold exposure is a natural number of 3 or more. In the permanent pattern forming method according to <33>, multiple drawing is performed when N in N double exposure is a natural number of 3 or more. As a result, due to the effect of filling, variations in the resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to a shift in the mounting position and mounting angle of the exposure head are more precisely leveled.
<34> Use pixel part designation means,
A light spot position detecting means for detecting a light spot position on a surface to be exposed as a pixel unit generated by a picture element unit and constituting an exposure area on the surface to be exposed;
<29> to <33>, further comprising: a pixel part selection unit that selects a pixel part to be used for realizing N double exposure based on a detection result by the light spot position detection unit. This is a permanent pattern forming method.
<35> The permanent pattern forming method according to any one of <29> to <34>, wherein the used pixel part specifying unit specifies the used pixel part used for realizing N double exposure in units of rows. It is.

<36> Based on the at least two light spot positions detected by the light spot position detection means, the column direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is inclined are formed. The inclination angle θ ′ is specified, and the picture element selection means selects the use picture element part so as to absorb the error between the actual inclination angle θ ′ and the set inclination angle θ, from <34> to <35> The permanent pattern forming method according to any one of the above.
<37> The actual inclination angle θ ′ is an average value, a median value, and a plurality of actual inclination angles formed by a row direction of light spots on the surface to be exposed and a scanning direction of the exposure head when the exposure head is inclined. The permanent pattern forming method according to <36>, wherein the permanent pattern forming method is one of a maximum value and a minimum value.
<38> The pixel part selection means derives a natural number T close to t that satisfies the relationship of t tan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <34> to <37> for selecting the pixel part from the first line to the T-th line in a line element (where m represents a natural number of 2 or more) arranged as a used pixel part The permanent pattern forming method according to any one of the above.
<39> The pixel part selection means derives a natural number T close to t that satisfies the relationship of t tan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m In the picture element part arranged in a row (where m represents a natural number of 2 or more), the picture element part from line (T + 1) to m-th line is specified as an unused picture element part, and the unused picture element part is specified. The permanent pattern forming method according to any one of <34> to <38>, wherein the picture element part excluding the element part is selected as a use picture element part.

<40> In a region including at least an overlapped exposure region on an exposed surface formed by a plurality of pixel part columns,
(1) Means for selecting a used pixel portion so that a total area of an overexposed region and an underexposed region is minimized with respect to an ideal N-multiple exposure,
(2) Means for selecting a pixel part to be used so that the number of pixel units in an overexposed area and the number of pixel units in an underexposed area are equal to each other with respect to an ideal N double exposure;
(3) Means for selecting a pixel part to be used so that an area of an overexposed area is minimized and an underexposed area does not occur with respect to an ideal N double exposure, and (4) an ideal From <34>, which is one of means for selecting a used pixel part so that the area of the underexposed area is minimized and no overexposed area is generated with respect to typical N double exposure. <39> The method for forming a permanent pattern according to any one of the above.
<41> In the connection region between the heads, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads,
(1) With respect to the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connection region, the total area of the overexposed region and the underexposed region is minimized. Means for identifying a used pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
(2) Involvement in the exposure of the head-to-head connecting region so that the number of pixel units in the overexposed region and the number of pixel units in the underexposed region are equal to the ideal N-double exposure. Means for identifying an unused pixel part from the pixel part to be selected, and selecting the pixel part excluding the unused pixel part as a used pixel part;
(3) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the overexposed region is minimized and the underexposed region is not generated. A means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part; and
(4) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the underexposed region is minimized and the region that is overexposed is not generated. , Means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
The permanent pattern forming method according to any one of <34> to <40>.
<42> The permanent pattern forming method according to <41>, wherein the unused pixel parts are specified in units of rows.

<43> In order to specify the used pixel part in the used pixel part specifying unit, among the usable pixel elements, N (n-1) pixel element columns for N multiple exposures The permanent pattern forming method according to any one of <29> to <42>, wherein the reference exposure is performed by using only the picture element portion that constitutes. In the permanent pattern forming method according to <43>, in order to specify the used pixel part in the used pixel part specifying unit, among the usable pixel parts, N-1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.
<44> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel elements, a N / N line pixel part row is configured for N of N multiple exposures. The permanent pattern forming method according to any one of <29> to <43>, wherein the reference exposure is performed using only the picture element portion. In the permanent pattern forming method according to <44>, in order to designate the use pixel part in the use pixel part designating unit, among the usable picture element parts, N of N double exposure is 1 / Reference exposure is performed using only the pixel part constituting the pixel part column for every N rows, and a simple permanent pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<45> The <29> to <44>, wherein the used pixel part specifying means includes a slit and a photodetector as light spot position detecting means, and an arithmetic unit connected to the photodetector as a pixel part selecting means. The permanent pattern forming method according to any one of the above.
<46> The method for forming a permanent pattern according to any one of <29> to <45>, wherein N in N-exposure exposure is a natural number of 3 or more and 7 or less.

<47> The light modulation unit further includes a pattern signal generation unit that generates a control signal based on pattern information to be formed, and the control signal generated by the pattern signal generation unit generates light emitted from the light irradiation unit. The method for forming a permanent pattern according to any one of <29> to <46>, wherein the modulation is performed according to the method. In the permanent pattern forming apparatus according to <47>, since the light modulation unit includes the pattern signal generation unit, light emitted from the light irradiation unit is converted into a control signal generated by the pattern signal generation unit. Modulated accordingly.
<48> The method for forming a permanent pattern according to any one of <29> to <47>, wherein the light modulator is a spatial light modulator.
<49> The method for forming a permanent pattern according to <48>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<50> The permanent pattern forming method according to any one of <29> to <49>, wherein the picture element portion is a micromirror.
<51> From <29> to <29>, further comprising conversion means for converting the pattern information so that a dimension of a predetermined part of the pattern represented by the pattern information matches a dimension of a corresponding part that can be realized by the designated used pixel part. 50>. The permanent pattern forming method according to any one of 50>.

<52> The permanent pattern forming method according to any one of <29> to <51>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the method for forming a permanent pattern according to <52>, the light irradiation unit can synthesize and irradiate two or more lights, and thus exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, a very fine permanent pattern is formed.
<53> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser light emitted from each of the plurality of lasers and couples the laser light to the multimode optical fiber. The permanent pattern forming method according to any one of <29> to <52>. In the method for forming a permanent pattern according to <53>, the light irradiating means is configured such that laser light emitted from each of the plurality of lasers is condensed by the collective optical system and can be coupled to the multimode optical fiber. As a result, exposure is performed with exposure light having a deep focal depth. As a result, the exposure to the photosensitive film is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<54> The method for forming a permanent pattern according to any one of <24> to <53>, wherein the photosensitive layer is developed after the exposure. In the method for forming a permanent pattern described in <54>, a high-definition pattern is formed by developing the photosensitive layer after the exposure.
<55> The permanent pattern forming method according to <54>, wherein the permanent pattern is formed after the development.
<56> The method for forming a permanent pattern according to <55>, wherein after the development, the photosensitive layer is cured.
<57> The permanent pattern forming method according to <56>, wherein the curing process is at least one of an entire surface exposure process and an entire surface heat treatment performed at 120 ° C to 200 ° C.
<58> The method for forming a permanent pattern according to any one of <56> to <57>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.

<59> A permanent pattern formed by the pattern forming method according to any one of <24> to <58>. Since the permanent pattern according to <59> is formed by the pattern forming method, a smooth photosensitive layer is formed, the storage stability is good, and the definition is high. Useful for high-density mounting on build-up wiring boards.
<60> The pattern according to <59>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern according to <60> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, due to the insulating property, heat resistance, etc. of the film, the wiring may be subjected to external impact or bending. Protected from.

  <61> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to any one of <24> to <58>.

  According to the present invention, a photosensitive composition that can solve conventional problems, forms a smooth photosensitive layer, has good storage stability, and exhibits high sensitivity when using a blue-violet laser exposure system, A photosensitive film, a method for forming a permanent pattern using the photosensitive composition, and a printed board on which a permanent pattern is formed by the permanent pattern forming method can be provided.

(Photosensitive film)
The photosensitive film of the present invention has a support and a photosensitive layer on the support, preferably has a protective film on the photosensitive layer, and further has other configurations as necessary. It has.
The form of the photosensitive film is not particularly limited as long as it is provided with a support and a photosensitive layer in this order, and can be appropriately selected depending on the purpose. Examples include a form having a blocking layer, a photosensitive layer and a protective film in this order, and a form having a cushion layer, an oxygen blocking layer, a photosensitive layer and a protective film in this order on the support. The photosensitive layer may be a single layer or a plurality of layers.

[Support]
The support is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable that the photosensitive layer can be peeled off and has good light transmittance, and further has a smooth surface. It is more preferable that it is good.

The support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films such as ethylene, cellulosic film and nylon film can be mentioned. Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

There is no restriction | limiting in particular as thickness of the said support body, According to the objective, it can select suitably, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.
There is no restriction | limiting in particular as a shape of the said support body, According to the objective, it can select suitably, A long shape is preferable. There is no restriction | limiting in particular as the length of the said elongate support body, For example, the thing of the length of 10m-20,000m is mentioned.

(Photosensitive layer)
The photosensitive layer is formed from a photosensitive composition. The photosensitive composition includes a binder, a polymerizable compound, a photopolymerization initiator, a heat crosslinkable resin (thermal crosslinker), a colorant (pigment), an inorganic filler, and a thermosetting accelerator. It contains other components appropriately selected as necessary.
The photosensitive layer preferably has a thickness of 5 to 100 μm and an absorbance of 1 or less at a wavelength of 410 ± 5 nm.

〔binder〕
The binder includes an aromatic group that may include a heterocycle in the side chain and a polymer compound having an ethylenically unsaturated bond in the side chain, and the polymer compound has a carboxyl group in the side chain. preferable.
The binder is preferably a compound that is insoluble in water and swells or dissolves in an alkaline aqueous solution.

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

  The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, A thioether group, a silyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and the like, each of which may have a substituent, may be mentioned.

Examples of the alkyl group include linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups, and cyclic alkyl groups.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group. , Octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group , Cyclopentyl group, 2-norbornyl group and the like. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are preferable.

Examples of the substituent that the alkyl group may have include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. Examples of such substituents include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups. Group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfo Xyl group, acylthio group, acylamino group, N-a Killacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N '-Alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N', N ' -Dialkyl-N-alkylureido group, N ', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N ' -Diaryl-N-alkylureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N '-Aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N- Alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl Group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group ( Referred to as -SO 3 _H) and its conjugated base group (a sulfonato group), alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N- dialkyl sulfide Inamo yl group, N- Arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N - arylsulfamoyl group, (referred to as phosphonato group) N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group, a phosphono group _(-PO 3 _{H 2)} and its conjugated base group, Dialkylphosphono group (—PO ₃ (alkyl) ₂ ) (hereinafter “alkyl” means an alkyl group) Taste. ), A diarylphosphono group (—PO ₃ (aryl) ₂ ) (hereinafter “aryl” means an aryl group), an alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphone Group (—PO ₃ (alkyl)) and its conjugate base group (referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group) ), A phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as a phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (aryl)) ) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphonates Oxy group _(-OPO 3 H (alkyl)) and its conjugated base group (referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugate base (aryl phosphite Hona preparative oxy Group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups.
Specific examples of the aryl group in the substituent include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxy Phenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxy Carbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulphonatophenyl group, phosphonopheny Groups, such as phosphate Hona preparative phenyl group.

Specific examples of the alkenyl group in the substituent include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like.
Specific examples of the alkynyl group in the substituent include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
Examples of ^{R 01} of the acyl group in the substituents ^(R 01 CO-), a hydrogen atom, an alkyl group described above, and aryl groups.
Among these substituents, halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkylamino groups, acyloxy groups Group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N- Dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-aryl Sulfamoyl group, N-alkyl N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphosphonato group, phosphonooxy group, phosphonatoxy Group, aryl group, alkenyl group and the like are preferable.
Moreover, examples of the heterocyclic group in the substituent include a pyridyl group and a piperidinyl group, and examples of the silyl group in the substituent include a trimethylsilyl group.

On the other hand, examples of the alkylene group in the alkyl group include those obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms to obtain a divalent organic residue. For example, a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms are preferable.
Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and an isopropoxymethyl group. , Butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetra Methylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chloro Phenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonov Nyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples include propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

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

  Preferred examples of the substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl. Group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl Group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, Nyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methyl Phosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

Examples of the alkenyl group (—C (R ⁰² ) ═C (R ⁰³ ) (R ⁰⁴ )) and the alkynyl group (—C≡C (R ⁰⁵ )) include, for example, R ⁰² , R ⁰³ , R ⁰⁴ , and R ^Examples include a group in which ⁰⁵ is a monovalent nonmetallic atomic group.
Examples of R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Specific examples thereof include those shown as the above examples. Among these, a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group, and a cyclic alkyl group are preferable.

Preferable specific examples of the alkenyl group and alkynyl group include a vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, phenyl Examples include an ethynyl group.
As said heterocyclic group, the pyridyl group illustrated as a substituent of a substituted alkyl group etc. are mentioned, for example.

Examples of the oxy group (R ⁰⁶ O—) include those in which R ⁰⁶ is a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom.
Examples of such oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N- A diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, phosphonooxy group, phosphonatoxy group and the like are preferable.
Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Examples of the acyl group (R ⁰⁷ CO—) in the acyloxy group include those in which R ⁰⁷ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group mentioned above. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable.
Specific examples of preferred oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, carboxy Ethyloxy, methoxycarbonylethyloxy, ethoxycarbonylethyloxy, methoxyethoxy, phenoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, morpholinoethoxy, morpholinopropyloxy, allyloxyethoxyethoxy, phenoxy Group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group Group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, a phosphonatooxy group.

As the amino group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) which may contain an amide group, for example, R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ are monovalent nonmetallic atoms excluding a hydrogen atom A group consisting of a group is mentioned. R ⁰⁹ and R ⁰¹⁰ may combine to form a ring.
Examples of the amino group include N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acylamino group, N -Alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N '-Dialkyl-N-alkylureido group, N'-alkyl-N'-arylureido group, N', N'-dialkyl-N-alkylureido group, N ', N'- Alkyl-N′-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N ′ -Diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino Group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group and the like. It is done. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Also, ^{R 07} acylamino group, N- alkylacylamino group, N- arylacylamino group definitive acyl group ^(R 07 CO-) are as defined above. Of these, an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group are more preferable.
Specific examples of preferred amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

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

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

Examples of the carbonyl group (R ⁰¹³ —CO—) include those in which R ⁰¹³ is a group composed of a monovalent nonmetallic atomic group.
Examples of such carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, and N-arylcarbamoyl group. N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group and the like. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
As the carbonyl group, a formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, and N-arylcarbamoyl group are preferable. A group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group are more preferable.
Specific examples of the carbonyl group include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N- A methylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-diethylcarbamoyl group, a morpholinocarbonyl group and the like are preferable.

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

The phosphono group means one in which one or two hydroxyl groups on the phosphono group are substituted with another organic oxo group, for example, the above-mentioned dialkylphosphono group, diarylphosphono group, alkylarylphosphono group. , Monoalkylphosphono group, monoarylphosphono group and the like are preferable. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred.
More preferred specific examples of the phosphono group include a diethylphosphono group, a dibutylphosphono group, a diphenylphosphono group, and the like.

The phosphonato group _{(-PO 3 H 2 -, -} PO 3 H-) and, as mentioned above, the phosphono group _(-PO 3 _{H 2),} coupled from the first dissociation acid, or the second dissociated acid bases An anionic group is meant. Usually, it is preferable to use it with a counter cation. As such counter cations, generally known ones can be appropriately selected. For example, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

The phosphonato group may be a conjugated base anion group obtained by substituting one organic oxo group in the phosphono group. Specific examples thereof include the monoalkylphosphono group (—PO ₃ H (alkyl)) and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

The aromatic group can be produced by an ordinary radical polymerization method by using one or more radically polymerizable compounds containing an aromatic group and, if necessary, one or more other radically polymerizable compounds as a copolymerization component. .
Examples of the radical polymerization method generally include a suspension polymerization method and a solution polymerization method.

As the radically polymerizable compound containing an aromatic group, for example, a compound represented by the following structural formula (A) and a compound represented by the following structural formula (B) are preferable.
However, in said structural formula (A), R < ₁ >, R < ₂ > and R < ₃ > represent a hydrogen atom or monovalent organic group. L represents an organic group and may not be present. Ar represents an aromatic group that may contain a heterocycle.
However, in said structural formula (B), R < ₁ >, R < ₂ >, R < ₃ > and Ar represent the same meaning as the said structural formula (A).

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

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

In the compound represented by the structural formula (A) and the compound represented by the structural formula (B), the structural formula (A) is preferable in terms of sensitivity. Among the structural formulas (A), those having a linking group are preferable from the viewpoint of stability, and the organic group of L is an alkylene group having 1 to 4 carbon atoms that can remove non-image areas. It is preferable in terms of (developability).
The compound represented by the structural formula (A) is a compound containing a structural unit of the following structural formula (I). The compound represented by the structural formula (B) is a compound containing a structural unit of the following structural formula (II). Among these, the structural unit of the structural formula (I) is preferable from the viewpoint of storage stability.

However, in said structural formula (I) and (II), R < ₁ >, R < ₂ > and R < ₃ > and Ar represent the same meaning as said structural formula (A) and (B).
In the structural formulas (I) and (II), R ₁ and R ₂ are preferably a hydrogen atom, and R ₃ is preferably a methyl group, from the viewpoint of removability (developability) of a non-image area.
In addition, L in the structural formula (I) is preferably an alkylene group having 1 to 4 carbon atoms in terms of removability (developability) of non-image areas.

  Although there is no restriction | limiting in particular as a compound represented by the said structural formula (A) or a structural formula (B), For example, the following exemplary compound (1)-(30) is mentioned.

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

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

-Ethylenically unsaturated bond-
There is no restriction | limiting in particular as said ethylenically unsaturated bond, Although it can select suitably according to the objective, For example, what is represented by following Structural formula (III)-(V) is preferable.

However, in the structural formulas (III) to (V), R _{1 to} R ₃ and R _{5 to} R ₁₁ each independently represents a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R ₄ . Z represents an oxygen atom, a sulfur atom, —N—R ₄ , or a phenylene group. R ₄ represents a hydrogen atom or a monovalent organic group.

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

In the structural formula (4), examples of R _{4 to} R ₈ include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, and a substituent. An optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, and optionally having a substituent An alkylamino group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent are preferable, and a hydrogen atom, a carboxyl group, alkoxy A carbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.
Examples of the substituent that can be introduced include those listed in the structural formula (III).

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

Among the side chain ethylenically unsaturated bonds represented by the structural formulas (III) to (V), those having the structural formula (III) are more preferable because of high polymerization reactivity and high sensitivity.
The content of the ethylenically unsaturated bond in the polymer compound is not particularly limited, but is preferably 0.5 to 3.0 meq / g, more preferably 1.0 to 3.0 meq / g, 1.5 ˜2.8 meq / g is particularly preferred. When the content is less than 0.5 meq / g, the curing reaction amount is small, so that the sensitivity may be low. When the content exceeds 3.0 meq / g, the storage stability may be deteriorated.
Here, the content (meq / g) can be measured by, for example, iodine value titration.

The method for introducing an ethylenically unsaturated bond represented by the structural formula (III) into the side chain is not particularly limited. For example, the polymer compound containing a carboxyl group in the side chain and the ethylenically unsaturated bond and It can be obtained by addition reaction of a compound having an epoxy group.
The polymer compound containing a carboxyl group in the side chain is usually composed of, for example, one or more radically polymerizable compounds containing a carboxyl group and, if necessary, one or more other radically polymerizable compounds as a copolymerization component. The radical polymerization method includes, for example, suspension polymerization method, solution polymerization method and the like.

The compound having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these, but for example, a compound represented by the following structural formula (VI) and a compound represented by (VII) are preferable. In particular, the use of the compound represented by the structural formula (VI) is preferable from the viewpoint of increasing sensitivity.
However, in the structural formula (VI), R ₁ represents a hydrogen atom or a methyl group. L ₁ represents an organic group.
However, in the structural formula (VII), R ₂ represents a hydrogen atom or a methyl group. L ₂ represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.
Of the compound represented by the structural formula (VI) and the compound represented by the structural formula (VII), the compound represented by the structural formula (VI) is preferable. In the structural formula (VI), L ₁ is The thing of a C1-C4 alkylene group is more preferable.

Although there is no restriction | limiting in particular as a compound represented by the said structural formula (VI) or a structural formula (VII), For example, the following exemplary compounds (31)-(40) are mentioned.

  Examples of the radical polymerizable compound containing a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxyl styrene, and particularly preferred is acrylic acid. And methacrylic acid.

  Examples of the introduction reaction to the side chain include tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, and tetraethylammonium chloride, pyridine, triphenylphosphine, and the like. Can be carried out by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours.

The structural unit having an ethylenically unsaturated bond in the side chain is not particularly limited. For example, the structure represented by the following structural formula (i), the structure represented by the structural formula (ii), and these Those represented by mixing are preferred.
However, in said structural formula (i) and (ii), Ra-Rc represents a hydrogen atom or monovalent organic group. R ₁ represents a hydrogen atom or a methyl group. L ₁ represents an organic group which may have a linking group.

  The content in the polymer compound having the structure represented by the structural formula (i) or the structural formula (ii) is preferably 20 mol% or more, more preferably 20 to 50 mol%, and more preferably 25 to 45 mol%. Particularly preferred. If the content is less than 20 mol%, the curing reaction amount is small, so that the sensitivity may be low. If the content exceeds 50 mol%, the storage stability may be deteriorated.

-Carboxyl group-
The polymer compound of the present invention may have a carboxyl group in order to improve various performances such as non-image area removability.
The carboxyl group can be imparted to the polymer compound by copolymerizing a radical polymerizable compound having an acid group.
Examples of the acid group having such radical polymerizability include carboxylic acid, sulfonic acid, and phosphoric acid group, and carboxylic acid is particularly preferable.
The radical polymerizable compound having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p -Carboxylstyrene etc. are mentioned, Among these, acrylic acid, methacrylic acid, and p-carboxylstyrene are preferable. These may be used individually by 1 type and may use 2 or more types together.

Content in the binder of the said carboxyl group is 1.0-4.0 meq / g, and 1.5-3.0 meq / g is preferable. If the content is less than 1.0 meq / g, the developability may be insufficient, and if it exceeds 4.0 meq / g, the image strength may be easily damaged by alkali water development.
Here, the content (meq / g) can be measured, for example, by titration using sodium hydroxide.

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

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

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

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

  The solvent used in synthesizing the polymer compound of the present invention is not particularly limited and can be appropriately selected depending on the purpose. For example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, Butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, Examples include dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. These may be used alone or in combination of two or more.

The molecular weight of the polymer compound of the present invention is preferably 10,000 or more and less than 100,000, and more preferably 10,000 to 50,000 in terms of mass average molecular weight. When the mass average molecular weight is less than 10,000, the cured film strength may be insufficient, and when it exceeds 100,000, the developability tends to decrease.
Further, the polymer compound of the present invention may contain an unreacted monomer. In this case, the content of the monomer in the polymer compound is preferably 15% by mass or less.

The polymer compound according to the present invention may be used alone or in combination of two or more. Moreover, you may mix and use another high molecular compound.
Examples of the other polymer compounds are not particularly limited and may be appropriately selected depending on the purpose. For example, JP-A Nos. 51-131706, 52-94388 and 64- Examples thereof include epoxy acrylate compounds having an acidic group described in JP-A-62375, JP-A-2-97513, JP-A-3-289656, JP-A-61-2243869, JP-A-2002-296776, and the like.
Here, the epoxy acrylate compound is a compound having a skeleton derived from an epoxy compound and containing an ethylenically unsaturated double bond and a carboxyl group in the molecule. Such a compound can be obtained by, for example, a method of reacting a polyfunctional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.
Examples of the other polymer compound include vinyl copolymers having a (meth) acryloyl group and an acidic group in the side chain other than the present invention.
In this case, the content of the other polymer compound in the polymer compound of the present invention is preferably 50% by mass or less, and more preferably 30% by mass or less.

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

<Polymerizable compound>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. The compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. For example, at least one selected from monomers having a (meth) acryl group is preferable.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, Polyfunctional alcohols such as glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, and the like, and (meth) acrylated after addition reaction of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication Urethane acrylates described in publications such as JP 50-6034 and JP 51-37193; JP 48-64183, JP 49-4319 Polyester acrylates described in various publications such as JP, JP 30-30490, and polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. It is done. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  The blending ratio of the polymerizable compound used in the photosensitive composition is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass with respect to the total solid content. It is. If the amount of the polymerizable compound is too small, the photosensitivity tends to be low, and if it is too large, the dispersion stability of the pigment tends to be lowered.

<Photopolymerization initiator or photopolymerization initiation compound>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators, for example, visible from the ultraviolet region. Those having photosensitivity to light are preferable, and may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and initiates cationic polymerization according to the type of monomer. It may be an initiator.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having an oxadiazole skeleton), phosphine oxide, hexaarylbiimidazole, Examples include oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and ketoxime ethers.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

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

Examples of the compound described in the British Patent 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl)- 4-amino-6-trichloromethyl-1,3,5-triazine and the like can be mentioned.
Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl]- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in the specification of German Patent 3333724 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4 -Methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan-2 Vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine etc. are mentioned.

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

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

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

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

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  Examples of the oxime derivative suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

Further, as photopolymerization initiators other than those described above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbonyl (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP JP-A 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, and the like, and amines (for example, ethyl 4-dimethylaminobenzoate). , 4-dimethylaminobenzoic acid n-butyl, 4-dimethyl Phenethyl aminobenzoate, 2-dimethylimidoethyl 4-dimethylaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentamethylenebis (4-dimethylaminobenzoate), phenethyl 3-dimethylaminobenzoate, pentamethylene Ester, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethyl Ruaniline, tridodecylamine, aminofluoranes (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc., acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η ⁵ -cyclopentadienyl-η ⁶ -cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) JP, 53-133428, A JP, Sho 57-1819, JP-the 57-6096 and JP, US Patent compounds described in the 3,615,455 Patent specification mentioned.

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

<< Sensitizer >>
In addition to the photopolymerization initiator, a sensitizer can be added for the purpose of adjusting the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer described later.
The sensitizer can be appropriately selected by a visible light, an ultraviolet laser, a visible light laser or the like as a light irradiation means described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

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

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

  As content of the said sensitizer, 0.05-30 mass% is preferable with respect to all the components in the said photosensitive composition, 0.1-20 mass% is more preferable, 0.2-10 mass% Is particularly preferred. When the content is less than 0.05% by mass, the sensitivity to active energy rays is reduced, the exposure process takes time, and productivity may be reduced. The sensitizer may be precipitated from the photosensitive layer.

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

  The blending ratio of the photopolymerization initiator or photopolymerization initiator compound used in the photosensitive composition is preferably 0.01 to 20% by mass, more preferably 1 to 15% by mass, based on the total solid content. Especially preferably, it is 1-10 mass%. If the amount of the photopolymerization initiator or photopolymerization initiator compound is too small, the photosensitivity tends to be low, and if too large, the adhesion tends to decrease.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, developability For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.

  Examples of the epoxy compound having at least two oxirane groups in one molecule include a bixylenol type or biphenol type epoxy resin (“YX4000, manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, an isocyanurate skeleton, and the like. (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810; manufactured by Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol F type epoxy Resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy) Si resin, brominated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenolmethane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin (" HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc. "), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resins, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resins (Phthalic acid diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy Resins (3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; Manufactured by Daicel Chemical Industries, Ltd.), imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidylxylenoylethane resin Naphthalene group-containing epoxy resins (naphthol aralkyl type epoxy resins, naphthol novolac type epoxy resins, tetrafunctional naphthalene type epoxy resins, commercially available products such as “ESN-190, ESN-360; new "Manufactured by Nippon Steel Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc."), phenol compounds and diolefin compounds such as divinylbenzene and dicyclopentadiene Reaction product of polyphenol compound obtained by addition reaction of chloroquine and epichlorohydrin, ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracetic acid, epoxy resin having linear phosphorus-containing structure, cyclic Epoxy resin having phosphorus-containing structure, α-methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, Glycidyl methacrylate copolymer Epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxy) Phenyl) adamantane type epoxy resin and the like can be mentioned, but not limited thereto. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

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

From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the β-position is substituted with β-alkyl in all epoxy groups in the total amount of the epoxy compound contained in the photosensitive composition. The proportion of glycidyl groups is preferably 70% or more.
The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, β-butylglycidyl group. Among these, a β-methylglycidyl group is preferred from the viewpoint of improving the storage stability of the photosensitive resin composition and the ease of synthesis.

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

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

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

  Examples of the epoxy compound containing an epoxy group having an alkyl group at the β-position include di-β-alkyl glycidyl ether of bisphenol A, di-β-alkyl glycidyl ether of bisphenol F, and di-β-alkyl glycidyl of bisphenol S. Di-β-alkyl glycidyl ethers of bisphenol compounds such as ethers; di-β-alkyl glycidyl ethers of biphenols such as di-β-alkyl glycidyl ethers of biphenols and di-β-alkyl glycidyl ethers of tetramethylbiphenol; dihydroxynaphthalene Β-alkyl glycidyl ethers of naphthol compounds such as di-β-alkyl glycidyl ether of dinaphthol, di-β-alkyl glycidyl ether of binaphthol; poly- of phenol-formaldehyde polycondensate β-alkyl glycidyl ethers; poly-β-alkyl glycidyl ethers of monoalkyl substituted phenol-formaldehyde polycondensates of 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ethers of cresol-formaldehyde polycondensates; xylenol-formaldehyde Poly-β-alkyl glycidyl ethers of dialkyl-substituted phenol-formaldehyde polycondensates having 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ethers of condensates; poly-β-alkyl glycidyl ethers of bisphenol A-formaldehyde polycondensates Bisphenol compounds such as poly-β-alkyl glycidyl ethers of formaldehyde polycondensates; poly-β-alkyl glycidyl ethers of polyaddition products of phenol compounds and divinylbenzene; The

Among these, a bisphenol compound represented by the following general formula (IV), a β-alkyl glycidyl ether derived from a polymer obtained from the bisphenol compound and epichlorohydrin, and the phenol compound represented by the following general formula (V) -Poly-β-alkyl glycidyl ethers of formaldehyde polycondensates are preferred.
However, in said general formula (IV), R represents either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.
However, in the said general formula (V), R and R 'may be the same or different, and represent either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.

  These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more. It is also possible to use an epoxy compound having at least two oxirane groups in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

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

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

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

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

  As other thermal crosslinking agents, aldehyde condensation products other than melamine, resin precursors, and the like can be used. Specifically, N, N′-dimethylolurea, N, N′-dimethylolmalonamide, N, N′-dimethylolsuccinimide, 1,3-N, N′-dimethylolterephthalamide, 2,4,4 Examples thereof include 6-trimethylolphenol, 2,6-dimethylol-4-methyloanisole, 1,3-dimethylol-4,6-diisopropylbenzene, and the like. Instead of these methylol compounds, the corresponding ethyl or butyl ether, or acetic acid or propionic acid ester may be used.

  The blending ratio of the thermal crosslinking agent used in the photosensitive composition is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, and particularly preferably 5 to 15% by mass with respect to the total solid content. %. If the amount of the thermal crosslinking agent is too small, the adhesiveness of the cured film to the substrate tends to be low, and if it is too large, the storage stability tends to be low.

<Colorant>
The photosensitive composition according to the present invention includes, as a colorant (pigment), a yellow pigment containing 5 to 50% by mass of halogen atoms in one molecule, a blue color not containing halogen atoms in one molecule, and blue. And an organic pigment having a halogen content of 900 ppm or less in the total solid content.

  Among the colorants (pigments), a pigment that does not contain a halogen atom in the molecule and exhibits a blue color with respect to visible light (hereinafter sometimes referred to as a blue pigment) includes a phthalocyanine pigment, Specific examples of the phthalocyanine pigment include copper phthalocyanine blue (CI Pigment Blue 15: 3).

  In addition, as a pigment having an average particle diameter of 100 to 1,000 nm and exhibiting yellow with respect to visible light (hereinafter sometimes referred to as a yellow pigment), a pigment containing a halogen atom in the molecule is preferable. As a monoazo compound, C.I. I. Pigment yellow 2, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 6, C.I. I. Pigment yellow 49, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 75, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 111, and C.I. I. Pigment Yellow 116, and among the disazo compounds, the diarylide compounds are C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 63, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 87, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 121, C.I. I. Pigment yellow 124, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 136, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 170, C.I. I. Pigment yellow 171, C.I. I. Pigment yellow 172, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 176, and C.I. I. Pigment Yellow 188, and as a rake type, C.I. I. Pigment yellow 168. Further, as bisacetoacetalide compounds, C.I. I. Pigment yellow 16 and benzimidazolone compounds include C.I. I. Pigment yellow 154. As isoindoline and isoindolinone compounds, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, and C.I. I. Pigment yellow 173. Other examples include quinophthalone C.I. I. And CI Pigment Yellow 138. Of these, C.I. I. Pigment yellow 173, C.I. I. Pigment yellow 138, and C.I. I. Pigment Yellow 110 is particularly preferable because of its excellent heat resistance.

As a method for dispersing the colorant (pigment) contained in the photosensitive composition according to the present invention, powder pigment particles are mixed with a dispersing binder and, if necessary, an organic solvent solution of a dispersion aid, A known method is applicable. That is, the dispersion treatment is preferably performed by kneading using a dispersion / kneading apparatus such as a paint shaker, an ultrasonic disperser, a three roll, a ball mill, a sand mill, a bead mill, a homogenizer, or a kneader.
At this time, a resin having a carboxylic acid group can be used as the dispersing resin, but in the case of the present invention, the alkali-soluble crosslinkable resin can be used.
The amount of the dispersing resin used is preferably 0.1 to 200% by mass of the organic pigment, more preferably 1 to 100% by mass, and particularly preferably 2 to 50% by mass. If the amount of resin is too small, the dispersion stability of the pigment tends to decrease.
The organic solvent is preferably used in an amount of at least 100% by mass with respect to the total amount of the pigment and resin at the time of dispersion. If the amount is less than 100% by mass, the viscosity at the time of dispersion is too high, and dispersion may be difficult particularly when dispersed by a ball mill, a sand mill, a bead mill or the like.
The organic solvent is preferably a solvent that dissolves the dispersing resin and has high wettability to the pigment to be used. Aromatic hydrocarbons, acetates, ethers, alcohols, glycol monoethers, glycol monoethers Ether acetates and ketones are preferred.

In the dispersion treatment, the entire amount of the dispersion resin may be used together with the pigment during the dispersion treatment, or a part of the resin may be added after the dispersion treatment. Similarly, the entire amount of the organic solvent may be used together with the pigment during the dispersion treatment, or a part of the organic solvent may be added after the dispersion treatment.
Examples of the dispersion aid include anionic dispersants such as polycarboxylic acid type polymer surfactants and polysulfonic acid type polymer surfactants, nonionic dispersants such as polyoxyethylene / polyoxypropylene block polymers, anthraquinone type , Organic dyes such as perylene, phthalocyanine, quinacudrine, and other organic dyes having a substituent such as carboxyl group, sulfonate group, carboxylic acid amide group, hydroxyl group, etc. The pigment dispersibility and dispersion stability are improved, which is preferable. These pigment dispersants and organic dye derivatives are preferably used in an amount of 50% by mass or less based on the pigment. If it exceeds 50% by mass, the chromaticity tends to shift.

The blending amount of the yellow pigment and the blue pigment in the colorant is preferably 1:10 to 10: 1, more preferably 1: 5 to 5: 1, and most preferably 2: 5 to 5: 2.
By blending the yellow pigment and the blue pigment in the above range, the resulting photosensitive composition or its cured film is substantially green.
Even if the color of the photosensitive composition itself of the present invention is not necessarily green, the cured product of the photosensitive composition of the present invention only needs to be green on the bronze-colored copper-clad laminate. .

Further, the blending amount of the colorant in the photosensitive composition of the present invention is not particularly limited. However, when the colorant contains an organic solvent, the amount of the solder resist composition of the present invention excluding the organic solvent is not limited. It is preferable that 0.01-10 mass% is contained in all the components, It is more preferable that 0.05-8 mass% is contained, It is most preferable that 0.1-5 mass% is contained.
When the amount of the pigment contained in the photosensitive composition is too small, the color density of the photosensitive layer tends to be low, and when the amount is too large, the photosensitivity tends to decrease. That is, when the blending amount of the pigment is within the above range, a permanent protective film having good visibility at the time of visual inspection can be formed while suppressing a decrease in resin curability due to a decrease in ultraviolet transmittance.

In order to provide a photosensitive composition (photosensitive layer) that achieves high sensitivity to a blue-violet laser, the average particle size of the yellow pigment contained in the colorant is important, and the average particle size is 100 to 1,000 nm is preferable, 150 to 750 nm is more preferable, and 200 to 500 nm is most preferable.
If the average particle size of the yellow pigment is less than 100 nm, the transmittance of the resulting photosensitive layer in the photosensitive wavelength region is reduced, resulting in low sensitivity. To do.
The average particle size of the blue pigment contained in the colorant is not particularly limited, but is preferably 10 to 1,000 nm, more preferably 50 to 1,000 nm, and most preferably 100 to 500 nm. .
Here, coarse particles of 1,000 nm or more, preferably 500 nm or more, may be removed by a centrifugal separation method, a sintered filter, a membrane filter filtration method, or the like, because the coated surface shape is impaired during coating of the photosensitive layer coating solution. preferable.
If the average particle size is less than 10 nm, the degree of coloring (optical density) decreases, so the amount of addition must be increased to obtain the required degree of coloring, and the cost increases. If the thickness exceeds 1,000 nm, sufficient resolution cannot be obtained due to the influence of light scattering.

When preparing the photosensitive composition according to the present invention, in addition to the colorant, the alkali-soluble photosensitive resin, the photopolymerizable compound, the thermal crosslinking agent, and the photopolymerization initiator or photopolymerization start described above. The system compound and the thermosetting accelerator, inorganic filler, and other components described later are mixed, but these may be mixed before the dispersion treatment of the colorant or mixed after the dispersion treatment. Good.
The entire amount of the dispersing resin may not be used at the time of dispersion, and the remainder may be mixed later, particularly at the time of preparing the photosensitive layer coating solution. The amount of each component used is adjusted from the time of preparation of the photosensitive composition so that the final blending ratio in the photosensitive composition is obtained.

<Thermosetting accelerator>
The thermosetting accelerator has a function of accelerating the thermosetting of the epoxy resin compound or the polyfunctional oxetane compound, and is preferably added to the photosensitive resin. The content (solid content ratio) of the thermal crosslinking accelerator relative to the photosensitive composition is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and most preferably 0.5 to 3% by mass. . If the thermal crosslinking accelerator is too small, the adhesion of the cured film to the substrate tends to be low, and if it is too large, the storage stability tends to be low.
The thermosetting accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy. Amine compounds such as -N, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole and 2-methyl Imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methyl Imidazole Any imidazole derivatives bicyclic amidine compounds and salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2 -Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid S-triazine derivatives such as adducts, boron trifluoride-amine complex, organic hydrazide cumulative, phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) , Benzo Aromatic acid anhydrides such as phenonetetracarboxylic anhydride, aliphatic acid anhydrides such as maleic anhydride and tetrahydrophthalic anhydride, polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac and alkylphenol novolac Etc. can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the polyfunctional oxetane compound is a curing catalyst, or any compound capable of promoting the reaction of the carboxyl group with these, and any compound capable of promoting thermal curing other than the above. May be used.
The solid content in the solid content of the photosensitive composition solution of the epoxy resin, the polyfunctional oxetane compound, and a compound capable of accelerating thermal curing between these and the carboxylic acid is usually 0.01 to 20% by mass. It is.

<Inorganic filler>
The inorganic filler has the functions of improving the surface hardness of the permanent pattern, keeping the coefficient of linear expansion low, and keeping the dielectric constant and dielectric loss tangent of the cured layer itself low.
The inorganic filler is not particularly limited and can be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, gas phase method silica, none Examples include regular silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.

  The average particle size of the inorganic filler is preferably less than 3 μm, more preferably 0.1 to 2 μm. If the average particle size is 3 μm or more, resolution may be deteriorated due to light scattering.

  The blending ratio of the inorganic filler used in the photosensitive composition is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 40% with respect to the total solid content. % By mass. When the amount of the inorganic filler is too small, the hardness of the cured film tends to be low, and when the amount is too large, the photosensitivity tends to decrease.

Further, organic fine particles can be added as necessary. Suitable organic fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. Further, silica having an average particle size of 0.1 to ² μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  Since the inorganic filler contains particles having an average particle diameter of 0.1 to 2 μm, even if the permanent pattern is thinned to a thickness of 5 to 20 μm along with the thinning of the printed wiring board, The inorganic filler particles do not cross-link the front and back surfaces of the permanent pattern, and as a result, no ion migration occurs even in the high acceleration test (HAST), and a permanent pattern excellent in heat resistance and moisture resistance can be obtained. .

<Other ingredients>
The photosensitive composition (photosensitive layer coating solution) according to the present invention has a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, etc.) for suppressing dark reaction, and adhesion to the substrate. Titanate coupling agent for improving (silane coupling agent having vinyl group, epoxy group, amino group, mercapto group, isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate, etc.), film smoothness Various additives such as surfactants (fluorine-based, silicon-based, hydrocarbon-based, etc.) and other ultraviolet absorbers, antioxidants, etc. can be used as needed.

  The organic solvent includes an organic pigment, an alkali-soluble photosensitive resin, a polymerizable compound, a photopolymerization initiator or a photopolymerization initiator compound, a thermal crosslinking agent, a thermosetting accelerator, and an inorganic substance in the photosensitive composition (photosensitive layer coating solution). It is preferable that the total solid content including the filler is used in a range of 5 to 40% by mass. When total solid content exceeds 40 mass%, a viscosity will become high and there exists a tendency for applicability | paintability to worsen. On the other hand, if the total solid content is less than 5% by mass, the viscosity tends to be low and the applicability tends to deteriorate.

〔Protective film〕
The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said protective film, Although it can select suitably according to the objective, Usually, it provides on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, etc. Among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.

When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the above-mentioned relationship of adhesive force can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples include discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

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

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

[Other layers]
In addition to the photosensitive layer, the support, and the protective film, the photosensitive film of the present invention includes other components such as a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorbing layer, and a surface protective layer. You may have a layer of.
There is no restriction | limiting in particular in the arrangement | positioning, thickness, etc. in the said photosensitive film of the said other layer, According to the objective, it can select suitably.
The cushion layer is preferably a layer that has no tackiness at room temperature and melts and flows when laminated under vacuum and heating conditions.
The PC layer is preferably a film having a thickness of about 1.5 μm formed mainly of polyvinyl alcohol.

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

The photosensitive film of the present invention has a photosensitive layer on which a photosensitive composition that exhibits excellent storage stability and exhibits excellent chemical resistance, surface hardness, heat resistance and the like after development is laminated. For this reason, it can be suitably used for the production of printed wiring boards, color filters, pillar materials, rib materials, spacers, display members such as partition walls, holograms, micromachines, proofs, etc., especially for the formation of permanent patterns on printed circuit boards. It can be used suitably for use.
In particular, since the photosensitive film of the present invention has a uniform thickness, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned, the high acceleration test is performed. In (HAST), there is no occurrence of ion migration, and a high-definition permanent pattern excellent in heat resistance and moisture resistance can be obtained, so that the substrate is more precisely laminated.

(Permanent pattern formation method)
According to the method for forming a permanent pattern according to the present invention, the photosensitive film of the present invention is laminated on the surface of the substrate under at least one of heating and pressing, and then the photosensitive film is exposed. A permanent pattern is formed by development.
Hereinafter, through the description of the method for forming a permanent pattern according to the present invention, details of the permanent pattern produced by the method will be clarified.

-Substrate-
The substrate is not particularly limited and can be appropriately selected from known materials having a high surface smoothness to a surface having an uneven surface. A plate-like substrate (substrate) is preferable and specific. Examples include known printed wiring board forming substrates (for example, copper-clad laminates), glass plates (for example, soda glass plates), synthetic resin films, paper, metal plates, etc. Among these, A printed wiring board forming substrate is preferable, and the printed wiring board forming substrate is particularly formed with wiring in that a high-density mounting of a semiconductor or the like on a multilayer wiring board or a build-up wiring board is possible. preferable.

  In the laminate, the photosensitive layer is formed on a substrate, and an area exposed by an exposure process described later is cured on the photosensitive layer, and a permanent pattern can be formed by a development process described later.

[Lamination process]
The method for forming the laminate is not particularly limited and may be appropriately selected depending on the purpose. It is preferable to stack the photosensitive layers so that they overlap.
There is no restriction | limiting in particular as said heating temperature, According to the objective, it can select suitably, For example, 70-130 degreeC is preferable and 80-110 degreeC is more preferable.
There is no restriction | limiting in particular as said pressurization pressure, According to the objective, it can select suitably, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, heat press, a heat roll laminator (For example, Taisei Laminator Co., Ltd. make, VP) -II), a vacuum laminator (for example, VP130 manufactured by Nichigo Morton Co., Ltd.) and the like are preferable.

[Exposure process]
About the exposure method of the pattern forming material (photosensitive laminate, etc.) of the present invention, a maskless pattern exposure method for forming a two-dimensional image by performing relative scanning and exposure while modulating light based on image data The description will focus on an exposure process using (digital exposure).

  Digital exposure is an exposure method in which two-dimensional images are formed by using two-dimensional spatial light modulation devices and performing relative scanning while modulating light based on image data.

  An object called a “mask” in which an image (exposure pattern; hereinafter also referred to as a pattern) is formed with a material that does not transmit or weakly transmits exposure light is disposed in the optical path of the exposure light, and the photosensitive layer is formed as described above. This is an exposure method in which a photosensitive layer is exposed in a pattern using the “mask”, compared to a conventional mask exposure method (also referred to as analog exposure) in which a pattern corresponding to an image is exposed.

In digital exposure, an ultra-high pressure mercury lamp or a laser is used as a light source.
An ultra-high pressure mercury lamp is a discharge lamp in which mercury is sealed in a quartz glass tube or the like, and is a lamp set with a high vapor pressure of mercury to improve luminous efficiency (the mercury vapor pressure during lighting is about 5 MPa). (W. Ellenbaas: Light Sources, Philips Technical Library 148-150). Of the bright line spectrum, a single exposure wavelength of 405 nm ± 40 nm is used, and h-line (405 nm) is mainly used.

  Lasers are oscillators and amplifiers that make use of the phenomenon of stimulated emission that occurs in materials with an inversion distribution, and that produce monochromatic light with stronger coherence and directivity by amplification and oscillation of light waves. , Glass, liquid, pigment, gas, etc., and these mediums are known as solid laser (YAG laser), liquid laser, gas laser (argon laser, He-Ne laser, carbon dioxide laser, excimer laser), semiconductor laser, etc. Lasers can be used in the wavelength region.

  The semiconductor laser uses a light emitting diode that induces and emits coherent light at a pn junction when electrons and holes flow out to the junction due to carrier injection, excitation by an electron beam, ionization by collision, optical excitation, and the like. It is a laser. The wavelength of the emitted coherent light is determined by the semiconductor compound. The wavelength of the laser is a single exposure wavelength of 405 nm ± 40 nm.

  In the present invention, the single exposure wavelength means the dominant wavelength when using a laser, and when using an ultrahigh pressure mercury lamp, the emission wavelength other than 405 nm is cut with an ND filter to a wavelength longer than 365 nm or 405 nm to obtain the dominant wavelength. This means one wavelength only.

  There is no restriction | limiting in particular as said exposure method, According to the objective, it can select suitably, Digital exposure using a laser is preferable among these.

  The means for digital exposure is not particularly limited and may be appropriately selected depending on the purpose. For example, the light irradiation described in JP-A-2005-311305 and JP-A-2007-10785 is applied. And light modulating means for modulating light emitted from the light irradiating means based on pattern information to be formed.

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose. For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is used. For example, the photosensitive layer is arranged in a two-dimensional array of n (where n is a natural number of 2 or more) that receives and emits light from the light irradiation means and the light irradiation means. An exposure head provided with a light modulation unit capable of controlling the drawing unit according to pattern information, wherein the column direction of the drawing unit is relative to the scanning direction of the exposure head. An exposure head arranged so as to form a predetermined set inclination angle θ is used, and the exposure head is subjected to N double exposure (where N is 2) among the usable pixel parts by the use pixel part specifying means. The natural number above) Designate the element part, and control the element part for the exposure head so that only the element part specified by the element part for specifying the used element part is involved in the exposure by the element part controlling unit. A method is preferred in which the exposure head is moved relative to the photosensitive layer in the scanning direction.

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

  There is no restriction | limiting in particular as a wavelength of the laser in this invention, According to the objective, it can select suitably, For the objective of aiming at shortening of the exposure time of a photosensitive composition, 330-650 nm is preferable, and 365-445 nm is more. It is preferably 395 to 415 nm.

The beam diameter of the laser is not particularly limited, but among them, from the viewpoint of the resolution of the dark color separation barrier, the 1 / e ² value of the Gaussian beam is preferably 5 to 30 μm, and more preferably 7 to 20 μm.
Although it does not specifically limit as energy amount of a laser beam, From a viewpoint of exposure time and resolution, 1-100 mJ / cm < ² > is preferable especially and 5-50 mJ / cm < ² > is more preferable.

  In the present invention, it is necessary to spatially modulate laser light according to image data. For this purpose, it is preferable to use a digital micro device which is a spatial light modulation element described in Japanese Patent Application Laid-Open No. 2005-311305 [0173] to [0174].

  As the exposure apparatus, for example, a laser direct imaging apparatus “INPREX IP-3000 (manufactured by FUJIFILM Corporation)” can be used, but the exposure apparatus in the present invention is not limited to this.

[Other processes]
There is no restriction | limiting in particular as said other process, It can select suitably from the processes in well-known pattern formation, For example, a image development process, a hardening process process, etc. are mentioned.

[Development process]
The developing step is a step of forming a permanent pattern by exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region.

  There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  The developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkali metal or alkaline earth metal hydroxide or carbonate, hydrogen carbonate, aqueous ammonia, quaternary ammonium salt An aqueous solution of Among these, an aqueous sodium carbonate solution is particularly preferable.

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

[Curing process]
The method for forming a permanent pattern according to the present invention preferably further includes a curing treatment step.
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed permanent pattern after the development step is performed.

  There is no restriction | limiting in particular as said hardening process, According to the objective, it can select suitably, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

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

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

When the substrate is a printed wiring board such as a multilayer wiring board, a permanent pattern can be formed on the printed wiring board, and soldering can be performed as follows.
That is, the hardened layer which is the permanent pattern is formed by the developing process, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.

  In the method for forming a permanent pattern according to the present invention, it is preferable to form at least one of a protective film and an interlayer insulating film. When the permanent pattern formed by the method for forming a permanent pattern is the protective film or the interlayer insulating film, the wiring can be protected from external impact and bending, and in particular, the interlayer insulating film. For example, it is useful for high-density mounting of semiconductors and components on multilayer wiring boards, build-up wiring boards, and the like.

The method for forming a permanent pattern according to the present invention enables pattern formation at a high speed, and therefore can be widely used for forming various patterns, and can be particularly suitably used for forming a wiring pattern.
Further, the permanent pattern formed by the method for forming a permanent pattern according to the present invention has excellent surface hardness, insulation, heat resistance, moisture resistance, etc., and is suitable as a protective film, an interlayer insulating film, a solder resist pattern, etc. Can be used for

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Synthesis Example 1)
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was placed and heated to 85 ° C. under a nitrogen stream. To this, a solution of 159 g of 1-methoxy-2-propanol containing 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 2 hours. After completion of the dropwise addition, the reaction was continued by heating for 5 hours. Subsequently, the heating was stopped to obtain a copolymer of benzyl methacrylate / methacrylic acid (ratio of 30/70 mol%).
Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and stirred to dissolve. After dissolution, 2.4 g of tetraethylammonium chloride was added and heated to 100 ° C. to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 1-Methoxy-2-propanol was added to prepare a solution of polymer compound 1 shown in Table 1 below having a solid content of 50% by mass.
It was 15,000 as a result of measuring the mass mean molecular weight (Mw) of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used the polystyrene as a reference material.
From the titration with sodium hydroxide, the acid value (carboxyl group content) per solid content was 2.2 meq / g.
Furthermore, the content of ethylenically unsaturated bonds per solid (C = C value) determined by iodine value titration was 2.1 meq / g.

(Synthesis Example 2)
In a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution, and a stirrer, 70 parts by mass of Bremer GS (manufactured by NOF Corporation, chlorine-reduced glycidyl methacrylate, halogen content is 1 ppm or less), 30 parts by weight of methyl methacrylate, 100 parts by weight of carbitol acetate, and 3 parts by weight of azobisisobutyronitrile were added, and the mixture was polymerized by heating at 80 ° C. for 5 hours under a nitrogen stream with stirring. A coalesced solution was obtained.
Hydroquinone 0.05 parts by weight, acrylic acid 37 parts by weight and dimethylbenzylamine 0.2 parts by weight were added to the obtained 50% by weight copolymer solution, and an addition reaction was performed at 100 ° C. for 24 hours.
Subsequently, 45 parts by mass of tetrahydrophthalic anhydride and 79 parts by mass of carbitol acetate were added and reacted at 100 ° C. for 3 hours to obtain a 50% by mass solution (A2) of an ultraviolet curable resin.

(Dispersion example 1)
As shown in Table 1, the following pigment dispersion composition and 30 parts of glass beads having a diameter of 2 mm are placed in a 200 ml polyethylene container and dispersed for 1 hour with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). A pigment dispersion 1 was obtained. When the particles of the obtained dispersion 1 were measured using a laser scattering type particle size distribution analyzer, the average particle size was 340 nm. The results are shown in Table 1.

(Pigment dispersion composition)
-High molecular compound 1 ... 9.1 parts by mass-Sandrin Yellow 6GL (Ciba Specialty Chemicals, CI Pigment Yellow 173), the following structural formula (1)) ... 10 parts by mass, Solsperse S-20000 (manufactured by ICI) ...・ ・ ・ ・ ・ ・ 0.28 parts by mass
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

(Distribution example 2)
Dispersion 2 was prepared in the same manner as Dispersion Example 1, except that the dispersion time was 2 hours. The results are shown in Table 1. The average particle size was 160 nm.

(Distribution example 3)
Dispersion 3 was prepared in the same manner as Dispersion Example 1, except that the dispersion time was 0.5 hour. The results are shown in Table 1. The average particle size was 1,250 nm.

(Dispersion example 4)
As shown in Table 1, after a dispersion having the same composition as dispersion example 1 was mixed in advance, a motor mill M-200 (manufactured by Eiger Co., Ltd.) was used, and zirconia beads having a diameter of 1.0 mm were used. The mixture was dispersed for 24 hours at s to prepare a dispersion 4 of yellow pigment. The results are shown in Table 1. From the transmission electron microscope (TEM) observation and the photograph, the size of 20 particles was arbitrarily measured, and it was found that the average particle size was 60 nm.

(Dispersion example 5)
As shown in Table 1, the following pigment dispersion composition and 30 parts of glass beads having a diameter of 2 mm were placed in a 200 ml polyethylene container and dispersed for 1 hour with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). A pigment dispersion 5 was obtained. When the particles of the obtained dispersion liquid 5 were measured using a laser scattering type particle size distribution analyzer, the average particle diameter was 260 nm. The results are shown in Table 1.

(Pigment dispersion composition)
・ Polymer compound 1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9.1 parts by mass ・ Seika First Yellow 2770 (Daiichi Seika Kogyo Co., Ltd.) CI Pigment Yellow 83), the following structural formula (2)): 10 parts by mass, Solsperse S-20000 (ICI Co., Ltd.) Product) 0.28 parts by mass
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

(Dispersion example 6)
As shown in Table 1, the following pigment dispersion composition and 30 parts of glass beads having a diameter of 2 mm were placed in a 200 ml polyethylene container and dispersed for 2 hours with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). A pigment dispersion 6 was obtained. When the particles of the obtained dispersion 6 were measured using a laser scattering particle size distribution analyzer, the average particle size was 520 nm. The results are shown in Table 1.

(Pigment dispersion composition)
-High molecular compound 1 ... 9.1 parts by mass-Yellow 2 RLT (Ciba Specialty Chemicals, C.I.) I. Pigment Yellow 109), the following structural formula (3)) ··················· 10 parts by mass · Solsperse S-20000 (manufactured by ICI Corporation) ··· ... 0.28 parts by mass
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

(Dispersion example 7)
As shown in Table 1, the following pigment dispersion composition and 30 parts of glass beads having a diameter of 2 mm were placed in a 200 ml polyethylene container and dispersed for 2 hours with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). A pigment dispersion 7 was obtained. When the particles of the obtained dispersion liquid 7 were measured using a particle size distribution analyzer of a laser scattering system, the average particle diameter was 350 nm. The results are shown in Table 1.

(Pigment dispersion composition)
-Polymer compound 1 ... 9.1 parts by mass-Chromophthal Yellow 3RT (Ciba Specialty Chemicals, C.I.) I. Pigment Yellow 110), the following structural formula (4)) ····· 10 parts by mass · Solsperse S-20000 (manufactured by ICI Corporation) ··· 0.28 mass Part
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

(Dispersion example 8)
As shown in Table 1, the following pigment dispersion composition and 30 parts of glass beads having a diameter of 2 mm were placed in a 200 ml polyethylene container and dispersed for 2 hours with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). A pigment dispersion 8 was obtained. When the particles of the obtained dispersion 8 were measured using a laser scattering type particle size distribution analyzer, the average particle size was 400 nm. The results are shown in Table 1.

(Pigment dispersion composition)
・ Polymer Compound 1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9.1 parts by mass ・ Pariotol Yellow D0960 (manufactured by BASF, CI Pigment) Yellow 138), the following structural formula (5)) ... 10 parts by mass, Solsperse S-20000 (manufactured by ICI) ... .... 0.28 parts by mass
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

(Distribution example 9)
As shown in Table 2, the following pigment dispersion composition and 30 parts of glass beads having a diameter of 2 mm were placed in a 200 ml polyethylene container and dispersed with a paint shaker (manufactured by Toyo Seiki Co., Ltd.) for 2 hours. A pigment dispersion 9 was obtained. When the particles of the obtained dispersion liquid 9 were measured using a laser scattering type particle size distribution analyzer, the average particle diameter was 420 nm. The results are shown in Table 2.

(Pigment dispersion composition)
・ Polymer Compound 1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9.1 parts by mass ・ First Yellow FGL (manufactured by Dainichi Seika Kogyo Co., Ltd., CI Pigment Yellow 97), the following structural formula (6)) ... 10 parts by mass, Solsperse S-20000 (ICI) Made by Co., Ltd.) 0.28 parts by mass
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

(Dispersion Example 10)
As shown in Table 2, the following pigment dispersion composition and 30 parts of glass beads having a diameter of 2 mm were placed in a 200 ml polyethylene container and dispersed for 2 hours with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). A pigment dispersion 10 was obtained. When the particles of the obtained dispersion 10 were measured using a laser scattering type particle size distribution analyzer, the average particle size was 380 nm. The results are shown in Table 2.

(Pigment dispersion composition)
・ Polymer compound 1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9.1 parts by mass ・ Disazo Yellow AAPT (manufactured by Dainichi Seika Kogyo Co., Ltd.) CI Pigment Yellow 55), the following structural formula (7)) ... 10 parts by mass, Solsperse S-20000 (ICI) Made by Co., Ltd.) 0.28 parts by mass
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

(Dispersion Example 11)
As shown in Table 2, the following pigment dispersion composition and 30 parts of glass beads having a diameter of 2 mm were placed in a 200 ml polyethylene container and dispersed for 2 hours with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). A pigment dispersion 11 was obtained. When the particles of the obtained dispersion liquid 11 were measured using a laser scattering particle size distribution analyzer, the average particle diameter was 230 nm. The results are shown in Table 2.

(Pigment dispersion composition)
・ Polymer Compound 1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9.1 parts by mass ・ PALIOTOL YELLOW D1155 (manufactured by CLARIANT, CI Pigment) Yellow 185), following structural formula (8)) ········· 10 parts by mass · Solsperse S-20000 (manufactured by ICI Corporation) ··· 0.28 parts by mass
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

(Dispersion Example 12)
As shown in Table 2, the following pigment dispersion composition and 30 parts of glass beads having a diameter of 2 mm were placed in a 200 ml polyethylene container and dispersed for 2 hours with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). A pigment dispersion 12 was obtained. When the particles of the obtained dispersion liquid 12 were measured using a laser scattering type particle size distribution analyzer, the average particle diameter was 430 nm. The results are shown in Table 2.

(Pigment dispersion composition)
・ Polymer compound 1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9.1 parts by mass ・ Chromophthal yellow 2RF (Ciba Specialty Chemicals, CI Pigment Yellow 139), the following structural formula (9)) ·········· 10 parts by mass · Solsperse S-20000 (manufactured by ICI Corporation) ··· ... 0.28 parts by mass
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

(Dispersion Example 13)
As shown in Table 2, the following pigment dispersion composition and 30 parts of glass beads having a diameter of 2 mm were placed in a 200 ml polyethylene container and dispersed for 2 hours with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). A pigment dispersion 13 was obtained. When the particles of the obtained dispersion 13 were measured using a laser scattering type particle size distribution analyzer, the average particle size was 280 nm. The results are shown in Table 2.

(Pigment dispersion composition)
・ High molecular compound 1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9.1 parts by mass ・ HELIOGEN BLUE D707PB (manufactured by BASF, CI Pigment) Blue 15: 3), the following structural formula (10)) ... 10 parts by mass, Solsperse S-20000 (manufactured by ICI) ...・ ・ ・ ・ ・ ・ 0.28 parts by mass
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

(Dispersion Example 14)
As shown in Table 2, the following pigment dispersion composition and 30 parts of glass beads having a diameter of 2 mm were placed in a 200 ml polyethylene container and dispersed for 1 hour with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). A pigment dispersion 14 was obtained. When the particles of the resulting dispersion 13 were measured using a laser scattering type particle size distribution analyzer, the average particle size was 330 nm. The results are shown in Table 2.

(Pigment dispersion composition)
・ Polymer compound 1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9.1 parts by mass ・ Cyanine blue 5025 (manufactured by Dainichi Seika Kogyo Co., Ltd.) CI Pigment Blue 15: 1), the following structural formula (11)) ... 10 parts by mass, Solsperse S-20000 ( ICI Co., Ltd.) 0.28 parts by mass
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

(Dispersion Example 15)
As shown in Table 2, the following pigment dispersion composition and 30 parts of glass beads having a diameter of 2 mm were placed in a 200 ml polyethylene container and dispersed for 2 hours with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). A pigment dispersion 15 was obtained. When the particles of the obtained dispersion liquid 15 were measured using a laser scattering type particle size distribution analyzer, the average particle diameter was 380 nm. The results are shown in Table 2.

(Pigment dispersion composition)
・ Polymer compound 1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9.1 parts by mass ・ Cyanine Green 2G-550-D CI Pigment Green 7), following structural formula (12)) ············ 10 parts by mass · Solsperse S-20000 (ICI) Made by Co., Ltd.) 0.28 parts by mass
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

(Solution C1 without pigment)
As shown in Table 2, a solution C1 containing no pigment was obtained by dissolving the following pigment dispersion composition.

[Solution composition]
・ Polymer compound 1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9.1 parts by mass ・ Solsperse S-20000 (manufactured by ICI) ・ ・... 0.28 parts by mass
・ Propylene glycol monomethyl ether acetate: 50.4 parts by mass

Example 1
A photosensitive composition comprising the following composition comprising Dispersion 1 (Yellow Pigment Dispersion) of Dispersion Example 1 and Dispersion 13 (Blue Pigment Dispersion) of Dispersion Example 13 in a mixing ratio (mass ratio) of 1: 2. A solution was prepared, applied to a 16 μm thick polyethylene terephthalate support (16FB50 manufactured by Toray Industries, Inc.), dried to form a 35 μm thick photosensitive layer, and then a polypropylene film as a protective film on the photosensitive layer (Oji Paper Co., Ltd. product: Alphan E200, film thickness 20 micrometers) was laminated | stacked by lamination, and it wound up with the winder, and produced the photosensitive film.

[Composition of photosensitive composition solution]
・ Polymer compound 1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 63.3 parts by mass ・ DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexa) Acrylic 76% by weight diluted product) ... 22.2 parts by mass, represented by general formula (VI) Bisphenol A β-methyl epoxy resin (epoxy equivalent: 214 g / eq, viscosity: 62 Pa · s) ···················· 18.8 parts by mass · N-phenylglycine ···・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.2 parts by mass ・ Sensitizer represented by the following general formula (VII) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・・ ・ 0.20 mass part ・ CGI325 (photopolymerization initiator)
(Oxime derivative represented by the following general formula (VIII), manufactured by Ciba Specialty Chemicals Co., Ltd.) ...・ ・ 2.3 parts by mass ・ Dicyandiamide (thermal curing accelerator) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.93 parts by mass ・ Triazine and isocyanuric acid adduct (thermosetting accelerator)
(2MAOK, manufactured by Shikoku Kasei Co., Ltd.) ··········· 0.53 parts by mass · Dispersion 1 (yellow pigment) ···・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.37 parts by mass ・ Dispersion 13 (blue pigment) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.75 Parts / barium sulfate dispersion ^{* 2)} (49.4% by mass) ... 81.4 parts by mass-hydroquinone monomethyl ether ...・ ・ 0.06 parts by mass ・ Coating aid (Fluorine-based surfactant F780F, 30 mass% methyl ethyl ketone solution) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・... 0.24 parts by mass
・ Methyl ethyl ketone ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 45.4 parts by mass
^{* 2) The} barium sulfate dispersion was composed of 29.2 parts by mass of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30), 20.9 parts by mass of the polymer compound 1 (50% by mass) solution, 1-methoxy After mixing with 36 parts by mass of 2-propyl acetate in advance, the motor mill M-200 (manufactured by Eiger) was used to disperse for 3.5 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 1.0 mm. Prepared.

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

--Exposure process--
Using a laser direct imaging apparatus “INPREX IP-3000 (manufactured by FUJIFILM Corporation)” from the support side to the photosensitive layer in the prepared laminate, a 405 nm laser beam is emitted in steps of 10 μm from 20 μm to 100 μm. Then, an exposure pattern was irradiated and exposed so as to obtain a pattern in which holes having different diameters were formed, and a partial region of the photosensitive layer was cured.

<Pattern forming device>
A combined laser light source described in JP-A-2005-311305 as the light irradiating means, and a micromirror array in which 1024 micromirrors 58 are arranged in the main scanning direction schematically shown in FIG. 2 as the light modulating means. However, among the 768 sets arranged in the sub-scanning direction, DMD 36 controlled to drive only 1,024 × 256 rows, and an optical system for imaging the light shown in FIG. 1 on the photosensitive transfer material, The pattern forming apparatus 10 including the exposure head 30 having the above is used.

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

First, the state of the exposure pattern on the exposed surface was examined in order to correct the variation in resolution and uneven exposure in double exposure. The results are shown in FIG. In FIG. 3, a light spot group from a micromirror 58 that can be used for the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the photosensitive transfer material 12 with the stage 14 being stationary. Showed the pattern. The state of the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part. Are shown for exposure areas 32 ₁₂ and 32 ₂₁ . In FIG. 3, for convenience of explanation, every other column exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

As shown in FIG. 3, as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ from the ideal state, both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B are both. Thus, it can be seen that, in the exposure areas overlapping on the coordinate axes orthogonal to the scanning direction of the exposure head in the exposure areas 32 ₁₂ and 32 ₂₁ , an overexposed area is generated as compared with the ideal double exposure state.

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

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

Thereafter, the micromirrors corresponding to the light spots other than the light spots constituting the areas 78 and 80 covered by the oblique lines in FIG. 4 were similarly covered by the area 82 and the shaded areas in FIG. Micromirrors corresponding to the light spots constituting the region 84 were identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. It was controlled not to be involved.
As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ , an ideal double exposure is performed in each area other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. Thus, the total area of the overexposed region and the underexposed region can be minimized.

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

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

<Evaluation>
Next, each of the obtained photosensitive films and each permanent pattern was evaluated for coloring degree, hue, photosensitive region absorbance, halogen content, exposure sensitivity, resolution, storage stability, and cured resist performance.

<< Evaluation of coloring and hue >>
The degree of coloring of the produced photosensitive film was expressed as Macbeth optical density obtained by measuring a Macbeth photometer with a red filter. As an evaluation standard, 0.5 or more is preferable. The hue was determined visually. The results are shown in Table 6.

<< Evaluation of absorbance in photosensitive region >>
Moreover, the absorption spectrum of the photosensitive film produced using the spectrophotometer was measured, and the light absorbency of the photosensitive area | region in 405 nm was measured. As an evaluation standard, 1.0 or less is preferable. The results are shown in Table 6.

<< Evaluation of dispersion stability >>
The photosensitive layer coating solution was stored at 40 ° C. for 7 days, and the presence or absence of pigment aggregation was observed. When there is pigment aggregation, “X” is displayed, and when there is no pigment aggregation, “◯” is displayed. The results are shown in Table 6.

<< Measurement and evaluation of halogen content >>
The photosensitive layer (10 g) of the produced photosensitive film is combusted in a combustion flask, the generated gas is absorbed in pure water, and the halogen content in the obtained absorbing solution is detected by ion chromatography. And quantified. The results are shown in Table 6.

<< Evaluation of exposure sensitivity >>
In the permanent pattern obtained by pattern exposure / development / washing as described above, the thickness of the cured region of the remaining photosensitive layer was measured. Next, a sensitivity curve is obtained by plotting the relationship between the laser light irradiation amount and the thickness of the cured layer. From the sensitivity curve thus obtained, the thickness of the cured region on the wiring was 30 μm, and the amount of light energy when the surface of the cured region was a glossy surface was determined as the amount of light energy necessary for curing the photosensitive layer. The results are shown in Table 6.

<< Resolution >>
The surface of the obtained printed circuit board on which the permanent pattern had been formed was observed with an optical microscope, and the minimum hole diameter with no residual film in the hole portion of the cured layer pattern was measured. The smaller the numerical value, the better the resolution. The results are shown in Table 6.

<< edge roughness >>
Double exposure is performed by irradiating the obtained polyethylene terephthalate film (support) of the laminate to form a horizontal line pattern perpendicular to the scanning direction of the exposure head using the pattern forming apparatus. Then, exposure of the line width is performed with the line / space = 1/1 and the line width of 30 μm.
The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer measured by the evaluation of the exposure sensitivity. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate.
The entire surface of the photosensitive layer on the copper-clad laminate is sprayed with a 1% by weight aqueous sodium carbonate solution at 30 ° C. at a spray pressure of 0.15 MPa for twice the shortest development time determined in the evaluation of the development time, and the uncured area Is dissolved and removed.
Among the permanent patterns obtained in this manner, any five points on a line having a line width of 30 μm were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×), and within the field of view. Of the edge position of the swelled, the difference between the most swollen part (mountain peak) and the most constricted part (valley bottom) was obtained as an absolute value, and the average value of the five observed points was calculated, and this was used as edge roughness . The edge roughness is preferably as the value is small because it exhibits good performance. The results are shown in Table 6.

<< Storage stability >>
Next, in order to evaluate changes in developability over time, a roll-shaped sample sandwiched between the above various protective sheets, wrapped in a light-proof moisture-proof bag (BF3X manufactured by Tokai Aluminum Foil Co., Ltd.), and closed at both ends with a bush. It was stored for 3 days in a constant temperature and humidity chamber under accelerated conditions (30 ° C., 90% RH), and changes in developability were measured.
The storage stability was evaluated according to the following criteria from the value of the ratio (t ₀ / t _3d ) by comparing the initial shortest development time t ₀ and the shortest development time t _3d after the acceleration condition.
○: 1 times or more and less than 2 times △: 2 times or more and less than 3 times (Available level)
X: The results are shown in Table 6 by 3 times or more.

-Resist performance after curing-
The above-mentioned photosensitive laminate was vacuum laminated on a copper-clad laminate without a circuit pattern after peeling off the protective film. After cooling this to room temperature, it is exposed under the conditions of an exposure amount of 23 mJ / cm ² , curing is performed at 150 ° C. for 60 minutes in a hot air circulating drying furnace, and then cooled to room temperature, and an evaluation sample for pencil hardness and adhesion test Got. Using this evaluation sample, the performance of the cured film was evaluated in the following items. The results are shown in Table 7.

<< Pencil hardness >>
Using a pencil hardness tester in accordance with the test method of JIS K-5400, the highest hardness at which the film was not damaged when a load of 1 kg was applied to the sample was determined. The results are shown in Table 7.

<< Adhesion >>
According to the test method of JIS D-0202, the evaluation sample was cross-cut, and then the state of peeling after the peeling test with a cellophane adhesive tape was visually determined. The judgment criteria are as follows. The results are shown in Table 7.
○: No peeling at all △: Only a slight peeling ×: Completely peeling

<< Electrical insulation >>
The protective film is peeled off from the photosensitive film on the IPC-B-25 comb electrode B coupon, laminated with a vacuum laminator, cooled to room temperature, exposed to light with an exposure amount of 23 mJ / cm ² , and hot air circulation. Curing was performed at 150 ° C. for 60 minutes in an oven to obtain an evaluation sample. A bias voltage of DC500V was applied to the comb electrode, and the insulation resistance value was measured. The results are shown in Table 7.

<< Acid resistance test >>
The same evaluation sample as used for << electrical insulation >> was taken out after being immersed in a 10% by volume sulfuric acid aqueous solution at 20 ° C. for 30 minutes, and the state and adhesion of the coating film were comprehensively evaluated. The results are shown in Table 7. The judgment criteria are as follows.
○: No change is observed Δ: Only a slight change ×: The coating has blisters or bloating

<< Alkali resistance test >>
Test evaluation was performed in the same manner as in the above << Oxidation resistance test >> except that the 10 vol% sulfuric acid aqueous solution was changed to a 10 vol% sodium hydroxide aqueous solution. The results are shown in Table 7.

<< Electroless gold plating resistance >>
The test substrate was subjected to electroless gold plating according to the steps described below, and the test substrate was subjected to a change in appearance and a peeling test using a cellophane adhesive tape, and the peeling state of the resist film was evaluated according to the following criteria. The results are shown in Table 7.
○: No change in appearance and no peeling of resist film.
Δ: Although there is no change in appearance, the resist film is slightly peeled off.
X: Lifting of the resist film is observed, plating dipping is observed, and peeling of the resist film is large in the peeling test.

-Electroless gold plating process-
-Degreasing-
The test substrate was immersed for 3 minutes in an acidic degreasing solution at 30 ° C. (20% by volume aqueous solution of Meltex L-5B, manufactured by Nippon MacDermid Co., Ltd.).
--- Washing--
The test substrate was immersed in running water for 3 minutes.
--Soft etch--
The test substrate was immersed in a 14.3% by mass ammonium persulfate aqueous solution at room temperature for 3 minutes.
--- Washing--
The test substrate was immersed in running water for 3 minutes.
--- Acid soaking--
The test substrate was immersed in a 10% by volume sulfuric acid aqueous solution at room temperature for 1 minute.
--- Washing--
The test substrate was immersed in running water for 30 seconds to 1 minute.
--Catalyst application--
The test substrate was immersed for 7 minutes in a 30 ° C. catalyst solution (manufactured by Meltex Co., Ltd., 10 volume% aqueous solution of 350 metal plate activator).
--- Washing--
The test substrate was immersed in running water for 3 minutes.
--- Electroless nickel plating--
The test substrate was immersed in a nickel plating solution (manufactured by Meltex, Melplate Ni-865M, 20 vol% aqueous solution) at 85 ° C. and pH = 4.6 for 20 minutes.
--- Acid soaking--
The test substrate was immersed in a 10% by volume sulfuric acid aqueous solution at room temperature for 1 minute.
--- Washing--
The test substrate was immersed in running water for 30 seconds to 1 minute.
--- Electroless gold plating--
The test substrate was immersed for 10 minutes in a gold plating solution of 95 ° C. and pH = 6 (manufactured by Meltex Co., Ltd., an aqueous solution of 15% by volume of Aurolectroles UP and 3% by volume of potassium cyanide cyanide).
--- Washing--
The test substrate was immersed in running water for 3 minutes.
--- Washing--
The test substrate was immersed in warm water at 60 ° C., thoroughly washed with water for 3 minutes, thoroughly drained and dried.
Through the above steps, an electroless gold-plated test substrate was obtained.

<< PCT resistance >>
The protective film is peeled off from each of the above laminates on the printed wiring board, laminated with a vacuum laminator, cooled to room temperature, exposed to light with an exposure amount of 90 mJ / cm ² , and cured in a hot air circulation drying oven at 150 ° C. For 60 minutes to obtain an evaluation sample.
After cooling this to room temperature, it processed for 168 hours on the conditions of 121 degreeC and 2 atmospheres using the PCT test apparatus (TABAI ESPEC HAST SYSTEM TPC-412MD), and the state of the cured film was evaluated. The results are shown in Table 7. The judgment criteria are as follows.
○: No peeling, discoloration or elution.
Δ: Any of peeling, discoloration and elution.
X: Many peeling, discoloration, and elution are seen.

(Example 2)
As shown in Table 3, the composition containing dispersion liquid 2 (yellow pigment dispersion liquid) of dispersion example 1 and dispersion liquid 13 (blue pigment dispersion liquid) of dispersion example 13 at a mixing ratio (mass ratio) of 1: 2. A photosensitive composition (photosensitive layer coating solution) was prepared as Example 2 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, the photosensitive layer coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, And the change with time of development time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Example 3)
As shown in Table 3, the composition containing dispersion 3 (yellow pigment dispersion) of dispersion example 3 and dispersion 13 (yellow pigment dispersion) of dispersion example 13 at a mixing ratio (mass ratio) of 1: 2. A photosensitive composition (photosensitive layer coating solution) was prepared as Example 3 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

Example 4
As shown in Table 3, the composition containing dispersion 4 (yellow pigment dispersion) of dispersion example 4 and dispersion 13 (blue pigment dispersion) of dispersion example 13 in a mixing ratio (mass ratio) of 1: 2. A photosensitive composition (photosensitive layer coating solution) was prepared as Example 4 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Example 5)
As shown in Table 3, the composition containing dispersion 1 (yellow pigment dispersion) of dispersion example 1 and dispersion 13 (blue pigment dispersion) of dispersion example 13 at a mixing ratio (mass ratio) of 1: 1. A photosensitive composition (photosensitive layer coating solution) was prepared as Example 5 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Example 6)
As shown in Table 3, the composition containing dispersion 1 (yellow pigment dispersion) of dispersion example 1 and dispersion 13 (blue pigment dispersion) of dispersion example 13 at a mixing ratio (mass ratio) of 1: 3. A photosensitive composition (photosensitive layer coating solution) was prepared as Example 6 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Example 7)
As shown in Table 3, the composition containing dispersion 1 (yellow pigment dispersion) of dispersion example 1 and dispersion 13 (blue pigment dispersion) of dispersion example 13 at a mixing ratio (mass ratio) of 1: 4. A photosensitive composition (photosensitive layer coating solution) was prepared as Example 7 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Example 8)
As shown in Table 4, the composition containing dispersion 5 (yellow pigment dispersion) of dispersion example 1 and dispersion 13 (blue pigment dispersion) of dispersion example 13 at a mixing ratio (mass ratio) of 1: 2. A photosensitive composition (photosensitive layer coating solution) was prepared as Example 8 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

Example 9
As shown in Table 4, the composition containing the dispersion 6 (yellow pigment dispersion) of Dispersion Example 1 and the dispersion 13 (blue pigment dispersion) of Dispersion Example 13 in a mixing ratio (mass ratio) of 1: 2. A photosensitive composition (photosensitive layer coating solution) was prepared as Example 7 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Example 10)
As shown in Table 4, the composition containing Dispersion 1 (Yellow Pigment Dispersion) of Dispersion Example 7 and Dispersion 13 (Blue Pigment Dispersion) of Dispersion Example 13 in a mixing ratio (mass ratio) of 1: 2. A photosensitive composition (photosensitive layer coating solution) was prepared as Example 10 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Example 11)
As shown in Table 4, the composition containing the dispersion 8 (yellow pigment dispersion) of dispersion example 8 and the dispersion 13 (blue pigment dispersion) of dispersion example 13 in a mixing ratio (mass ratio) of 1: 2. A photosensitive composition (photosensitive layer coating solution) was prepared as Example 11 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Example 12)
As shown in Table 4, the composition containing Dispersion 9 (Yellow Pigment Dispersion) in Dispersion Example 9 and Dispersion 13 (Blue Pigment Dispersion) in Dispersion Example 13 at a mixing ratio (mass ratio) of 1: 2. A photosensitive composition (photosensitive layer coating solution) was prepared as Example 12 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Example 13)
As shown in Table 4, the composition containing dispersion 10 (yellow pigment dispersion) of dispersion example 10 and dispersion 13 (blue pigment dispersion) of dispersion example 13 at a mixing ratio (mass ratio) of 1: 2. A photosensitive composition (photosensitive layer coating solution) was prepared as Example 13 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Example 14)
As shown in Table 4, the dispersion 1 of dispersion example 1 (yellow pigment dispersion) and the dispersion 13 of dispersion example 13 (blue pigment dispersion) have a mixing ratio (mass ratio) of 1: 2. A photosensitive composition (photosensitive layer coating solution) having an addition amount half of that of Example 1 and containing a solution C1 containing no pigment instead was prepared as Example 14 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Example 15)
As shown in Table 4, 63.3 parts by mass of the polymer compound 1 solution in the photosensitive composition (photosensitive layer coating solution) of Example 1 was mixed with 50.6 parts by mass of the polymer compound 1 solution and lipoxy PR-300 ( Showa Polymer Co., Ltd .: Resin obtained by ring-opening addition of cresol novolac epoxy resin with acrylic acid and then addition reaction of tetrahydrophthalic anhydride, acid value = 81, solid content concentration 68% propylene glycol monomethyl An ether acetate solution was prepared as Example 15 except that the solution was changed to 9.3 parts by mass, and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Example 16)
In the pattern forming apparatus of the first embodiment, the set inclination angle θ is calculated with N = 1 based on the equation 3, and the natural number T closest to the value t satisfying the relationship of t tan θ ′ = 1 is derived based on the equation 4. Except having performed N double exposure (N = 1), it was carried out similarly to Example 1, and about the obtained photosensitive film roll, a laminated body, and a permanent pattern, coloring degree, hue, the light absorbency in 405 nm, halogen, Content, shortest development time, sensitivity, and resolution, edge roughness, and development time change over time were evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Comparative Example 1)
As shown in Table 5, a photosensitive composition (photosensitive layer coating solution) having a composition containing the dispersion 15 (green pigment dispersion) of Dispersion Example 15 was prepared as Comparative Example 1 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Comparative Example 2)
As shown in Table 5, the composition containing Dispersion 12 (Yellow Pigment Dispersion) of Dispersion Example 12 and Dispersion 14 (Blue Pigment Dispersion) of Dispersion Example 14 at a mixing ratio (mass ratio) of 1: 1. A photosensitive composition (photosensitive layer coating solution) was prepared as Comparative Example 2 and applied to a support.
In addition, EHPE3150 described in Table 5 is an epoxy resin manufactured by Daicel Chemical Industries, Ltd., Irgacure 907 is a photopolymerization initiator manufactured by Ciba Specialty Chemicals, and Kayacure DETX-S is manufactured in Japan. It is a photopolymerization initiator manufactured by Kayaku Co., Ltd. Silica having an average particle diameter of 1 μm was used.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Comparative Example 3)
As shown in Table 5, the composition containing Dispersion 11 (Yellow Pigment Dispersion) of Dispersion Example 11 and Dispersion 13 (Blue Pigment Dispersion) of Dispersion Example 13 at a mixing ratio (mass ratio) of 1: 2. A photosensitive composition (photosensitive layer coating solution) was prepared as Comparative Example 3 and applied to a support. The coating solution showed aggregates after 7 days at 40 ° C., but it was used for coating without any problem immediately after preparation.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Comparative Example 4)
As shown in Table 5, the composition containing dispersion 12 (yellow pigment dispersion) of dispersion example 12 and dispersion 13 (blue pigment dispersion) of dispersion example 13 at a mixing ratio (mass ratio) of 1: 2. A photosensitive composition (photosensitive layer coating solution) was prepared as Comparative Example 4 and applied to a support. The coating solution showed aggregates after 7 days at 40 ° C., but it was used for coating without any problem immediately after preparation.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Comparative Example 5)
As shown in Table 5, the composition containing Dispersion 1 (Yellow Pigment Dispersion) in Dispersion Example 1 and Dispersion 13 (Blue Pigment Dispersion) in Dispersion Example 13 at a mixing ratio (mass ratio) of 2: 1. A photosensitive composition (photosensitive layer coating solution) was prepared as Comparative Example 5 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Comparative Example 6)
As shown in Table 5, the composition containing dispersion 1 (yellow pigment dispersion) of dispersion example 1 and dispersion 13 (blue pigment dispersion) of dispersion example 13 in a mixing ratio (mass ratio) of 1: 5. A photosensitive composition (photosensitive layer coating solution) was prepared as Comparative Example 6 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Comparative Example 7)
As shown in Table 5, a photosensitive composition (photosensitive layer coating solution) having a composition containing only the dispersion 13 (blue pigment dispersion) of Dispersion Example 13 was prepared as Comparative Example 7 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen content, shortest development time, sensitivity, resolution, edge roughness, and development The change with time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

(Comparative Example 8)
As shown in Table 5, a photosensitive composition (photosensitive layer coating solution) having a composition not containing a color pigment was prepared as Comparative Example 8 and applied to a support.
The stability of the photosensitive layer coating solution was evaluated in the same manner as in Example 1. Further, using the photosensitive film and the photosensitive laminate, in the same manner as in Example 1, coloring degree, hue, absorbance at 405 nm, halogen atom content, shortest development time, sensitivity and resolution, edge roughness, And the change with time of development time was evaluated. The results are shown in Table 6. The performance of the cured film was similarly evaluated. The results are shown in Table 7.

From the results of Tables 6 to 7, a pigment containing one halogen atom in one molecule and a blue color, and a halogen atom in the range of 5 to 40% by mass with an average particle diameter of 100 to 1,000 nm The photosensitive composition and photosensitive film of Examples 1 to 14 containing a pigment exhibiting a yellow color and containing a colorant exhibiting a green color can provide a smooth photosensitive layer, excellent storage stability, and blue It was confirmed that a high-definition permanent pattern can be obtained when a violet laser exposure system is used.
In addition, the photosensitive compositions and photosensitive films of Examples 1 to 16 in which the content of halogen atoms in the photosensitive composition is 250 to 800 ppm and the exposure sensitivity of the photosensitive layer is 20 to 35 mJ / cm ² are dispersed. It was confirmed that the stability was good and a high-definition permanent pattern was obtained when using a blue-violet laser exposure system.
From the results of Example 16, it was confirmed that Examples 1 to 15 employing multiple exposure were particularly excellent in terms of “sensitivity”, “resolution”, and “edge roughness”.

On the other hand, from the results shown in Tables 6 to 7, Comparative Example 1 is not preferable for safety because the halogen content in the photosensitive layer exceeds 900 ppm, and Comparative Example 2 has a small halogen content in the photosensitive composition. In spite of (90 ppm), the sensitivity was remarkably low, and the storage stability of the photosensitive layer was not preferable.
In addition, Comparative Examples 3 to 4 including a pigment that does not contain a halogen atom in one molecule and that exhibits a blue color and a pigment that exhibits a yellow color that does not contain a halogen atom have dispersion stability and storage stability of the photosensitive layer. Resulted in an undesirable result.
Further, in Comparative Examples 5 to 8, although the storage stability of the photosensitive layer was favorable, the mixing ratio of the blue pigment not containing halogen and the yellow pigment containing halogen was outside the range of 1: 1 to 4: 1. In Comparative Example 5 and Comparative Example 6, the absorbance and exposure sensitivity in the photosensitive region are unfavorable, and in Comparative Example 7 and Comparative Example 8, the hue is blue or colorless. The coating was difficult or impossible to identify, resulting in undesirable results.

  The photosensitive composition and photosensitive film of the present invention have good dispersion stability and storage stability, and a high-definition permanent pattern can be obtained when using a blue-violet laser exposure system. Can be suitably used as a printed wiring board (multi-layer wiring board, build-up wiring board, etc.), color filters, pillar materials, rib materials, spacers, display members such as partition walls, holograms, micromachines, proofs, etc. It can be widely used for pattern formation, and can be particularly suitably used for permanent pattern formation of printed circuit boards.

FIG. 1A is a top view showing an example of a detailed configuration of the exposure head. FIG. 1B is a side view showing an example of a detailed configuration of the exposure head. FIG. 2 is a partially enlarged view showing an example of the DMD of the pattern forming apparatus. FIG. 3 is an explanatory diagram showing an example of unevenness in the pattern on the exposed surface when there is a relative position shift and an attachment angle error between adjacent exposure heads. FIG. 4 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG.

Explanation of symbols

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

Claims (11)

Including an alkali-soluble photosensitive resin, a polymerizable compound, a photopolymerization initiator, and a photoinitiator compound, a thermally crosslinkable resin, and a colorant;
A pigment containing 5% by mass to 50% by mass of a halogen atom in one molecule and a yellow pigment, and a pigment that does not contain a halogen atom in one molecule and exhibits a blue color: A photosensitive composition, which is contained at a mixing ratio (mass ratio) of 1 to 1: 4, exhibits a green color by blending these pigments, and has a halogen content in the total solid content of 900 ppm or less. The blue pigment is a phthalocyanine pigment,
Yellow pigments include monoazo compounds, disazo compounds, diarylide non-rake compounds and lake compounds, bisacetoacetalide compounds, benzimidazolone compounds, metal complex compounds, A pigment containing a halogen atom selected from an aminoanthraquinone compound and a heterocyclic anthraquinone pigment among the quinophthalone compound, isoindoline compound, and condensed polycyclic compound in the molecule. The photosensitive composition according to claim 1.   Pigments exhibiting yellow color are C.I. I. Pigment yellow 2, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 6, C.I. I. Pigment yellow 49, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 75, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 10, C.I. I. Pigment yellow 60, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 63, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 87, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 121, C.I. I. Pigment yellow 124, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 136, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 170, C.I. I. Pigment yellow 171, C.I. I. Pigment yellow 172, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 188, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 173, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 166, and C.I. I. The photosensitive composition according to claim 2, which is selected from any one of CI Pigment Yellow 138.   The photosensitive composition according to any one of claims 1 to 3, wherein a halogen atom contained in the photosensitive composition is 500 ppm or less.   The photosensitive composition according to claim 1, wherein the yellow pigment has an average particle diameter of 100 nm to 500 nm.   The photosensitive film which has a photosensitive layer obtained by apply | coating the photosensitive composition in any one of Claim 1 to 5 on a support body, and drying after that.   A method for forming a permanent pattern, comprising exposing and developing a photosensitive layer formed of the photosensitive composition according to claim 1.   The permanent pattern forming method according to claim 7, wherein the substrate is a printed wiring board on which wiring is formed.   The permanent pattern formation method according to any one of claims 7 to 8, wherein the exposure is performed using a laser beam having a wavelength of 350 nm to 415 nm.   The permanent pattern forming method according to claim 7, wherein after the development, the photosensitive layer is cured.   A permanent pattern is formed by the permanent pattern formation method according to claim 7.