JP2007322755A - Photosensitive composition, method for preparing same, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition having a long pot life, excellent in tackiness, plane trouble, surface shape and edge roughness, having high sensitivity, high resolution, excellent resistance to electroless gold plating and excellent property of filling via and through holes, and capable of efficiently forming high-definition permanent patterns (such as a protective film, an interlayer insulation film and a solder resist pattern), by specifying a binder and a heat crosslinking agent used together with the binder, and to provide a method for preparing the photosensitive composition, a photosensitive film, a photosensitive laminate, a permanent pattern forming method using the photosensitive laminate, and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method. <P>SOLUTION: The photosensitive composition comprises a binder, a polymerizable compound, a photopolymerization initiator, a pigment and a heat crosslinking agent and has an average particle diameter of particles being ≤2 μm. There are also provided the method for preparing the photosensitive composition, the photosensitive film, the photosensitive laminate, the permanent pattern forming method using the photosensitive laminate, and the printed circuit board on which a permanent pattern is formed by the permanent pattern forming method. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention has a long pot life, excellent tackiness when formed into a film, surface failure, surface shape, edge roughness, high sensitivity and high resolution, electroless gold plating resistance, and via and through hole embedding. Photosensitive composition capable of efficiently forming excellent and high-definition permanent patterns (protective film, interlayer insulating film, solder resist pattern, etc.) and manufacturing method thereof, photosensitive film, photosensitive laminate, and photosensitive laminate The present invention relates to a method for forming a permanent pattern using, and a printed circuit board on which a permanent pattern is formed by the method for forming a permanent pattern.

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

As the photosensitive composition, for the purpose of improving stability and the like, a copolymer of a (meth) acrylic monomer having an aliphatic hydrocarbon group having 1 to 6 carbon atoms and (meth) acrylic acid is used. A photosensitive composition containing a polymer compound to which a (meth) acrylate compound having an epoxy group is added has been proposed (see Patent Document 1). In addition, a photosensitive composition comprising a polymer compound in which an unsaturated compound having an alicyclic epoxy group is added to a copolymer having a carboxyl group in a side chain has been proposed for the same purpose as the above proposal. (See Patent Document 2). Furthermore, for the purpose of improving performance such as heat resistance and chemical resistance, it has an unsaturated double bond, and has a binder polymer having an acid value and molecular weight within a specific range, and an unsaturated double bond, And the photosensitive composition which contains the epoxy compound of a specific acid value and an epoxy equivalent in a composition is proposed (refer patent document 3).
However, these photosensitive compositions also have insufficient sensitivity and storage stability. In particular, in the pattern latent image formation by laser scanning exposure, the exposed area is not sufficiently cured, and the image area is removed in the alkali development process. If the photosensitive composition is made into a long roll by forming the photosensitive composition into a long roll, the fusion of the end surface occurs over time, and the fused part falls to the exposed surface of the laminate during lamination, thereby exposing the film. There was a problem that failure such as disconnection of the exposure pattern sometimes occurred. In addition, when an alkali-soluble epoxy resin is used, there is a problem that adhesion to the substrate becomes poor in the gold plating process, the photosensitive composition is lifted, and a phenomenon in which plating submergence is observed occurs. It was.

In order to solve this problem, a photosensitive composition using a finely divided epoxy compound hardly soluble in an organic solvent has been disclosed (see Patent Documents 4 and 5). In the photosensitive composition using such a hardly soluble epoxy compound, when it develops with alkaline aqueous solution, an exposed part is not attacked by a developing solution, but developability and adhesiveness with a board | substrate can be improved.
However, in Patent Document 4, since the hardly soluble epoxy compound and other components are kneaded by three rolls, the particles of the hardly soluble epoxy compound are coarse, and the photosensitive composition solution is applied to a substrate for photosensitivity. When the layer is formed, there is a problem that the photosensitive layer is rough and inferior in smoothness, causes a surface fault, and the resolution of the formed permanent pattern is deteriorated. On the other hand, in Patent Document 5, a hardly soluble epoxy resin is finely divided into units of several microns with a sand mill and dispersed in a solvent. However, pigments such as talc and silica are kneaded without being finely divided. Also, the surface failure of the photosensitive layer and the deterioration of the surface shape of the permanent pattern could not be solved. Further, in the method for producing the photosensitive composition, when the hardly soluble epoxy resin is made into fine particles, it is heated and melted to a temperature equal to or higher than the melting point of the epoxy resin, cooled to a constant temperature, recrystallized, and then sand mill There is also a problem that it cannot be efficiently manufactured, including complicated and time-consuming processes such as making the particles finely dispersed.
In addition, as a photocurable composition (photosensitive composition) suitable for direct drawing with laser light, particles having a particle diameter of 5 μm or less account for 50% or more of all particles, an ethylenically unsaturated compound, photopolymerization Photocurable, characterized by being dispersed in an epoxy-containing composition containing an initiator, an unsaturated group, and an alkali-soluble resin containing a carboxyl group-containing epoxy resin and a crystalline epoxy compound having a melting point of 50 ° C. or higher. A composition has been proposed (see Patent Document 6).
In this case, however, the dispersion of the epoxy compound is only finely pulverized with a mill roll such as a three-roll, so that the average particle diameter is only in a fine particle state in which particles having a particle diameter of 3 μm or less occupy 80% or more of all particles. However, since the inorganic fine particles such as talc and barium sulfate are only added and stirred at room temperature, the surface failure of the photosensitive layer and the deterioration of the surface shape of the permanent pattern cannot be solved.

  Therefore, even if there are few coarse particles in the photosensitive composition and a complicated and laborious process is not required, the pot life is long, the tack property, the surface failure, the surface shape, the edge roughness are excellent, the high sensitivity and the high Photosensitive composition capable of efficiently forming high-definition permanent patterns (protective film, interlayer insulating film, solder resist pattern, etc.) with excellent resolution, electroless gold plating resistance, via and through-hole embedding characteristics, and the like A manufacturing method, a photosensitive film, a photosensitive laminate, a permanent pattern forming method using the photosensitive laminate, and a printed board on which a pattern is formed by the permanent pattern forming method have not yet been provided, and further improvements The current situation is that development is desired.

JP-A-3-172301 Japanese Patent Laid-Open No. 10-10726 JP 7-199457 A Japanese Patent Publication No. 7-17737 JP-A-6-95384 JP 2005-84114 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention specifies a binder and a thermal crosslinking agent to be used in combination, and has a long pot life, excellent tackiness, surface failure, surface shape, edge roughness, high sensitivity and high resolution, and resistance to electroless gold plating. , And a photosensitive composition excellent in embedding property of vias and through holes, and capable of efficiently forming a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern), a manufacturing method thereof, a photosensitive film, It is an object of the present invention to provide a photosensitive laminate, a permanent pattern forming method using the photosensitive laminate, and a printed board on which a pattern is formed by the permanent pattern forming method.

  As a result of intensive studies by the present inventors in order to solve the above problems, the photosensitive composition in the photosensitive composition contains a binder, a polymerizable compound, a photopolymerization initiator, a pigment, and a thermal crosslinking agent. When the average particle size of the particles is 2 μm or less and the average particle size of the pigment and the thermal crosslinking agent is 2 μm or less, pot life, tackiness, surface failure, surface shape, edge roughness, etc. It is possible to achieve both excellent characteristics as a photosensitive composition and excellent characteristics as a cured product such as electroless gold plating resistance, and high sensitivity and high resolution for via and through hole embedding. It was found that an excellent and high-definition permanent pattern can be formed efficiently.

The present invention is based on the above knowledge of the present inventor, and means for solving the above problems are as follows. That is,
<1> A photosensitive composition comprising a binder, a polymerizable compound, a photopolymerization initiator, a pigment, and a thermal crosslinking agent, and having an average particle size of 2 μm or less.
<2> The photosensitive composition according to <1>, wherein the pigment and the thermal crosslinking agent include a dispersion, and an average particle diameter thereof is 2 μm or less.
<3> The photosensitive composition according to <1>, wherein the content of coarse particles of 5 μm or more is 1% or less.
<4> From the above <1>, wherein the thermal crosslinking agent is at least two selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. 3>. The photosensitive composition according to any one of 3).
<5> The thermal crosslinking agent is an epoxy compound, and the epoxy compound is any two selected from a novolac type epoxy compound, a bisphenol type epoxy compound, a heterocyclic ring-containing epoxy compound, and an alicyclic epoxy compound. It is the photosensitive composition as described in said <4>.
<6> The photosensitive composition according to any one of <4> to <5>, which is a crystalline epoxy compound having a melting point of 60 ° C. or higher.
<7> The thermal crosslinking agent has an epoxy equivalent of 90 to 9,000 g / eq. <4> to the photosensitive composition in any one of <6> containing the epoxy compound of this.
<8> The photosensitive composition according to any one of <1> to <7>, wherein at least one of the thermal crosslinking agents is alkali-insoluble.
<9> The photosensitive composition according to any one of <1> to <8>, wherein the pigment contains at least one selected from organic pigments and inorganic pigments.
<10> The photosensitive composition according to any one of <1> to <9>, wherein the organic pigment contains at least one selected from a color pigment and organic crosslinkable fine particles.
<11> The above-mentioned <1 comprising at least a pigment and a thermal cross-linking agent, and a mixture of a finely dispersed dispersion having an average particle size of 2 μm or less, a binder, a polymerizable compound, and a photopolymerization initiator. > To <10>.
<12> The photosensitive composition according to <11>, wherein the dispersion further includes a binder.
<13> The photosensitive composition according to any one of <1> to <12>, including a thermosetting accelerator.

<14> At least one polymer compound wherein the binder is selected from at least one epoxy acrylate compound and at least one vinyl copolymer having a (meth) acryloyl group and an acid group in the side chain. The photosensitive composition according to any one of <1> to <13>.
<15> The photosensitive composition according to any one of <1> to <14>, wherein the binder includes a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain.
<16> The binder according to any one of <1> to <15>, wherein the binder includes a polymer compound having an acidic group, an aromatic group that may include a heterocyclic ring, and an ethylenically unsaturated bond in a side chain. Of the photosensitive composition.
<17> The photosensitive composition according to any one of <14> to <16>, wherein the polymer compound contains 0.5 to 3.0 meq / g of an ethylenically unsaturated bond.
<18> Any of <14> to <17>, wherein the acidic group of the polymer compound is a carboxyl group, and the content of the carboxyl group in the polymer compound is 1.0 to 4.0 meq / g. It is a photosensitive composition as described above.
<19> The photosensitive composition according to any one of <14> to <18>, wherein the polymer compound has a mass average molecular weight of 3,000 or more and less than 100,000.
<20> The photosensitive composition according to any one of <14> to <19>, wherein the polymer compound contains 20 mol% or more of a structural unit represented by the following structural formula (I).
However, in said structural formula (I), 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.

<21> The photosensitive composition according to any one of <1> to <20>, wherein the polymerizable compound includes a compound having one or more ethylenically unsaturated bonds.
<22> The photosensitive composition according to any one of <1> to <20>, wherein the polymerizable compound includes at least one selected from monomers having a (meth) acryl group.
<23> The photopolymerization initiator is selected from halogenated hydrocarbon derivatives, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, metallocenes, and acylphosphine oxide compounds. The photosensitive composition according to any one of <1> to <22>, including at least one of the above.
<24> The photosensitive composition according to any one of <1> to <23>, including a sensitizer.
<25> The photosensitive composition according to <24>, wherein the sensitizer is a hetero-fused ring compound.

<26> The method for producing a photosensitive composition according to any one of <1> to <25>,
A dispersion step in which at least a pigment and a thermal cross-linking agent are finely divided and dispersed to form a dispersion;
A mixing step of mixing the dispersion, a binder, a polymerizable compound, and a photopolymerization initiator;
Having at least
A method for producing a photosensitive composition, comprising obtaining a photosensitive composition having an average particle diameter of 2 μm or less.
<27> A method for producing a photosensitive composition in which a binder is further dispersed in a dispersion.

<28> A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive composition according to any one of <1> to <25> on the support.
<29> The photosensitive film according to <28>, wherein the support includes a synthetic resin and is transparent.
<30> The photosensitive film according to any one of <28> to <29>, wherein the support has a long shape.
<31> The photosensitive film according to any one of <28> to <30>, which is long and wound in a roll shape.
<32> The photosensitive film according to any one of <28> to <31>, having a protective film on the photosensitive layer in the photosensitive film.

<33> A photosensitive laminate comprising a photosensitive layer made of the photosensitive composition according to any one of <1> to <25> on a substrate.
<34> The photosensitive laminate according to <33>, wherein the photosensitive layer is formed of the photosensitive film according to any one of <28> to <32>.
<35> The photosensitive laminate according to any one of <33> to <34>, wherein the photosensitive layer has a thickness of 1 to 100 μm.

<36> A photosensitive layer in the photosensitive laminate according to any one of <33> to <35>,
A pattern forming apparatus comprising at least light irradiating means capable of irradiating light and light modulating means for modulating light from the light irradiating means and exposing the photosensitive layer of the photosensitive film. is there. In the pattern forming apparatus according to <36>, 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.
<37> The light modulation means further includes pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation means is emitted from the light irradiation means. It is a pattern formation apparatus as described in said <36> modulated according to this. In the pattern forming apparatus according to <37>, 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.
<38> The light modulation means includes n pixel parts, and forms any less than n pixel parts arranged continuously from the n pixel parts. The pattern forming apparatus according to any one of <36> to <37>, which can be controlled according to pattern information. In the pattern forming apparatus according to <38>, any less than n pixel parts arranged continuously from n pixel parts in the light modulation unit are controlled according to pattern information. Thereby, the light from the light irradiation means is modulated at high speed.
<39> The pattern forming apparatus according to any one of <36> to <38>, wherein the light modulation unit is a spatial light modulation element.
<40> The pattern forming apparatus according to <39>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<41> The pattern forming apparatus according to any one of <38> to <40>, wherein the picture element portion is a micromirror.
<42> The pattern forming apparatus according to any one of <36> to <41>, wherein the light irradiation unit is capable of combining and irradiating two or more lights. In the pattern forming apparatus according to <42>, 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.
<43> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser light irradiated from each of the plurality of lasers and couples the laser light to the multimode optical fiber. The pattern forming apparatus according to any one of <36> to <42>. In the pattern forming apparatus according to <43>, the light irradiation unit can condense the laser beams irradiated from the plurality of lasers by the collective optical system and couple the laser beams to the multimode optical fiber. Thus, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<44> A method for forming a permanent pattern, comprising exposing the photosensitive layer in the photosensitive laminate according to any one of <33> to <35>.
<45> The method for forming a permanent pattern according to <44>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
<46> The permanent pattern formation method according to any one of <44> to <45>, wherein the exposure is performed imagewise based on pattern information to be formed.

<47> Exposure has light irradiation means, and n (where n is a natural number of 2 or more) two-dimensionally arranged pixel parts that receive and emit light from the light irradiation means, An exposure head provided with a light modulation means capable of controlling the picture element portion in accordance with pattern information, wherein the column direction of the picture element portion forms a predetermined set inclination angle θ with respect to the scanning direction of the exposure head. Using an exposure head arranged as follows:
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
The permanent pattern forming method according to any one of <44> to <46>, wherein the exposure head is moved relative to the photosensitive layer in a scanning direction. In the method for forming a permanent pattern according to <47>, 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.
<48> The exposure is performed by a plurality of exposure heads, and the drawing element specifying means relates 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. It is the permanent pattern forming method according to <47>, in which, among the element parts, the image element part to be used for realizing N double exposure in the inter-head connection region is designated. In the method for forming a permanent pattern according to <48>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating means is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. 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.
<49> The exposure is performed by a plurality of exposure heads, and the used picture element designation means is involved in exposure other than the inter-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The permanent pattern forming method according to the above <48>, wherein among the picture element parts, the picture element part used for realizing N double exposure in an area other than the inter-head connection area is designated. In the method for forming a permanent pattern according to <49>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating means is an overlapping exposure region on an 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.
<50> 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 <47> to <49>.
<51> The method for forming a permanent pattern according to any one of <47> to <50>, wherein N in N-fold exposure is a natural number of 3 or more. In the method for forming a permanent pattern according to <51>, 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.

<52> Use pixel part designation means,
A light spot position detecting means for detecting a light spot position as a pixel unit that is generated by the picture element unit and constitutes an exposure area on the exposed surface;
<47> to <51>, further comprising: a pixel part selection unit that selects a pixel part to be used for realizing the N-fold exposure based on a detection result by the light spot position detection unit. This is a permanent pattern forming method.
<53> The permanent pattern forming method according to any one of <47> to <52>, wherein the used pixel part specifying unit specifies, in line units, the used pixel part used for realizing N double exposure. It is.

<54> The fact that the light spot position detector detects the row direction of the light spot on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted based on the detected at least two light spot positions. The inclination angle θ ′ is specified, and the picture element selection means selects the use picture element part so as to absorb an error between the actual inclination angle θ ′ and the set inclination angle θ. The permanent pattern forming method according to any one of the above.
<55> The actual inclination angle θ ′ is an average value, a median value, and a plurality of actual inclination angles formed by the row direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is inclined. The permanent pattern forming method according to <54>, wherein the permanent pattern forming method is one of a maximum value and a minimum value.
<56> The pixel part selection means derives a natural number T close to t that satisfies the relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <52> to <55> for selecting the pixel part from the first line to the T-th line as a used pixel part in a line element (where m represents a natural number of 2 or more). The permanent pattern forming method according to any one of the above.
<57> The pixel part selection means derives a natural number T close to t satisfying a relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m In the picture element part arranged in a row (where m represents a natural number of 2 or more), the picture element part in the (T + 1) -th line to the 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 <52> to <56>, wherein the pixel part excluding the element part is selected as a use pixel part.

<58> 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-fold exposure;
(2) Means for selecting a pixel part to be used so that the number of pixel units in an overexposed area and the number of pixel units in an underexposed area are equal to each other with respect to an ideal N double exposure;
(3) Means for selecting a pixel part to be used so that the area of an overexposed area is minimized and an underexposed area does not occur with respect to an ideal N double exposure, and (4) Ideal From the above <52>, which is one of means for selecting a pixel part to be used so that the area of an underexposed area is minimized and an overexposed area does not occur with respect to typical N double exposure <57> The method for forming a permanent pattern according to any one of the above.
<59> 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 method for forming a permanent pattern according to any one of <52> to <58>.
<60> The permanent pattern forming method according to <59>, wherein the unused pixel parts are specified in units of rows.

<61> 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 <47> to <60>, wherein the reference exposure is performed using only the image element portion that constitutes. In the permanent pattern forming method according to <61>, 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.
<62> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, a pixel part row is formed every 1 / N lines for N of N multiple exposures. The permanent pattern forming method according to any one of <47> to <60>, wherein the reference exposure is performed using only the pixel part. In the permanent pattern forming method according to <62>, in order to designate the use pixel part in the use pixel part designating unit, among the usable picture element parts, N is one for N double exposure. / A reference exposure is performed using only the pixel part constituting the pixel part column for every N rows, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<63> From the above <47> to <62>, the used pixel part designation means includes a slit and a photodetector as the light spot position detection means, and an arithmetic unit connected to the photodetector as the pixel part selection means. The permanent pattern forming method according to any one of the above.
<64> The method for forming a permanent pattern according to any one of <47> to <63>, wherein N in N-fold exposure is a natural number of 3 or more and 7 or less.

<65> The light modulation means further includes pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation means is emitted from the light irradiation means. The method for forming a permanent pattern according to any one of <47> to <64>, wherein the modulation is performed according to. In the permanent pattern forming method according to <65>, since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit is included in the control signal generated by the pattern signal generation unit. Modulated accordingly.
<66> The method for forming a permanent pattern according to any one of <47> to <65>, wherein the light modulator is a spatial light modulator.
<67> The method for forming a permanent pattern according to <65>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<68> The permanent pattern forming method according to any one of the items <47> to <67>, wherein the picture element portion is a micromirror.
<69> From <47> to <47> further including conversion means for converting the pattern information so that the dimension of the predetermined portion of the pattern represented by the pattern information matches the dimension of the corresponding portion that can be realized by the designated used pixel part. 68>.

<70> The method for forming a permanent pattern according to any one of <47> to <69>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the method for forming a permanent pattern according to <70>, 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 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.
<71> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams irradiated from the plurality of lasers and couples the laser beams to the multimode optical fiber. <47> to the permanent pattern forming method according to any one of <70>. In the method for forming a permanent pattern according to <71>, the light irradiating means is configured such that laser light emitted from each of the plurality of lasers is collected 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.

<72> The method for forming a permanent pattern according to any one of <44> to <71>, wherein the photosensitive layer is developed after the exposure. In the method for forming a permanent pattern according to <72>, a high-definition pattern is formed by developing the photosensitive layer after the exposure.
<73> The method for forming a permanent pattern according to <72>, wherein the permanent pattern is formed after the development.
<74> The method for forming a permanent pattern according to <73>, wherein after the development, the photosensitive layer is cured.
<75> The method for forming a permanent pattern according to <74>, wherein the curing treatment is at least one of a whole surface exposure treatment and a whole surface heat treatment performed at 120 to 200 ° C.

<76> A permanent pattern formed by the pattern forming method according to any one of <44> to <75>. Since the permanent pattern according to <72> is formed by the pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance and the like, and has high definition, and is a multilayer wiring board for semiconductors and components. This is useful for high-density mounting on PCBs and build-up wiring boards.
<77> The pattern according to <76>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern according to <77> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, due to the insulation and heat resistance of the film, the wiring may be subjected to an impact or bending from the outside. Protected from.

  <78> A printed circuit board wherein a permanent pattern is formed by the permanent pattern forming method according to any one of <44> to <77>.

  According to the present invention, conventional problems can be solved, and by specifying a binder and a thermal crosslinking agent to be used in combination, the pot life is long, the tackiness, surface failure, surface shape, edge roughness are excellent, and high sensitivity And high-resolution, electroless gold plating resistance, via and through-hole embedding, and high-definition permanent patterns (such as protective films, interlayer insulating films, and solder resist patterns) can be efficiently formed. And the manufacturing method, the photosensitive film, the photosensitive laminated body, the permanent pattern formation method using the said photosensitive laminated body, and the printed circuit board by which a pattern is formed by the said permanent pattern formation method can be provided.

(Photosensitive composition)
The photosensitive composition of the present invention contains a binder, a polymerizable compound, a photopolymerization initiator, a pigment, and a thermal crosslinking agent, preferably contains a thermosetting accelerator, and optionally contains other components. .
As the photosensitive composition of the present invention, it is necessary that the average particle size of the contained particles is 2 μm or less, and the pigment and the thermal cross-linking agent are used at least dispersed, and the average particle size thereof Needs to be 2 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, particularly preferably 0.6 μm or less, and most preferably 0.35 μm or less. When the average particle diameter exceeds 2 μm, the planarity of the photosensitive layer is deteriorated, tackiness, sensitivity, resolution and the like are lowered, and a defect may be generated on the formed pattern surface.
In the photosensitive composition of the present invention, the content of coarse particles of 5 μm or more is preferably 1% or less, and preferably 0.1% or less. When the content of coarse particles of 5 μm or more exceeds 1%, the planarity of the photosensitive layer is poor, tackiness, sensitivity, resolution and the like are lowered, and defects may be generated on the formed pattern surface.
As the content of the coarse particles, the content of coarse particles of 2 μm or more is preferably 1% or less, and the content of coarse particles of 1 μm or more is more preferably 1% or less. In particular, the content of coarse particles of 1 μm or more is preferably 0.1% or less.

[Pigment]
There is no restriction | limiting in particular as said pigment, According to the objective, it can select suitably, For example, an inorganic pigment (extreme pigment), an organic pigment, etc. are mentioned. Examples of the organic pigment include colored pigments and organic crosslinkable fine particles.
In addition, there is no restriction | limiting in particular as an average particle diameter of the pigment as a raw material before dispersion | distribution, You may use what was crushed moderately before dispersion | distribution or atomized to about several micrometers-about 10 micrometers previously.

<Inorganic pigment (external pigment)>
The inorganic pigment is added for the purpose of improving the surface hardness of the permanent pattern, suppressing the linear expansion coefficient, or suppressing the dielectric constant or dielectric loss tangent of the cured film itself. Organic fine particles can also be added.
The inorganic pigment is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor phase method silica, amorphous Examples thereof include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.
There is no restriction | limiting in particular as said organic fine particle, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. Further, silica having an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  As solid content in the said photosensitive composition solid content of the said extender, 5-60 mass% is preferable. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, the cured film is formed when a cured film is formed on the surface of the photosensitive layer. When the wiring is formed using a permanent pattern, the function as a protective film for the wiring may be impaired.

<Coloring pigment>
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (CI. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow HR). Yellow 83), C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 154, C.I. I. Pigment Yellow 185, Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel・ Pink B Supra (CI Pigment Red 81) Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI Pigment Black 1), Carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more. Moreover, the dye suitably selected from well-known dye can be used as needed.

  The solid content of the color pigment in the solid content of the photosensitive composition can be determined in consideration of exposure sensitivity, resolution, etc. of the photosensitive layer during permanent pattern formation. Generally, 0.01 to 10% by mass is preferable, and 0.05 to 5% by mass is more preferable.

(Thermal crosslinking agent)
The thermal crosslinking agent is preferably a crystalline epoxy compound having a melting point of 60 ° C. or higher or an epoxy compound having a softening point of 70 ° C. or higher, more preferably a crystalline epoxy compound having a melting point of 60 ° C. or higher. Epoxy compounds are preferred. Furthermore, you may use together other thermal crosslinking agents, such as a low melting point epoxy compound, a liquid epoxy compound, and the epoxy compound which has a low softening point, as needed.

<Crystalline epoxy compound with a melting point of 60 ° C. or higher>
Specific examples of crystalline epoxy compounds having a melting point of 60 ° C. or higher include bixylenols such as Epicron EXA-7035 (melting point 127 ° C.) manufactured by Dainippon Ink and Chemicals, and YX4000 (melting point 105 ° C.) manufactured by Japan Epoxy Resin. Type epoxy compound, tetraphenol type epoxy compound such as GTR-1800 (melting point: 165 to 175 ° C.) manufactured by Nippon Kayaku Co., Ltd., TEPIC (90 to 100 ° C.) manufactured by Nissan Chemical Industries, Ltd., YDC-1312 manufactured by Toto Kasei Co., Ltd. (Melting point: 138-145 ° C.), YSLV-80XY (melting point: 75-85 ° C.), YSLV-120TE (melting point: 115-125 ° C.) and other bisphenol type epoxy compounds, YSLV-90CR (melting point: 85-95 ° C.), Nagase Chemtex Fluorene type such as EX series (EX-1010, melting point 60-169 ° C) An epoxy compound etc. are mentioned suitably. These may be used alone or in combination of two or more.

  As solid content in the said photosensitive composition of the crystalline epoxy compound of melting | fusing point 60 degreeC or more, 1-40 mass% is preferable, and 2-30 mass% is more preferable. When the solid content is less than 1% by mass, the hygroscopicity of the cured film is increased, resulting in deterioration of the insulating property, the adhesiveness with the substrate may be deteriorated, and the plating property may be deteriorated. When it exceeds 40 mass%, developability may deteriorate and exposure sensitivity may decrease.

<Other thermal crosslinking agents>
The other thermal crosslinking agent that can be used in combination with the crystalline epoxy compound having a melting point of 60 ° C. or higher is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of gold plating resistance, it may be insoluble in alkali. preferable. The compound 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, it is suitable for developability and the like. For example, two or more selected from epoxy compounds, oxetane compounds, polyisocyanate compounds, compounds obtained by reacting a polyisocyanate compound with a blocking agent, and melamine derivatives can be used as long as no adverse effects are exerted.

  Examples of the epoxy compound include an epoxy compound having at least two oxirane groups in one molecule and an epoxy compound having at least two epoxy groups having an alkyl group at the β-position in one molecule.

  Examples of the epoxy compound having at least two oxirane groups in one molecule include bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, Cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, 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 and Chemicals, Inc.") ), Glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl) Ester etc.) Hydantoin type epoxy resin, cycloaliphatic epoxy resin (3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide , “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc.), imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol Ru-A novolac type epoxy resin, glycidyl phthalate resin, naphthalene group-containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolak type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products such as “ESN-190, ESN-360; "Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; Dainippon Ink and Chemicals Co., Ltd."), phenol compounds and diolefin compounds such as divinylbenzene and dicyclopentadiene Reaction product of polyphenol compound obtained by reaction and epichlorohydrin, ring-opening polymer of 4-vinylcyclohexene-1-oxide epoxidized with peracetic acid, epoxy resin having linear phosphorus-containing structure, cyclic phosphorus-containing An epoxy resin having a 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 resins of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) adamantane type epoxy resins, and the like. It is not limited to. 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 at the β-position can be used, and the β-position is an alkyl group. Particularly preferred are compounds containing an epoxy group (more specifically, a β-alkyl-substituted glycidyl group or the like) substituted with.
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.

  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 biphenols, biphenol compounds such as tetramethylbiphenol, naphthol compounds such as dihydroxynaphthalene and binaphthol, phenol novolac resins such as phenol-formaldehyde polycondensates, and C 1-10 carbon atoms such as cresol-formaldehyde polycondensates Bialkyl such as monoalkyl-substituted phenol-formaldehyde polycondensate, xylenol-formaldehyde polycondensate, etc., dialkyl-substituted phenol-formaldehyde polycondensate, bisphenol A-formaldehyde polycondensate, etc. Phenolic compounds - 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 bisphenol compounds such as di-β-alkyl glycidyl ether of bisphenol A and di-β-alkyl glycidyl ether of bisphenol F. Di-β-alkyl glycidyl ether of biphenol such as di-β-alkyl glycidyl ether of biphenol, di-β-alkyl glycidyl ether of tetramethylbiphenol; di-β-alkyl glycidyl ether of dihydroxynaphthalene, binaphthol Β-alkyl glycidyl ethers of naphthol compounds such as di-β-alkyl glycidyl ethers; poly-β-alkyl glycidyl ethers of phenol-formaldehyde polycondensates; cresol-formal C1-C10 monoalkyl-substituted phenol-formaldehyde polycondensate poly-β-alkyl glycidyl ethers such as polyhydric polycondensates of dehydride polycondensates; poly-β-alkyls of xylenol-formaldehyde polycondensates Poly-β-alkyl glycidyl ethers of C1-C10 dialkyl-substituted phenol-formaldehyde polycondensates such as glycidyl ether; bisphenol compounds such as poly-β-alkyl glycidyl ether of bisphenol A-formaldehyde polycondensate-formaldehyde polycondensation Poly-β-alkyl glycidyl ether of a product; poly-β-alkyl glycidyl ether of a polyaddition product of a phenol compound and divinylbenzene;
Among these, a bisphenol compound represented by the following structural formula (i), a β-alkyl glycidyl ether derived from a polymer obtained from the bisphenol compound and epichlorohydrin, and the following structural formula (ii) Phenol compound-formaldehyde polycondensate poly-β-alkyl glycidyl ether is preferred.
However, in said structural formula (i), R represents either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.
In the Structural Formula (ii), R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R "represents any one of hydrogen atom, and CH _3, n is 0 Represents an integer of ~ 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.

  Furthermore, as the epoxy compound, commercially available products and mixtures thereof described in JP-A-2005-182004 [0037] can be suitably used.

Examples of the oxetane compound include oxetane compounds having at least two oxetanyl groups in one molecule.
Specifically, for example, 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 or oligomers or copolymers thereof, compounds having an oxetane group; Novolac resin, poly (p-hydroxystyrene), cardo type bisphenol , Calixarenes, calixresorcinarenes, and ether compounds such as silsesquioxane and other hydroxyl group-containing resins. In addition to these, an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate A polymer etc. are also mentioned.

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

  As a socyanate group blocking agent in a compound obtained by reacting a blocking agent with the polyisocyanate compound, that is, a compound obtained by reacting a blocking agent with an isocyanate group of polyisocyanate and its derivatives, alcohols (for example, 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.) and the like. 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.

  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.

  When the thermal crosslinking agent is used in combination, for example, a combination of bifunctional compounds, a combination of a bifunctional compound and a trifunctional or higher compound, a combination of a monofunctional compound and a polyfunctional compound can be mentioned. It is done. Among these, the combination of bifunctional compounds and the combination of a bifunctional compound and a trifunctional or higher compound are particularly preferable.

  The epoxy equivalent of the thermal crosslinking agent is 90 to 9,000 g / eq. Is preferable, and 100 to 5,000 g / eq. Is more preferable, and 120-3,000 g / eq. Is particularly preferred. In addition, an epoxy equivalent can be measured based on JISK7236.

  As solid content in the said photosensitive composition of the thermal crosslinking agent containing the crystalline epoxy compound whose melting | fusing point is 60 degreeC or more, 1-50 mass% is preferable, and 2-30 mass% is more preferable. When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 50% by mass, developability and exposure sensitivity may be deteriorated.

[Thermosetting accelerator]
In order to accelerate the thermal curing of the epoxy compound or the oxetane compound as the thermal crosslinking agent, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N- Dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, , Dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, -Cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, Benzoguanamine etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino -S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
Solid content in the said photosensitive composition solid content of the said epoxy compound, the said oxetane compound, and the thermosetting accelerator which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally. is there.

〔binder〕
As the binder, a polymer compound containing an acidic group and an ethylenically unsaturated bond in the side chain, an epoxy acrylate compound, or the like is preferably used, and among these, an acidic group and an ethylenically unsaturated bond are included in the side chain. A polymer compound is particularly preferably used.
<Polymer compound containing acidic group and ethylenically unsaturated bond in side chain>
Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group, and a carboxyl group is preferable from the viewpoint of obtaining raw materials.
The binder is preferably a compound that is insoluble in water and swells or dissolves in an alkaline aqueous solution.
In addition, as the binder, at least one polymerizable double bond in the molecule, for example, an acrylic group such as a (meth) acrylate group or a (meth) acrylamide group, a vinyl ester of carboxylic acid, a vinyl ether, an allyl ether, etc. Various polymerizable double bonds can be used. More specifically, an acrylic resin containing a carboxyl group as an acidic group, a cyclic ether group-containing polymerizable compound such as a glycidyl ester of an unsaturated fatty acid such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, or an alicyclic epoxy group. Examples include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound having a (meth) acryloyl group (for example, an epoxy group such as cyclohexene oxide in the same molecule). In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group, a hydroxyalkyl ( Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as (meth) acrylate. Also included are compounds obtained by copolymerizing a cyclic ether group-containing polymerizable compound such as glycidyl methacrylate and a vinyl monomer such as (meth) acryloyl alkyl ester and adding (meth) acrylic acid to the side chain epoxy group. It is done.
Specific examples thereof include compounds described in Japanese Patent No. 2762775, Japanese Patent Laid-Open No. 3-172301, and Japanese Patent Laid-Open No. 2000-232264.

Among these, the binder is obtained by adding a cyclic ether group (for example, a group having an epoxy group or an oxetane group in a partial structure) -containing polymerizable compound to a part of the acidic group of the polymer compound, and the polymer compound More preferably, the polymer is selected from any of those obtained by adding a carboxyl group-containing polymerizable compound to a part or all of the cyclic ether group. In this case, the addition reaction between the acidic group and the compound having a cyclic ether group is preferably carried out in the presence of a catalyst. In particular, the catalyst is preferably selected from an acidic compound and a neutral compound.
Among them, from the viewpoint of development stability of the photosensitive composition over time, the binder is a polymer compound containing an aromatic group which may contain a carboxyl group and a heterocycle in the side chain, and an ethylenically unsaturated bond in the side chain. Is preferred.

-Aromatic group which may contain a heterocycle-
Examples of the aromatic group that may contain 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, are exemplified.

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 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.
Examples of the heterocyclic group in the substituent include a pyridyl group and 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 a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. 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, and 3-butynyl group.

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 group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy Group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group 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 be bonded to form a ring.
Examples of the amino group include N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acylamino group, N -Alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N '-Dialkyl-N-alkylureido group, N'-alkyl-N'-arylureido group, N', N'-dialkyl-N-alkylureido group, N ', N'- Alkyl-N′-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N ′ -Diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino Group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group and the like. It is done. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Also, ^{R 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 conjugated 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- Preferable examples include a methylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-diethylcarbamoyl group, a morpholinocarbonyl group, and the like.

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 a group in which one or two hydroxyl groups on the phosphono group are substituted with another organic oxo 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 a counter cation, 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 a normal radical polymerization method using at least one radical polymerizable compound containing an aromatic group and, if necessary, at least one other radical polymerizable compound 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 structural formula (A) and a compound represented by the 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, polyvalent anthracene and the like.

  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 >, 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 compounds (1)-(30) are 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 deteriorated.

-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 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, an alkyl group which may have a substituent, or the like, 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, preferably 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, examples of the substituent that can be introduced include those listed in the structural formula (III).
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. 5 to 2.8 meq / g is particularly preferable. When the content is less than 0.5 meq / g, the curing reaction amount is small, so the sensitivity may be low. When the content is more than 3.0 meq / g, the storage stability may be deteriorated.
Here, the content (meq / g) can be measured by, for example, iodine value titration.

The method for introducing 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 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 radical polymerizable compounds containing a carboxyl group and, if necessary, one or more other radical 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 in terms 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.

The compound represented by the structural formula (VI) or the compound represented by the structural formula (VII) is not particularly limited, and examples thereof include the following exemplified compounds (31) to (40).

  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 (iii), the structure represented by the structural formula (iv), and these Those represented by mixing are preferred.
However, in the structural formulas (iii) and (iv), Ra to Rc represent a hydrogen atom or a monovalent organic group. R ₁ represents a hydrogen atom or a methyl group. L ₁ represents an organic group that may have a linking group.

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

-Carboxyl group-
The polymer compound 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. For example, 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 alone or in combination of two or more.

  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 alkaline water development.

In order to improve various performances such as image strength, the polymer compound is preferably copolymerized with another radical polymerizable compound in addition to the above-described radical polymerizable compound.
Examples of the other radical polymerizable compound 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. Examples include rumethylstyrene and 4-fluoro-3-trifluoromethylstyrene.
These radically polymerizable compounds may be used individually by 1 type, and may use 2 or more types together.

  The solvent used for synthesizing the polymer compound is not particularly limited and may be appropriately selected depending on the intended 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, dimethyl sulfoxide , Toluene, ethyl acetate, methyl lactate, ethyl lactate and the like. These may be used alone or in combination of two or more.

The molecular weight of the polymer compound is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, and particularly preferably 10,000 to 50,000 in terms of mass average molecular weight. When the mass average molecular weight is less than 3,000, the cured film strength may be insufficient, and when it exceeds 100,000, developability may be deteriorated.
The polymer compound 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 said high molecular compound may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, you may mix and use another high molecular compound. In this case, the content of the other polymer compound in the polymer compound is preferably 50% by mass or less, and more preferably 30% by mass or less.

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

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

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

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

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

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

  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.

[Polymerizable compound]
There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, For example, the compound which has one or more ethylenically unsaturated bonds is preferable.

  Examples of the ethylenically unsaturated bond include (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester, and the like.

  The compound having one or more ethylenically unsaturated bonds is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one selected from monomers having a (meth) acryl group is Preferably mentioned.

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

  5-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. If the solid content is less than 5% by mass, problems such as deterioration of developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. is there.

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

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, Examples include ketone compounds (benzylmethyl ketal compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, etc.), aromatic onium salts, metallocenes, and the like. Of these, phosphine oxide compounds, oxime derivatives, and ketone compounds are preferred from the viewpoints of sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the printed wiring board forming substrate. Among these, phosphine oxide compounds are preferred. Particularly preferred are oxime derivatives.
Specifically, for example, compounds described in [0288] to [0309] of JP-A-2005-258431 can be mentioned. The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.

  The content of the photopolymerization initiator in the photosensitive composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 15% by mass.

[Other ingredients]
Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, and the like, and further adhesion promoters and other auxiliaries (for example, conductive particles, fillers) on the substrate surface. , Antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) may be used in combination.
By appropriately containing these components, properties such as stability, photographic properties, and film properties of the intended photosensitive composition can be adjusted.

<Sensitizer>
In order to adjust the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer, it is possible to add a sensitizer in addition to the photopolymerization initiator.
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

  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.

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, Methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin, acriflavine, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane), anthraquinones (eg anthraquinone), squalium (Eg, squalium), acridones (eg, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone (eg, 2-chloro-10-butylacridone) 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-methoxyc Phosphorus, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5 7-dipropoxycoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc. And the like, and thioxanthone compounds (thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, Quantacure QTX, etc.) and the like. , Aromatic rings and compounds A compound in which an elemental ring is condensed (condensed compound), and an amine compound substituted with at least two aromatic hydrocarbon rings or aromatic heterocyclic rings are preferred.

  Among the condensed ring compounds, hetero-fused ketone compounds (acridone compounds, thioxanthone compounds, coumarin compounds, etc.) and acridine compounds are more preferable. Among the hetero-fused ketone compounds, an acridone compound and a thioxanthone compound are particularly preferable.

  The amine compound substituted with any one of the at least two aromatic hydrocarbon rings and the aromatic heterocyclic ring is preferably a sensitizer having an absorption maximum with respect to light in a wavelength region of 330 to 450 nm, For example, a disubstituted aminobenzophenone compound, a disubstituted amino-benzene compound having a heterocyclic group as a substituent at a carbon atom at the para position relative to an amino group on the benzene ring, Disubstituted amino-benzene compounds having a substituent containing a sulfonylimino group at the carbon atom at the position, disubstituted amino-benzene compounds having a carbostyryl skeleton, and at least two aromatic rings on the nitrogen atom Examples thereof include compounds having a di-substituted amino-benzene as a partial structure, such as a compound having a bonded structure.

The said sensitizer may be used individually by 1 type and may use 2 or more types together.
The content of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, and particularly preferably 0.05 to 1% by mass in the total solid content of the photosensitive composition.
When the content is less than 0.01% by mass, the sensitivity may decrease, and when the content exceeds 4% by mass, the shape of the pattern may be deteriorated.

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

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

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

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

<Adhesion promoter>
In order to improve the adhesion between the layers of the photosensitive film including the photosensitive layer formed using the photosensitive composition of the present invention or the adhesion between the photosensitive film and the substrate, a so-called known layer is known for each layer. An adhesion promoter can be used.

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

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

  Since the photosensitive composition of the present invention has an average particle diameter of 2 μm or less, it has a long pot life, excellent tackiness, surface failure, surface shape and edge roughness, high sensitivity and high resolution, It has excellent resistance to electrolytic gold plating and fillability of vias and through holes, and can efficiently form a high-definition permanent pattern. For this reason, it can be widely used for the formation of permanent patterns such as printed wiring boards, display members such as color filters, pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc. It can be suitably used for forming.

(Method for producing photosensitive composition)
The manufacturing method of the said photosensitive composition of this invention has a dispersion | distribution process and a mixing process, and has another process as needed.
[Dispersing process]
The dispersion step is a step of forming a dispersion by finely dispersing at least a pigment and a thermal crosslinking agent.
The dispersion method is not particularly limited, and a known method can be appropriately selected depending on the purpose. The particle diameter of the beads may be 0.1 mmΦ to 3.0 mmΦ depending on the target particle diameter.) By a dispersing means such as a high-speed stirring disperser (such as an ultra-high pressure homogenizer) Examples thereof include a method of pulverizing and mixing, and dispersing in water or a solvent.
Further, when forming the dispersion, a binder may be further added to the pigment and the thermal crosslinking agent, and these may be dispersed by the dispersing means. In this way, by adding a binder to the dispersion, aggregation of the pigment-containing pigment and the thermal crosslinking agent can be prevented. In addition to the binder, the dispersibility may be improved by using a dispersant such as a polymer or a pigment structure analog, or a pigment surface treatment agent such as a silane coupling agent.
The dispersion preferably has an average particle size of 2 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, particularly preferably 0.6 μm or less, and most preferably 0.35 μm or less. When the average particle diameter exceeds 2 μm, the planarity of the photosensitive layer is deteriorated, tackiness, sensitivity, resolution and the like are lowered, and defects may be generated on the formed permanent pattern surface.
The solvent is preferably an organic solvent, and examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketones such as cyclohexanone and diisobutyl ketone; esters such as ethyl acetate, propyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; toluene, Aromatic hydrocarbons such as xylene, benzene, ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene Tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-ethers such as methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more.

[Mixing process]
The mixing step is a step of mixing the dispersion obtained in the dispersing step and other components.
The mixing method is not particularly limited, and a known method can be appropriately selected according to the purpose. The dispersion and other compositions are dissolved and emulsified in water or a solvent similar to the dispersion step. Or the method of dispersing is mentioned.

  By the method for producing the photosensitive composition of the present invention, the photosensitive composition of the present invention having an average particle size of 2 μm or less is prepared.

  In the method for producing a photosensitive composition of the present invention, when the average particle size of the particles is 2 μm or less, the pot life is long, the tack property, the surface failure, the surface shape, the edge roughness are excellent, the high sensitivity and It is possible to efficiently produce a photosensitive composition having high resolution, excellent electroless gold plating resistance, via and through-hole embedding properties, and capable of obtaining a high-definition permanent pattern. For this reason, it can be widely used as a method for producing photosensitive components for forming permanent patterns such as printed wiring boards, color filters, pillar materials, rib materials, spacers, partition members, display members, holograms, micromachines, proofs, etc. In particular, it can be used suitably for the manufacturing method of the photosensitive composition for permanent pattern formation of a printed circuit board.

(Photosensitive film)
The photosensitive film of the present invention has at least a support and a photosensitive layer made of the above-described photosensitive composition of the present invention on the support. These layers are laminated.

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

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

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

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

<Photosensitive layer>
The photosensitive layer is formed using the photosensitive composition of the present invention.
In the case where the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 400 mJ / cm ² . Preferably, it is 0.2 to 200 mJ / cm ² , more preferably 0.5 to 100 mJ / cm ² , and particularly preferably 1 to 50 mJ / cm ² .
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs, it exceeds 400 mJ / cm ^2, increases the time necessary for exposure, processing speed is slow Sometimes.

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

  There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 1-100 micrometers is preferable, 2-80 micrometers is more preferable, and 4-50 micrometers is especially preferable.

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

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

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

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

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

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

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

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

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

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

(Photosensitive laminate)
The photosensitive laminate of the present invention is formed by laminating at least a photosensitive layer made of the photosensitive composition of the present invention on a substrate and other layers appropriately selected according to the purpose.

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed, or a member to be transferred onto which at least the photosensitive layer of the photosensitive film of the present invention is transferred. For example, it can be arbitrarily selected from those having high surface smoothness to those having an uneven surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include a known printed wiring board (printed board), a glass plate (soda glass plate, etc.), a synthetic resin film, paper, and a metal plate.

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

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

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

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

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

  There is no restriction | limiting in particular as an apparatus which performs at least one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator VP-II, Nichigo Morton Co., Ltd. V130) Etc. are preferable.

By using the photosensitive composition of the present invention, the photosensitive film and the photosensitive laminate of the present invention have a long pot life, excellent tackiness, surface failure, surface shape, and edge roughness, high sensitivity and high resolution. Because it is excellent in electroless gold plating resistance and via and through-hole embedding, and high-definition permanent patterns can be efficiently formed, such as permanent patterns such as protective films, interlayer insulating films, and solder resist patterns, etc. It can be suitably used for various pattern formation, for manufacturing liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, and for pattern formation for holograms, micromachines, proofs, etc. It can be suitably used for forming a permanent pattern.
In particular, the photosensitive film of the present invention is excellent in tackiness, surface failure, surface shape and edge roughness, and has a uniform thickness. Therefore, when forming a permanent pattern, a permanent pattern (protective film, interlayer insulating film) Even if the solder resist is thinned, ion migration does not occur in the high acceleration test (HAST), and a high-definition permanent pattern with excellent heat resistance and moisture resistance can be obtained. It is done more finely.

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

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

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

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

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

  The analog exposure is not particularly limited and may be appropriately selected depending on the purpose.For example, a method of performing exposure with a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or the like through a negative mask having a predetermined pattern. Can be mentioned.

  The digital exposure 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”. Further, in the following description, “N multiple drawing” and “multiple exposure” are used as terms corresponding to “N double exposure” and “multiple exposure” for an embodiment in which the exposure apparatus or exposure method of the present invention is implemented as a drawing apparatus or drawing method. The term “multiple drawing” shall be used.
N in the N-fold exposure is not particularly limited as long as it is a natural number of 2 or more, and can be appropriately selected according to the purpose. However, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is more preferable. .

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

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

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

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

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

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

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

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

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

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

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

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

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

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

-Light modulation means-
The light modulating means has n (where n is a natural number of 2 or more) two-dimensionally arranged image elements, and can control the image elements according to the pattern information. If it is, there will be no restriction | limiting in particular, According to the objective, it can select suitably, For example, a spatial light modulation element is preferable.

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

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

Hereinafter, an example of the light modulation means will be described with reference to the drawings.
As shown in FIG. 6, the DMD 36 is a mirror device in which a large number of micromirrors 58 are arranged in a lattice pattern on a SRAM cell (memory cell) 56 as a pixel portion constituting each pixel (pixel). . In this embodiment, the DMD 36 in which the micromirrors 58 of 1,024 columns × 768 rows are arranged is used. Of these, the micromirrors 58 that can be driven by the controller connected to the DMD 36, that is, usable, are 1,024. It is assumed that there are only columns × 256 rows. The data processing speed of the DMD 36 is limited, and the modulation speed per line is determined in proportion to the number of micromirrors to be used. Thus, by using only some of the micromirrors in this way, Modulation speed increases. Each micromirror 58 is supported by a support column, and a material having high reflectivity such as aluminum is deposited on the surface thereof. In the present embodiment, the reflectance of each micromirror 58 is 90% or more, and the arrangement pitch thereof is 13.7 μm in both the vertical direction and the horizontal direction. The SRAM cell 56 is of a silicon gate CMOS manufactured in a normal semiconductor memory manufacturing line via a support including a hinge and a yoke, and the whole is configured monolithically (integrated).

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

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

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

For example, the wavelength of ultraviolet to visible light is preferably 300 to 1,500 nm, more preferably 320 to 800 nm, and particularly preferably 330 to 650 nm.
For example, the wavelength of the laser beam is preferably 200 to 1,500 nm, more preferably 300 to 800 nm, still more preferably 330 to 500 nm, and particularly preferably 400 to 450 nm.

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

  Examples of means (fiber array light source) capable of irradiating the combined laser include means described in JP-A-2005-258431 [0109] to [0146].

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

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

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

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

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

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

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

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

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

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

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

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

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

−Selection of used pixel part−
Using the actual inclination angle θ ′ thus specified, the arithmetic unit connected to the photodetector is expressed by the following equation 4
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived, and the first to T-th row micromirrors on the DMD 36 are selected as micromirrors that are actually used during the main exposure. In this way, in the exposure region near the 512th column, a micromirror that minimizes the total area of the overexposed region and the underexposed region with respect to the ideal double exposure is actually obtained. It can be selected as a micromirror to be used for.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Thereafter, with respect to the micromirror corresponding to the light spot other than the light spots constituting the regions 78 and 80 covered with diagonal lines in FIG. In FIG. 19, the micromirrors corresponding to the light spots constituting the shaded area 82 and the shaded area 84 are specified 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. Not involved.

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

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

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

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

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

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

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

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

FIG. 22 is an explanatory diagram showing an example of a form in which reference exposure is performed using only a plurality of (N-1) rows of micromirrors using a plurality of exposure heads.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference is made using only the micromirrors corresponding to the odd-numbered light spot rows of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction, which are indicated by solid lines in FIG. Exposure is performed, and a reference exposure result is output as a sample. Based on the output reference exposure result, the variation in resolution and density unevenness in the area other than the joint area between the heads formed on the exposed surface by the two exposure heads are confirmed, or the actual inclination angle is estimated. Thus, the micromirror to be used at the time of the main exposure can be designated.
For example, the micromirrors other than the micromirrors corresponding to the light spot rows in the area 86 shown by hatching in FIG. 22 and the shaded area 88 are among the micromirrors constituting the odd-numbered light spots, during the main exposure. Specified as actually used. For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and a micromirror used in the main exposure may be designated, or the same pattern as that for the odd-numbered pixel columns may be applied. Good.
In this way, in the main exposure using both the odd-numbered and even-numbered micromirrors by designating the micromirrors that are actually used during the main exposure, the two exposure heads form the surface to be exposed. A state close to ideal double exposure can be realized in a region other than the head-to-head connection region.

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

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

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

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

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

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

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

  As the developer, a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development are accelerated. For this purpose, an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.) may be used in combination. The developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or an organic solvent alone.

[Curing process]
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the development. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
An apparatus for performing the entire surface exposure is not particularly limited and may be appropriately selected according to the purpose. It is mentioned in. The exposure amount is usually 10 to 2,000 mJ / cm ² .

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the development. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
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.
The heating time in the entire surface heating is preferably 10 to 120 minutes, and more preferably 15 to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

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

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

  Since the method for forming a permanent pattern of the present invention uses the photosensitive laminate of the present invention, it is used for forming various patterns such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, and a pillar material. It can be suitably used for the production of liquid crystal structural members such as rib members, spacers, partition walls, etc., and the production of holograms, micromachines, proofs, etc., and in particular, it can be suitably used for the formation of permanent patterns on printed boards.

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

<Example of binder synthesis>
(Polymer Compound 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 further 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 represented by the following structural formula having a solid content of 30% by mass.
The mass average molecular weight (Mw) of the obtained polymer compound was 15,000 as a result of measurement by gel permeation chromatography (GPC) using polystyrene as a standard substance.
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.
* 1 represents a mixture of a structure represented by the following structural formula (a) and a structure represented by the following structural formula (b).

(Polymer Compound 2)
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was added and heated to 85 ° C. under a nitrogen stream. To this was added dropwise a solution of 1-methoxy-2-propanol 159 g of methyl methacrylate 36 g, methacrylic acid 72.3 g, V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 4.15 g over 2 hours. After completion of the dropwise addition, the reaction was further continued by heating for 5 hours. Subsequently, the heating was stopped to obtain a copolymer of methyl 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 2 represented by the following structural formula having a solid content of 30% by mass.
The mass average molecular weight (Mw) of the obtained polymer compound was 15,000 as a result of measurement by gel permeation chromatography (GPC) using polystyrene as a standard substance.
Moreover, from the titration using sodium hydroxide, the acid value per solid content is 2.3 meq / g.
Met.
Furthermore, the content (C = C value) of ethylenically unsaturated bonds per solid content determined by iodine value titration was 2.6 meq / g.
* 1 represents a mixture of the structure represented by the structural formula (a) and the structure represented by the structural formula (b).

(Polymer Compound 3)
110 parts by mass of phenol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., YDPN-702) was dissolved in 150 parts by mass of propylene glycol monomethyl ether acetate, and then 34 parts by mass of acrylic acid and 0.8 parts by mass of benzyldimethylamine were dissolved. In addition, after continuing the reaction at 100 to 120 ° C. for 8 hours, 35 parts by mass of tetrahydrophthalic anhydride was added and reacted at 100 ° C. for 8 hours to obtain an epoxy acrylate compound having an acid value of 70 mgKOH / g.

(Polymer Compound 4)
Styrene / maleic anhydride copolymer (Admast 1000 manufactured by Idemitsu Petrochemical Co., Ltd., maleic anhydride content 50 mol%) 130.9 g, cellosolve acetate 162.5 g, triethylamine 1.5 g and hydroquinone 0.28 g were charged into a flask. The temperature was raised to 0 ° C., 0.55 equivalents of 2-hydroxyethyl methacrylate (46.4 g) was added dropwise over 30 minutes with respect to the maleic anhydride residue, and then reacted for 6 hours. Air was kept blowing during the reaction. Furthermore, 0.45 equivalent of ethanol (13.5 g) was added to the maleic anhydride residue and reacted for 4 hours to give a photopolymerizable resin solution (a1 having a solid content of 54% by mass and an acid value of 160 mgKOH / g). )

Example 1
-Preparation of photosensitive composition-
By the following process, each component was mix | blended with the following quantity, and the photosensitive composition solution was prepared.
[Each component amount of photosensitive composition solution]
-High molecular compound 1 (binder, 30 mass% solid content in the 1-methoxy-2-propanol solution) ... 87.4 parts by mass-Dipentaerythritol hexaacrylate (polymerizable compound) ... 12 Mass parts / photopolymerization initiator I-1 (manufactured by Ciba Specialty Chemicals, Irgacure 819 (acylphosphine oxide compound))... 6 parts by mass Sensitizer represented by the following formula S-1 (thioxanthone series) Compound) ... 0.6 parts by mass Fluorosurfactant (Megafac F-176, manufactured by Dainippon Ink & Chemicals, 30 mass% 2-butanone solution) ... 0.2 parts by mass Dispersion: 40 parts by mass / methyl ethyl ketone: 15 parts by mass

-Dispersion process-
As the dispersion, 30 parts by mass of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30), the polymer compound 1 (solid content of 30% by mass in the 1-methoxy-2-propanol solution) solution 29.2 Parts by mass, TEPIC-S (thermal crosslinking agent manufactured by Nissan Chemical Industries, epoxy equivalent 100 g / eq.) 15 parts by mass, C.I. I. Pigment Blue 15: 3 0.2 parts by mass, C.I. I. After mixing 0.05 parts by mass of Pigment Yellow 185 and 40.55 parts by mass of methyl ethyl ketone, the motor speed was 9 m / s using a motor mill M-200 (manufactured by Eiger) with zirconia beads having a diameter of 0.6 mm. For 3.5 hours.
When the particle size distribution of the dispersion was measured using a particle size distribution meter (UPA-9340, manufactured by Nikkiso Co., Ltd.), the average particle size was 0.2 μm, and the ratio of coarse particles of 1 μm or more was 0.02%. there were.

--Mixing process--
The dispersion obtained above and the other composition were mixed to prepare a photosensitive composition of Example 1. The average particle diameter in the photosensitive composition of Example 1 was not aggregated by mixing at 0.2 μm, and the content of coarse particles of 5 μm or more was 0%.

-Preparation of photosensitive laminate-
Next, the substrate was prepared by subjecting the surface of a copper-clad laminate (no through-hole, copper thickness 12 μm) on which wiring had been formed to chemical polishing treatment. On the copper-clad laminate, the photosensitive composition was applied by a screen printing method using a 120 mesh Tetron screen so that the thickness after drying was 30 μm, and a hot air circulating dryer at 80 ° C. for 15 minutes. Was dried to form a photosensitive layer, and a photosensitive laminate in which the copper-clad laminate and the photosensitive layer were laminated in this order was prepared.

  About the photosensitive laminate, surface failure, tackiness, shortest development time, sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, pot life (storage stability), permanent pattern surface are respectively obtained by the following methods. The shape and edge roughness were evaluated. The results other than the shortest development time are shown in Table 2.

<Evaluation of sheet failure>
The coated surface of the photosensitive layer obtained above was visually observed to evaluate the surface failure of the coated surface. As the evaluation method of the surface failure, the number of surface failures (foreign matter, pigment aggregates, etc.) of less than 40 μm and the number of surface failures of 40 μm or more per 1 m ² of the surface of the photosensitive layer were counted. Based on the number, the planar faultiness was evaluated according to the following evaluation criteria. In Example 1, there were 12 surface faults of less than 40 μm and 1 surface fault of 40 μm or more, indicating an excellent coated surface state. The results are shown in Table 2. Incidentally, the addition of the color pigment was excellent in the visibility of the surface, and it was easy to count the number of surface failures.
-Evaluation criteria-
◯: Less than 20 surface faults of less than 40 μm and less than 3 surface defects of 40 μm or more showed excellent coated surface conditions.
△ ... 20 or less, less than 50 surface defects of less than 40 μm, or 3 or more and less than 30 surface defects of 40 μm or more, which is slightly inferior to the coated surface, but is practically problematic Don't be.
X: 50 or more surface failures of less than 40 μm, or 30 or more surface failures of 40 μm or more, which is extremely inferior to the coated surface.

<Evaluation of tackiness>
The tackiness of the surface of the photosensitive layer in the laminate obtained as described above was also evaluated based on the following criteria. The results are shown in Table 2.
〔Evaluation criteria〕
○: Strong tackiness was not observed on the surface of the photosensitive layer. Δ: Slight tackiness was observed on the surface of the photosensitive layer. ×: Strong tackiness was observed on the surface of the photosensitive layer.

<Evaluation of the shortest development time>
A 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa, and the photosensitive layer on the copper clad laminate is dissolved from the start of spraying of the sodium carbonate aqueous solution. The time required for removal was measured and this was taken as the shortest development time. The shortest development time was 14 seconds.

<Evaluation of sensitivity>
The photosensitive layer in the photosensitive laminate prepared above by using a pattern forming apparatus described below, the light energy different light from 0.1 mJ / cm ² to 100 mJ / cm ² at ^{2 1/2} times the interval Were exposed twice to cure a part of the photosensitive layer. After standing at room temperature for 10 minutes, a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed over the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa for twice the shortest development time. The uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve, the amount of light energy when the thickness of the cured region was the same 30 μm as that of the photosensitive layer before exposure was determined as the amount of light energy necessary for curing the photosensitive layer.

<< Pattern Forming Apparatus >>
A combined laser light source described in Japanese Patent Laid-Open No. 2005-258431 as the light irradiating means, and a micro-array in which 1,024 micromirrors 58 are arranged in the main scanning direction schematically shown in FIG. 6 as the light modulating means. The DMD 36 controlled to drive only 1,024 × 256 rows among 768 pairs of mirror rows arranged in the sub-scanning direction and the light shown in FIGS. 5A and 5B are imaged on the photosensitive film. The pattern forming apparatus 10 provided with the exposure head 30 having an optical system to be used was used.

As the set inclination angle of each exposure head 30, that is, each DMD 36, an angle slightly larger than the angle θ _{ideal at} which double exposure is performed using a usable 1,024 columns × 256 rows of micromirrors 58 was adopted. This angle θ _ideal corresponds to the number N of N double 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 state when the exposure head 30 is tilted. 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. 16, the pattern of light spots from the micromirror 58 usable by the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the photosensitive layer 12 with the stage 14 being stationary. showed that. 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. 16, for convenience of explanation, every other column exposure pattern of the micromirror 58 that can be used is divided into an exposure pattern by the pixel column group A and an exposure pattern by 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. 16, 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. 17 were identified as micromirrors that are not used during the main exposure.

Thereafter, the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered with the oblique lines in FIG. 17 were similarly covered with the shaded areas 82 and the shaded areas in FIG. Micromirrors corresponding to the light spots constituting the region 84 were identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. It was controlled not to be involved.
As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ , an ideal double exposure is performed in each area other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. Thus, the total area of the overexposed region and the underexposed region can be minimized.

<Evaluation of resolution>
The photosensitive laminate was prepared under the same method and conditions as the evaluation method for the shortest development time and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the photosensitive layer of the obtained photosensitive laminate, exposure of each line width is performed in increments of 1 μm from line / space = 1/1 to a line width of 10 to 100 μm using the pattern forming apparatus. The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer. After standing at room temperature for 10 minutes, the photosensitive layer on the copper-clad laminate was 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, Dissolve and remove uncured areas. The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, and the cured resin pattern line is free of irregularities such as lumps and twists, and the minimum line width that allows space formation is measured. This is the resolution. The smaller the numerical value, the better the resolution.

<Permanent pattern surface shape>
The permanent pattern surface (50 μm × 50 μm) formed in the resolution measurement was photographed with a scanning electron microscope (SEM), and the shape of the formed permanent pattern surface was evaluated according to the following evaluation criteria. The results are shown in Table 2.
-Evaluation criteria-
A: There are no defects or 1 to 5 defects, and the shape of the formed permanent pattern is not affected.
B: There are 6-10 defects, but the shape of the formed permanent pattern is not affected.
C: There are 11 to 20 defects, and the defects can cause a shape abnormality on the end face of the permanent pattern.
D: There are 21 or more defects, and the defects cause a shape abnormality on the end face of the permanent pattern.

<Evaluation of 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.
-Evaluation criteria-
○: 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 was observed, plating stagnation was observed, and peeling of the resist film was large in the peeling test.
--- Electroless gold plating process--
About the said photosensitive laminated body, after the patterning by the said laser exposure and image development, the whole surface exposure (post exposure) is carried out at 100 mJ / cm < ² > with an ultrahigh pressure mercury lamp, and the heat processing (post baking process) for 150 degreeC are performed. A test substrate as a printed circuit board on which a solder resist pattern (permanent pattern) is formed is immersed in an acidic degreasing solution (manufactured by Nihon McDermitt, 20% by mass aqueous solution of Metex L-5B) for 3 minutes, followed by running water. For 3 minutes and washed with water.
Next, after immersing in a 14.3% by mass antimony persulfate aqueous solution for 3 minutes at room temperature, after immersing in running water for 3 minutes and washing with water, and further immersing the test substrate in a 10% by mass sulfuric acid aqueous solution at room temperature for 1 minute, It was immersed in running water for 30 seconds to 1 minute and washed with water.
Next, the substrate was immersed in a 30 ° C. catalyst solution (Meltex, 10% by weight aqueous solution of metal plate activator 350) for 7 minutes, then immersed in running water for 3 minutes, and then washed at 85 ° C. with nickel. After dipping in a plating solution (Meltex, Melplate Ni-865M, 20 vol% aqueous solution, pH 4.6) for 20 minutes and performing electroless nickel plating, after dipping in a 10 wt% sulfuric acid aqueous solution at room temperature for 1 minute Then, it was immersed in running water for 30 seconds to 1 minute and washed with water.
Next, the test substrate was immersed in a gold plating solution at 75 ° C. (Okuno Pharmaceutical Co., Ltd., OPC Muden Gold, pH 12-13, thick gold plating 0.3 μm) for 4 minutes, and after electroless gold plating, After immersing in running water for 3 minutes and washing with water, further immersing in warm water at 60 ° C. for 3 minutes, washing thoroughly with water, drying, and electroless gold-plated test substrate was obtained.

<Through hole fillability>
As the substrate, a copper-clad laminate having an insulating layer thickness of 200 μm and a copper thickness of 18 μm and through-holes having a diameter of 100 μm at a pitch of 5 mm was prepared by subjecting the surface to chemical polishing treatment. On the copper-clad laminate, the photosensitive composition was applied by screen printing using a 120 mesh Tetron screen so that the thickness after drying was 30 μm, and then heated at 80 ° C. for 15 minutes with a hot air circulating dryer. The photosensitive layer is formed by drying, and the photosensitive layer is formed on the surface opposite to the side where the photosensitive layer is further formed by applying and drying the dried layer to a thickness of 30 μm. A photosensitive laminate in which a photosensitive layer was formed on both sides of a copper clad laminate was prepared. Thereafter, the vicinity of the through-hole portion was cut with scissors and polished with a sandpaper (roughing: # 600 and main cutting: # 1200) until the cross-section of the through-hole portion could be observed. The through-hole cross section was observed, and the embedding property was evaluated based on the following criteria.
〔Evaluation criteria〕
○: The through hole was completely embedded.
Δ: Slight voids were observed in the through hole, but 90% or more of the observed cross-sectional area was embedded.
X: A void was clearly recognized in the through hole, and the embedded area was less than 90% of the observed cross-sectional area.

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

<Evaluation of pot life>
The viscosity at 25 ° C. immediately after the preparation of the photosensitive composition solution and the viscosity after storage for 72 hours at 25 ° C. were measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Based on the viscosity, pot life was evaluated based on the following criteria.
〔Evaluation criteria〕
A: The viscosity after 72 hours is less than 1.5 times the viscosity immediately after preparation.
Δ: The viscosity after 72 hours is less than twice the viscosity immediately after preparation.
X: The viscosity after 72 hours is twice or more the viscosity immediately after the preparation.

(Example 2)
-Production of photosensitive film-
The photosensitive composition solution obtained in Example 1 was applied to a PET (polyethylene terephthalate) film having a thickness of 16 μm, a width of 300 mm, and a length of 200 m as the support with a bar coater, and dried at 80 ° C. with hot air circulation. It was dried in the machine to form a photosensitive layer having a thickness of 30 μm. Next, a polypropylene film having a thickness of 20 μm, a width of 310 mm, and a length of 210 m was laminated on the photosensitive layer as a protective film by lamination to produce the photosensitive film.

-Preparation of photosensitive laminate-
Next, on the same copper clad laminate as that of Example 1 as the substrate, the photosensitive film of the photosensitive film was in contact with the copper clad laminate, and the protective film on the photosensitive film was peeled off, and a vacuum laminator ( Nichigo Morton Co., Ltd., V130) was used to prepare a photosensitive laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order. .
The pressure bonding conditions were a 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.

  The photosensitive laminate was evaluated for sensitivity, resolution, electroless gold plating resistance, through hole embedding property, and edge roughness. The resolution, electroless gold plating resistance, and edge roughness were evaluated in the same manner as in Example 1. The results are shown in Table 2.

<Evaluation of sensitivity>
For the photosensitive layer of the photosensitive film in the prepared photosensitive laminate, a part of the photosensitive layer is cured from the support side in the same manner as in Example 1 by the pattern forming apparatus described in Example 1. It was. After leaving still at room temperature for 10 minutes, the said support body was peeled off from the said photosensitive laminated body, and it carried out similarly to Example 1, and measured the amount of light energy required in order to harden a photosensitive layer.

<Through hole fillability>
The substrate was prepared by subjecting a surface of a copper-clad laminate having an insulating layer thickness of 200 μm and a copper thickness of 18 μm and a through hole having a diameter of 100 μm to a pitch of 5 mm to a chemical polishing treatment. While peeling the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film is in contact with the copper-clad laminate on both surfaces of the copper-clad laminate, a vacuum laminator (Nichigo Morton Co., Ltd., V130 ) To prepare a photosensitive laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were a 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.
Thereafter, the embedding property was evaluated in the same manner as in Example 1.

(Example 3)
In Example 2, as shown in Table 1, TEPIC-S (thermal crosslinking agent) in the photosensitive composition was replaced with YX4000K (thermal crosslinking agent manufactured by Japan Epoxy Resin, epoxy equivalent of 187 g / eq.). Except for the above, in the same manner as in Example 2, the sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness were evaluated. The results are shown in Table 2.
The average particle size of the dispersion liquid in Example 3 was 0.22 μm, and the ratio of coarse particles of 1 μm or more was 0.02%.
Moreover, the average particle diameter in the photosensitive composition in Example 3 was 0.22 μm, and it did not aggregate when mixed, and the content of coarse particles of 5 μm or more was 0%.

Example 4
In Example 2, as shown in Table 1, TEPIC-S (thermal crosslinking agent) in the photosensitive composition was changed to YDC-1312 (thermal crosslinking agent manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 175 g / eq.). Except for the change, the evaluation of sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness was performed in the same manner as in Example 2. The results are shown in Table 2.
The average particle size of the dispersion in Example 4 was 0.25 μm, and the proportion of coarse particles of 1 μm or more was 0.03%.
Moreover, the average particle diameter in the photosensitive composition in Example 4 was not aggregated by mixing at 0.25 μm, and the content of coarse particles of 5 μm or more was 0%.

(Example 5)
In Example 2, as shown in Table 1, TEPIC-S (thermal crosslinking agent) in the photosensitive composition was changed to YSLV-120TE (thermal crosslinking agent manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 240 g / eq.). Except for the change, the evaluation of sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness was performed in the same manner as in Example 2. The results are shown in Table 2.
The average particle size of the dispersion in Example 5 was 0.24 μm, and the ratio of coarse particles of 1 μm or more was 0.02%.
Moreover, the average particle diameter in the photosensitive composition in Example 5 was 0.24 μm, and it did not aggregate when mixed, and the content of coarse particles of 5 μm or more was 0%.

(Example 6)
In Example 2, except that the polymer compound 1 in the photosensitive composition was replaced with the polymer compound 2 (87.4 parts by mass) obtained above as shown in Table 1. In the same manner as in Example 2, the sensitivity, resolution, electroless gold plating resistance, through hole embedding property, and edge roughness were evaluated. The results are shown in Table 2.
In addition, the average particle diameter of the dispersion liquid in Example 6 was 0.21 μm, and the ratio of coarse particles of 1 μm or more was 0.02%.
Moreover, the average particle diameter in the photosensitive composition in Example 6 was 0.21 micrometer, it did not aggregate by mixing, and content of the coarse particle of 5 micrometers or more was 0%.

(Example 7)
In Example 2, except that the polymer compound 1 in the photosensitive composition was replaced with the polymer compound 3 (50 parts by mass) obtained above as shown in Table 1, Example 2 and Similarly, sensitivity, resolution, electroless gold plating resistance, through hole embedding property, and edge roughness were evaluated. The results are shown in Table 2.
The average particle size of the dispersion in Example 7 was 0.32 μm, and the proportion of coarse particles of 1 μm or more was 0.05%.
Moreover, the average particle diameter in the photosensitive composition in Example 7 was 0.32 μm, and it did not aggregate when mixed, and the content of coarse particles of 5 μm or more was 0.01%.

(Example 8)
In Example 2, the photopolymerization initiator I-1 in the photosensitive composition was added to 2 parts by mass of a compound represented by the following formula I-2, and the sensitizer was 0.6 parts by mass of N-methylacridone. Except for substituting, sensitivity, resolution, electroless gold plating resistance, through hole embedding property, and edge roughness were evaluated in the same manner as in Example 2. The results are shown in Table 2.
Moreover, the average particle diameter in the photosensitive composition in Example 8 was 0.2 micrometer, it did not aggregate by mixing, and content of the coarse particle of 5 micrometers or more was 0%.

Example 9
In Example 3, as shown in Table 1, the photopolymerization initiator in the photosensitive composition was changed to 2 parts by mass of the compound represented by the formula I-2, as in Example 3. The sensitivity, resolution, electroless gold plating resistance, through hole embedding property, and edge roughness were evaluated. The results are shown in Table 2.
Moreover, the average particle diameter in the photosensitive composition in Example 9 was 0.22 μm, and it did not aggregate when mixed, and the content of coarse particles of 5 μm or more was 0%.

(Example 10)
In Example 4, as shown in Table 1, the photopolymerization initiator in the photosensitive composition was changed to 2 parts by mass of the compound represented by the following formula I-3, and was the same as Example 4. The sensitivity, resolution, electroless gold plating resistance, through hole embedding property, and edge roughness were evaluated. The results are shown in Table 2.
Moreover, the average particle diameter in the photosensitive composition in Example 10 was 0.25 μm, and it did not aggregate when mixed, and the content of coarse particles of 5 μm or more was 0%.

(Example 11)
In Example 5, the photopolymerization initiator was replaced with 2 parts by mass of the compound represented by the following formula I-4 as shown in Table 1. Electrolytic gold plating resistance, through-hole embedding, and edge roughness were evaluated. The results are shown in Table 2.
Moreover, the average particle diameter in the photosensitive composition in Example 11 was 0.24 μm, and it did not aggregate when mixed, and the content of coarse particles of 5 μm or more was 0%.

(Example 12)
In Example 2, instead of the pattern forming apparatus, a glass negative mask having the same pattern as this was separately prepared, and this negative mask was brought into contact with the photosensitive laminate, and exposure was performed at 40 mJ / cm ² with an ultrahigh pressure mercury lamp. Exposed in quantity. Thereafter, the sensitivity, resolution, electroless gold plating resistance, through hole embedding property, and edge roughness were evaluated in the same manner as in Example 2 except that development was performed in the same manner as in Example 2 and the resolution was measured. . The results are shown in Table 2.

(Example 13)
In Example 12, except for using the same photosensitive film as in Example 3, evaluation of sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness was performed in the same manner as in Example 12. It was. The results are shown in Table 2.

(Example 14)
In Example 2, in the photosensitive composition solution, as shown in Table 1, a mixture of a bisphenol A-based epoxy compound and a bisphenol F-based epoxy compound, which are liquid epoxy compounds (Epototo ZX-1059, manufactured by Tohto Kasei Co., Ltd.) , Epoxy equivalent 165 g / eq.) 5 parts by mass, and the dispersion solution was changed as follows, and the sensitivity, resolution, electroless gold plating resistance, through hole were the same as in Example 2. The embedding property and edge roughness of the film were evaluated. The results are shown in Table 2.
-Dispersion process-
As the dispersion, 30 parts by mass of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30), 2 parts by mass of silica (R974 manufactured by Nippon Aerosil Co., Ltd.), the polymer compound 1 (in the 1-methoxy-2-propanol solution) 29.2 parts by mass of a solid content of 30% by mass), 10 parts by mass of YX4000K (thermal crosslinking agent manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of 187 g / eq.), C.I. I. Pigment Blue 15: 3 0.2 parts by mass, C.I. I. After mixing 0.05 parts by weight of Pigment Yellow 185 and 40.55 parts by weight of methyl ethyl ketone in advance, a motor mill M-200 (manufactured by Eiger) was used to use zirconia beads having a diameter of 0.9 mm and a peripheral speed of 9 m / s. For 5 hours.
When the particle size distribution of the dispersion was measured using a particle size distribution meter (UPA-9340, manufactured by Nikkiso Co., Ltd.), the average particle size was 0.45 μm, and the ratio of coarse particles of 1 μm or more was 0.12%. .
Moreover, the average particle diameter in the photosensitive composition in Example 14 was 0.45 μm, and it did not aggregate when mixed, and the content of coarse particles of 5 μm or more was 0.03%.

(Example 15)
In Example 2, in the photosensitive composition solution, as shown in Table 1, a cresol novolak type epoxy resin (Dainippon Ink & Chemicals, Epicron N-695, epoxy) which is an epoxy compound of a solution-like epoxy compound, as shown in Table 1. (Equivalent 210 g / eq.) 2 parts by weight were added, and the dispersion solution was changed as follows, and the sensitivity, resolution, electroless gold plating resistance, through-hole embedding were the same as in Example 2. The properties and edge roughness were evaluated. The results are shown in Table 2.
-Dispersion process-
As the dispersion, 30 parts by mass of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30), the polymer compound 1 (solid content of 30% by mass in the 1-methoxy-2-propanol solution) solution 29.2 Parts by mass, 15 parts by mass of YX4000K (thermal crosslinking agent manufactured by Japan Epoxy Resin, epoxy equivalent of 187 g / eq.), C.I. I. Pigment Blue 15: 3 0.2 parts by mass, C.I. I. After mixing 0.05 parts by weight of Pigment Yellow 185 and 40.55 parts by weight of methyl ethyl ketone in advance, a motor mill M-200 (manufactured by Eiger) was used to use zirconia beads having a diameter of 0.9 mm and a peripheral speed of 9 m / s. And dispersed for 1 hour.
When the particle size distribution of the dispersion was measured using a particle size distribution meter (UPA-9340, manufactured by Nikkiso Co., Ltd.), the average particle size was 0.43 μm, and the ratio of coarse particles of 1 μm or more was 0.13%. there were.
Moreover, the average particle diameter in the photosensitive composition in Example 15 was 0.43 μm, and it did not aggregate when mixed, and the content of coarse particles of 5 μm or more was 0.03%.

(Example 16)
In Example 2, as shown in Table 1, in the photosensitive composition solution, a mixture of a bisphenol A-based epoxy compound and a bisphenol F-based epoxy compound, which are solution-like epoxy compounds (Etototo ZX-, manufactured by Toto Kasei Co., Ltd.). 1059, epoxy equivalent of 165 g / eq.) 5 parts by mass were added, and the dispersion solution was changed as follows. In the same manner as in Example 2, the sensitivity, resolution, electroless gold plating resistance, through The hole embeddability and edge roughness were evaluated. The results are shown in Table 2.
-Dispersion process-
As the dispersion, 30 parts by mass of barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., B30), polymer compound 1 (solid content of 30% by mass in the 1-methoxy-2-propanol solution) 29.2 masses of solution Part, YX4000K (thermal crosslinking agent manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 187 g / eq.) 10 parts by mass, C.I. I. Pigment Blue 15: 3 0.5 parts by mass, 0.2% by mass of dicyandiamide, and 40.55 parts by mass of propyl acetate were mixed in advance, and then a motor mill M-200 (manufactured by Eiger) was used. Using zirconia beads, it was prepared by dispersing for 1 hour at a peripheral speed of 9 m / s.
When the particle size distribution of the dispersion was measured using a particle size distribution meter (UPA-9340, manufactured by Nikkiso Co., Ltd.), the average particle size was 0.41 μm, and the ratio of coarse particles of 1 μm or more was 0.11%. .
Moreover, the average particle diameter in the photosensitive composition in Example 16 was 0.41 μm, and it did not aggregate when mixed, and the content of coarse particles of 5 μm or more was 0.05%.

(Example 17)
In the second embodiment, the set inclination angle θ is calculated with N = 1 based on the equation 3, the natural number T closest to the value t satisfying the relationship of t tan θ ′ = 1 is derived based on the equation 4, and N double exposure ( Except for performing N = 1), the evaluation of sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness was performed in the same manner as in Example 2. The results are shown in Table 2.

(Example 18)
In Example 2, except that the dispersion was prepared by using zirconia beads having a diameter of 3 mm and dispersing for 2 hours at a peripheral speed of 9 m / s, the sensitivity, resolution, electroless gold plating resistance, through hole were the same as in Example 2. The embedding property and edge roughness of the film were evaluated. The results are shown in Table 2.
The average particle size of the dispersion in Example 18 was 1.61 μm, and the ratio of coarse particles of 5 μm or more was 0.8%.
Moreover, the average particle diameter in the photosensitive composition in Example 18 was 1.6 μm, and it did not aggregate when mixed, and the content of coarse particles of 5 μm or more was 0.8%.

Example 19
In Example 2, the sensitivity, resolution, electroless gold plating resistance, through hole were the same as in Example 2 except that the dispersion was prepared by using zirconia beads having a diameter of 2 mm and dispersing for 2 hours at a peripheral speed of 9 m / s. The embedding property and edge roughness of the film were evaluated. The results are shown in Table 2.
The average particle size of the dispersion in Example 19 was 0.92 μm, and the ratio of coarse particles of 5 μm or more was 0.1%.
Moreover, the average particle diameter in the photosensitive composition in Example 19 was 0.92 μm, and it did not aggregate when mixed, and the content of coarse particles of 5 μm or more was 0.1%.

(Example 20)
In Example 2, except that the dispersion was prepared by using zirconia beads having a diameter of 1.5 mm for 2 hours at a peripheral speed of 9 m / s, sensitivity, resolution, electroless gold plating resistance, Through hole embedding and edge roughness were evaluated. The results are shown in Table 2.
The average particle size of the dispersion in Example 19 was 0.76 μm, the ratio of coarse particles of 2 μm or more was 0.7%, and the ratio of coarse particles of 5 μm or more was 0.09%.
Moreover, the average particle diameter in the photosensitive composition in Example 19 is 0.76 μm and does not aggregate when mixed, and the content of coarse particles of 2 μm or more is 0.7%, which is 5 μm or more. The content of coarse particles was 0.09%.

(Example 21)
In Example 2, except that the dispersion was prepared by using zirconia beads having a diameter of 1.2 mm for 2 hours at a peripheral speed of 9 m / s, sensitivity, resolution, electroless gold plating resistance, Through hole embedding and edge roughness were evaluated. The results are shown in Table 2.
The average particle size of the dispersion in Example 19 was 0.58 μm, the ratio of coarse particles of 2 μm or more was 0.2%, and the ratio of coarse particles of 5 μm or more was 0.05%.
Moreover, the average particle diameter in the photosensitive composition in Example 19 is 0.58 μm and does not aggregate when mixed, and the content of coarse particles of 2 μm or more is 0.2%, which is 5 μm or more. The content of coarse particles was 0.05%.

(Comparative Example 1)
In Example 1, the dispersing step was not performed, and in the mixing step, all the components were mixed and then kneaded with three rolls for 4 hours to prepare a photosensitive composition. Using the resulting photosensitive composition, a photosensitive film was produced in the same manner as in Example 2 to prepare a photosensitive laminate.
Using the obtained photosensitive laminate, the sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness were evaluated in the same manner as in Example 2. The results are shown in Table 2.
The average particle diameter of the thermal crosslinking agent and the pigment in Comparative Example 1 was 3.2 μm.
Moreover, the average particle diameter in the photosensitive composition in Comparative Example 1 was 3.2 μm, and it did not aggregate when mixed, but the content of coarse particles of 5 μm or more was 5%.

(Comparative Example 2)
In Example 2, the sensitivity, resolution, electroless gold plating resistance, through-hole embedding property, and edge roughness were the same as in Example 2 except that the photosensitive composition was prepared as follows. Was evaluated. The results are shown in Table 2.

-Preparation of photosensitive composition-
By the following process, each component was mix | blended with the following quantity, and the photosensitive composition solution was prepared.
[Amount of each component of the resin composition]
-High molecular compound 4 ... 500 parts by mass-2-Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (photopolymerization initiator, Iruigure 907 manufactured by Ciba-Geigy) ) ... 40 parts by mass. 2,4-diethylthioxanthone (DETX-S manufactured by Nippon Kayaku Co., Ltd.) .. 4 parts by mass. Thermosetting accelerator (dicyandiamide) .. 3 parts by mass. Phthalocyanine green (color pigment) , Cyanine Green TK manufactured by Toyo Ink Manufacturing Co., Ltd.) 5 parts by mass, fine silica (thixotropic agent, nip seal E-220 manufactured by Nippon Silica Kogyo Co., Ltd.) 20 parts by mass, talc (extreme pigment) ... 80 parts by mass Parts / antifoaming agent (silicone): 15 parts by mass

  In the composition, components other than the epoxy compound and the antifoaming agent were premixed and then sufficiently kneaded with a three-roll mill. Next, the kneaded product and the antifoaming agent were mixed with a small planetary mixer to obtain a resin composition.

[Each component amount of epoxy dispersion]
Epoxy compound 1; triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, TEPIC-S, epoxy equivalent 100 g / eq.) 100 parts by mass Epoxy compound 2; phenol novolac type epoxy resin (Dainippon Ink and Chemicals, Inc.) Manufactured, Epicron N-730) ... 30 parts by mass NK ester A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd., ethylenically unsaturated trimethylolpropane triacrylate) ... 140 parts by mass Cellosolve acetate (organic solvent) 60 parts by mass Take 100 parts by mass of the epoxy compound 1 (TEPIC-S), 30 parts by mass of the epoxy compound 2 (Epiclon N-730), and 60 parts by mass of the cellosolve acetate (organic solvent) in a flask. The solution was heated to a temperature and completely dissolved. Next, after cooling to 80 ° C., 140 parts by mass of the NK ester A-TMPT was added with a predetermined amount while blowing air, further cooled and recrystallized, and dispersed using a sand mill, A dispersion was obtained.
The average particle size of the epoxy dispersion was 1 μm when the particle size distribution was measured using a light scattering particle size distribution meter.

The resin composition obtained above and the epoxy dispersion were sufficiently mixed to prepare a photosensitive composition of Comparative Example 2.
The average particle size in the photosensitive composition of Comparative Example 2 was 4.1 μm, and it was found that the pigment was not sufficiently finely divided by mixing. The content of coarse particles of 5 μm or more was 11%.

From the result of Table 2, in Examples 1-21, since the photosensitive composition of this invention whose average particle diameter of particle | grains is 2 micrometers or less is used, pot life is long, tack property, surface failure, surface shape, edge It was found to be excellent in roughness, electroless gold plating resistance and through hole embedding. In particular, in Examples 2 to 21 in which photosensitive films were produced, it was found that the sensitivity was excellent and the resolution was high. Moreover, in Examples 1-11 and 14-21 which performed laser exposure, it turned out that it is excellent in edge roughness.
On the other hand, it was found that the patterns of Examples 1 to 11 and 18 to 21 in which the variation in resolution and the exposure unevenness in the double exposure were corrected also had small edge roughness.

The photosensitive composition of the present invention, and the photosensitive film and photosensitive laminate using the same, have an average particle size of 2 μm or less, and thus have a long pot life, tackiness, and surface failure. Excellent surface shape, edge roughness, high sensitivity and high resolution, excellent electroless gold plating resistance, via and through-hole embedding, and can efficiently form high-definition permanent patterns. Suitable for various pattern formation such as insulating film and permanent pattern such as solder resist pattern, manufacturing of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, etc. In particular, it can be suitably used for forming a permanent pattern on a printed circuit board.
In the method for producing a photosensitive composition of the present invention, the average particle size of the particles in the photosensitive composition can be 2 μm or less, the pot life is long, and tackiness, surface failure, surface shape, and edge roughness are reduced. Protective film because it can easily and efficiently produce a photosensitive composition with excellent, high sensitivity, high resolution, electroless gold plating resistance, via and through hole embedding, and capable of forming high-definition permanent patterns. Suitable for various pattern formation such as permanent pattern such as interlayer insulation film and solder resist pattern, manufacture of liquid crystal structure members such as color filter, pillar material, rib material, spacer, partition wall, hologram, micromachine, proof In particular, it can be suitably used for forming a permanent pattern on a printed circuit board.
Since the permanent pattern forming method of the present invention uses the photosensitive laminate of the present invention, it is used for forming various patterns such as a protective film, an interlayer insulating film, a permanent pattern such as a solder resist pattern, a color filter, a column material, It can be suitably used for the production of liquid crystal structural members such as ribs, spacers and partition walls, the production of holograms, micromachines, and proofs, and can be particularly suitably used for the formation of permanent patterns on printed boards.

FIG. 1 is a perspective view showing an appearance of an example of a pattern forming apparatus. FIG. 2 is a perspective view showing an example of the configuration of the scanner of the pattern forming apparatus. FIG. 3A is a plan view showing an exposed region formed on the exposed surface of the photosensitive layer. FIG. 3B is a plan view showing an arrangement of exposure areas by each exposure head. FIG. 4 is a perspective view showing an example of a schematic configuration of the exposure head. FIG. 5A is a top view showing an example of a detailed configuration of the exposure head. FIG. 5B is a side view showing an example of a detailed configuration of the exposure head. FIG. 6 is a partially enlarged view showing an example of the DMD of the pattern forming apparatus of FIG. FIG. 7A is a perspective view for explaining the operation of the DMD. FIG. 7B is a perspective view for explaining the operation of the DMD. FIG. 8 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is an exposure head mounting angle error and pattern distortion. FIG. 9 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit. FIG. 10 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 11 is an explanatory diagram showing a state in which unevenness generated in a pattern on an exposed surface is improved as a result of using only selected micromirrors for exposure. FIG. 12 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift between adjacent exposure heads. FIG. 13 is a top view showing a positional relationship between an exposure area by two adjacent exposure heads and a corresponding slit. FIG. 14 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 15 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 12 are actually moved and the unevenness in the pattern on the exposed surface is improved. FIG. 16 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift and a mounting angle error between adjacent exposure heads. FIG. 17 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG. FIG. 18A is an explanatory diagram showing an example of magnification distortion. FIG. 18B is an explanatory diagram showing an example of beam diameter distortion. FIG. 19A is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 19B is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 20 is an explanatory diagram showing a first example of reference exposure using a plurality of exposure heads. FIG. 21A is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 21B is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 22 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads.

Explanation of symbols

10 pattern forming device 12 photosensitive laminate (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)
111 Multicavity laser 113 Rod lens 114 Lens array 140 Laser array

Claims (13)

  A photosensitive composition comprising a binder, a polymerizable compound, a photopolymerization initiator, a pigment, and a thermal crosslinking agent, and having an average particle diameter of 2 μm or less.   The photosensitive composition according to claim 1, wherein the pigment and the thermal crosslinking agent include a dispersion, and an average particle diameter thereof is 2 μm or less.   The photosensitive composition according to claim 1, wherein the content of coarse particles of 5 μm or more is 1% or less.   The thermal crosslinking agent is an epoxy compound, and the epoxy compound is at least one selected from a novolac type epoxy compound, a bisphenol type epoxy compound, a heterocyclic ring-containing epoxy compound, and an alicyclic epoxy compound. 4. The photosensitive composition according to any one of 3.   The photosensitive composition according to claim 4, wherein the thermal crosslinking agent is a crystalline epoxy compound having a melting point of 60 ° C. or higher.   The photosensitive composition in any one of Claim 1 to 5 in which a pigment contains at least 1 sort (s) selected from an organic pigment and an inorganic pigment.   The mixture of a dispersion containing at least a pigment and a thermal cross-linking agent, finely dispersed to have an average particle size of 2 μm or less, a binder, a polymerizable compound, and a photopolymerization initiator. The photosensitive composition in any one.   The photosensitive composition in any one of Claim 1 to 7 containing a thermosetting accelerator.   The binder comprises at least one polymer compound selected from at least one epoxy acrylate compound and at least one vinyl copolymer having a (meth) acryloyl group and an acid group in the side chain. Item 9. The photosensitive composition according to any one of Items 1 to 8. It is a manufacturing method of the photosensitive composition in any one of Claim 1 to 9, Comprising:
A dispersion step in which at least a pigment and a thermal cross-linking agent are finely divided and dispersed to form a dispersion;
A mixing step of mixing the dispersion, a binder, a polymerizable compound, and a photopolymerization initiator;
Having at least
A method for producing a photosensitive composition, comprising obtaining a photosensitive composition having an average particle diameter of 2 μm or less.   A photosensitive film comprising a support and a photosensitive layer comprising the photosensitive composition according to claim 1 on the support.   The photosensitive layer in the photosensitive laminated body which has a photosensitive layer formed with either the photosensitive composition in any one of Claims 1-9, and the photosensitive film of Claim 11 on a base | substrate. A method of forming a permanent pattern, comprising performing exposure. A printed circuit board, wherein a permanent pattern is formed by the permanent pattern forming method according to claim 12.