TWI403837B - Photo-sensitive composition, photo-sensitive film, permanent pattern-forming method using the same and printing substrate - Google Patents

Abstract

This invention provides a photosensitive composition, which can simultaneously realize excellent storage stability and high sensitivity and can form a permanent pattern such as a protective film or an insulating film with high definition in an efficient manner, a photosensitive film, a method for permanent pattern formation using the photosensitive composition, and a printed board comprising a permanent pattern formed by the method for permanent pattern formation. In a preferred embodiment, the photosensitive composition satisfies a relationship of 0.5 < T<SUB>2</SUB>/T<SUB>1</SUB> < 3 WHEREIN T<SUB>1</SUB> represents a time (shortest development time) necessary for removing an unexposed part of a photosensitive composition stacked on a base with a developing solution after stacking of a photosensitive composition containing at least a binder, a polymerizable compound, a photopolymerization initiator, and a heat crosslinking agent onto a base and standing of the stacked photosensitive composition at 25ºC in a dark place for 20 min; and T<SUB>2</SUB> represents a time (shortest development time) necessary for removing an unexposed part of the photosensitive composition stacked on the base with a developing solution after standing of the stacked photosensitive composition at 40ºC in a dark place for 72 hr.

Description

Photosensitive composition, photosensitive film, permanent pattern forming method using the same, and printed circuit board

The present invention relates to a photosensitive composition capable of forming a high-definition pattern (a protective film, an interlayer insulating film, a solder resist pattern, etc.) excellent in sensitivity, resolution, and storage stability with good efficiency, and using the photosensitive film. A permanent pattern forming method of a photosensitive composition, and a printed substrate of a permanent pattern formed by the permanent pattern forming method.

In the past, when a permanent pattern such as a solder resist pattern is formed, a photosensitive film which is formed by applying a photosensitive composition on a support and drying it is always used.

In the method for producing a permanent pattern described above, for example, a photosensitive film may be laminated on a substrate of a copper-clad laminate or the like on which the permanent pattern is formed to form a laminate, and the photosensitive layer in the laminate may be exposed. After the exposure, the photosensitive layer is developed to form a pattern, and then the permanent pattern is formed by performing a hardening treatment or the like.

With respect to the above-mentioned photosensitive composition, a photosensitive composition for the purpose of achieving stability and the like has been proposed, which includes a (meth)acryl fluorenyl group having an aliphatic hydroxy group having 1 to 6 carbon atoms. A polymer compound having a (meth) acrylate compound having an epoxy group added to a copolymer of (meth)acrylic acid (see Patent Document 1).

Further, a photosensitive composition which achieves the same purpose as the foregoing has been proposed, and includes 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. (Refer to Patent Document 2).

Further, a photosensitive composition for improving the properties such as heat resistance and chemical resistance is proposed, which comprises polymerizing an adhesive having an unsaturated double bond and holding a specific range of acid value and molecular weight in the composition. An epoxy resin having an unsaturated double bond and holding a specific acid value and an epoxy equivalent (refer to Patent Document 3).

However, even in such photosensitive compositions, the sensitivity and storage stability are not sufficient, especially when the latent image is formed by laser scanning exposure, since the hardening of the exposed portion is insufficient, it is feared In the case where the image portion is removed in the alkaline development step, when the photosensitive composition is thinned into a long cylindrical state, the end face is melted over time, and When the fused portion is laminated, the exposure surface of the laminated body is lowered to cause a problem such as breakage of the exposure pattern during exposure.

Further, in the photosensitive composition using an alkali-soluble epoxy resin, the adhesion between the substrate and the substrate was poor during the metal plating treatment, and the photosensitive composition was found to be bulged and observed. A problem that causes the phenomenon of plating potential.

Therefore, the current state of the art is that a high-definition pattern (protective film, interlayer insulating film, solder resist pattern, etc.) which is excellent in sensitivity, resolution, and storage stability can be formed with good efficiency by using a specified polymer. The photosensitive composition, the photosensitive film, the pattern forming method using the photosensitive composition, and the printed circuit board of the permanent pattern formed by the permanent pattern forming method are further desired to be further improved.

[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei.

The present invention has been made in view of the above-mentioned circumstances, and is to solve the above-mentioned problems of the prior art, and to achieve the following objects. In other words, the object of the present invention is to provide a photosensitive composition which is excellent in temporal development stability and which can form a high-definition pattern (protective film, interlayer insulating film, solder resist pattern, etc.) with good efficiency. A photosensitive composition, a photosensitive film, a permanent pattern forming method using the photosensitive composition and the photosensitive film, and a permanent printed circuit board formed by the permanent pattern forming method.

The means for solving the above problems are as follows. That is, <1> a photosensitive composition characterized by comprising at least a photosensitive composition of a binder, a polymerizable compound, a photopolymerization initiator compound, and a thermal crosslinking agent; The composition is deposited on the substrate, and after 20 minutes in the dark at 25 ° C, the time required for the unexposed portion of the photosensitive composition deposited on the substrate to be removed by the developing solution (the shortest development time) is removed by the developing solution. It is denoted as T ₁ ; and for the photosensitive composition laminated on the substrate, the photosensitive layer is placed in a dark place at 40 ° C for 72 hours, and the layer deposited on the substrate is removed by a developing solution. The time required for the unexposed portion of the photosensitive composition (the shortest development time) is expressed as T ₂ and satisfies the relationship of 0.5 < T ₂ / T ₁ < 3.

The photosensitive composition as described in the above <1>, wherein the binder includes a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain.

The photosensitive composition according to any one of the above aspects, wherein the binder is a polymer compound having a cyclic ether group added to the polymer compound in the presence of a catalyst. a part of the acidic group and a polymer which is obtained by adding a carboxyl group-containing polymerizable compound to a part or all of the cyclic ether group of the polymer compound in the presence of a catalyst. a compound; and the aforementioned catalyst is arbitrarily selected from the group consisting of an acidic compound and a neutral compound.

The photosensitive composition according to any one of the above aspects, wherein the binder comprises an aromatic group having an acidic group in a side chain, a heterocyclic group, and an ethylenic unsaturated group. The polymer compound of the bond.

The photosensitive composition of any one of the above-mentioned <2>, wherein the polymer compound contains an ethylenically unsaturated bond of 0.5 to 3.0 meq/g.

The photosensitive composition of any one of the above-mentioned <2>, wherein the polymer compound has a carboxyl group in a side chain, and the content of the carboxyl group in the polymer compound is 1.0~. 4.0 meq/g.

The photosensitive composition of any one of the above-mentioned <2>, wherein the polymer compound has an average molecular weight of 10,000 or more and less than 100,000.

The photosensitive composition of any one of the above-mentioned <2> to <7>, wherein the polymer compound contains 20 mol% or more of the structural unit represented by the following structural formula (I); However, in the above structural formula (I), R ₁ , R ₂ and R ₃ represent a hydrogen atom or a monovalent organic group; L represents an organic group, if not, and Ar represents a heterocyclic ring. Aromatic group.

The photosensitive composition of any one of the above-mentioned <1> to <8>, wherein the polymerizable compound is a compound which has one or more ethylenically unsaturated bonds.

The photosensitive composition according to any one of the above-mentioned <1>, wherein the polymerizable compound is at least one selected from the group consisting of a (meth)acryl group.

The photosensitive composition as described in any one of <1> to <10> wherein the photopolymerization initiator includes a halogenated hydroxy derivative, a hexaarylbiimidazole, an organic peroxide, and sulfur. At least one selected from the group consisting of a compound, a ketone compound, an aromatic onium salt, a metallocene, and a fluorenylphosphine oxide compound.

The photosensitive composition of any one of the above-mentioned <1>, wherein the thermal crosslinking agent is an epoxy compound, an oxetane group, a polyisocyanate compound, and a polyisocyanate. At least one selected from the group consisting of a compound obtained by a reaction of a block agent and a melamine derivative.

The photosensitive composition of any one of the above-mentioned <1> to <12>, wherein the thermal crosslinking agent is alkali-insoluble.

The photosensitive composition of any one of the above-mentioned <1> to <13>, wherein the Mohr ratio of the crosslinking group of the thermal crosslinking agent / the molar ratio of the acidic group of the binder is 0.1~ 1.5.

The photosensitive composition of any one of the above-mentioned <1> to <13>, wherein the Mohr ratio of the crosslinking group of the thermal crosslinking agent / the molar ratio of the acidic group of the binder is 0.2~ 1.3.

The photosensitive composition of any one of the above-mentioned <1> to <13>, wherein the Mohr ratio of the crosslinking group of the thermal crosslinking agent / the molar ratio of the acidic group of the binder is 0.3~ 1.2.

The photosensitive composition of any one of the above-mentioned <1> to <16>, wherein the photosensitive composition is a sensitizer.

The photosensitive composition of any one of the above-mentioned <1> to <17>, wherein the sensitizer is a heterocyclic ring-based compound.

The photosensitive composition according to any one of the above-mentioned <1>, wherein the photosensitive composition has at least one of the following: a partial structural substitution The total amount of the solvent-soluble components of the group is 5% or less, and the component amount of all the bases having a partial substituent in the structure is 7% or less.

The photosensitive composition according to any one of the above-mentioned <1>, wherein the photosensitive composition has at least one of the following: a partial structurally substituted base The total amount of the solvent-soluble components of the group is 4% or less, and the component amount of all the bases having a partial substituent in the structure is 5% or less.

The photosensitive composition according to any one of the above-mentioned <1>, wherein the photosensitive composition has at least one of the following: a partial structural substitution The total amount of the solvent-soluble components of the group is 2% or less, and the component amount of all the bases having a partial substituent in the structure is 4% or less.

The photosensitive composition according to any one of the above-mentioned <1>, wherein the photosensitive composition has at least one of the following: a partial structural substitution The total amount of the solvent-soluble components of the group is 1% or less, and the component amount of all the bases having a partial substituent in the structure is 2% or less.

The photosensitive composition of any one of the above-mentioned <19> to <22>, wherein the base substituent is a 1st to 3rd amino group, a 4th ammonium group, and an amine group III. The base group, the imidazole group, and the guanamine group are optionally selected.

<24> preceding <1> to <23> The photosensitive composition of any one of claims, wherein T ₁ is 5 to 120 seconds, and T ₂ is 5 to 240 seconds.

The photosensitive composition of any one of the above-mentioned <1> to <24> which does not change the exposed part of the photosensitive layer after the exposure and imaging in the said exposure. The minimum energy of the thickness of light is 0.1 to 500 mJ/cm ² .

The photosensitive composition of any one of the above-mentioned <1> to <25>, wherein the photopolymerization initiator is arbitrarily selected from the fluorenyl phosphine oxide compound and the ketone compound.

<27> A photosensitive film comprising a support and a photosensitive layer formed of the photosensitive composition according to any one of the above <1> to <26>.

<28> The photosensitive film according to the above <27>, which has a thermoplastic resin layer and a photosensitive layer in this order on the support.

The photosensitive film as described in any one of the above-mentioned <27> to <28>, which is a long shape, and is wound into a cylindrical shape.

The photosensitive film of any one of the above-mentioned <27>, wherein the photosensitive layer has a thickness of 1 to 100 μm.

The photosensitive film of any one of the above-mentioned <27>, wherein the support system contains a synthetic resin and is transparent.

The photosensitive film as described in any one of the above-mentioned <27> which has a protective film on the photosensitive layer.

<33> A permanent pattern forming device having at least a light irradiation mechanism that can illuminate light, and a light that is modulated from the light irradiation mechanism, and by any one of <1> to <26> as described above The photosensitive composition described above is coated on a surface of a substrate and dried to form a photosensitive layer for exposure. In the permanent pattern forming apparatus according to the above <33>, the light irradiation means is configured to illuminate the light modulation means. The light modulation mechanism adjusts the received light from the light irradiation means. The light that is modulated by the optical modulation mechanism is exposed to the photosensitive layer. For example, when the development of the aforementioned photosensitive layer is performed, a high-definition pattern can be formed. A permanent pattern forming method characterized in that exposure is performed and development is performed.

<34> A permanent pattern forming apparatus comprising the photosensitive film according to any one of <27> to <32>, wherein at least the light irradiation means capable of illuminating light and the modulation are derived from the light irradiation A light modulation mechanism that exposes the light of the mechanism and exposes the photosensitive layer in the photosensitive composition. In the permanent pattern forming apparatus according to the above <34>, the light irradiation means is configured to illuminate the light modulation means. The light modulation mechanism adjusts the received light from the light irradiation means. The light that is modulated by the optical modulation mechanism is exposed to the photosensitive layer. For example, when the development of the aforementioned photosensitive layer is performed, a high-definition pattern can be formed.

The permanent pattern forming apparatus according to any one of the above-mentioned <33>, wherein the pattern signal generating means for generating a control signal based on the pattern information formed by the optical modulation means is further provided. It is configured to modulate the light irradiated from the light irradiation means in accordance with a control signal generated by the pattern signal generating means. In the permanent pattern forming apparatus according to the above <35>, the optical modulation mechanism described above is provided with the pattern signal generating means described above, and is modulated by the control signal generated by the pattern signal generating means. Light emitted from the light irradiation mechanism.

The permanent pattern forming apparatus according to any one of the above-mentioned <33>, wherein the light modulation mechanism is composed of n pixel parts and is capable of following the formed pattern information. It is controlled that less than n of the aforementioned pixel parts are continuously arranged in the n pixel parts. In the permanent pattern forming apparatus according to the above <36>, by controlling the pattern elements to control any of the n pixel elements that are continuously arranged in the n pixel elements in the light modulation mechanism, It is possible to modulate the light irradiated from the aforementioned light irradiation means at a high speed.

The permanent pattern forming apparatus according to any one of the items <33> to <36> wherein the optical modulation means is a spatial light modulation element.

<38> The permanent pattern forming device according to the above <37>, wherein the spatial light modulation element is a digital microlens device (DMD).

The permanent pattern forming apparatus according to any one of the items <36> to <38> wherein the pixel portion is a microlens.

The permanent pattern forming apparatus according to any one of the above-mentioned items, wherein the light-irradiating means can combine two or more lights to perform irradiation. In the permanent pattern forming apparatus according to the above <40>, the light irradiation means that can illuminate by combining two or more lights is used to expose the light with a deep exposure depth. As a result, the exposure of the aforementioned photosensitive layer can be performed with extremely high definition. For example, when the development of the photosensitive layer is performed, an extremely fine pattern can be formed.

The permanent pattern forming apparatus according to any one of the above-mentioned items, wherein the light-irradiating mechanism has a plurality of lasers, a multimode optical fiber, and each of the plurality of lasers is irradiated The laser light is collected to form a collection optical system in combination with the aforementioned multimode optical fiber. In the permanent pattern forming apparatus according to the above <41>, the light irradiation means collects laser light that is individually irradiated from the plurality of laser beams by the above-described collective light system, and can be combined. The above-mentioned multimode optical fiber is exposed to light having a deep exposure depth. As a result, the exposure of the aforementioned photosensitive layer can be performed with extremely high definition. For example, when the development of the photosensitive layer is performed, an extremely fine pattern can be formed.

The method of forming a permanent pattern according to any one of the above-mentioned <27> to <32>, wherein at least one of the above-mentioned <27> to <32> is used in at least one of the heating and the pressurization. After the photosensitive layer is laminated on the surface of the substrate, the photosensitive layer is exposed.

<43> The permanent pattern forming method according to the above <42>, wherein the exposure system uses laser light having a wavelength of 350 to 415 nm.

The permanent pattern forming method according to any one of <42> to <43> wherein the exposure is based on the formed pattern information to form an image pattern.

The method for forming a permanent pattern according to any one of the above-mentioned items, wherein the exposure system uses an exposure head, which is provided with a light irradiation mechanism, and has light received from the light irradiation mechanism and is given a pixel unit of a quadratic arrangement in which n (but, n is a natural number of 2 or more), an exposure head capable of controlling the optical modulation mechanism of the pixel unit in response to pattern information, and configured The column direction of the pixel portion and the scanning direction of the exposure head are formed to form a predetermined set inclination angle θ, and the exposure head is used among the aforementioned pixel portions by using the pixel portion specifying mechanism. Specifying the aforementioned pixel portion for N exposure (however, N is a natural number of 2 or more); for the above-mentioned exposure head, by the pixel portion control mechanism, according to the above-mentioned use of the pixel specifying mechanism The specified pixel portion is subjected to exposure to control the pixel portion; and the exposure head is moved in the scanning direction to expose the photosensitive layer. In the permanent pattern forming method according to the above <45>, in the exposure head described above, the pixel portion specifying means is used to specify N exposures among the available pixel portions (however, a step of the aforementioned pixel portion of N being a natural number of 2 or more; and controlling by the pixel control unit in such a manner that only the aforementioned pixel portion specified by the use of the pixel specifying unit is involved in exposure The aforementioned picture part. Exposing the photosensitive layer to the exposure head by moving the exposure head relative to the scanning direction may cause the pattern formed on the exposed surface of the photosensitive layer due to variations in the mounting position and the mounting angle of the exposure head. The variation of resolution and the phenomenon of density heterogeneity are uniformized. As a result, the exposure of the photosensitive layer is performed with high precision, and then a high-definition pattern is formed by performing development of the photosensitive layer.

<46> The permanent pattern forming method according to the above <45>, wherein the exposure system is performed by a plurality of exposure heads, and the exposed portion formed by the plurality of exposure heads is used by the pixel portion specifying means. In the pixel portion participating in the exposure of the inter-head contact region of the repeated exposure range, the pixel portion used for realizing N exposure in the inter-head contact region is designated. In the permanent pattern forming method according to the above <46>, the exposure is performed by a plurality of exposure heads, and the pixel portion specifying means is used to repeatedly expose the exposed surface formed by the plurality of exposure heads. In the pixel portion of the range of the head-to-head contact area, the pixel portion for use in the N-th exposure is specified in the inter-head contact region, whereby the mounting position of the exposure head is The variation in the mounting angle causes the variation in the resolution of the pattern formed on the exposed surface of the photosensitive layer and the density unevenness to be uniformized. As a result, the exposure of the photosensitive layer described above is performed with high precision. For example, a high-definition pattern is then formed by performing the development of the aforementioned photosensitive layer.

<47> The permanent pattern forming method according to the above <46>, wherein the exposure system is performed by a plurality of exposure heads, and the exposed surface formed by the plurality of exposure heads is used by the pixel portion specifying means. In the pixel portion participating in the exposure other than the inter-head contact region of the repeated exposure range, the pixel portion used for realizing N exposure in the region other than the inter-head contact region is specified. In the permanent pattern forming method according to the above <47>, the exposure system can be performed by a plurality of exposure heads, and the pixel portion specifying means is used to repeat from the exposed surface formed by the plurality of exposure heads. In the pixel portion participating in the exposure other than the connection region between the heads of the exposure range, the aforementioned pixel portion used for realizing N exposure in the region other than the inter-head contact region may be specified as described above. The variation in the resolution of the pattern formed on the exposed surface of the photosensitive layer and the density unevenness are uniformized by variations in the mounting position and the mounting angle of the exposure head. As a result, the exposure of the photosensitive layer described above is performed with high precision. For example, a high-definition pattern is then formed by performing development of the aforementioned photosensitive layer.

The permanent pattern forming method according to any one of the above-mentioned, wherein the set inclination angle θ is set to have a relationship conforming to θ ≧ θ _ideal , and the aforementioned θ _{ideal is} relative to The number N of N exposures, the number s of the direction of the pixel portion, the interval p between the directions of the pixel portions, and the direction perpendicular to the scanning direction of the exposure head when the exposure head is inclined The distance δ between the column directions of the pixel portion is in accordance with the following formula: s psin θ _ideal ≧N δ.

The method of forming a permanent pattern according to any one of the above-mentioned <45>, wherein the N-time exposure N is a natural number of 3 or more. In the permanent pattern forming method according to the above <49>, the multi-drawing is performed by setting N of the N exposures to a natural number of 3 or more. As a result, due to the effect of the correction, the variation of the resolution and the density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to the variation in the mounting position and the mounting angle of the exposure head can be made more precise. The ground is uniform.

The permanent pattern forming method according to any one of the aspects of the present invention, wherein the pixel portion specifying means includes: a spot position detecting means for detecting a via element a mechanism for generating a position of a spot on the surface to be exposed which is a pixel unit of an exposure range on the exposed surface; and a pixel selection mechanism that is detected based on the spot position detecting means As a result, the mechanism for realizing the pixel portion used for N exposures is selected.

The permanent pattern forming method according to any one of the above-mentioned <45>, wherein the pixel specifying means is used to specify a use factor for use in N exposures in units of rows. unit.

The method of forming a permanent pattern according to any one of the above-mentioned items, wherein the spot position detecting means defines the exposure based on the detected at least two spot positions. When the head is inclined, the direction of the light spot on the exposed surface is substantially inclined angle θ ' formed by the scanning direction of the exposure head, and the pixel selection mechanism is configured to absorb the aforementioned substantial tilt angle θ ' The pixel portion is selected in such a manner as to set an error between the tilt angles θ.

<53> The permanent pattern forming method according to the above <52>, wherein the substantial inclination angle θ′ is a direction of the light spot on the exposed surface and a scan of the exposure head in a state where the exposure head is tilted Any of a plurality of substantial tilt angles formed by the direction, a median value, a maximum value, and a minimum value.

The permanent pattern forming method according to any one of the items <50> to <53> wherein the pixel portion selecting mechanism derives based on the substantial tilt angle θ' to satisfy t tan θ '=N (only, N It is a natural number T close to the relationship t of the number N of exposures, and is selected from the first row to the Tth of the pixel portion in which m rows (only m is a natural number of 2 or more) are arranged. The aforementioned pixel portion of the line is used as the pixel unit.

<55> The permanent pattern forming method according to any one of <50> to <54> wherein the pixel portion selecting mechanism derives based on the substantial tilt angle θ' to satisfy t tan θ '=N (only, N The natural number T which is close to t, which is the relationship of the number of N times of exposure N, will be the (T+1)th line to the pixel part in which the m line (only m is a natural number of 2 or more) is arranged. The aforementioned pixel portion of the m line is defined as not using the pixel portion, and the pixel portion other than the pixel portion is selected as the use pixel portion.

The permanent pattern forming method according to any one of the above-mentioned, wherein the pixel selection mechanism is at least included on an exposed surface formed by a plurality of pixel portions. (1) in the region of the repeated exposure range selects the mechanism using the pixel portion in such a manner as to minimize the total area of the exposure of the ideal N exposures and the area of the underexposed region, and (2) according to the ideal The number of pixel units of the overexposed area of the N exposures is equal to the number of pixel units of the underexposed area to select the mechanism using the pixel part, and (3) according to the area of the exposed area for the ideal N exposures. Selecting the mechanism using the pixel portion to minimize the amount of the underexposed region, and (4) in such a manner as to minimize the area of the underexposed region for the ideal N exposures and not to generate an excessively exposed region. Choose any of the organizations that use the Graphical Department.

The method of forming a permanent pattern according to any one of the above-mentioned, wherein the pixel selection mechanism is repeated exposure on an exposed surface formed by a plurality of pixel portions. (1) in the range of the head-to-head contact area, in order to minimize the total area of the exposed area of the ideal N exposures and the area of the underexposed area, the pixel from the exposure of the aforementioned inter-head contact area The part defines the non-use of the pixel part, and selects the aforementioned pixel part other than the pixel part as the mechanism using the pixel part, and (2) the figure which makes the exposure excess area for the ideal N exposures. The number of prime units is equal to the number of pixel units of the underexposed area, and the pixel portion is not defined from the pixel portion of the exposure of the inter-head contact region, and the aforementioned pixel other than the pixel portion is selected. The part is used as the mechanism using the pixel part, and (3) the exposure from the area between the heads is made in such a manner as to minimize the area of the excessive exposure area for the ideal N exposures and does not generate an underexposed area. The picture of the Ministry The pixel portion is not used, and the pixel portion other than the pixel portion is selected as the mechanism for using the pixel portion, and (4) the area of the underexposed region for the ideal N exposure is made The method of minimizing the area in which the overexposed area is not generated, and defining the non-use of the pixel part from the pixel part of the exposure of the inter-head contact area, and selecting the pixel part other than the pixel part as the Use any of the institutions of the Graphic Department.

<58> The permanent pattern forming method according to the above <57>, wherein the pixel portion is not defined in units of rows.

The method of forming a permanent pattern according to any one of the above-mentioned <45>, wherein the pixel unit is usable in order to specify the use of the pixel unit in the pixel specifying unit. Among them, the reference exposure is performed using only the pixel portion constituting the pixel portion of each (N-1) column with respect to N of the N exposures. In the permanent pattern forming method according to the above <59>, in order to specify the use of the pixel portion in the pixel specifying unit, among the pixel portions that are usable, the N of the N exposures is The reference exposure is performed using only the above-described pixel portion constituting the pixel portion of each (N-1) column, and a simple pattern of a slightly one-time drawing can be obtained. As a result, the aforementioned pixel portion in the aforementioned inter-head contact region can be easily specified.

The method of forming a permanent pattern according to any one of the above-mentioned <45>, wherein the pixel unit is usable in order to specify the use of the pixel unit in the pixel specifying unit. Among them, with respect to N of the N exposures, only the pixel portion constituting the pixel portion line per 1/N row is used for reference exposure. In the permanent pattern forming method according to the above <60>, in order to specify the use of the pixel portion in the pixel specifying unit, among the pixel portions that are usable, the N of the N exposures is The reference exposure is performed using only the aforementioned pixel portion constituting each of the 1/N rows of the pixel portion, and a simple permanent pattern of a slightly one-time drawing can be obtained. As a result, the aforementioned pixel portion in the aforementioned inter-head contact region can be easily specified.

The permanent pattern forming method according to any one of the above-mentioned, wherein the pixel specifying unit has a slit and a photodetector as a spot position detecting mechanism, and The calculation device connected to the photodetector as the pixel selection mechanism.

The method of forming a permanent pattern according to any one of the above-mentioned <45>, wherein N of the N exposures is a natural number of 3 or more and 7 or less.

The method of forming a permanent pattern according to any one of the above aspects, wherein the optical modulation mechanism further comprises a pattern signal generating means for generating a control signal based on the formed pattern information. And modulating the light irradiated from the light irradiation means with the control signal generated by the pattern signal generating means. In the permanent pattern forming method according to the above <63>, the light modulation means includes the pattern signal generating means to modulate the light from the light by the control signal generated by the pattern signal generating means. The light irradiated by the illumination mechanism.

The permanent pattern forming method according to any one of <45> to <63> wherein the light modulation mechanism is a spatial light modulation element.

<65> The permanent pattern forming method according to the above <64>, wherein the spatial light modulation element is a digital microlens device (DMD).

The method of forming a permanent pattern according to any one of the items <45>, wherein the pixel portion is a microlens.

The permanent pattern forming method according to any one of <45> to <66> which has a predetermined portion of a pattern indicating pattern information and a useable pixel which can be specified by The conversion mechanism of the above-described pattern information is converted in such a manner that the size of the corresponding portion to be realized is the same.

The method of forming a permanent pattern according to any one of the above-mentioned items, wherein the light-irradiating means can combine two or more lights to perform irradiation. In the permanent pattern forming method according to the above <68>, since the light irradiation mechanism can combine two or more lights to perform irradiation, exposure light having a deep depth of focus can be exposed to perform exposure. As a result, the exposure of the photosensitive film described above is performed extremely finely. For example, when the development of the photosensitive layer is performed again, an extremely fine pattern can be formed.

The method of forming a permanent pattern according to any one of the above-mentioned items, wherein the light-irradiating mechanism has a plurality of lasers, a multimode optical fiber, and each of the plurality of lasers is irradiated The laser light is collected to form a combined optical system in combination with the aforementioned multimode fiber. In the permanent pattern forming method according to the above <69>, the laser light irradiated by the plurality of lasers can be condensed by the light irradiation means to be combined with the multimode fiber described above. In combination with the collective optical system, exposure light having a deep depth of focus can be exposed for exposure. As a result, the exposure of the photosensitive film described above is performed extremely finely. For example, when the development of the photosensitive layer is performed again, an extremely fine pattern can be formed.

The method of forming a permanent pattern according to any one of the items <42> to <69>, wherein after the exposure is performed, the photosensitive layer is subjected to a development process. In the permanent pattern forming method according to the above <70>, after the exposure is performed, the photosensitive layer is subjected to development processing to form a high-definition pattern.

<71> The permanent pattern forming method according to <70> above, wherein the permanent pattern is formed after the development.

<72> The permanent pattern forming method according to the above <71>, wherein the photosensitive layer is subjected to a curing treatment after the development.

<73> The permanent pattern forming method according to the above <72>, wherein the hardening treatment is at least one of a total exposure treatment and a total heat treatment at 120 to 200 °C.

The permanent pattern forming method according to any one of the above-mentioned <72>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed. The permanent pattern forming method according to the above <74> is formed by forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, so that the film can be protected by insulation, heat resistance, and the like. Wiring to avoid impact and bending from the outside.

<75> A printed circuit board, which is a permanent pattern formed by the permanent pattern forming method according to any one of <42> to <74>.

According to the present invention, the problem of the conventional use can be solved, and by containing a specified polymer compound, it is possible to provide a photosensitive composition which is excellent in temporal development stability and can form a high-definition pattern with good efficiency (protective film A photosensitive composition such as an interlayer insulating film and a solder resist pattern, a photosensitive film, a permanent pattern forming method using the photosensitive film, and a permanent printed circuit board formed by the permanent pattern forming method.

In addition, by specifying the type and amount of the polymer compound and the coexisting compound, it is possible to provide a photosensitive composition excellent in temporal development stability in the presence of a thermal crosslinking agent, a photosensitive film, and the use of the aforementioned photosensitive composition. A permanent pattern forming method of the object, and a printed substrate of the permanent pattern formed by the permanent pattern forming method.

[The best form for implementing the invention] (photosensitive composition)

The photosensitive composition of the present invention comprises at least a binder, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent, preferably containing a sensitizer, and further containing a coloring pigment or a filler pigment as occasion demands A thermosetting agent (hardening accelerator for a thermal crosslinking agent), a thermal polymerization inhibiting agent, and other components such as a surfactant.

Further, in the case of performing exposure development on the photosensitive layer composed of the photosensitive composition, it is preferable to use the minimum energy for the exposure which does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development. It is 0.1~500 mJ/cm ² .

In the case where the photosensitive layer is subjected to exposure development, the minimum energy of the light used in the above-mentioned exposure which does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 500. mJ/cm ² is not particularly limited, and may be appropriately selected, for example, from 0.2 to 200 mJ/cm ² , more preferably from 0.5 to 100 mJ/cm ² , particularly preferably from 1 to ² , depending on the purpose. 50 mJ/cm ² .

When the minimum energy mentioned above is less than 0.1 mJ/cm ² , in the process of processing under the yellow lamp, whitening may occur; when it exceeds 500 mJ/cm ² , the time required for exposure becomes long, The processing speed is slow.

The "minimum energy of light used in the foregoing exposure which does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development" as referred to herein is a so-called development sensitivity, for example, The relationship between the light energy (exposure amount) used in the above-described exposure at the time of exposure of the photosensitive layer and the aforementioned hardened layer thickness (the sensitivity curve) which is caused by the continuation of the aforementioned exposure processing. And ask for it.

The thickness of the hardened layer described above increases as the amount of exposure described above increases, and is then approximately the same as the thickness of the photosensitive layer before exposure, and is approximately constant. The above-described development sensitivity is obtained by reading the exposure amount when the thickness of the hardened layer described above is approximately constant.

Here, when the difference between the thickness of the hardened layer described above and the thickness of the photosensitive layer before the exposure is within ±1 μm, it can be considered that the thickness of the hardened layer is not changed by exposure development.

The method for measuring the thickness of the hardened layer and the thickness of the photosensitive layer before the exposure is not particularly limited, and may be appropriately selected depending on the purpose, and for example, may be a film thickness measuring device or a rough surface. A method of measuring by a measuring machine (for example, Safkheim 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)).

Further, after the photosensitive composition was laminated on the substrate, after 20 minutes in the dark at 25 ° C, the unexposed portion of the photosensitive composition laminated on the substrate was removed by a developing solution. The required time (the shortest development time) is denoted as T ₁ ; and for the photosensitive composition laminated on the substrate, the photosensitive layer is placed in a dark place at 50 ° C for 24 hours, by a developing solution The time required for removing the unexposed portion of the photosensitive composition deposited on the substrate (the shortest development time) is expressed as T ₂ and satisfies the relationship of 0.5 < T ₂ / T ₁ < 3. At this time, T _{1 is} preferably 5 to 120 seconds, and T _{2 is} preferably 5 to 240 seconds. Further, it is preferable that the T ₂ /T ₁ satisfies 0.6<T ₂ /T ₁ ≦2.7, and more preferably satisfies 0.7. <T ₂ /T ₁ <2.4, particularly preferably satisfies 0.8<T ₂ /T ₁ ≦2. When the T ₂ /T ₁ is outside the above range, the stability of the photosensitive composition over time is not good, and varies with the development time, so that the photosensitive composition is coated on the substrate. In the state of storage, the sandwich structure of the protective film on which the photosensitive layer is provided on the substrate is difficult to use in the form of a long-length or cylindrical dry film.

Further, the photosensitive composition described above can be used in a permanent pattern forming method which will be described later by laminating a photosensitive layer of the photosensitive composition on a substrate.

In the present invention, the halogen atom content in the photosensitive layer is preferably 5,000 ppm or less, more preferably 2,000 ppm or less, more preferably 1,000 ppm or less, and particularly preferably 500 ppm. the following.

In addition, the phrase "after 20 minutes in a dark place at 25 ° C" means "after being kept at 25 ° C in a light-shielded state for 20 minutes".

<Binder>

The above-mentioned binder is preferably a compound which is insoluble in water and which is swollen and dissolved by an aqueous alkaline solution.

The above binder is preferably a polymer compound containing an acidic group and an ethylenically unsaturated bond in a side chain. The above-mentioned acidic group is, for example, preferably a carboxyl group, a phosphoric acid group, a sulfonic acid group or the like; however, from the viewpoint of obtaining a raw material, a carboxyl group is preferred.

Further, as the binder, at least one polymerizable double bond may be used in the molecule, and for example, a vinyl ester of an acrylic carboxylic acid such as (meth) acrylate or acrylamide or a vinyl ether may be used. Various polymerizable double bonds such as allyl ether. More specifically, for example, it may be a compound obtained by adding a cyclic ether group-containing polymerizable compound to an acrylic resin containing a carboxyl group as an acidic group, and the like, for example, glycidol acrylate may be added. a glycidyl ester of an unsaturated acid such as an ester, glycidyl methacrylate or cinnamic acid, or an alicyclic epoxy group (for example, an epoxy group having a cyclohexene oxide or the like in the same molecule) and (a) An epoxy group-containing polymerizable compound or the like which is a compound of an acrylonitrile group. Further, for example, it may be a compound obtained by adding a polyisocyanate group-containing polymerizable compound such as (meth)acrylic acid polyisocyanate ethyl ester to an acrylic resin containing an acidic group and a hydroxyl group, and containing an anhydride. A compound obtained by adding a hydroxyl group-containing polymerizable compound such as a hydroxyalkyl (meth)acrylate to the acrylic resin is added to the base resin. Further, a cyclic ether group-containing polymerizable compound such as glycidyl methacrylate or a vinyl monomer such as (meth)acryl decyl alkyl ester is copolymerized and (meth)acrylic acid is added to the side chain. The compound obtained by adding an epoxy group to it.

For example, Patent No. 2,763,775, JP-A-3-172301, JP-A-2000-232264, and the like.

In the above, the binder is preferably a cyclic ether group (for example, a group having an epoxy group or an oxetane group in a partial structure) on an acidic group of a part of the polymer compound. A polymer compound selected from any one of an adduct of a polymerizable compound and an adduct of a carboxyl group-containing polymerizable compound added to a part or all of a cyclic ether group of the polymer compound. In this case, the addition reaction between the compound having an acidic group and a cyclic ether group is preferably carried out in the presence of a catalyst, and in particular, the catalyst is preferably selected from acidic compounds and neutral compounds.

Among these, the binder preferably contains a carboxyl group in a side chain, an aromatic group which may contain a hetero ring, and a side chain from the viewpoint of stability of the time-lapse development of the photosensitive composition. A polymer compound containing an ethylenically unsaturated bond.

- an aromatic group which may contain a heterocyclic ring -

The above-mentioned aromatic group which may contain a hetero ring (hereinafter, simply referred to as "aromatic group") may be, for example, a benzene ring or a condensed ring of two to three benzene rings. The benzene ring and the 5-membered unsaturated ring are condensed and formed.

Specific examples of the above aromatic group may, for example, be a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, a dihydroindenyl group, a fluorenyl group, a benzopyrrole group, or a benzofuran ring. Base, benzothienyl ring, pyrazole ring group, different Oxazolyl, isothiazolyl, indazole, benzo Oxazolyl, benzisothiazole ring, imidazocyclyl, Oxazolyl, thiazole ring, benzimidazole ring, benzo Oxazole group, benzothiazole ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, hydrazine Base, pyrimidine ring, pyridyl Ring base a cyclic group, a quinazoline ring group, a quinoxaline ring group, an acridine ring group, a phenanthryl ring group, a carbazole ring group, a porphyrin ring group, a pyrancyclo group, a piperidinyl group, an anthracene ring group,吲 Ring group, chromene ring group, Phytocyclic group, acridine ring group, morphine Cyclic group, tetrazole ring group, three Ring base, etc. Among these, a hydrocarbon aromatic group is preferred, and a phenyl group or a naphthyl group is more preferred.

The aforementioned aromatic group may have a substituent; the aforementioned substituent may, for example, be a halogen atom, an amine group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a sulfur group, a thioether A group, an alkyl group, a nitro group, a cyano group, an amine group, an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, a heterocyclic group or the like which may have a substituent, respectively.

The alkyl group may be, for example, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group or a cyclic alkyl group.

Specific examples of the aforementioned alkyl group, for example, may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, Dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t-butyl, iso Pentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-positive Base. 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.

The substituent which the aforementioned alkyl group may have, for example, may be a group composed of a monovalent non-metal atom group other than a hydrogen atom. Such a substituent, for example, a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a thiol group, an alkylthio group, an arylthio group, an alkyldithio group , aryldithio, amine, N-alkylamino, N,N-dialkylamino, N-arylamino, N,N-diarylamine, N-alkyl-N-arylamine , anthraceneoxy, amine methyl methoxy, N-alkyl amine methyl methoxy, N-aryl amine methyl methoxy, N, N-dialkyl amine methoxy, N, N-diaryl Ketomethyl methoxy, N-alkyl-N-arylamine methoxycarbonyl, alkylsulfonyloxy, arylsulfonyloxy, decylthio, decylamino, N-alkyl Mercaptothio, N-aryldecylamino, ureido, N'-ureido, N', N'-dialkylureido, N'-arylureido, N', N'-di Arylureido, N'-alkyl-N'-arylureido, N-alkylureido, N-arylureido, N'-alkyl-N-alkylureido, N'-alkane -N-arylureido, N',N'-dialkyl-N-alkylureido, N',N'-dialkyl-N-alkylureido, N', N'-di Alkyl-N-arylureido, N'-aryl-N-alkylureido, N'-alkyl- N-arylureido, N',N'-diaryl-N-alkylureido, N',N'-diaryl-N-arylureido, N'-alkyl-N'- Aryl-N-alkylureido, etc., N'-alkyl-N'-aryl-N-arylureido, alkoxy, carbonylamino, aryloxycarbonylamino, N-alkyl -N-alkoxycarbonylamino, N-alkyl-N-aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamino, N-aryl=N-aryloxy Amine, carbolyl, fluorenyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, N-alkylamine, fluorenyl, N,N-dialkylamine, fluorenyl, N -Arylamine, mercapto, N,N-diarylamine, N-alkyl-N-arylamine, alkyl sulfinyl, arylsulfinyl, alkyl Sulfonyl, arylsulfonyl, sulfonic acid (-SO ₃ H) and its conjugated base (referred to as sulfonate), alkoxysulfonyl, aryloxysulfonyl, amine sulfin Indenyl, N-alkylamine sulfinyl, N,N-dialkylamine sulfinyl, N-arylamine sulfinyl, N,N-diarylamine sulfinyl, N -alkyl-N-arylamine sulfinyl, aminoxime , N-alkylamine sulfonyl, N,N-dialkylamine sulfonyl, N-arylamine sulfonyl, N,N-diarylamine sulfonyl, N-alkyl-N - an arylamine sulfonyl group, a phosphonic acid group (-PO ₃ H ₂ ) and a conjugated base thereof (referred to as a phosphonate group), and a dialkylphosphonic acid group (-PO ₃ (alkyl) ₂ ) (hereinafter, "alkyl" means an alkyl group.), a diarylphosphonic acid group (-PO ₃ (aryl) ₂ ) (hereinafter, "aryl" is an aryl group), an alkylarylphosphonic acid group ( -PO ₃ (alkyl)(aryl)), monoalkylphosphonic acid group (-PO ₃ (alkyl)) and its conjugated base (referred to as alkylphosphonate group), monoarylphosphonic acid group (-PO) ₃ H(aryl)) and its conjugated base (referred to as arylphosphonate), phosphonic acidoxy (-OPO ₃ H ₂ ) and its conjugated base (referred to as phosphonateoxy), dioxane Alkylphosphonic acid (-OPO ₃ H(alkyl) ₂ ), diarylphosphonic acidoxy (-OPO ₃ (aryl) ₂ ), alkyl aryl phosphonic acid oxy (-OPO ₃ (alkyl) (aryl )), monoalkylphosphonic acidoxy (-OPO ₃ H(alkyl)) and its conjugated base (referred to as alkylphosphonateoxy), monoarylphosphonic acid group (-OPO ₃ H (aryl) And its conjugated base (called arylphosphonateoxy), cyano, Group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkyl silicon and the like.

Specific examples of the alkyl group in the substituents, for example, may be the aforementioned alkyl group.

Specific examples of the aryl group in the above substituent may be, for example, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a cumyl group, a chlorophenyl group, or the like. Bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, ethoxylated phenyl, benzhydryloxyphenyl, methylsulfide Phenyl, phenylthiophenyl, methylaminophenyl, dimethylaminophenyl, ethionylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, phenoxy Phenylcarbonylphenyl, N-phenylamine-nonylphenyl, cyanophenyl, sulfophenyl, sulfonylphenyl, phosphonicphenyl, phosphonatephenyl, and the like.

Specific examples of the alkenyl group in the above substituent may, for example, be a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, a 2-chloro-1-ether group or the like.

Specific examples of the alkynyl group in the above substituent may be, for example, an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethyldecylalkylethynyl group or the like.

The substituents R ⁰¹ of the acyl group (R ⁰¹ CO-) of, for example, which may be for example a hydrogen atom, an alkyl group of the aryl group and the like.

Among these substituents, a halogen atom (-F, -Br, -Cl, -I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N,N-Dialkylamino, decyloxy, N-alkylamine methyl methoxy, N-arylamine methyl methoxy, decylamino, decyl, decyl, carboxy, alkoxy Carbonyl, aryloxycarbonyl, aminemethanyl, N-alkylaminecarbamyl, N,N-dialkylaminecarbamyl, N-arylaminecarbamyl, N-alkyl-N-aryl Base amide, sulfonate, sulfonate, sulfonamide, N-alkylamine sulfonyl, N,N-dialkylamine sulfonyl, N-arylamine sulfonyl, N -alkyl-N-arylamine sulfonyl, phosphonic acid, phosphonate, dialkylphosphonic acid, diarylphosphonic acid, monoalkylphosphonic acid, alkylphosphonic acid, monoaryl Phosphonic acid group, arylphosphonate group, phosphonic acidoxy group, phosphonic acid group, aryl group, alkenyl group and the like.

Further, the heterocyclic group in the above substituent may, for example, be a pyridyl group, a piperidinyl group or the like; the alkylene group in the above substituent, for example, it may be a trimethyldecyl group Wait.

On the other hand, the alkylene group in the above alkyl group, for example, may be a divalent organic residue which removes any one of hydrogen atoms on the alkyl group having 1 to 20 carbon atoms; for example, It is preferably 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.

Preferred specific examples of the substituted alkyl group obtained by combining such a substituent with an alkylene group are, for example, chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, Methoxymethyl, isopropoxymethyl, butoxymethyl, s-butoxybutyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, A Thiomethylmethyl, tolylthiomethyl, pyridylmethyl, tetramethylpiperidinylmethyl, N-ethinyltetramethylpiperidinylmethyl, trimethyldecylmethyl, methoxy Ethyl, ethylaminoethyl, diethylaminopropyl, morpholinylpropyl, ethoxymethyloxy, benzhydryloxymethyl, N-cyclohexylaminemethyloxyethyl, N-phenylamine methyl methoxyethyl, ethionylaminoethyl, N-methylbenzhydrylaminopropyl, 2-sided oxyethyl, 2-sided oxypropyl, carboxypropyl , methoxycarbonylethyl, allyloxycarbonylbutyl, chlorophenoxycarbonylmethyl, aminemethylmethylmethyl, N-methylamine, decylethyl, N,N-dipropylamine Mercaptomethyl, N-(methoxyphenyl)amine, mercaptoethyl, N-methyl-N (phosphonophenyl)amine methyl hydrazinomethyl, sulfonate butyl, sulfonyl butyl, sulfonyl butyl, N-ethylamine sulfonylmethyl, N,N-dipropyl Amine sulfonyl, N-anilinoamine sulfonylpropyl, N-methyl-N-(phosphonophenyl)amine sulfonyl octyl, phosphonic butyl, phosphonic hexyl, two Ethylphosphonyl butyl, diphenylphosphonic propyl, methylphosphonic butyl, methylphosphonic butyl, tolylphosphonic hexyl, tolylphosphonate hexyl, phosphonic acid oxygen Propyl, phosphonithooxypropyl, benzyl, phenethyl, α -methylbenzyl, 1-methyl-1-phenylethyl, p-methylbenzyl, cinnamyl, allyl , 1-propenylmethyl, 2-butenyl, 2-methylallyl, 2-methylpropenylmethyl, 2-propynyl, 2-butynyl, 3-butynyl, and the like.

The above-mentioned aryl group may be, for example, a benzene ring, a condensed ring formed from 2 to 3 benzene rings, a condensed ring formed from a benzene ring and a 5-membered unsaturated ring, and the like.

Specific examples of the aforementioned aryl group may, for example, be a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, a dihydroindenyl group, a fluorenyl group or the like. Among these, phenyl or naphthyl is preferred.

The above-mentioned alkyl group may have a substituent, such as a substituted alkyl group (hereinafter, referred to as a "substituted aryl group"), and for example, it may be a ring formation of the aforementioned aryl group. The carbon atom has a substituent composed of a monovalent non-metal atom group other than a hydrogen atom as a substituent.

The substituent which may be possessed by the above-mentioned aryl group is, for example, preferably exemplified as the substituent which the above-mentioned alkyl group, substituted alkyl group, or the above-mentioned alkyl group may have.

Preferred specific examples of the above substituted aryl group include, for example, a biphenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a cumyl group, a chlorophenyl group, a bromophenyl group, and a fluorobenzene. Base, chloromethylphenyl, trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylsulfide Phenyl, tolylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinylphenyl, ethoxylated phenyl, benzhydryloxyphenyl, N-cyclohexylamine a nonyloxyphenyl group, an N-phenylamine methyl methoxy phenyl group, an ethyl decyl phenyl phenyl group, an N-methyl benzoguanidino phenyl group, a carboxy phenyl group, a methoxycarbonyl phenyl group, Allyloxycarbonylphenyl, chlorophenoxycarbonylphenyl, amine methyloxyphenyl, N-methylamine methyloxyphenyl, N,N-dipropylamine methyloxyphenyl , N-(methoxyphenyl)amine methyl methoxyphenyl, N-methyl-N-(sulfophenyl)amine methyl methoxy phenyl, sulfonic phenyl, sulfonate benzene Amine, sulfonylphenyl, N-ethylamine sulfonylphenyl, N,N-dipropyl Sulfonylphenyl, N-methylphenylsulfonylphenyl, N-methyl-N-(sulfonylphenyl)amine sulfonylphenyl, phosphonic phenyl, phosphonate phenyl, Diethylphosphonic phenyl, diphenylphosphonyl phenyl, methylphosphonic phenyl, methylphosphonic phenyl, tolylphosphonic phenyl, tolylphosphonyl phenyl, Allylphenyl, 1-propenylmethylphenyl, 2-butenylphenyl, 2-methylallylphenyl, 2-methylpropenylphenyl, 2-propynylphenyl, 2-butynylphenyl, 3-butynylphenyl, and the like.

The aforementioned alkenyl group (-C(R ⁰² )=C(R ⁰³ )(R ⁰⁴ )) and alkynyl group (-C≡C(R ⁰⁵ ), for example, may be R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ are radicals composed of monovalent non-metal radicals.

The above R ⁰² , R ⁰³ , R ⁰⁴ and R ^{05 may} , for example, be a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or the like. Specific examples of such, for example, may be exemplified as the foregoing examples. Among these, a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group or a cyclic alkyl group is preferable.

Preferred specific examples of the aforementioned alkenyl group and alkynyl group are, for example, vinyl, 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1- Octenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 2-methyl-1-butenyl, 2-phenyl-1-vinyl, 2-chloro-1 a vinyl group, an ethynyl group, a propynyl group, a 1-butynyl group, a phenylethynyl group or the like.

The aforementioned heterocyclic group may, for example, be a pyridyl group or the like exemplified as a substituent of the substituted alkyl group.

The aforementioned oxy group (R ⁰⁶ O-), for example, may be a group in which R ⁰⁶ is a group composed of a monovalent non-metal atomic group other than a hydrogen atom.

An oxy group like this is, for example, preferably an alkoxy group, an aryloxy group, a decyloxy group, an amine carbaryloxy group, an N-alkylamine carbhydryloxy group, or an N-arylamine mercaptooxy group. , N,N-dialkylamine, fluorenyloxy, N,N-diarylamine, fluorenyloxy, N-alkyl-N-arylamine, decyloxy, alkyl sulfonic acid Alkoxy, arylsulfonyloxy, phosphonicoxy, phosphonooxy, and the like.

The alkyl group and the aryl group among these may be, for example, exemplified as the above-mentioned alkyl group, substituted alkyl group, aryl group and substituted aryl group. Further, the aforementioned oxime group (R ⁰⁷ CO-), for example, R ⁰⁷ may be an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group exemplified as the prior examples. Among these substituents, an alkoxy group, an aryloxy group, a decyloxy group, and an arylsulfonic acid group are preferred.

Specific examples of preferred oxy groups, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, alkene Propyloxy, phenethyloxy, carboxyethyloxy, methoxycarbonyloxy, ethoxycarbonylethoxy, methoxyethoxy, methoxyethoxyethoxy, ethoxy Ethoxyethoxy, morpholinylethoxy, morpholinylpropoxy, allyloxyethoxyethoxy, phenoxy, tolyloxy, xylyloxy, tri Tolyloxy, tricresyloxy, isopropyloxy, methoxyphenyloxy, ethoxyphenyloxy, chlorophenyloxy, bromophenyloxy, ethoxylated oxy , benzhydryloxy, naphthyloxy, phenylsulfonyloxy, phosphonic acidoxy, phosphonateoxy, and the like.

An amine group (R ⁰⁸ NH-, (R ⁰⁹ )(R ⁰¹⁰ )N-) which may contain a guanamine group, for example, which may be one of R ⁰⁸ , R ⁰⁹ and R ⁰¹⁰ except for a hydrogen atom A base composed of a valence of non-metal radicals. In addition, R ⁰⁹ and R ⁰¹⁰ may also be linked to form a ring.

The aforementioned amine group, for example, may be an N-alkylamino group, an N,N-dialkylamino group, an N-arylamino group, an N,N-diarylamino group, an N-alkyl group. -N-arylamino, decylamino, N-alkyldecylamino, N-aryldecylamine, ureido, N'-alkylureido, N', N'-di Alkyl urea group, N'-aryl urea group, N', N'-diaryl urea group, N'-alkyl-N'-aryl urea group, N-alkyl urea group, N-aryl group Urea, N'-alkyl-N-alkylureido, N'-alkyl-N-arylureido, N', N'-dialkyl-N-alkylureido, N'-alkane -N'-arylureido, N',N'-dialkyl-N-alkylureido, N',N'-dialkyl-N'-arylureido, N'-aryl -N-alkylureido, N'-aryl-N-arylureido, N',N'-diaryl-N-alkylureido, N',N'-diaryl-N- Arylureido, N'-alkyl-N'-aryl-N-alkylureido, N'-alkyl-N'-aryl-N-arylureido, alkoxycarbonylamino, aromatic Oxycarbonylamine, N-alkyl-N-alkoxycarbonylamino, N-alkyl-N-aryloxycarbonylamino, N-aryl-N-alkane Carbonyl group, N- aryl -N- aryloxycarbonyl group and the like. The alkyl group and the aryl group among these may be, for example, exemplified as the above-mentioned alkyl group, substituted alkyl group, aryl group and substituted aryl group. And, R ⁰⁷ lines acyl group, N- acyl amino-alkyl, N- aryl-acyl group of acyl (R ⁰⁷ CO-) of the preceding. Among these, it is more preferably an N-alkylamino group, an N,N-dialkylamino group, an N-arylamino group or a mercaptoamine group.

Specific examples of preferred amine groups, for example, may be methylamino, ethylamino, diethylamino, morpholinyl, piperidinyl, pyridyl, phenylamino, Benzomethylamino group, acetylamino group, and the like.

The aforementioned sulfonyl group (R ⁰¹¹ -SO ₂ -), for example, may be a compound in which R ⁰¹¹ is a group composed of a monovalent non-metal atomic group.

A sulfonyl group such as, for example, an alkylsulfonyl group, an arylsulfonyl group or the like. The alkyl group and the aryl group among these may be, for example, those exemplified as the above-mentioned alkyl group, substituted alkyl group, aryl group and substituted aryl group.

Specific examples of the aforementioned sulfonyl group may, for example, be a butylsulfonyl group, a phenylsulfonyl group, a chlorophenylsulfonyl group or the like.

The aforementioned sulfonate group (-SO ₃ ^- ), as described above, means a conjugated base anion of a sulfonic acid group (-SO ₃ H), and is usually preferably used together with a counter cation.

Such a cationic system may be suitably selected from those generally known, and for example, it may be an anthracene (for example, ammonium, sulfonium, anthraquinone, anthraquinone, acridine, etc.), Metal ions (for example, Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^{2+ ,} etc.).

The aforementioned carbonyl group (R ⁰¹³ -CO-), for example, may be a compound in which R ⁰¹³ is a group composed of a monovalent non-metal atomic group.

A carbonyl group such as, for example, it may be a fluorenyl group, a fluorenyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine methyl sulfonyl group, an N-alkylamine methyl fluorenyl group, N, N- Dialkylamine methyl sulfonyl, N-arylamine carbhydryl, N,N-diarylaminecarbamyl, N-alkyl-N'-arylaminecarbamyl and the like. The alkyl group and the aryl group among these may be, for example, exemplified as the above-mentioned alkyl group, substituted alkyl group, aryl group and substituted aryl group.

The aforementioned carbonyl group is preferably a decyl group, a fluorenyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, an N-alkylamine carbhydryl group, an N,N-dialkylamine fluorenyl group. , N-arylaminecarbamyl; more preferably is indenyl, fluorenyl, carboxy, alkoxycarbonyl, aryloxycarbonyl.

Specific examples of the aforementioned carbonyl group include, for example, a mercapto group, an ethyl fluorenyl group, a benzamidine group, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an allyloxycarbonyl group, and a dimethyl group. Aminophenyl ether carbonyl, methoxycarbonylmethoxycarbonyl, N-methylaminecarbamyl, N-phenylaminecarbamyl, N,N-diethylaminecarbamyl, morpholinylcarbonyl, etc. .

The aforementioned sulfinyl group (R ⁰¹⁴ -SO-), for example, may be such that R ⁰¹⁴ is a group composed of a monovalent non-metal atomic group.

A sulfinyl group such as, for example, may be an alkylsulfinyl group, an arylsulfinyl group, an amine sulfinyl group, an N-alkylamine sulfinyl group, N, N- A dialkylamine sulfinyl group, an N-arylamine sulfinyl group, an N,N-diarylamine sulfinylene group, an N-alkyl-N-arylamine sulfinyl group, and the like. The alkyl group and the aryl group among these may be, for example, exemplified as the above-mentioned alkyl group, substituted alkyl group, aryl group and substituted aryl group. Among these, an alkylsulfinyl group or an arylsulfinyl group is preferred.

Specific examples of the above-mentioned substituted sulfonyl group include, for example, a hexylsulfonyl group, a benzylsulfonyl group, a tolylsulfonyl group and the like.

The above-mentioned phosphonic acid group means that one or two hydroxyl groups on the phosphonic acid group are substituted by other organic side oxy groups; for example, it is preferably the aforementioned dialkylphosphonic acid group, two An arylphosphonic acid group, an alkylarylphosphonic acid group, a monoalkylphosphonic acid group, a monoarylphosphonic acid group or the like. Among these, a dialkylphosphonic acid group or a diarylphosphonic acid group is more preferable.

A preferred specific example of the above phosphonic acid group is, for example, a diethylphosphonic acid group, a dibutylphosphonic acid group or a diphenylphosphonic acid group.

The aforementioned so-called phosphonate group (-PO ₃ H ₂ -, -PO ₃ H-), as described above, refers to the first dissociation of the acid of the phosphonic acid group (-PO ₃ H ₂ ) or the second dissociation of the acid. The meaning of the conjugated base anion. Generally, it is preferred to use it together with a cation. Such a cationic system may be suitably selected from those generally known, and for example, it may be an anthracene (for example, ammonium, sulfonium, anthraquinone, anthraquinone, acridine, etc.), Metal ions (for example, Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^{2+ ,} etc.).

The aforementioned phosphonate group may be a conjugated base anion group in which a hydroxyl group within the phosphonic acid group is substituted with an organic pendant oxy group, and as such a specific example, for example, it may be the aforementioned A conjugated base of a monoalkylphosphonic acidoxy group (-PO ₃ H(alkyl)) or a monoarylphosphonic acid group (-PO ₃ H(aryl)).

The aromatic group may be a generalized radical group by copolymerizing one or more aromatic group-containing radical polymerizable compounds and, if necessary, one or more other radical polymerizable compounds. Manufactured by polymerization.

The radical polymerization method described above may be, for example, a general suspension polymerization method or a solution polymerization method.

The above-mentioned aromatic-containing radical polymerizable compound is preferably a compound represented by the structural formula (A) or a compound represented by the structural formula (B).

However, in the above structural formula (A), R ₁ , R ₂ and R ₃ represent a hydrogen atom or a monovalent organic group. The L system represents an organic group and is not acceptable. The Ar system represents an aromatic group which may contain a hetero ring.

However, in the above structural formula (B), R ₁ , R ₂ and R ₃ and Ar represent the same meanings as the above structural formula (A).

The organic group of the above L, for example, may be a polyvalent organic group composed of a non-metal atom, from 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 A substance formed by a hydrogen atom of 100 and a sulfur atom of 0 to 20.

More specifically, the organic group of L described above may be, for example, a composition composed of the following structural units, polyvalent naphthalene, polyvalent hydrazine or the like.

The linking group of L may have a substituent, and the substituent may be, for example, a halogen atom, a hydroxyl group, a carboxyl group, a sulfonate group, a nitro group, a cyano group, a decylamino group, an amine group, or the like. Alkyl, alkenyl, alkynyl, aryl, substituted oxy, substituted sulfonyl, substituted carbonyl, substituted sulfinyl, sulfonate, phosphonic acid, phosphonate, decyl, heterocyclic.

Among the compounds represented by the structural formula (A) and the compounds represented by the structural formula (B), the structural formula (A) is preferred from the viewpoint of sensitivity. Further, in the above structural formula (A), it is preferred to have a linking group from the viewpoint of stability; and the organic group of L is preferably carbon in view of the removal property (developability) of the non-image portion. The number is 1 to 4 alkyl groups.

The compound represented by the above structural formula (A) is a compound containing a structural unit of the following structural formula (I). Further, the compound represented by the above structural formula (B) is a compound containing a structural unit of the following structural formula (II). Among these, from the viewpoint of preserving stability, it is preferable to use the structural unit of the structural formula (I).

However, in the above structural formulae (I) and (II), R ₁ , R ₂ , R ₃ and Ar represent the same meanings as the above structural formulae (A) and (B).

In the above structural formulae (I) and (II), from the viewpoint of the removability (developability) of the non-image portion, it is preferred that R ₁ and R ₂ are a hydrogen atom and R ₃ is a methyl group.

In addition, L of the above structural formula (I) is preferably an alkyl group having a carbon number of 1 to 4 from the viewpoint of the removability (developability) of the non-image portion.

The compound represented by the above structural formula (A) or the compound represented by the above structural formula (B) is not particularly limited, but, for example, it may be, for example, the following exemplified compound (1) ~(30).

Among the above-exemplified compounds (1) to (30), it is preferred to be (5), (6), (11), (14) and (28); among these, from the preservation stability and display From the point of view of sex, it is more appropriate to be (5) and (6).

In the above-mentioned binder, the content of the aromatic group which may contain a hetero ring is not particularly limited. However, when the total structural unit of the polymer compound is 100 mol%, it is preferable to contain 20 mol% or more. More preferably, it is a structural unit represented by the above structural formula (I) containing 30 to 45 mol% or more. When the content is less than 20 mol%, the storage stability is lowered, and when it exceeds 45 mol%, the development is lowered.

- Ethylene unsaturated bond -

The above-mentioned ethylenically unsaturated bond is not particularly limited and may be appropriately selected according to the purpose. For example, it is preferably represented by the following structural formulae (III) to (V).

However, in the above structural formulae (III) to (V), R ₁ to R _{11 each} independently represent a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom, or -N-R ₄ . The Z series represents an oxygen atom, a sulfur atom, or -N-R ₄ or a phenyl group. R ₄ represents a hydrogen atom or a monovalent organic group.

R ₁ in the above structure (III) is, for example, preferably an individual independently representing a hydrogen atom, an alkyl group which may have a substituent, etc., and is also highly reactive with a hydrogen atom or a methyl group, and thus ideal.

The above R ₂ and R ₃ may, for example, be each independently a hydrogen atom, a halogen atom, an amine group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, a nitro group, a cyano group, or 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 alkylamine group which may have a substituent, an arylamine group which may have a substituent, may have a substitution The alkylsulfonyl group, the arylsulfonyl group which may have a substituent, etc.; from the viewpoint of high reactivity of the radical, it is more preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or an alkyl group which may have a substituent An aryl group which may have a substituent.

The above R _{4 is} , for example, preferably an alkyl group which may have a substituent, and the like; and from the viewpoint of high reactivity of the radical, it is more preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group.

Here, the aforementioned substituent which may be introduced, for example, may be an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amine group, an alkylamine group, An arylamine group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, a nitro group, a cyano group, a decylamino group, an alkylsulfonyl group, an arylsulfonyl group or the like.

R ₄ to R ₈ in the above structure (4) are, for example, a hydrogen atom, a halogen atom, an amine group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, a nitro group, a cyano group, or the like. 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 alkylamine group which may have a substituent, and an aromatic group which may have a substituent An amino group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, etc.; more preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, may have a substitution Base aryl.

The aforementioned substituents which can be introduced are, for example, those exemplified in the above-mentioned configuration (III).

R ₉ in the above structural formula (5) is, for example, preferably a hydrogen atom or an alkyl group which may have a substituent, and is preferably a hydrogen atom or a methyl group from the viewpoint of high reactivity of the radical.

In the foregoing R ₁₀ and R ₁₁ , for example, each may independently be a hydrogen atom, a halogen atom, an amine group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, a nitro group, a cyano group, or the like. 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 alkylamine group which may have a substituent, and an aromatic group which may have a substituent An aminoalkyl group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like; and a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or the like, from the viewpoint of high reactivity of a radical, An alkyl group which may have a substituent, an aryl group which may have a substituent.

Here, the aforementioned substituent which can be introduced, for example, the exemplified ones listed in the above configuration (III).

The aforementioned Z series represents an oxygen atom, a sulfur atom, -NR ₁₃ - or a stretched phenyl group which may have a substituent. R ₁₃ represents an alkyl group which may have a substituent, and is preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group from the viewpoint of high reactivity of a radical.

Among the side chain ethylenically unsaturated bonds represented by the above structural formulae (III) to (V), those having a high polymerization reactivity and a high sensitivity are more preferably those of the structural formula (III).

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, and particularly preferably 1.5 to 2.8. Meq/g. When the content is less than 0.5 meq/g, there is a case where the amount of hardening reaction is small and low sensitivity is caused. When it is higher than 3.0 meq/g, the preservation stability may be deteriorated.

Herein, the aforementioned content (meq/g) can be measured, for example, by iodine titration.

The method of introducing the ethylenically unsaturated bond represented by the above structural formula (III) into the side chain is not particularly limited, and for example, it may be, for example, a polymer having a carboxyl group in a side chain. The compound is obtained by an addition reaction with a compound having an ethylenically unsaturated bond and an epoxy group.

In the above-mentioned polymer compound having a carboxyl group in the side chain, for example, a radical polymerizable compound containing one or more kinds of carboxyl groups and, if necessary, one type as required by a general radical polymerization method can be used. The radical polymerization component of the above other radical polymerizable compound is produced. The radical polymerization method may be, for example, a suspension polymerization method or a solution polymerization method.

The above-mentioned compound having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has such a compound, and, for example, it is preferably a compound represented by the following structural formula (VI) and A compound represented by the formula (VII). In particular, from the viewpoint of sensitivity, a compound represented by the structural formula (VI) is preferred.

However, in the above structural formula (VI), R ₁ represents a hydrogen atom or a methyl group. The L ₁ group represents an organic group.

However, in the above structural formula (VII), R ₂ represents a hydrogen atom or a methyl group. The L ₂ system represents an organic group. The W system represents an aliphatic hydrocarbon group of a 4 to 7 member ring.

Among the compounds represented by the above structural formula (VI) and the compound represented by the structural formula (VII), a compound represented by the structural formula (VI) is preferred; and L1 in the above structural formula (VI) is more preferred. The carbon number is 1 to 4 alkyl groups.

In the compound represented by the above structural formula (VI) and the compound represented by the structural formula (VII), although not particularly limited, for example, it may be, for example, the following exemplified compound (31) ~(40).

The above-mentioned carboxyl group-containing radical polymerizable compound may, for example, be acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, p-carboxystyrene or the like, particularly preferably acrylic acid or methyl group. Acrylic, etc.

The above-mentioned reaction for introducing into the side chain may, for example, be a tertiary amine such as triethylamine or benzylamine, dodecylmethylammonium chloride, tetramethylammonium chloride or tetraethylammonium chloride. The fourth-order ammonium salt, pyridine, triphenylphosphine or the like is used as a catalyst, and the reaction is carried out 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 above-mentioned side chain is not particularly limited. However, for example, it is preferably a structure represented by the following structural formula (i) and a structure represented by the structural formula (ii). And what is represented by the mixture of these.

However, in the above structural formulae (i) and (ii), Ra to Rc represents a hydrogen atom or a monovalent organic group. R ₁ represents a hydrogen atom or a methyl group. The L ₁ group represents an organic group which may have a linking group.

The content of the structure represented by the structural formula (i) or the structure represented by the structural formula (ii) in the polymer compound is preferably 20 mol% or more, more preferably 20 to 50 mol%. Very good for 25~45%. When the content is less than 20 mol%, the amount of hardening reaction may be low and the sensitivity may be low. When the amount is more than 50 mol%, the storage stability may be deteriorated.

-carboxyl-

In the polymer compound of the present invention, a carboxyl group may be provided in order to improve various properties such as non-image portion removability.

The above carboxyl group can be supplied to the polymer compound by copolymerizing a compound having a radical polymerizable compound.

The acid group of the radical polymerizable compound as described above may be, for example, a carboxylic acid, a sulfonic acid or a phosphoric acid group, and particularly preferably a carboxyl group.

The radical polymerizable compound having a carboxyl group as described above is not particularly limited and may be appropriately selected depending on the purpose, and for example, it may be acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, or horse. Acid, p-carboxystyrene, etc. Among these, acrylic acid, methacrylate, and p-carboxystyrene are preferred. These may be used alone or in combination of two or more.

The content of the aforementioned carboxyl group in the binder is preferably from 1.0 to 4.0 meq/g, more preferably from 1.5 to 3.0 meq/g. When the content is less than 1.0 meq/g, the development is insufficient, and when it exceeds 4.0 meq/g, the strength of the image is easily damaged by the development of alkali water.

In order to enhance various properties such as image quality, the polymer compound of the present invention is preferably further copolymerized with other radical polymerizable compounds in addition to the above-mentioned radical polymerizable compound.

The other radical polymerizable compound, for example, may be, for example, a radical polymerizable compound selected from the group consisting of acrylates, methacrylates, and styrenes.

Specifically, for example, it may be an acrylate such as an alkyl acrylate, a methacrylate such as an aryl acrylate or an alkyl methacrylate, an aryl methacrylate, styrene or an alkylbenzene. A styrene such as ethylene, an alkoxy styrene, a halogenated styrene or the like.

The above acrylates, preferably having a carbon atom of an alkyl group, are 1 to 20, for example, they may be methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, acrylic acid. Ethylhexyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxyethyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylic acid Ester, glycidyl monoacrylate, glycidyl acrylate, benzyl acrylate, methyl benzyl acrylate, furfuryl acrylate, tetramethylolfuran methyl acrylate, and the like.

The aforementioned aryl acrylate may, for example, be phenyl acrylate or the like.

The above-mentioned methacrylates preferably have an alkyl group having 1 to 20 carbon atoms. For example, they may be methyl methacrylate, propyl methacrylate or isopropyl methacrylate. Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, A 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethyl methacrylate, glycidyl methacrylate, Furan methyl methacrylate, tetramethylol methyl methacrylate, and the like.

The aforementioned aryl methacrylate may, for example, be phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate or the like.

The aforementioned styrenes, for example, may be methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl. Styrene, hexyl styrene, cyclohexyl styrene, mercapto styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, ethoxymethyl benzene Ethylene and the like.

The alkoxystyrene described above may be, for example, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene or the like.

The aforementioned halogenated styrene may be, for example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene. , fluorostyrene, tristyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, and the like.

These radical polymerizable compounds may be used alone or in combination of two or more.

The solvent to be used in the synthesis of the polymer compound of the present invention is not particularly limited and may be appropriately selected according to the purpose, and for example, it may be, for example, dichloroethylene, cyclohexanone, methyl ethyl ketone or acetone. , methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyacetate, 1-methoxy-2-propanol, 1-methoxy-2- Propyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylphosphine oxide, 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 of the present invention is preferably 10,000 or more, and more preferably 10,000 to 50,000, based on the mass average molecular weight. When the mass average molecular weight described above is as low as 10,000, the strength of the cured film is insufficient; when it exceeds 50,000, the developing property tends to decrease.

Further, the polymer compound of the present invention may contain an unreacted monomer. In this case, the content of the monomer in the polymer compound is preferably 15% by mass or less.

The polymer compound of the present invention may be used alone or in combination of two or more. Further, it may be used in combination with other polymer compounds. In this case, the content of the other polymer compound in the polymer compound of the present invention is preferably 50% by mass or less, and more preferably 30% by mass or less.

The content of the binder in the photosensitive composition is preferably from 5 to 80% by mass, more preferably from 10 to 70% by mass.

[Polymerizable compound]

The above-mentioned polymerizable compound is not particularly limited, and may be appropriately selected according to the purpose, but is preferably a compound having at least one or more ethylenically unsaturated bonds.

It can be used as an ethylenically unsaturated bond. For example, it may be a vinyl group such as a (meth) acrylonitrile group, a (meth) acryl amide group, a styryl group, a vinyl ester or a vinyl ether. An aryl group such as an aryl ester or an aryl ether.

The compound having one or more ethylenically unsaturated bonds is not particularly limited and may be appropriately selected according to the purpose, but, for example, it is preferable to use a monomer having a (meth) acrylonitrile group. At least one of the selected ones.

The aforementioned monomer having a (meth)acryl fluorenyl group is not particularly limited and may be appropriately selected according to the purpose of the object; for example, it may be polyethylene glycol mono(meth)acrylate, for example Monofunctional acrylate or monofunctional methacrylate such as polypropylene glycol mono(meth)acrylate or phenoxyethyl (meth)acrylate; polyethylene glycol di(meth)acrylate, polypropylene glycol Di(meth)acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di(meth)acrylate, pentaerythritol IV (Meth) acrylate, pentaerythritol tri(meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane diol di(meth) acrylate, trishydroxy Methylpropane tris(propylene methoxypropyl)ether, tris(propylene decyloxyethyl)isocyanate, tris(propylene decyloxyethyl) cyanurate, glycerol tris(methyl Acrylate, trimethylolpropane, glycerin, bisphenol, etc. on a polyfunctional alcohol for epoxy A (meth) acrylated product obtained by an addition reaction of an alkyl group or a propylene oxide; it is described in each of the publications of Japanese Patent Publication No. Sho 48-41708, Japanese Patent Publication No. Sho-50-6034, and No. Sho 51-37193 The urethane acrylates described in each of the publications of JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490; epoxy resins and (meth)acrylic acid; The polyfunctional acrylate or methacrylate of an epoxy acrylate or the like of the reaction product. Among these, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate is particularly preferable.

The solid content of the polymerizable compound in the solid content of the photosensitive composition is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. When the content of the solid content is less than 5% by mass, problems such as deterioration in developability and deterioration in exposure sensitivity occur, and when it exceeds 50% by mass, the adhesion of the photosensitive layer may become too strong.

<Photopolymerization Initiating Compound>

The other photopolymerization initiating compound described above includes a photopolymerization initiator (a radical generator and a hydrogen donor, etc.), and may further include a sensitizer.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and may be appropriately selected from known photopolymerization initiators, however, for example, it is preferably The ultraviolet ray to visible light sensitizing substance may be an active agent which generates any active radical by any action of a photoexcited sensitizer, or may be an initiator which initiates cationic polymerization according to the type of the monomer.

Further, the photopolymerization initiator is preferably one containing at least one molecular absorption coefficient of at least about 50 in the range of about 300 to 800 nm (more preferably 330 to 500 nm).

<<Photopolymerization initiator>>

The aforementioned photopolymerization initiator may, for example, be a halogenated hydrocarbon derivative (for example, having three Skeleton A bisazole skeleton, etc.), a hexaarylbiimidazole, an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a metallocene, and a fluorenylphosphine oxide. Among these, from the viewpoint of preservability, it is preferred to have a mercaptophosphine oxide or a ketone compound.

The aforementioned has three The halogenated hydrocarbon compound of the skeleton may be, for example, a compound described in Japanese Society of Chemistry, Vol. 42, No. 2924 (1969), and a compound described in the specification of British Patent No. 1388492. The compound described in the specification of the patent publication No. 53-133428, the compound described in the specification of the German Patent No. 3337024, and the compound described in the Journal of Organic Chemistry, Vol. 29, p. 1527 (1964), JP-A-62-58241 The compound described in the Japanese Patent Publication No. Hei 5-281728, the compound described in JP-A No. 5-34920, and the compound described in the specification of No. 4,212,976, and the like.

The above-mentioned compound, such as the Japanese Chemical Society, Vol. 42, pp. 2924 (1969), for example, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5 -three , 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-(4-tolyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2,4,6-tris(trichloromethyl)-1,3,5-three 2-methyl-4,6-bis(trichloromethyl)-1,3,5-three ,2-n-mercapto-4,6-bis(trichloromethyl)-1,3,5-three And 2-( α , α , β -trichloroethyl)-4,6-bis(trichloromethyl)-1,3,5-three Wait.

The compound described in the above-mentioned British Patent No. 1388492, for example, 2-styryl-4,6-bis(trichloromethyl)-1,3,5-three ,2-(4-methylstyryl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-three 2-(4-methoxystyryl)-4-amino-6-trichloromethyl-1,3,5-three Wait.

The compound described in JP-A-53-133428, for example, is, for example, 2-(4-methoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-1. 3,5-three 2-(4-Ethoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3,5-three 2-[4-(2-Ethoxyethyl)-naphthalen-1-yl]-4,6-bis(trichloromethyl)-1,3,5-three ,2-(4,7-Dimethoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3,5-three And 2-(ethanenaphthalen-5-yl)-4,6-bis(trichloromethyl)-1,3,5-three Wait.

The compound described in the specification of the aforementioned German Patent No. 3337024, for example, 2-(4-styrylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-(4-methoxystyryl)phenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(1-naphthyl-extended vinylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three 2-chlorostyrene phenyl-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-thiophene-2-extended vinylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-thiophene-3-strandylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-furan-2-extended vinylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three Wait.

The aforementioned FC Schaefer is equivalent to the compound described in the Journal of Organic Chemistry, Vol. 29, p. 1527 (1964), for example, 2-methyl-4,6-bis(tribromomethyl)-1,3,5. -three , 2,4,6-tris(tribromomethyl)-1,3,5-three , 2,4,6-tris(dibromomethyl)-1,3,5-three 2-amino-4-methyl-6-tris(bromomethyl)-1,3,5-three And 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-three Wait.

The compound described in the above-mentioned Japanese Patent Publication No. 62-58241, for example, is 2-(4-phenylethynylphenyl)-4,6-bis(trichloromethyl)-1,3, 5-three , 2-(4-naphthyl-1-ethynylphenyl-4,6-bis(trichloromethyl)-1,3,5-three 2-(4-(4-Tolylethynyl)phenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-(4-methoxyphenyl)ethynylphenyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-(4-(4-isopropylphenylethynyl)phenyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-(4-(4-ethylphenylethynyl)phenyl)-4,6-bis(trichloromethyl)-1,3,5-three Wait.

The compound described in Japanese Laid-Open Patent Publication No. Hei 5-281728, for example, 2-(4-trifluoromethylphenyl)-4,6-bis(trichloromethyl)-1,3,5 -three ,2-(2,6-difluorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-(2,6-dichlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-(2,6-dibromophenyl)-4,6-bis(trichloromethyl)-1,3,5-three Wait.

The compound described in Japanese Laid-Open Patent Publication No. Hei 5-34920, for example, is, for example, 2,4-bis(trichloromethyl)-6-[4-(N,N-diethoxycarbonylmethylamino) )-3-bromophenyl]-1,3,5-three Trihalomethyl-s-three as described in the specification of US Patent No. 4,239,850 The compound may further be 2,4,6-tris(trichloromethyl)-s-three 2-(4-chlorophenyl)-4,6-bis(tribromomethyl)-s-three Wait.

The compound described in the specification of the aforementioned U.S. Patent No. 4,212,976, for example, 2-trichloromethyl-5-phenyl-1,3,4- Diazole, 2-trichloromethyl-5-(4-chlorophenyl)-1,3,4- Diazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4- Diazole, 2-trichloromethyl-5-(2-naphthyl)-1,3,4- Diazole, 2-tribromomethyl-5-phenyl-1,3,4- Diazole, 2-tribromomethyl-5-(2-naphthyl)-1,3,4- Diazole, 2-trichloromethyl-5-styryl-1,3,4- Diazole, 2-trichloromethyl-5-(4-chlorostyryl)-1,3,4- Diazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3,4- Diazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4- Diazole, 2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4- Diazole, 2-tribromomethyl-5-styryl-1,3,4- Diazole, etc.).

The aforementioned hexaarylbiimidazole, for example, may be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2' - bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'- Tetraphenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorobenzene -4,4',5,5'-tetrakis(3-methoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-four (4-methoxyphenyl)biimidazole, 2,2'-bis(4-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2 ,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-nitrophenyl)-4,4',5,5'- Tetraphenylbiimidazole, 2,2'-bis(2-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-trifluoromethyl) Phenyl)-4,4',5,5'-tetraphenylbiimidazole, a compound described in WO 00/52529, and the like.

The aforementioned biimidazoles, for example, can be easily obtained by the method disclosed in Japanese Society of Chemistry, Vol. 33, p. 565 (1960), and Japanese Organic Chemistry, Vol. 36 (16), p. 2262 (1971). synthesis.

The aforementioned anthracene derivative, for example, may be 3-benzylideneoxyimidobutan-2-one, 3-ethyloxyiminobutan-2-one, 3- Propyl methoxyiminobutan-2-one, 2-ethoxymethoxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropan-1-one, 2-Benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy Iminoamino-1-phenylpropan-1-one and the like.

The aforementioned ketone compound, for example, may be benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxyl Benzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, diphenyl Ketone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis(dialkylamino)benzophenone (for example, 4,4'-bis(dimethylamino)benzophenone , 4,4'-(bisdicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino) Benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone , 4-dimethylaminoacetophenone, benzyl, hydrazine, 2-t-butylhydrazine, 2-methylindole, phenanthrenequinone, , thioxanthone, 2-hydrothioxanthone, 2,4-diethoxythioxanthone, anthrone, 2-benzyl-dimethylamino-1-(4-morpholinylphenyl)-1 -butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-hydroxy-2-methyl-[4-(1-methyl) Vinyl)phenyl]propanol oligomer, benzoin, benzoin ether (for example, benzoin methyl ether, benzoin ether, benzoin propyl ether, benzoin isopropyl ether, benzoate) Indoline, benzyldimethylketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, and the like.

The aforementioned metallocenes, for example, may be bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1) -yl)-phenyl)titanium, η ⁵ -cyclopentadienyl-η ⁶ -isopropylphenyl-iron (1+)-hexafluorophosphate (1-), JP-A-53-133428, The compound described in Japanese Patent Publication No. Sho 57-1819, Japanese Patent Publication No. Sho 57-6096, and the specification of U.S. Patent No. 3,615,455.

The aforementioned fluorenylphosphine oxide compound, for example, may be bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzene) Mercapto)-2,4,4-trimethyl-pentylphenylphosphine oxide, Luciferin TPO, Luciferin TPO-L, and the like.

Further, the photopolymerization initiator other than the above may be, for example, an acridine derivative (for example, 9-phenyl acridine or 1,7-bis(9,9'-acridinyl)g. Alkane or the like, N-phenylglycine, etc., polyhalogen compounds (for example, carbon tetrabromide, phenyltribromomethylhydrazine, phenyltrichloromethyl ketone, etc.), coumarins (for example, 3) -(2-benzofuranyl)-7-diethylamino coumarin, 3-(2-benzofuranyl)-7-(1-pyrrolidinyl)coumarin, 3-benzylformamide -7-diethylamino coumarin, 3-(2-methoxybenzimidyl)-7-diethylamino coumarin, 3-(4-dimethylaminobenzoic acid Mercapto)-7-diethylamino coumarin, 3,3'-carbonyl bis(5,7-di-n-propoxycoumarin), 3,3'-carbonyl bis (7-di Ethylamine coumarin), 3-benzylidene-7-methoxycoumarin, 3-(2-furylfluorenyl)-7-diethylamino coumarin, 3-(4 -diethylamino cinnamyl)-7-diethylamino coumarin, 7-methoxy-3-(3 pyrrolidinylcarbonyl)coumarin, 3-benzylidene-5, 7-dipropoxycoumarin, 7- And triazol-2-ylcoumarin, and also in the special Kaiping 5-19475, special Kaiping 7-271028, special opening 2002-363206, special opening 2002-363207, special opening 2002-363208, special opening A coumarin compound or the like described in JP-A-2002-363209, an amine (for example, ethyl 4-dimethylamino benzoate, n-butyl 4-dimethylaminobenzoate, 4- Diethylamino benzoic acid phenethyl ester, 4-dimethylamino benzoic acid 2-noniminoethyl ester, 4-dimethylamino benzoic acid 2-methyl propylene methoxyethyl ester, five Methylene bis(4-dimethylamino benzoate), phenylethyl 3-methylaminobenzoic acid, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2- Chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzimidyl) acetate, 4-piperidylacetophenone , 4-dimethylamino benzoin, N,N-dimethyl-4-toluidine, N,N-diethyl-3-m-ethoxyaniline, tribenzylamine, dibenzylphenyl Amine, N-methyl-N-phenylbenzylamine, 4-bromo-N,N-dimethylaniline Reference dodecylamine, fluoroalkyl amine type (ODB, ODB Ⅱ, etc.), crystal violet lactone, leuco crystal violet, etc.) and the like.

Further, in the case of the sucrose-based polyketal aldehyde-based compound described in the specification of U.S. Patent No. 2,367,660, the occlusion ether described in the specification of U.S. Patent No. 2,448,828 and the specification of U.S. Patent No. 2,722,512, The hydrocarbon-substituted aromatic porphyrin compound, the polynuclear ruthenium compound described in the specification of U.S. Patent No. 3,046, 127 and the specification of U.S. Patent No. 2,591,758, and the organic boron compound and radical generator described in JP-A-2002-229194 a triarylsulfonium salt (for example, a salt of hexafluoroantimony or hexafluorophosphate), a phosphonium salt compound (for example, (phenylthiophenyl)diphenylphosphonium salt, etc.), (an effective cationic initiator), An onium salt compound or the like described in WO 01/71428.

The photopolymerization initiator may be used singly or in combination of two or more.

A particularly preferable example of the photopolymerization initiator described above may be, for example, the above-mentioned mercaptophosphine oxides capable of corresponding to laser light having a wavelength of 405 nm in the exposure described later, and the aforementioned α -amino group. Alkyl ketones, the aforementioned three have three A complex photopolymerization initiator, a hexaarylbiimidazole compound, or an oxetane, which is a combination of a halogenated hydroxy compound of a skeleton and a compound which is a sensitizer described later.

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

<<sensitizer>>

In order to achieve the purpose of adjusting the exposure sensitivity and the light-sensing wavelength at the time of exposure to the photosensitive layer, a sensitizer may be added in addition to the photopolymerization initiator described above.

The sensitizer described above can be appropriately selected by a visible light ray, an ultraviolet ray laser, a visible light laser or the like which is a light irradiation means to be described later.

The sensitizer described above can be excited by an active energy ray, and interacts with other substances (for example, a radical generator, an acid generator, etc.) (for example, energy movement, electron movement, etc.) A useful group of a radical or an acid is produced.

The combination of the above-mentioned photopolymerization initiator and the above-mentioned sensitizer is, for example, an electron-transporting initiator as described in JP-A-2001-305734 [(1) Electronic supply type Starting agent and sensitizing dye, (2) electron-accepting initiator and sensitizing dye, (3) electron-donating initiator, sensitizing dye and electron-accepting initiator (ternary starting system), etc. The combination.

The aforementioned sensitizer is not particularly limited and may be appropriately selected from known sensitizers; for example, it may be a well-known polynuclear aromatic compound (for example, ruthenium, osmium, tri-o-phenylene). , Classes (eg, luciferin, eosin, erythromycin, rhodamine B, rose bengal), cyanines (eg, quinoxaline carbocyanine, thioquinoline carbocyanine, Quinoline carbocyanine), merocyanine (eg, merocyanine, carbonyl cyclamate), thia Classes (eg, Lloyd's violet, methylene blue, toluidine blue), acridines (eg, acridine orange, chlorsulfurin, quercetin, 9-phenyl acridine, 1,7-double (9,9') - acridinyl) heptane), anthraquinones (eg, anthracene), square anthracenes (eg, square anthracene), acridone (eg, acridone, chloroacridone, N-methylhydrazine) Ketone, N-butylacridone, N-butyl-chloroacridone, 2-chloro-10-butylacridone, etc., coumarins (for example, 3-(2-benzofuran) Mercapto)-7-diethylamino coumarin, 3-(2-benzofuranyl)-7-(1-pyrrolidinyl)coumarin, 3-benzylidene-7-di Ethylamino coumarin, 3-(2-methoxybenzimidyl)-7-diethylamino coumarin, 3-(4-dimethylaminobenzimidyl)-7 -diethylamino coumarin, 3,3'-carbonyl bis(5,7-di-n-carboxycoumarin), 3,3'-carbonyl bis(7-diethylamino coumarin ), 3-benzyl-7-methoxycoumarin, 3-(2-furylfluorenyl)-7-diethylaminocoumarin, 3-(4-diethylaminocinnamyl) )-7-diethylamino coumarin, 7-methoxy -3-(3-pyridylcarbonyl)coumarin, 3-benzylidene-5,7-dipropoxycoumarin, etc., in addition to 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., coumarin compounds, etc., and thioxanthone compounds (thioxanthene) Ketone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 1-chloro-4-propoxy a ketone, a Kunta hardened QTX, etc.), etc., among these, a compound in which an aromatic ring or a heterocyclic ring is a condensed ring (condensed ring compound), and more preferably at least two aromatic hydrogen hydrides. An amine compound substituted with any of a ring and an aromatic hetero ring.

Among the above condensed ring-based compounds, a heterocyclic ketone compound (an acridone compound, a thioxanthone compound, a coumarin compound, etc.), and three are more preferable. a compound. Among the above heterocyclic ketone compounds, an acridone compound and a thioxanthone compound are particularly preferred.

The above-mentioned amine compound substituted with at least two aromatic hydroxyhydrogen rings and aromatic heterocyclic rings is preferably a sensitizer having maximum absorption for light in the wavelength range of 330 to 450 nm. For example, it may be, for example, a disubstituted aminobenzophenone type compound, a disubstituted amine group having a heterocyclic group having a substituent of a carbon atom which is a para atom to the amine group on the benzene ring - a benzene-based compound, a disulfonylamino group-containing disubstituted amino-benzene compound having a substituent of a carbon atom which is a para to the amine group on the benzene ring, and a carbonylstyrene-based skeleton A substituted-amino-benzene-based compound and a disubstituted amino-benzene compound having a structure in which at least two aromatic rings are partially bonded to a nitrogen atom.

These sensitizers may be used alone or in combination of two or more.

The blending amount of the above-mentioned sensitizer is preferably from 0.01 to 4% by mass, more preferably from 0.02 to 2% by mass, particularly preferably from 0.05 to 1% by mass, based on the total solid content of the photosensitive composition.

When the content is less than 0.01% by mass, the sensitivity is lowered; when it exceeds 4% by mass, the pattern shape is deteriorated.

<thermal crosslinking agent>

The above-mentioned thermal crosslinking agent is not particularly limited, and may be appropriately selected according to the purpose, and may be used for the purpose of improving the film strength after curing of the photosensitive layer formed using the photosensitive composition described above, for example, without An epoxy compound having at least two ethylene oxide groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule are used in the range in which the properties are adversely affected.

The epoxy compound having at least two ethylene oxide groups in one molecule, for example, may be dimethicone or a biphenol type epoxy resin ("YX4000, manufactured by Nippon Epoxy Co., Ltd." Or a mixture of these; a heterocyclic epoxy resin having an isomeric cyanate skeleton ("TEPIC, manufactured by Nissan Chemical Industries, Ltd.", "Ala Louise PT810, manufactured by Ciba Specialty Chemicals Co., Ltd.", etc.) , bisphenol A epoxy resin, novolak epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, A Phenolic novolak type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, highly halogenated epoxy resin, brominated phenol novolak type epoxy resin, etc.), aryl group-containing bisphenol A type epoxy Resin, trisphenol methane type epoxy resin, diphenyl diphenylene type epoxy resin, epoxy resin having dicyclopentadiene skeleton ("HP-7200, HP-7200H, Dainippon Ink Chemical Industry Co., Ltd. )Company system, etc.), glycidylamine type epoxy resin (diaminodiphenyl group) Type epoxy resin, diglycidyl aniline, triglycidyl phenol, etc.), glycidyl ether type epoxy resin (diglycidyl phthalate, diglycidyl adipate, hexahydrofurfurate) Glycidyl ester, dimer acid diglycidyl ester, etc.), hindered amine type epoxy resin, alicyclic epoxy resin (3,4-epoxycycloheptylmethyl-3', 4'-epoxy Cycloheptanecarboxylate, bis(3,4-epoxycycloheptylmethyl)adipate, dicyclopentadiene epoxide, "GT-300, GT-400, ZEHPE3150; Daisy Chemical industry, etc.), bismuth imine type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylethane type epoxy resin, tannic acid Glycidyl ester resin, tetraglycidyl xylenol ethane resin, naphthalene-containing epoxy resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, 4-functional naphthalene type epoxy resin) Commercially available products include "ESN-190, ESN-360, manufactured by Nippon Steel Chemical Co., Ltd.", "HP-4032, EXA-4750 and EXA-4700, manufactured by Dainippon Ink Chemical Industry Co., Ltd. And a polyphenol compound obtained by an addition reaction between a phenol compound and a diolefin compound such as divinylbenzene or dicyclopentadiene, and a reaction product with epichlorohydrin, and a peracetic acid or the like. a ring-opening polymer of vinylcycloheptane-1-oxide to be epoxidized, an epoxy resin having a linear phosphorus-containing structure, an epoxy resin having a cyclic phosphorus-containing structure, and an α -methyl oxime type Liquid crystal epoxy resin, benzophenoxy phenoxy liquid crystal epoxy resin, azophenyl liquid crystal epoxy resin, azomethylene phenyl liquid crystal epoxy resin, binaphthyl liquid crystal epoxy resin吖 Epoxy resin, glycidyl methacrylate copolymer epoxy resin ("CP-50S and CP-50M, manufactured by Nippon Oil & Fats Co., Ltd."); cyclohexylmaleimide and glycidol methacrylate Epoxy resin copolymer, bis(glycidyloxyphenyl)fluorene type epoxy resin, bis(glycidyloxyphenyl)adamantane type epoxy resin, and the like. These epoxy resins may be used alone or in combination of two or more.

Further, in addition to the above-mentioned epoxy compound having at least two ethylene oxide groups in one molecule, an epoxy compound containing at least one epoxy group having an alkyl group at the β position may be used in at least one molecule. Particularly preferred is a compound containing an epoxy group substituted at the β -position with an alkyl group (more specifically, a β -alkyl group substituted with a glycidyl group, etc.).

The above-mentioned epoxy compound containing at least an epoxy group having an alkyl group at the β -position may be a β -alkyl-substituted glycidyl group, and all of the two or more epoxy groups contained in one molecule may be The epoxy group which may be at least one is a β -alkyl substituted glycidyl group.

The above-mentioned epoxy compound containing at least an epoxy group having an alkyl group at the β -position, and the total epoxy compound contained in the photosensitive composition from the viewpoint of storage stability at room temperature The ratio of the β -alkyl substituted glycidyl group in all the epoxy groups is preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more.

The aforementioned β -alkyl substituted glycidyl group is not particularly limited and may be appropriately selected depending on the purpose, and for example, it may be β -methyl glycidyl group, β -ethyl glycidyl group, β- a propyl glycidyl group, a β -butyl glycidyl group, etc., among these, from the viewpoint of improving the storage stability of the photosensitive resin composition and the ease of synthesis, β -methyl group Glycidyl group.

The aforementioned epoxy compound containing an epoxy group having an alkyl group at the β -position, for example, is preferably an epoxy compound derived from a polyvalent phenol compound and a β -alkylepihalool.

The aforementioned β -alkylepihalohydrin is not particularly limited and may be appropriately selected according to the purpose, and for example, it may be β -methylepichlorohydrin, β -methylepibromohydrin, β -a. the fluoro-alcohol group beta] table - methyl-epihalohydrin; beta] - ethyl-epichlorohydrin, β - ethyl epibromohydrin, β - fluoro-ethyl alcohol, etc. table beta] - ethyl-epihalohydrin; beta] - propionic Β -propyl epihalohydrin such as chlorohydrin, β -propyl epibromohydrin or β -propyl epifluorohydrin; β -butyl epichlorohydrin, β -butyl epibromohydrin, β -butyl A β -butyl epihalohydrin or the like such as epifluorohydrin. Among these, from the viewpoint of reactivity with the polyvalent phenol and fluidity, it is preferred to use β -methylepichlorohydrin.

The polyvalent phenol compound is not particularly limited as long as it is a compound having 2 or more aromatic hydroxyl groups in one molecule, and may be appropriately selected according to the purpose. For example, it may be bisphenol. A, a bisphenol compound such as bisphenol F or bisphenol S; a biphenolic compound such as a biphenol or a tetramethylphenol; a naphthol compound such as a dihydronaphthalene or a binaphthol; a novolac such as a phenol-formaldehyde polycondensate; a monoalkyl-substituted phenol-formaldehyde polycondensate having a carbon number of 1 to 10, such as a phenol-formaldehyde polycondensate; a dialkyl-substituted phenol-formaldehyde having a carbon number of 1 to 10, such as a xylenol-formaldehyde polycondensate a polycondensate; a phenol-formaldehyde polycondensate of bisphenol A-formaldehyde polycondensate; a copolycondensate of phenol and an alkyl substituted phenol and formaldehyde having a carbon number of 1 to 10; and a heavy addition of a phenol compound and divinylbenzene Things and so on. Among these, for example, when the purpose of selecting fluidity and preserving stability is upward, it is preferred to be the aforementioned bisphenol compound.

The beta] contained on the position of an epoxy compound having an epoxy group in the alkyl group, for example, which may be, for example, bisphenol-A - β - substituted alkyl ether, bisphenol F di - β - substituted alkyl ether, bisphenol S di - β - alkyl substituted bisphenol glycidyl ether compound bis - β - substituted alkyl ethers; biphenol di - β - alkyl substituted glycidyl ether, tetramethyl biphenol di - β - alkyl substituted glycidyl ether of biphenol compound di - β - substituted alkyl glycidyl ether; dihydronaphthalene di - β - substituted alkyl glycidyl ether, double naphthol di - beta] - alkyl-substituted glycidyl ether compound of naphthol di - beta] - alkyl-substituted glycidyl ether; phenol - formaldehyde polycondensate di - beta] - alkyl-substituted glycidyl ether; cresol - formaldehyde polycondensate di - beta] - alkyl-substituted glycidyl ether of a carbon number of 1 to 10 monoalkyl-substituted phenol - formaldehyde polycondensate di - beta] - alkyl-substituted glycidyl ether; xylenol - formaldehyde polycondensate di - β - substituted alkyl glycidyl ether, etc. The number of 1 to 10 dialkyl-substituted phenol - formaldehyde polycondensate di - beta] - alkyl-substituted glycidyl ether; bisphenol A- formaldehyde polycondensate di - beta] - alkyl-substituted glycidyl ether of a phenol - formaldehyde polycondensate di - β - substituted alkyl glycidyl ether; and adducts of dimeric phenol compound and divinylbenzene - β - substituted alkyl glycidyl ether.

Among these, it is preferred to use a β -alkyl glycidyl ether derived from a bisphenol compound represented by the following structure (iii), a polymer obtained therefrom and an epihalohydrin, and the like (iv) A poly- β -alkyl glycidyl ether represented by a phenol compound-formaldehyde polycondensate.

However, in the above structure (iii), R represents any one of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 20.

However, in the above structure (iv), R represents any one of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and R" represents any of a hydrogen atom and CH ₃ . An integer from 0 to 20.

These epoxy compounds containing an epoxy group having an alkyl group at the β -position may be used alone or in combination of two or more. Further, an epoxy compound having at least two ethylene oxide groups in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β -position may be used in combination.

The aforementioned oxetane compound, for example, may be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-) 3-oxetanyl methoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4- Bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl 3-oxetanyl)methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetane An oxetanyl group other than a polyfunctional oxetane such as a methyl methacrylate or an oligomer or a copolymer thereof, a novolac resin, or a poly(p-hydroxystyrene), An ether compound in which a bulky external bisphenol, a calixarene, a cup-resorcinol aromatic hydrocarbon, a resin having a hydroxyl group such as sesquiterpene oxide or the like is contained; in addition to, for example, It may be an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate. Copolymers, etc.

Further, in order to promote thermal hardening of the aforementioned epoxy compound and the aforementioned oxetane compound, for example, an amine compound (for example, cyanogen, benzyldimethylamine, 4-(dimethylamino)-) may be used. N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compound (for example , triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (for example, dimethylamine, etc.), imidazole derivatives, bicyclic guanidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-B Imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)- 2-ethyl-4-methylimidazole or the like), a phosphorus compound (for example, triphenylphosphine, etc.), a guanamine compound (for example, melamine, guanamine, acetamide, benzoguanamine, etc.), S-three Derivatives (for example, 2,4-diamino-6-methacryloxyethyl-S-three 2-vinyl-2,4-diamino-S-three 2-vinyl-4,6-diamino-S-three Iso- cyanuric acid adduct, 2,4-diamino-6-methylpropenyloxyethyl-S-three A different isocyanate adduct, etc.). These may be used alone or in combination of two or more. In addition, as long as it is a curing catalyst of the epoxy compound and the oxetane compound, or a reaction with the carboxyl group can be promoted, it is not particularly limited, and heat other than the above can be used. Hardened compound.

The above-mentioned epoxy compound, the above-described oxetane compound, and a compound which is thermally hardened with the carboxylic acid, and the solid content of the photosensitive component solid component is usually It is 0.01 to 15% by mass.

Further, the above-mentioned thermal crosslinking agent may be a polyisocyanate compound described in JP-A-5-9407, and the polyisocyanate compound may be an aliphatic compound or a cyclic aliphatic compound containing at least two isocyanate groups. Or derived from an aromatic-substituted aliphatic compound. Specifically, for example, it may be a bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene) Diisocyanate, 1,3- and 1,4-dimethylbenzene diisocyanate, bis(4-isocyanatophenyl)methane, bis(4-isocyanatoethylcyclohexyl)methane, isophorone Diisocyanate, hexyl diisocyanate, trimethylhexyl diisocyanate, etc.), the bifunctional isocyanate, polyfunctional alcohol with trimethylolpropane, pentaerythritol, glycerin, etc., addition of alkylene oxide of the polyfunctional alcohol And an adduct of the above-mentioned bifunctional isocyanate; a cyclic trimer of exohexyl diisocyanate, exohexyl-1,6-diisocyanate and derivatives thereof, and the like.

Further, for the purpose of improving the preservability of the photosensitive composition of the present invention, a compound obtained by reacting the isocyanate group of the above polyisocyanate and its derivative with a block agent may be used.

The above-mentioned isocyanato blocker may, for example, be an alcohol (for example, isopropanol, tert-butanol, etc.), an intrinsic amine (for example, ε-caprolactam, etc.), Phenols (for example, phenol, cresol, p-tert-butyl phenol, p-sec-butyl phenol, p-sec-aminophenol, p-octyl phenol, p-nonyl phenol, etc.), heterocyclic ring a hydroxy compound (for example, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), an active methylene compound (for example, dialkyl malonate, methyl ethyl ketone oxime, acetamidine acetone, alkyl acetoacetic acid) Ester oxime, acetone oxime, cyclohexanone oxime, etc.). In addition, a compound having at least one polymerizable double bond and at least one block isocyanate group in the molecule described in JP-A-6-295060 can be used.

Further, a melamine derivative can be used as the aforementioned thermal crosslinking agent. The melamine derivative may, for example, be methylol melamine or alkylated methylol melamine (a compound which etherifies a methylol group such as a methyl group, an ethyl group or a butyl group). These may be used alone or in combination of two or more. Among these, from the viewpoint of maintaining good stability and effectively improving the surface hardness of the photosensitive layer or the film strength of the cured film itself, it is preferred to use alkylated methylol melamine, particularly preferably hexamethylated. Hydroxymethyl melamine.

In the solid content of the photosensitive composition, the solid content of the thermal crosslinking agent is preferably from 1 to 50% by mass, more preferably from 3 to 30% by mass. When the solid content is less than 1% by mass, the film strength of the cured film cannot be confirmed to increase, and when it exceeds 50% by mass, the developability is lowered and the exposure sensitivity is lowered.

<Other ingredients>

The other components mentioned above may be, for example, a thermal polymerization inhibitor, a plasticizer, a colorant (coloring pigment or dye), a filler pigment, etc., and may also be a adhesion promoter to the surface of the substrate. Other additives (for example, conductive particles, a filler, an antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, a surface tension adjuster, a chain shifting agent, etc.) are used together. By appropriately containing these components, the properties of the photosensitive film such as stability, filminess, and film properties can be adjusted.

<<Thermal polymerization inhibitor>>

The above-mentioned thermal polymerization inhibiting agent may be added for the purpose of preventing thermal polymerization or polymerization over time of the above polymerizable compound.

The aforementioned thermal polymerization inhibiting agent may, for example, be 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, benzenetriol, 2- Hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, benzothiazide , chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-t-butylphenol ), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, reaction product of copper with an organic chelating agent, methyl salicylate and benzothiazide a nitroso compound, a chelate compound of a nitroso compound and Al, and the like.

The content of the above-mentioned thermal polymerization inhibiting agent is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, particularly preferably 0.01 to 1% by mass, based on the polymerizable compound. When the content is less than 0.001% by mass, the storage stability may be lowered, and when it exceeds 5% by mass, the sensitivity to the active energy ray may be lowered.

<<Coloring pigment>>

The coloring pigment is not particularly limited and may be appropriately selected depending on the purpose; for example, it may be, for example, Victoria Pure Blue BO (CI42595), Goldamine (CI41000), Lip Black HB (CI26150). , single pigment yellow GT (CI pigment yellow 12), permanent yellow GR (CI pigment yellow 17), permanent yellow HR (CI pigment yellow 83), permanent magenta FBB (CI pigment red 146), Horst red ESB (CI Pigment Violet 19), Everlasting Ruby Red FBH (CI Pigment Red 11), Fixative Ultra Pink B (CI Pigment Red 81), Single Star Fast Blue (CI Pigment Blue 15), Single Pigment Fast Black B (CI Pigment Black 1), Carbon Black, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215 CI Pigment Green 7, CI Pigment Green 36, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 22, CI Pigment Blue 60, and CI Pigment Blue Pigment Blue 64. These may be used alone or in combination of two or more. Further, a dye appropriately selected from known dyes may be used as the case requires. Further, a dye appropriately selected from known dyes may be used as the case requires.

The solid content of the coloring pigment in the solid content of the photosensitive composition can be determined in consideration of the exposure sensitivity and the resolution of the photosensitive layer at the time of formation of the permanent pattern, and may vary depending on the type of the color pigment. However, it is generally preferably from 0.05 to 10% by mass, more preferably from 0.1 to 5% by mass.

<<filling pigment>>

In the above-mentioned photosensitive composition, it may be added as needed to enhance the surface hardness of the permanent pattern, or to suppress a decrease in the coefficient of linear expansion, or to suppress the dielectric constant of the cured film itself and the reduction of the dielectric tangent. Pigments and organic microparticles.

The above-mentioned inorganic pigment is not particularly limited and may be appropriately selected from known ones, for example, it may be kaolin, barium sulfate, barium titanate, cerium oxide powder, fine powder cerium oxide, gas phase method. Stone, amorphous vermiculite, crystalline vermiculite, molten vermiculite, globular vermiculite, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, mica, and the like. The above inorganic pigment preferably has an average particle diameter of less than 10 μm, more preferably 3 μm or less. When the average particle diameter is 10 μm or more, the resolution may be deteriorated due to light scattering.

The organic fine particles described above are not particularly limited and may be appropriately selected according to the purpose, and may be, for example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin or the like. Further, spherical porous fine particles formed of vermiculite having an average particle diameter of 1 to 5 μm and an oil absorption of about 100 to 200 m 2 /g or a crosslinked resin can be used.

The amount of the above-mentioned filler pigment added is preferably from 5 to 60% by mass. When the amount of addition is less than 5% by mass, there is a case where the coefficient of linear expansion cannot be sufficiently lowered; and when it exceeds 60% by mass, in the case where a cured film is formed on the surface of the photosensitive layer, the film of the cured film is It becomes brittle; in the case where wiring is formed using a permanent pattern, there is a function of impairing the protective film as a wiring.

<<Intimate accelerator>>

In order to improve the adhesion between the layers or the adhesion between the photosensitive layer and the substrate, a known so-called adhesion promoter can be used for each layer.

For example, the adhesion promoter described in the above-mentioned Japanese Patent Application Laid-Open No. Hei 5- No. Hei No. Hei. Specific examples, for example, may be benzimidazole, benzo Oxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoene Azole, 2-mercaptobenzothiazole, 3-morpholinylmethyl-1-phenyl-triazol-2-one, 3-morpholinylmethyl-5-phenyl- Dioxazol-2-one, 5-amino-3-morpholinylmethyl-thiadiazol-2-one, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzo Triazole, carboxybenzotriazole, amine-containing benzotriazole, and decane coupling agent.

The content of the adhesion promoter is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, particularly preferably 0.1 to 5% by mass, based on the total amount of the components in the photosensitive layer.

For example, the method of forming the photosensitive layer may be a method of applying the photosensitive composition onto the surface of the substrate and drying it, for example, for example, It is a method of laminating a photosensitive layer on the surface of a substrate under at least any one of heating and pressurization in the second aspect.

In the method of forming the photosensitive layer according to the first aspect described above, the photosensitive composition is applied onto the substrate and dried to form a photosensitive layer.

The method of coating and drying described above is not particularly limited, and may be appropriately selected depending on the purpose; for example, the photosensitive composition may be dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive film. The composition solution is applied directly to the surface of the above-mentioned substrate, and dried and laminated.

The solvent of the photosensitive composition solution described above is not particularly limited and may be appropriately selected according to the purpose, and for example, it may be methanol, ethanol, n-propanol, isopropanol, n. An alcohol such as butanol, sec-butanol or n-hexanol; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or diisobutyl ketone; ethyl acetate; Esters of butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl decanoate, ethyl benzoate and methoxypropyl acetate; toluene, xylene, benzene , aromatic hydrocarbons such as ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, dichloromethane, monochlorobenzene, etc.; tetrahydrofuran, diethyl Ethers such as ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl hydrazine,环丁碸 and so on. These may be used alone or in combination of two or more. Further, a known surfactant may be added.

The coating method described above is not particularly limited and may be appropriately selected depending on the purpose, and for example, it may be a spin coater, a slit coater, a roll coater, a die coater, or a curtain. A coating machine or the like is a method of directly coating the substrate.

Although the drying conditions described above vary depending on the components, the type of the solvent, the ratio of use, and the like, they are usually carried out at a temperature of 60 to 110 ° C for about 30 seconds to 15 minutes.

The thickness of the photosensitive layer described above is not particularly limited and may be appropriately selected depending on the purpose, and is, for example, preferably from 3 to 100 μm, more preferably from 5 to 70 μm.

In the method of forming the photosensitive layer of the second aspect, at least one of heat and pressure is applied to the photosensitive film having the support and the photosensitive layer formed of the photosensitive composition laminated on the support. One is to laminate a photosensitive film on the surface of the substrate. In the case where the photosensitive film described above has a protective film to be described later, it is preferred to laminate the protective film so that the photosensitive layer and the base are combined.

(photosensitive film)

The photosensitive film is preferably provided with at least a support and a photosensitive layer, and preferably has a protective film, and further has a buffer layer, an oxygen barrier layer (PC layer) or the like as needed.

The form of the photosensitive film is not particularly limited, and may be appropriately selected according to the purpose. For example, it may be a form in which the photosensitive layer and the protective film are sequentially formed on the support; a form in which the PC layer, the photosensitive layer, and the protective film are sequentially formed on the support; and the buffer layer, the PC layer, the photosensitive layer, and the protective film are sequentially formed on the support. form. Further, the photosensitive layer may be a single layer or a plurality of layers.

<support>

The above-mentioned support is not particularly limited, and may be appropriately selected depending on the purpose. However, it is preferable that the photosensitive layer can be peeled off and the light transmittance is good, and it is more preferable that the surface is excellent in smoothness.

The aforementioned support is preferably made of a synthetic resin and is transparent. For example, it may be polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, triacetate. , cellulose diacetate, alkyl poly(meth)acrylate, poly(meth)acrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride Ethylene copolymer, polyamine, polyimine, vinyl chloride. Various plastic films such as vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose film, and nylon film. Among these, polyethylene terephthalate is particularly preferred. These may be used alone or in combination of two or more.

In addition, as described above, the above-mentioned support can be used as described in Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei 5- No. Hei. Support body.

The thickness of the aforementioned support is not particularly limited and may be appropriately selected depending on the purpose; for example, it is preferably 4 to 300 μm, more preferably 5 to 175 μm.

The shape of the aforementioned support body is not particularly limited, and may be appropriately selected depending on the purpose; for example, it is preferably elongated. The length of the aforementioned elongated support is not particularly limited, and for example, it may be from 10 meters to 20,000 meters.

- Photosensitive layer of photosensitive film -

The photosensitive layer of the photosensitive film is formed by using the photosensitive composition described above.

The position at which the photosensitive layer is provided in the photosensitive film is not particularly limited, and may be appropriately selected depending on the purpose, and is usually laminated on the support.

The thickness of the photosensitive layer in the photosensitive film is not particularly limited and may be appropriately selected according to the purpose, and is, for example, preferably from 3 to 100 μm, more preferably from 5 to 70 μm.

The formation of the photosensitive layer of the photosensitive film can be carried out by the same method as the method of applying the photosensitive composition solution to the substrate and drying (method of forming the photosensitive layer of the first aspect), for example, For example, a method of applying the photosensitive composition solution by a spin coater, a slit coater, a roll coater, a die coater, or a curtain coater can be used.

<Protective film>

The protective film described above is capable of preventing stains and damage of the photosensitive layer and has a protective function.

The position at which the protective film is provided in the photosensitive film is not particularly limited, and may be appropriately selected depending on the purpose, and is usually provided on the photosensitive layer.

The protective film may be, for example, a material used on the support, a polyoxynized paper, a paper laminated with polypropylene or polyethylene, a polyolefin or a polytetrafluoroethylene sheet, or the like. Among these, a polyethylene film or a polypropylene film is preferred.

The thickness of the protective film is not particularly limited and may be appropriately selected depending on the purpose; for example, it is preferably 5 to 100 μm, more preferably 8 to 30 μm.

In the case of using the protective film described above, the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film preferably have the relationship of adhesive force A and adhesive force B. .

The combination of the foregoing support and the protective film (support/protective film), for example, may be (polyethylene terephthalate/polypropylene) or (polyethylene terephthalate/polyethylene) , (polyvinyl chloride / cellophane), (polyimide / polypropylene), and (polyethylene terephthalate / polyethylene terephthalate). Further, by performing surface treatment on at least one of the support and the protective film, the adhesive force can satisfy the above relationship. The surface treatment of the support may be performed to enhance the adhesion strength to the photosensitive layer. For example, an undercoat layer, a corona discharge treatment, a flame treatment, an ultraviolet irradiation treatment, a high-frequency wave irradiation treatment, a glow discharge may be applied. Treatment, active plasma irradiation treatment, and laser treatment.

Further, the static friction coefficient between the support and the protective film is preferably from 0.3 to 1.4, more preferably from 0.5 to 1.2.

When the aforementioned static friction coefficient is less than 0.3, the winding gap may be generated in the case of forming a reel due to excessive slidability; and when it exceeds 1.4, it is difficult to roll into a good reel shape.

The photosensitive film described above is, for example, a core wound in a cylindrical shape, and is preferably stored in a long roll shape. The length of the long strip-shaped photosensitive film is not particularly limited, and may be appropriately selected, for example, from 10 meters to 20,000 meters. Further, in order to make it easy for the user to use, it is also possible to form a long strip having a roll shape ranging from 100 meters to 1,000 meters in a slit shape. Further, in this case, it is preferable to wind the aforementioned support body to the outermost side. Further, the above-mentioned roll-shaped photosensitive film may be subdivided into a sheet shape. When storing, from the viewpoint of end face protection and corrosion prevention, it is preferable to provide a separator (especially a moisture-proof substance and a desiccant) on the end surface, and it is also preferable to use a bag and a moisture-permeable bag. Low material.

In order to adjust the adhesion between the protective film and the photosensitive layer, the aforementioned protective film can also be subjected to surface treatment. In the above surface treatment, for example, an undercoat layer composed of a polymer of polyorganosiloxane, fluorinated polyolefin, polyvinyl fluoride, or polyvinyl alcohol may be formed on the surface of the protective film. The undercoat layer may be formed by applying the coating liquid of the above polymer to the surface of the protective film, followed by drying at 30 ° C to 150 ° C (especially 50 ° C to 120 ° C) for 1 to 30 minutes.

Further, in addition to the photosensitive layer, the support described above, and the protective film described above, a layer such as a buffer layer, an oxygen barrier layer (PC layer), a release layer, an adhesive layer, a light absorbing layer, and a surface protective layer may be provided.

The aforementioned buffer layer is a layer which is non-tacky at normal temperature and which melts and flows when laminated under vacuum heating conditions.

The PC layer is usually a coating film of about 0.5 to 5 μm which is formed mainly of polyvinyl alcohol.

(Manufacturing method of photosensitive composition)

The photosensitive composition described above can be produced, for example, in the following manner.

First, a material contained in the photosensitive composition is dissolved, emulsified, or dispersed in water or a solvent to prepare a photosensitive composition solution for a photosensitive composition. Further, a known surfactant may be added.

Next, a photosensitive composition can be produced by applying the above-mentioned photosensitive composition solution onto the above-mentioned substrate or the above-mentioned support, and drying it to form a photosensitive layer.

The coating method of the photosensitive composition solution described above is not particularly limited, and may be appropriately selected according to the purpose, and may be, for example, a spray method, a roll coating method, a rotary coating method, a slit coating method, or extrusion. Various coating methods such as a press coating method, a curtain coating method, a die coating method, a gravure coating method, a bar coating method, and a knife coating method.

Although the conditions of the drying differ depending on the type of each component, the type of the solvent, the ratio of use, and the like, it is usually carried out at a temperature of 60 to 110 ° C for about 30 seconds to 15 minutes.

<Formation of laminated body>

When the photosensitive composition of the present invention is used for pattern formation, the photosensitive layer of the photosensitive composition is laminated on a substrate to form a laminate.

The above-mentioned substrate is not particularly limited and may be appropriately selected according to the purpose. For example, it may be arbitrarily selected from a surface smoothness to a surface having a concave-convex surface, but is preferably a plate-like substrate (printed substrate); For example, it may be a known printed wiring manufacturing substrate (for example, a copper-clad laminate), a glass plate (for example, an alkali glass plate, etc.), a synthetic resin-resin film, paper, a metal plate, or the like. .

The layer structure of the above-mentioned laminated body is not particularly limited, and may be appropriately selected according to the purpose. For example, it is preferred to have a layer structure in which the above-mentioned substrate, the above-mentioned photosensitive layer, and the above-mentioned support are sequentially provided. In the case where the photosensitive film described above has a protective film to be described later, it is preferred that the protective film is peeled off and the photosensitive layer is laminated to the above-mentioned basis weight.

The method for forming the laminate is not particularly limited, and may be appropriately selected according to the purpose, and it is preferred to apply a solution of the photosensitive composition for the photosensitive composition onto the surface of the substrate and dry it. In the laminated form, the photosensitive composition is laminated on the substrate while performing at least one of heating and pressurization.

The above heating temperature is not particularly limited and may be appropriately selected depending on the purpose, however, for example, it is preferably 70 to 130 ° C, more preferably 80 to 110 ° C.

The pressure of the pressurization is not particularly limited and may be appropriately selected according to the purpose, but is, for example, preferably 0.01 to 1.0 MPa, more preferably 0.05 to 1.0 MPa.

The apparatus for performing at least any of the above-described heating and pressurization is not particularly limited and may be appropriately selected according to the purpose. However, for example, a suitable laminator is a hot press or a hot roll laminator. (For example, VP-II manufactured by Dacheng Laminator Co., Ltd.), a vacuum laminator (for example, VP130 manufactured by Nichiymon Co., Ltd.), and the like.

Since the photosensitive composition of the present invention can form a high-definition pattern excellent in sensitivity and excellent in storage stability with good efficiency by containing a predetermined polymer, it can be suitably used for a protective film, an interlayer insulating film, and resistant. Permanent pattern formation for manufacturing liquid crystal structural components such as permanent patterns such as solder patterns, color filters, pillars, ribs, spacers, partition walls, etc., holography, micromachining, verification, etc. In particular, it can be suitably used for permanent pattern forming applications of printed boards.

The pattern forming apparatus of the present invention includes the above-described photosensitive layer, and has at least a light irradiation mechanism and a light modulation mechanism.

The permanent pattern forming method of the present invention comprises at least an exposure step and includes other steps of a suitably selected developing step or the like.

Further, the above-described pattern forming apparatus of the present invention has been clearly understood from the above description of the pattern forming method of the present invention.

[Exposure step]

The aforementioned exposure step is a step of exposing the photosensitive layer in the photosensitive composition of the present invention. The photosensitive composition and the material of the substrate of the present invention are as described above.

The object to be exposed is preferably a photosensitive layer in the photosensitive composition, and is not particularly limited, and may be appropriately selected according to the purpose. However, for example, it is preferably as described above. It is carried out by laminating a layer formed on a substrate by heating and pressurizing the photosensitive film.

Although the aforementioned exposure is not particularly limited, it may be appropriately selected according to the purpose, however, for example, it is preferably a digital exposure, an analog exposure, or the like; among these, digital exposure is preferred.

The aforementioned digital exposure is not particularly limited and may be appropriately selected according to the needs of the object, for example, using light generated based on the formed pattern forming information and modulated with the control signal; for example, It is preferable to use an exposure head for the photosensitive layer described above, which is provided with a light irradiation mechanism and a n-dimensional shape having n (but, n is a natural number of 2 or more) having received light from the light irradiation means and emitted. The aligned pixel portion, the exposure head capable of controlling the light modulation mechanism of the pixel portion in response to the pattern information, and configured to cause the column direction of the pixel portion to form a predetermined direction with the scanning direction of the exposure head The tilt angle θ is set. The above-described exposure head is specified by the use of the pixel portion specifying means for the N-time exposure (but N is a natural number of 2 or more) among the available pixel portions. In the above-mentioned exposure head, by means of the pixel control mechanism, the control is performed in such a manner that the aforementioned pixel portion specified by the above-mentioned use of the pixel designation institution is involved in the exposure. And a method of exposing the photosensitive layer by moving the exposure head relative to a scanning direction.

In the present invention, "N-time exposure" means a line parallel to the scanning direction of the exposure head in approximately the entire area of the exposed surface on the photosensitive layer, and N light irradiated on the exposed surface. The dot column (pixel column) is set to be crossed and exposed. In the present disclosure, the "spot array" is a direction which is smaller than the angle of the scanning direction of the exposure head among the pixel (pixel) columns of the pixel unit generated by the pixel portion. The list. Further, the arrangement of the aforementioned pixel portions does not necessarily have to be a rectangular lattice shape, and for example, may be a configuration of a parallelogram shape or the like.

The "about all regions" described herein, in terms of the both side edges of the respective pixel portions, reduce the use of pixels that intersect the scanning direction parallel to the exposure head by tilting the pixel portion. The number of pixels in the part, so in this case, even if a plurality of exposure heads are connected for use, a straight line parallel to the scanning direction is caused by an error in the mounting angle and arrangement of the exposure head. In the case of using the number of pixels in the pixel portion, the number of pixels in the pixel portion is slightly increased or decreased, and the resolution of each of the pixel portions in the pixel portion is divided into a minimum of the following, due to the mounting angle and the arrangement of the pixel portion. The error is such that the pitch of the pixel portion along the direction perpendicular to the scanning direction cannot be strictly coincident with the pitch of the pixel portion of the other portion, and thus the pixel portion intersecting with the straight line parallel to the scanning direction is used. The number of the pixel parts is increased or decreased within the range of ±1. In addition, in the following description, the N exposure of the natural number of N or more is called "multiple exposure." Furthermore, in the following description, the exposure apparatus and the exposure method of the present invention are implemented as a drawing apparatus and a drawing method, and the terms "N times drawing" and "multiple drawing" are used. It is a term corresponding to "N exposure" and "multiple exposure".

The N of the N-th exposure described above is not particularly limited as long as it is a natural number of 2 or more, and may be appropriately selected according to the purpose. However, it is preferably a natural number of 3 or more, and more preferably 3 or more and 7 or less. The natural number.

An example of a pattern forming apparatus relating to the permanent pattern forming method of the present invention will be described with reference to the drawings.

The above-described pattern forming apparatus, that is, a so-called flat head type exposure apparatus, as shown in Fig. 1, is provided with a sheet-like photosensitive material 12 in which at least the photosensitive layer is laminated on the photosensitive film (hereinafter There is a flat plate-like stage 14 which is adsorbed and held on the surface, which is called "photosensitive layer 12". On the upper surface of the thick plate-like mounting table 18 supported by the four leg portions 16, two guide members 20 extending in the direction in which the platform moves are provided. The length direction of the platform 14 is disposed toward the moving direction of the platform while being supported by the guide 20 to move back and forth. Further, in the pattern forming apparatus 10, a driving device (not shown) for driving the stage 14 along the guide 20 is provided.

At a central portion of the setting table 18, there is a moving path that can span the platform 14. Font gate 22. The ends of the font gates 22 are each fixed to both sides of the setting table 18. A scanner 24 is disposed on one side of the gate 22, and a plurality of (for example, two) detection sensors 26 for detecting the front end and the rear end of the photosensitive material 12 are disposed on the other side. The scanner 24 and the detecting sensor 26 are respectively mounted on the gate 22 and fixedly disposed above the moving path of the platform 14. In addition, the scanner 24 and the detection sensor 26 are connected to a controller that controls these without being shown.

Herein, for the sake of explanation, the X-axis and the Y-axis which are perpendicular to each other are defined as shown in FIG. 1 on a plane parallel to the surface of the stage 14.

In the end portion of the upstream side of the scanning direction of the stage 14 (hereinafter, simply referred to as "the upstream side"), a slit 28 having a U shape is formed in the X-axis direction at equal intervals. Form 10 pieces. Each of the slits 28 is formed by a slit 28a on the upstream side and a slit 28b on the downstream side. The slit 28a and the slit 28b are perpendicular to each other, and the slit 28a is -45 degrees with respect to the X-axis and the slit 28b has an angle of +45 degrees.

The position of the slit 28 is slightly coincident with the center of the aforementioned exposure head 30. Further, each slit 28 is sized to sufficiently cover the width of the exposure region 32 of the corresponding exposure head 30. Further, the position of the slit 28 is slightly coincident with the center position of the overlapping portion between the exposure completion regions 34. In this case, each slit 28 is sized to sufficiently cover the width of the overlapping portion between the exposure completion regions 34.

A single cell type of a spot position detecting mechanism that detects light in a pixel unit in the pixel specifying process described later is incorporated in a position below each slit 28 in the stage 14 Light detector (not shown). Further, each of the photodetectors is connected to an arithmetic unit (not shown) that performs the pixel unit selection unit that selects the pixel unit in the pixel unit specifying process to be described later.

The operation mode of the pattern forming apparatus during exposure may be such that the exposure head is continuously exposed while moving, or the exposure head may be moved stepwise to expose the exposure head to the position of each of the moving ends to perform exposure. The form of the action.

<<Exposure head>>

Each of the exposure heads 30 is attached to the scanner 24 so that the respective pixel portions (microlens) column directions of the internal digital microlens device (DMD) 36 to be described later and the scanning direction become a predetermined set inclination angle θ. Therefore, the exposure region 32 of each exposure head 30 is a rectangular region that is inclined with respect to the scanning direction. As the stage 14 moves, a strip-shaped exposure completion area 34 of each of the exposure heads 30 is formed on the photosensitive layer 12. In the examples shown in Figs. 2 and 3B, the scanner 24 is provided with ten exposure heads arranged in a matrix of two rows and five columns.

In addition, in the following, in the case of displaying the respective exposure heads arranged in the nth row of the mth row, it is described as the exposure head 30 _mn ; when the respective exposure heads arranged in the nth column of the mth row are displayed In the case of the exposure range, it is described as the exposure area 32 _mn .

Further, as shown in FIGS. 3A and 3B, each of the strip-shaped exposure completion regions 34 is partially overlapped with the adjacent exposure completion regions 34, and the exposure heads 30 of the respective rows arranged in a line shape are arranged. Each of them is disposed at a predetermined interval (a natural multiple of the long side of the exposure region, twice in the present embodiment), and is arranged in the arrangement direction without a gap. Therefore, the portion of the first row between the exposed region 32 ₁₁ and the exposed region 32 ₁₂ that is not exposed can be exposed by the exposure region 32 _{21 of} the second row.

Each of the exposure heads 30, as shown in FIG. 4, FIG. 5A, and FIG. 5B, is provided with a light modulation mechanism for modulating the incident light corresponding to the image data for each pixel portion. DMD36 (manufactured by Texas Instruments, Inc.) of the space light modulation component of the Ministry of Science and Technology. The DMD 36 is connected to a controller including a data processing unit and a lens drive control unit. The data processing unit of the controller generates a control signal for driving each microlens in the use region on the DMD 36 for each of the exposure heads 30 based on the input pattern information. Further, the lens drive control unit controls the angle of the reflection surface of each of the microlenses of the DMD 36 for each of the exposure heads 30 based on the control signal generated by the pattern information processing unit.

As shown in FIG. 4, the fibers of the laser emitting portion in which the emission end portions (light-emitting points) of the optical fibers are arranged in a line in the direction in which the longitudinal direction of the exposure region 32 is aligned are arranged in this order on the light incident side of the DMD 36. The array light source 38 corrects the laser light emitted from the fiber array light source 38 to condense the lens system 40 on the DMD, and the lens 42 that reflects the laser light transmitted through the lens system 40 toward the DMD 36. In addition, FIG. 4 is a schematic view schematically showing the lens system 40.

The lens system 40 described above, as shown in FIGS. 5A and 5B, is a pair of combined lenses 44 that collimate the laser light emitted from the fiber array light source 38 in parallel, and is optically parallelized. The laser beam is corrected by a pair of combined lenses 46 having a uniform light amount distribution and a collecting lens 48 for condensing the laser light having the corrected light amount distribution on the DMD 36.

Further, on the light reflection side of the DMD 36, a lens system 50 for imaging the laser light reflected by the DMD 36 on the exposure surface of the photosensitive layer 12 is disposed. The lens system 50 is formed by the two-plane lenses 52 and 54 which are disposed such that the exposure surfaces of the DMD 36 and the photosensitive layer 12 are in a conjugate relationship.

In the present embodiment, the laser light emitted from the fiber array light source 38 is set such that after substantially five times magnification, the light from each of the microlenses on the DMD 36 is shortened to about 5 μm via the lens 50 described above.

-Light modulation mechanism -

The light modulation mechanism described above is a pixel unit having n (but a natural number of 2 or more) and can control the pixel unit in accordance with the pattern information. However, it is not particularly limited, and may be appropriately selected according to the needs of the object, however, for example, it is preferably a spatial light modulation element.

For example, a spatial light modulation device (SLM, Special Light Modulator) having a digital microlens device (DMD) or a MEMS (Micro Electro Mechanical Systems) type is suitable. A spatial light modulator), an optical element (PLZT element) that modulates transmitted light by an electro-optical effect, a liquid crystal shutter (FLC), etc., among which, for example, DMD is preferable.

Further, the optical modulation means described above is preferably a pattern signal generating means for generating a control signal based on the formed pattern forming information. In this case, the optical modulation mechanism described above modulates the light with a control signal generated by the pattern signal generating means described above.

The aforementioned control signal is not particularly limited, and may be appropriately selected according to the needs of the object. However, for example, a suitable person may have a digital signal or the like.

Hereinafter, an example of the above-described optical modulation mechanism will be described with reference to the drawings.

As shown in Fig. 6, the DMD 36 is a microlens device in which a plurality of microlenses 58 constituting a pixel portion of each pixel (pixel) are arranged in a lattice on the SRAM unit (memory unit) 56. In the present embodiment, although the DMD 36 configured by the 1024 columns x 768 rows of microlenses 58 is used, the microlenses 58 that can be driven by the controllers connected to the DMDs 36 can be used. , only 1024 columns × 256 rows. Since the data processing speed of the DMD 36 is limited, since the modulation speed per column is determined by the ratio of the number of microlenses used, only a part of the lens can be used to make the modulation speed of each column faster. . Each of the microlenses 58 is supported by a pillar, and the surface thereof is a highly reflective material such as vapor-deposited aluminum. Further, in the present embodiment, the reflectance of each of the microlenses 58 is 90% or more, and the arrangement pitch is 13.7 μm in one example in the longitudinal direction and the lateral direction. The SRAM unit 56 is a CMOS gate which is manufactured on a general semiconductor memory production line via a pillar including a hinge and a yoke, and is entirely monolithic.

When the SRAM unit (memory unit) 56 of the DMD 36 inputs an image signal in which the density of each dot of the desired quaternary pattern is represented by two values, the microlens 58 supported on the pillar is centered on the diagonal line with respect to The substrate side on which the DMD 36 is disposed is inclined by ±α degrees (for example, ±10 degrees). Fig. 7A shows a state in which the microlens 58 is in an ON state, and a state of inclination + α degrees, and Fig. 7B shows a state in which the microlens 58 is in an OFF state and tilted by -α degrees. Therefore, by controlling the inclination of the microlens 58 in each pixel of the DMD 36 as shown in Fig. 6, as the pattern signal, the laser beam B incident on the DMD 36 is tilted toward the microlens 58 respectively. Directional reflection.

Fig. 6 is a view showing an example in which the DMD 36 is partially enlarged and each microlens 58 is controlled to a state of +α degrees or -α degrees. The ON, OFF (on, off) control of each microlens 58 is performed by the aforementioned controller connected to the DMD 36. Further, a light absorber (not shown) is disposed in the direction in which the laser light B reflected by the microlens 58 in the OFF state is performed.

-Light illumination mechanism -

The light irradiation mechanism is not particularly limited, and may be appropriately selected depending on the purpose. For example, it may be a (super) high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a photocopier, etc. A conventional light source such as a light pipe, an LED, or a semiconductor laser, or a mechanism that can synthesize two or more light beams, and among these, a mechanism that can synthesize two or more pieces of light is preferably used.

The light irradiated from the light irradiation means described above, for example, when irradiated with light through a support, may be, for example, transmitted through the support and activated by the photopolymerizable compound or sensitizer used. Electromagnetic wave, ultraviolet light, visible light, electron beam, X-ray, laser light, etc.; among these, it is more suitable for laser light, and it is more suitable to be a laser synthesized by two or more lights (hereinafter, referred to as "composite Boley shot"). Further, even when light is irradiated after peeling off the support, the same light can be used.

The wavelength of the ultraviolet to visible light is, for example, preferably 300 to 1,500 nm, more preferably 320 to 800 nm, and particularly preferably 330 to 650 nm.

The wavelength of the aforementioned laser light is, for example, preferably 200 to 1,500 nm, more preferably 300 to 800 nm, more preferably 330 to 500 nm, and particularly preferably 400 to 450 nm.

A mechanism that can illuminate the aforementioned composite laser beam, for example, preferably has a plurality of kinds of lasers, a multimode fiber, and a laser beam irradiated from each of the plurality of lasers, and is combined with each other on the multimode fiber. The mechanism of the collection optical system.

For example, the mechanism described in paragraphs [0109] to [0146] of JP-A-2005-258431 can be used.

<<Using the Ministry of the Ministry of Design>>

Preferably, the pixel portion specifying means is provided with a spot position detecting means that detects at least a spot position of the pixel unit on the exposed surface, and a detection result based on the spot position detecting means. A pixel selection mechanism for realizing the pixel portion used for N exposures is selected.

Hereinafter, a method of designating a pixel portion to be used for N exposures by using the pixel portion specifying means will be described.

(1) Designation method of using the pixel part in a single exposure head

In the first embodiment (1), in the case where the photosensitive material 12 is subjected to the exposure twice by the pattern forming apparatus 10, the resolution variation and the concentration which are caused by the mounting angle error of the respective exposure heads 30 are alleviated. Uniformity, and specifies the method of specifying the pixel portion to achieve the desired 2 exposures.

The set inclination angle θ with respect to the direction of the pixel portion (microlens 58) in the scanning direction of the exposure head 30 can be used as long as it is in an ideal state without an attachment angle error of the exposure head 30 or the like. Columns x 256 rows of pixels, and use an angle slightly larger than the angle θ _{ideal of} exactly 2 exposures.

The angle θ _ideal is the number N of N exposures, the number s of directions of the microlenses 58 that can be used, the interval p of the available microlenses, and the tilting state of the exposure head 30. Due to the scanning line pitch δ formed by the microlens, it has a relationship of the following formula 1: sp sin θ _ideal ≧N δ (Formula 1)

In the DMD 36 of the present embodiment, as described above, since the plurality of microlenses 58 having the same vertical and horizontal arrangement intervals are arranged in a rectangular lattice shape, p cos θ _ideal = δ (Expression 2)

Therefore, the above formula 1 becomes: s tan θ _ideal = N (Formula 3)

In the first embodiment (1), as described above, since s = 256 and N = 2, the angle θ _Ideal is about 0.45 degrees in accordance with the above formula 3. Thereby, the inclination angle θ is set, and for example, an angle of about 0.50 degrees can be employed. In the range in which the pattern forming apparatus 10 can be adjusted, the initial adjustment of the attachment angle of each of the exposure heads 30, that is, the DMD 36, is adjusted so as to approach the angle of the set inclination angle θ.

Fig. 8 is a view showing an example in which the pattern on the exposure surface is deviated due to the influence of the mounting angle error and the pattern distortion of the one exposure head 30 in the pattern forming apparatus 10 which is initially adjusted as described above. Illustrating. In the following drawings and descriptions, the spot of the pixel in the pixel unit constituting the exposure range of the exposed surface generated by each pixel portion (microlens) is described as the spot of the mth line as r(m), the light spot of the nth column is described as c(n), and the light spot of the mth row and the nth column is described as P(m, n).

The upper half of Fig. 8 shows the pattern of the spot group from the available microlenses 58 projected on the exposed surface of the photosensitive material 12 in a state where the stage 14 is stationary; the lower half Then, in the state in which the pattern of the spot group as shown in the above half appears, the state of the exposure pattern formed on the exposed surface when the stage 14 is moved to continuously perform exposure.

Further, in Fig. 8, the exposure pattern of the odd-numbered columns of the microlenses 58 that can be used and the exposure patterns of the even-numbered columns are separately shown for convenience of explanation, but the actual exposed surface is The exposure pattern on the top is formed by superimposing two exposure patterns.

In the example of Fig. 8, since the set inclination angle θ is a result of an angle slightly larger than the above-described angle θ _ideal , and the installation angle of the exposure head 30 is hardly adjusted, the actual installation angle and the above-described set inclination angle are caused. There is an error between θ, so that density unevenness occurs in any of the areas on the exposed surface. Specifically, both the exposure pattern of the odd-numbered microlens and the exposure pattern of the even-numbered microlenses are in the repeated exposure range of the exposed surface formed by the plurality of pixel portions, with respect to the ideal 2 exposures. In other words, it becomes too much exposure, so that an image becomes a redundant area, and a density unevenness phenomenon occurs.

Further, in the example of Fig. 8, an example of pattern deviation occurs on the surface to be exposed, and each pixel sequence projected on the surface to be exposed is "angle deviation" in which the inclination angle becomes uneven. The cause of such an angular deviation is, for example, various aberrations and alignment deviations of the optical system between the DMD 36 and the exposed surface, and variations in the DMD 36 itself and misalignment of the microlenses.

The angular deviation appearing in the example of Fig. 8 is a kind of inclination angle with respect to the scanning direction, and the smaller the column to the left of the figure is, the closer it is to the right side of the figure. As a result of such an angular deviation, it becomes an area where the exposure is excessive, and the smaller the exposure surface shown on the left side of the figure, the larger the exposure surface as shown on the right side of the figure.

As described above, in order to alleviate the density unevenness in the repeated exposure range formed on the exposed surface by the complex pixel portion, a combination of the slit 28 and the photodetector is used as the aforementioned spot. The position detecting means defines a substantial inclination angle θ ' of each of the exposure heads 30, and based on the substantial inclination angle θ', using the above-described arithmetic means connected to the optical detector as the pixel selection means The treatment of the microlenses used in the actual exposure is selected.

The substantial tilt angle θ ' is defined by at least two spot positions detected by the spot position detecting means to define the direction of the spot array on the exposed surface by tilting the exposure head, and the foregoing The angle formed by the scanning direction of the exposure head.

Hereinafter, the definition of the aforementioned substantial inclination angle θ ' and the use of the pixel selection processing will be described using Figs. 9 and 12 .

- Definition of the substantial tilt angle θ '

Fig. 9 is a top view showing the positional relationship between the exposure region 32 of one DMD 36 and the corresponding slit 28. The size of the slit 28 is large enough to adequately cover the width of the exposed area 32.

In the example of the first embodiment (1), the angle formed by the row of the 512th column at the approximate center position of the exposure region 32 and the scanning direction of the exposure head 30 is measured as the substantial inclination angle θ'. Specifically, the microlens 58 of the first row and the 512th column on the DMD 36 and the microlens 58 of the 256th and 512th columns are turned on, and the spot P (1, on the corresponding corresponding exposure surface is detected. The positions of 512) and P (256, 512), and the angle formed by the line connecting them and the scanning direction of the exposure head are defined as the substantial inclination angle θ '.

Fig. 10 is a top view showing the detection method of the position of the light spot (256, 512).

First, in a state where the microlens 58 of the 512th row and the 512th column are turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the spot P (256, 512) is upstream. A slit 28 is provided at any position between the slit 28a on the side and the slit 28b on the downstream side. At this time, the intersection between the slit 28a and the slit 28b is marked as (X0, Y0). The value of this coordinate (X0, Y0) is determined by the movement distance of the stage 14 until the drive signal given by the stage 14 shows the above position, and the position of the known slit 28 in the X direction, and is recorded.

Next, the platform 14 is moved and the slit 28 is relatively moved along the Y-axis to the right in FIG. Next, as shown by the dotted line in Fig. 10, when the light of the light spot P (256, 512) is detected by the photodetector through the slit 28b on the left side, the stage 14 is stopped. The intersection coordinates (X0, Y1) 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 platform 14 is moved and the slit 28 is relatively moved to the left in the 10th figure along the Y-axis. Next, as shown by the dotted line in Fig. 10, when the light of the light spot P (256, 512) is detected by the photodetector through the slit 28a on the left side, the stage 14 is stopped. The intersection coordinates (X0, Y2) 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 spot P (256, 512) on the surface to be exposed are X = X0 + (Y1 - Y2) / 2, Y = (Y1 + Y2) / 2 calculation decision. The position of the P (1, 512) is determined by the same measurement, and the angle formed by the line connecting the coordinates and the scanning direction of the exposure head 30 is derived and defined as the substantial inclination angle. θ '.

- Use the choice of the pixel part -

Using the substantial tilt angle θ ' defined by this method, the above-described arithmetic means connected to the above-described photodetector derives the value t which is closest to the relationship 4: t tan θ '= N (Expression 4) satisfying the following The natural number T, and the microlens from the first row to the T row on the DMD 36 are selected to process the microlens actually used in the exposure. Therefore, in the exposure range in the vicinity of the 512th column, the microlens which is the smallest area of the area which is excessively exposed and the area which is underexposed is the smallest in comparison with the ideal two exposures, and is actually used. Microlens.

In this context, the smallest natural number above the value t can also be derived instead of the derived natural number closest to the above value t. In this case, in the exposure range near the 512th column, the microlens having the area of the overexposed area which becomes the smallest and the underexposed area is not generated with respect to the ideal 2nd exposure can be selected as the actual use. Microlens when.

Also, the largest natural number below the value t can be derived. In this case, in the exposure range near the 512th column, the microlens having the area of the underexposed area which is minimized and the excessive exposure area is not generated with respect to the ideal 2nd exposure can be selected as the actual use. Microlens when.

Figure 11 shows the microlens in actual use as described above, and only the spot generated by the selected microlens is used for exposure to illustrate how to improve the unevenness on the exposure surface shown in Fig. 8. Illustration of the diagram.

In this example, T = 253 is derived as the natural number T described above, and the microlenses from the 1st line to the 253th line are selected. With respect to the selected microlenses of the 254th to 256th rows, the angles normally set to the OFF state are sent by the aforementioned pixel control mechanism, and the microlenses are substantially independent of the exposure. As shown in Fig. 11, in the exposure range in the vicinity of the 512th column, the phenomenon of excessive exposure and underexposure is almost completely canceled, so that uniform exposure which is extremely close to the ideal two exposures can be realized.

On the other hand, in the left-hand range of FIG. 11 (near c(1) in the figure), because of the aforementioned angular deviation, the inclination angle of the ray column on the exposed surface becomes closer to the center (in the figure) The angle of inclination of the ray column in the range near c(512) is even smaller. Therefore, only the microlenses selected based on the substantial tilt angle θ′ measured on the basis of c (512) are used for exposure, and the even-numbered exposure patterns and the odd-numbered exposure patterns are compared with the two exposures. If the words are exposed, I am afraid that there will be separate areas with only a few shortcomings.

However, in the actual exposure pattern in which the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns are overlapped, the underexposed regions complement each other, so that the exposure unevenness of the aforementioned angular deviation can be obtained by The complementary effect of the 2 exposures minimizes it.

Further, in the range on the right side of Fig. 11 (near c (1024) in the figure), the angle of inclination of the ray column on the exposed surface is closer to the center than in the vicinity of the center due to the aforementioned angular deviation (in the vicinity of c (512) in the figure) The tilt angle of the ray column in the range is larger. Therefore, only the microlenses selected based on the substantial tilt angle θ′ measured on the basis of c (512) are used for exposure, and the even-numbered exposure patterns and the odd-numbered exposure patterns are compared with the two exposures. Words are exposed, but I am afraid that there will be only a few extra areas.

However, in the actual exposure pattern in which the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns are overlapped, the areas where the exposure is excessively complement each other, and thus the unevenness of the exposure of the aforementioned angular deviation can be obtained by The complementary effect of the 2 exposures minimizes it.

In the first embodiment (1), as described above, the substantial inclination angle θ ' of the ray row of the 512th column is measured, and based on the T derived from the above formula (4) using the substantial inclination angle θ ' The microlens 58 to be used is selected. However, the definition of the substantial tilt angle θ ' can also be determined by respectively determining the direction of the column direction of the plurality of pixel portions (the spot array) and the number of scans of the exposure head. a substantial tilt angle, which defines one of the average, the central value, the maximum value, and the minimum value as the substantial tilt angle θ ', and then selects the microlens actually used during the substantial exposure by the above formula 4. The form.

When the average value or the central value is used as the substantial inclination angle θ ', it is possible to achieve a good balance between the excessive exposure region and the underexposed region with respect to the N exposures which are supposed to be reasonable. For example, it is possible to control the sum of the area of the overexposed area and the area of the underexposed area to be minimized, and the pixel unit (the number of spots) of the overexposed area and the pixel unit (the number of spots) of the underexposed area are equal. exposure.

Moreover, if the maximum value is used as the substantial inclination angle θ ', it is possible to eliminate the exposure which is important for the exposure area with respect to the N exposures. For example, the area of the underexposed area can be suppressed to The smallest, and does not produce exposure to areas that are overexposed.

In addition, if the minimum value is used as the substantial inclination angle θ ', it is possible to eliminate the exposure which is important for the underexposed area with respect to the N exposures. For example, the area of the excessive exposure area can be suppressed to The smallest, and does not produce exposure to underexposed areas.

On the other hand, the definition of the substantial inclination angle θ ' is not limited to a method based on at least two spot positions in the same pixel portion (spot array). For example, an angle may be obtained from one or a plurality of light spot positions in the same pixel portion c(n) and one or a plurality of light spot positions in the vicinity of the c(n) column. , defined as the substantial inclination angle θ '.

Specifically, it is possible to detect one or a plurality of spot positions included in one of the spot positions of c(n) and the line of dots along the line along the scanning direction of the exposure head and in the vicinity. From this position information, the substantial inclination angle θ ' is obtained. Furthermore, it is also possible to obtain an angle based on the position of two light spots (for example, two light spots arranged across c(n)) among the light spot columns in the vicinity of the c(n) column. Defined as the substantial tilt angle θ '.

As described above, according to the method of specifying the pixel portion in the first embodiment (1) using the pattern forming apparatus 10, the resolution of the exposure angle error and the pattern unevenness of each exposure head can be reduced. Variability and concentration are not uniform and can achieve the desired N exposures.

(2) Designation method for the use of the pixel part between the multiple exposure heads <1>

In the second embodiment, a case where the exposure of the photosensitive material 12 by the pattern forming apparatus 10 is performed twice, thereby reducing the repeated exposure range of the exposed surface formed by the plurality of exposure heads 30 is explained. In the connection area between the heads, the resolution difference and density unevenness caused by the relative positions of the two exposure heads (for example, one of the exposure heads 30 ₁₂ and 30 ₂₁ ) due to the gap with the ideal state, and Specify the method of using the pixel portion to achieve the desired 2 exposures.

Each of the exposure heads 30, that is, the set tilt angle θ of each of the DMDs 36, is used as long as it is an ideal state in which the mounting angle error of the exposure head 30 is not used, and the 1024-row by 256-row pixel portion microlens 58 is used and used. It happens to be the angle θ _ideal of 2 exposures.

Such an angle θ _ideal can be obtained by the above-described formulas 1 to 3 in accordance with the above embodiment (1). In the second embodiment, the initial adjustment of the pattern forming apparatus 10 is adjusted so that the attachment angle of each of the exposure heads 30, that is, the respective DMDs 36 is an angle θ _ideal .

Fig. 12 is a view showing the relative positional deviation with respect to the X-axis direction of the two exposure heads (for example, one of the exposure heads 30 ₁₂ and 30 ₂₁ ) in the pattern forming apparatus 10 which is initially adjusted as described above. An explanatory diagram of an example in which the influence of the ideal state causes a deviation in the pattern on the exposed surface. The deviation (gap) of the relative position of each exposure head with respect to the X direction is derived from the fact that the relative position between the exposure heads is difficult to perform fine adjustment.

The upper half of Fig. 12 shows the available microlenses 58 of the DMD 36 having the exposure heads 30 ₁₂ and 30 ₂₁ projected from the exposed surface of the photosensitive material 12 while the stage 14 is stationary. The pattern of the light spot group. The lower half of Fig. 12 shows that in the state where the pattern of the spot group as shown in the above half appears, when the stage 14 is moved to continuously perform exposure, the exposure areas 32 ₁₂ and 32 ₂₁ are exposed. The state of the exposure pattern formed on the surface.

Further, in Fig. 12, for the sake of convenience of explanation, the exposure patterns of the microlenses 58 which are available for use in one row are respectively exposed by the exposure pattern of the pixel group A and the pixel group B. The exposure pattern indicates that, however, the exposure pattern on the actual exposed surface is such that the two exposure patterns are overlapped.

In the example of Fig. 12, the above-mentioned relative position between the exposure heads 30 ₁₂ and 30 ₂₁ in the X-axis direction deviates from the ideal state, and both the exposure pattern of the pixel group A and the exposure pattern of the pixel group B are both. In the aforementioned inter-head contact region of the exposure regions 32 ₁₂ and 32 ₂₁ , a portion having an excessive exposure amount is generated as compared with the state of the ideal two exposures.

As described above, in order to reduce the aforementioned inter-head contact region formed on the surface to be exposed by a plurality of the above-described exposure heads, in the second embodiment, slits 28 and light detection are used. The combination of the above-described light spot position detecting means detects the number of light spots constituting the aforementioned inter-head contact region formed on the exposed surface among the light spot groups from the exposure heads 30 ₁₂ and 30 ₂₁ Its position (coordinate). Based on the position (coordinate), the processing for selecting the microlens used for the actual exposure is performed using the above-described arithmetic device connected to the photodetector as the pixel portion selecting means.

- Detection of position (coordinate) -

Fig. 13 is a top view showing the positional relationship between the exposure regions 32 ₁₂ and 32 ₂₁ and the corresponding slits 28 in the same manner as in Fig. ₁₂ . The size of the slit line 28 is large enough to sufficiently cover Exposure head 30 30 _{21 12} and the size of the complete width of region 34; i.e., can sufficiently cover the exposure head 30 by ₁₂ and 30 ₂₁ and on the exposed surface of the formed The size of the aforementioned inter-header connection area.

Fig. 14 is a top view showing an example of a detection method when the position of the light spot P (256, 1024) of the exposure region 32 ₂₁ is detected.

First, in a state where the microlens of the 256th row and the 1024th column are turned on, the stage 14 is gradually moved to relatively move the slit 28 along the Y-axis direction, and the spot P (256, 1024) is on the upstream side. A slit 28 is provided at any position between the slit 28a and the slit 28b on the downstream side. At this time, the intersection between the slit 28a and the slit 28b is marked as (X0, Y0). The value of this coordinate (X0, Y0) is determined by the movement distance of the stage 14 until the drive signal given by the stage 14 shows the above position, and the position of the known slit 28 in the X direction, and is recorded.

Next, the platform 14 is moved in the opposite direction, and the slit 28 is relatively moved along the Y-axis to the right in FIG. Next, as shown by the two-dot chain line in Fig. 14, when the light of the light spot P (256, 1024) is detected by the photodetector through the slit 28b on the left side, the stage 14 is stopped. The intersection coordinates (X0, Y1) 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, and the slit 28 is relatively moved to the left in Fig. 14 along the Y-axis. Next, as shown by the two-dot chain line in Fig. 14, when the light of the light spot P (256, 1024) is detected by the photodetector through the slit 28a on the right side, the stage 14 is stopped. The intersection coordinates (X0, Y2) of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 1024).

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

- Do not use the definition of the pixel part -

In the example of Fig. 12, first, the position of the spot P (256, 1) of the exposure region 32 ₁₂ is detected by the combination of the slit 28 and the photodetector as the spot position detecting means. Then, according to P (256, 1024), P (256, 1023). . . The order of the light spots on the light spot r (256) of the 256th line of the exposure area 32 ₂₁ is detected in turn, and the X coordinate larger than the light spot P (256, 1) of the exposure area 32 ₁₂ is detected. light spot 32 of the exposure area ₂₁ P (256, n), the detection operation that is completed. Then, the microlens corresponding to the spot of the light spot column c(n+1) to c(1024) constituting the spot of the exposed region 32 ₂₁ is defined as a microlens that is not used at the time of exposure (the pixel portion is not used) ).

For example, in FIG. 12, the spot P (256, 1020) of the exposure region 32 ₂₁ shows an X coordinate larger than the spot P (256, 1) of the exposure region 32 ₁₂ when the exposure region 32 is used. _When the spot P (256, 1020) of ₂₁ is detected as the completion of the detection operation, it corresponds to the 1021st line to the exposure area 32 ₂₁ constituting the portion 70 covered with the oblique line in FIG. A microlens of 1024 lines of light is defined as a microlens that is not used in this exposure.

Next, the position of the light spot P (256, N) of the exposure region 32 ₁₂ is detected with respect to the number N of N exposures. In the second embodiment (2), since N = 2, the spot P (256, 2) is detected.

Next, among the light spot columns of the exposure region 32 ₂₁ , in addition to the light spot row defining the microlenses that are not used in the above-described exposure, P (1, 1020) is used in accordance with P (1, 1020), P(2,1020). . . The order of the light spots of the 10th 20th column which constitutes the far right side is detected in turn, and when the spot P (m, 1020) of the X coordinate which is larger than the light spot P (256, 2) of the exposure area 32 ₁₂ is detected, , that is, to complete the checkout action.

Then, in the calculation device is connected to the photodetector to compare the exposure spot region ₃₂₁₂ of the P (256,2) of the X coordinate, and the light spot 32 of the exposure area ₂₁ P (m, 1020), and The X coordinate of P(m-1, 1020), when the X coordinate of the spot P(m, 1020) of the exposure region 32 ₂₁ approaches the spot P (256, 2) of the exposure region 32 ₁₂ , The microlenses corresponding to the spot P (1, 1020) to P (m-1, 1020) of the exposed region 32 ₂₁ are defined as microlenses that are not used at the time of exposure.

Further, when the X coordinate system of the light spot P (m-1, 1020) in the exposure region 32 ₂₁ approaches the light spot P (256, 2) of the exposure region 32 ₁₂ , the light spot of the exposure region 32 ₂₁ is used. P(1,1020) to P(m-2,1020) are defined as microlenses that are not used during exposure.

Furthermore, for the spot P (256, N-1) of the exposed region 32 ₁₂ , that is, the position of the spot P (256, 1), and the respective spots of the 1019th column constituting the next column of the exposed region 32 ₂₁ The position is also similarly detected and the microlenses that are not used are defined.

As a result, for example, the microlens corresponding to the spot of the range 72 covered by the halftone dots in Fig. 15 is added as a microlens which is not used at the time of actual exposure. Such microlenses are typically signals that transmit the angle at which the angle of the microlenses is set to an OFF state, and that the microlenses are not substantially used for exposure.

Thus, by defining microlenses that are not used during actual exposure, and selecting objects other than the unused microlenses as the microlenses used in actual exposure, the aforementioned heads in the exposed areas 32 ₁₂ and 32 ₂₁ In the interconnected region, the area of the area that is excessively exposed and the area that is underexposed may be minimized with respect to the ideal two exposures, and that the extremely close as shown in the lower half of Fig. 15 can be achieved. A uniform exposure of the ideal 2 exposures.

Further, in the above-described example, when the light spot constituting the range 72 covered by the halftone dot in Fig. 15 is defined, the X coordinate of the light spot P (256, 2) of the exposure region 32 ₁₂ may not be performed. Comparing the light spots P (m, 1020) of the exposure region 32 ₂₁ with the X coordinates of P (m-1, 1020), and directly corresponding to the light spot P (1, 1020) of the exposure region 32 ₂₁ to P The microlenses of (m-2, 1020) are defined as microlenses that are not used during exposure. In this case, it is possible to select, in the aforementioned inter-head contact region, a microlens having a region with an excessively exposed area which is the smallest in exposure and which does not cause an underexposed region, and is defined as Microlenses that are not actually used.

Further, the microlens corresponding to the spot P (1, 1020) to P (m-1, 1020) of the exposed region 32 ₂₁ may be defined as a microlens which is not used at the time of exposure. In this case, it is possible to select, in the aforementioned inter-head contact region, a microlens which is the smallest area of the underexposed area and does not generate an excessively exposed area with respect to the ideal two exposures, and defines it as Microlenses that are not actually used.

Further, in the above-described inter-head contact region, the number of pixel units (the number of light spots) and the number of pixel units of the underexposed region may be selected for the ideal secondary exposure (light) If the number of points is equal, it is defined as a microlens that is not used when exposed.

As described above, according to the method of specifying the pixel portion in the second embodiment (2) using the pattern forming apparatus 10, the resolution of the exposure angle error and the pattern unevenness of each exposure head can be reduced. Variability and concentration are not uniform and can achieve the desired N exposures.

(3) The method of specifying the use of the pixel part between the multiple exposure heads <2>

In the third embodiment, in the case where the photosensitive material 12 is exposed twice by the pattern forming apparatus 10, the repeated exposure range of the exposed surface formed by the plurality of exposure heads 30 is reduced. In the connection area between the heads, the relative position of the X exposure directions of the two exposure heads (for example, one of the exposure heads 30 ₁₂ and 30 ₂₁ ) is due to the gap (deviation) from the ideal state, and the mounting error of each exposure head. The resolution variation and density non-uniformity caused by the relative mounting angle error between the two exposure heads and the gap (deviation) between the relative positions, and the method of using the pixel portion for realizing the ideal two exposures is specified.

Each of the exposure heads 30, that is, the set tilt angle of each of the DMDs 36, can be used as long as it is in an ideal state without the mounting angle error of the exposure head 30, etc., and the available pixel portions of 1024 columns × 256 rows (microlenses 58) can be used. And adopt an angle slightly larger than the angle θ _{ideal of} exactly 2 exposures.

Such an angle θ _ideal can be obtained by the above-described embodiment (1) using the above formulas 1-3. In the present embodiment, as described above, s = 256 and N = 2, so the angle θ _ideal is about 0.45 degrees. Therefore, the inclination angle θ is set, and for example, an angle of about 0.50 degrees can be employed. In the range in which the pattern forming apparatus 10 can be adjusted, the initial adjustment of the attachment angle of each of the exposure heads 30, that is, the DMD 36, is adjusted so as to approach the angle of the set inclination angle θ.

Fig. 16 is a view showing the pattern forming apparatus 10 which has been initially adjusted as described above in each of the exposure heads 30, i.e., the DMD 36, since two exposure heads (for example, one of them is the exposure head 30) An explanation of an example in which the mounting error of ₁₂ and 30 ₂₁ ) and the relative positional deviation of each of the exposure heads 30 ₁₂ and 30 ₂₁ are different, and the pattern on the exposure surface produces a non-uniform phenomenon.

In Fig. 16, similarly to the example of Fig. 12, since a result of a gap between the relative positions of the exposure heads 30 ₁₂ and 30 _{21 in} the X-axis direction, a group of light spots (pixel groups) are separated by one column. Both of the exposure patterns of A and B) are repeated in the repeated exposure range on the coordinate axis of the exposure head of the exposure areas 32 ₁₂ and 32 ₂₁ on the exposed surface of the exposure head, resulting in a state of ideal two exposures. Below is a range 74 of excessive exposure, and causes a phenomenon of density non-uniformity.

Furthermore, in the example of Fig. 16, the set inclination angle θ of each exposure head is slightly larger than the angle θ _ideal satisfying the above formula (1), and since it is difficult to perform the mounting angle of each exposure head. Since the actual mounting angle is deviated from the above-described set tilt angle θ as a result of the adjustment, even in a range other than the range in which the exposure is repeated on the coordinate perpendicular to the scanning direction of the exposure head on the exposure surface, the interval is one column. The exposure patterns of the spot group (the pixel groups A and B) are also in the connection region between the pixel portions of the repeated exposure range of the exposed surface formed by the plurality of pixel portions. A state 76 in which the exposure is excessive is produced in comparison with the state of the ideal two exposures, thereby further causing the density unevenness.

In the third embodiment, first, in order to reduce the influence of the mounting angle error of each of the exposure heads 30 ₁₂ and 30 ₂₁ and the influence of the gap with respect to the mounting angle, density unevenness occurs, and the pixel selection processing is performed.

Specifically, a combination of the slit 28 and the photodetector is used as the aforementioned spot position detecting mechanism, and the exposure heads 30 ₁₂ and 30 ₂₁ respectively define a substantial inclination angle θ ', and based on the substantial inclination angle θ ', The processing for selecting the microlens used for the actual exposure is performed using the above-described arithmetic device connected to the photodetector as the pixel portion selecting means.

- Definition of the substantial tilt angle θ '

The substantial inclination angle θ ' is defined by the combination of the slit 28 and the photodetector used in the above-described embodiment (2), and the P in the exposure region 32 ₁₂ of the exposure head 30 ₁₂ is separately detected ( The positions of 1,1) and P(256,1), and the positions of P(1,1024) and P(256,1024) in the exposure area 32 ₂₁ of the exposure head 30 ₂₁ , the inclination of the line connecting them is measured. The angle is formed by the angle formed between the angle and the scanning direction of the exposure head.

- Do not use the definition of the pixel part -

Using the above-described arithmetic device connected to the above-described photodetector, the above-described arithmetic device connected to the above-described photodetector is used to derive the most for the exposure heads 30 ₁₂ and 30 ₂₁ in the same manner as the arithmetic device in the above-described embodiment (1). The natural number T satisfying the value t of the following relation 4: t tan θ '=N (formula 4) is approximated, and the microlens of the (T+1)th row to the 256th row on the DMD 36 is defined as being not in the exposure. Microlenses used.

For example, assume that T = 254 is derived for the exposure head 30 ₁₂ and T = 255 for the exposure head 30 ₂₁ , then the spot corresponding to the portions 78 and 80 that are covered by the oblique lines in Fig. 17 will be corresponding. The microlens is defined as a microlens that is not used in the exposure. Thereby, it is possible to make the area of the overexposed area and the area of the underexposed area with respect to the ideal two exposures in each range other than the inter-head contact area among the exposed areas 32 ₁₂ and 32 ₂₁ . The sum becomes the smallest.

In this context, the smallest natural number above the value t can also be derived instead of the derived natural number closest to the above value t. In this case, in each of the ranges other than the inter-head contact region of the repeated exposure range of the exposed areas formed by the plurality of exposure heads, the exposure regions 32 ₁₂ and 32 ₂₁ are opposed to the ideal two exposures. The area where the amount of exposure is excessive is minimized, and the area where the amount of exposure is insufficient is not generated.

Alternatively, the largest natural number below the value t can also be derived. In this case, it is possible to make each range outside the inter-head contact region of the repeated exposure range of the exposed surface formed by the plurality of exposure heads of the exposure regions 32 ₁₂ and 32 ₂₁ relative to the ideal In the case of the second exposure, the area of the underexposed area becomes the smallest, and the area where the exposure is excessive is not generated.

It is also possible to use a pixel which is an excessively exposed region with respect to an ideal secondary exposure in each range other than the inter-head contact region of the repeated exposure range on the exposed surface formed by the plurality of exposure heads. The unit (the number of spots) and the pixel unit (the number of spots) of the underexposed area are equal to each other to define the microlens that is not used in the exposure.

Then, the microlens corresponding to the light spot other than the spot of the portions 78 and 80 covered with oblique lines in Fig. 17 is processed in the same manner as in the third embodiment (3) described in Figs. The microlens corresponding to the spot 82 covered by the oblique line and the spot 84 covered by the halftone dot in Fig. 17 are defined, and the microlens which is not used at the time of exposure is added.

With respect to the defined microlenses that are not used during the exposure, the pixel control mechanism sends signals that are normally set to an OFF state, and the microlenses are substantially independent of exposure.

As described above, according to the method of specifying the pixel portion in the third embodiment (3) using the pattern forming apparatus 10, the deviation of the relative positions of the plurality of exposures in the X-axis direction and the exposure can be reduced. The difference in resolution and concentration of the head due to the mounting angle error of the head and the relative mounting angle between the exposure heads, and the ideal N exposure can be achieved.

As described above, the pattern forming apparatus 10 has been described in detail using the pixel portion specifying method. However, the above-described embodiments (1) to (3) are merely examples, and various types can be performed without departing from the scope of the present invention. Changed.

Further, in the above embodiments (1) to (3), a combination of the slit 28 and the single type photodetector is used as a mechanism for detecting the position of the spot on the exposed surface, but In addition to this, any formed object may be used, and for example, a 2-dimensional detector or the like may be used.

Further, in the above-described embodiments (1) to (3), the substantial inclination angle θ ' is obtained from the detection result of the position of the spot on the exposure surface of the combination of the slit 28 and the photodetector, and The microlens to be used is selected based on the substantial inclination angle θ '. However, the form of the microlens that can be used may be selected without deriving the substantial inclination angle θ '. Furthermore, for example, by using all available microlenses for reference exposure, visually confirming the resolution and density non-uniformity from the reference exposure result, the operator can manually specify the shape of the microlens to be used. It is also included in the scope of the invention.

Further, in addition to the angular deviation described in the above examples, the pattern deviation generated on the exposed surface may be in various other forms.

As an example, for example, the light rays from the respective microlenses 58 on the DMD 36 shown in Fig. 18A are in a form in which the magnifications of the exposure regions 32 on the exposure surface are uneven at different magnifications.

Further, as another example, the light rays from the respective microlenses 58 on the DMD 36 as shown in Fig. 18B are in a form in which the beam diameters of the exposure regions 32 on the exposure surface are not uniform with different beam diameters. These uneven magnifications and uneven beam diameters are caused by various variations and alignment gaps of the optical system between the DMD 36 and the exposure surface.

Further, in another example, for example, the light rays from the respective microlenses 58 on the DMD 36 are in a form in which the amount of light reaching the exposure region 32 on the exposure surface is uneven with different amounts of light. Such unevenness of light amount is due to various aberrations and arrangement gaps, and is also due to optical factors between the DMD 36 and the exposure surface (for example, lenses 5 and 5 of the 1st lens and lenses 52 and 54 of the 5B). The positional dependence of the light transmittance and the uneven amount of light of the DMD 36 itself. The pattern deviation of these forms also causes the resolution and density unevenness of the pattern formed on the exposed surface.

According to the above embodiments (1) to (3), after selecting the microlens actually used for the exposure, the residual factor of the pattern deviation of the above forms can be borrowed in the same manner as the residual factor of the angular deviation described above. By complementing and uniformizing the exposure, it is also possible to reduce the resolution and concentration unevenness of each exposure head in the entire range of exposure.

<<reference exposure>>

The modified examples (1) to (3) of the above embodiments are used only in the microlens array of the (N-1) row in the available microlenses or the equivalent of 1/1 in the all-light-point array. The microlens group of adjacent rows of N rows is subjected to reference exposure; for the purpose of achieving uniform exposure, microlenses that are not used during actual exposure may be defined in the microlenses used in the aforementioned reference exposure.

The result of the reference exposure by the reference exposure means is output as a sample, and the resolution of the resolution and the deviation of the concentration deviation, the estimation of the estimated substantial tilt angle, and the like are performed on the output reference exposure result. The analysis of the aforementioned reference exposure results can also be analyzed by visual observation by the operator.

19A and 19B are explanatory views showing an example of a form in which a single exposure head is used and reference exposure is performed using only microlenses in the interval (N-1).

In this example, since this exposure is performed twice, N=2. First, the reference exposure is performed using only the microlens corresponding to the dot array of the odd-numbered columns indicated by the solid line in Fig. 19A, and the reference exposure result is output as a sample. Based on the reference exposure result by the sample output, the microlens used in the present exposure can be specified by confirming the variation of the resolution and the concentration deviation and estimating the substantial tilt angle.

For example, microlenses other than the microlenses corresponding to the spot array indicated by oblique lines in Fig. 19B are designated as the actual use of the present lens among the microlenses constituting the odd-numbered column. In the case of the spot array of the even-numbered columns, the reference exposure can be similarly performed by other methods, and the microlens used for the exposure can be specified, and can also be applied to the same pattern as the pattern corresponding to the dot array of the odd-numbered columns. .

In such a manner, by designating the microlens used in the present exposure, it is possible to achieve a state close to the ideal two exposures in the present exposure using the microlenses of both the odd and even columns.

Fig. 20 is an explanatory view showing an example of a form in which a plurality of exposure heads are used and reference exposure is performed using only microlenses of the interval (N-1).

In this example, since this exposure is performed twice, N=2. First, only the micro-correlation column corresponding to the odd-numbered columns of the two exposure heads (for example, one of the exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to the X-axis direction indicated by the solid line in FIG. 20 is used. The lens is used for reference exposure, and the reference exposure result is output as a sample. Based on the reference exposure result outputted from the sample, the resolution of the resolution and the concentration deviation in the range other than the inter-head contact region formed on the exposed surface by the two exposure heads are confirmed, and the substantial tilt is estimated The angle, that is, the microlens used in the exposure can be specified.

For example, the microlens other than the microlens corresponding to the range 86 indicated by the slanted line in FIG. 20 and the spot array in the range 88 indicated by the halftone dot are among the microlenses constituting the array of the odd-numbered columns. It is designated as the actual use of this exposure. In the case of the spot array of the even-numbered columns, the reference exposure can be similarly performed by other methods, and the microlens used for the exposure can be specified, and can also be applied to the same pattern as the pattern corresponding to the dot array of the odd-numbered columns. .

In this way, by designating the microlens used in the present exposure, in the exposure using the microlenses of both the odd and even columns, it is possible to form on the exposed surface by the two exposure heads. In a range other than the connection area between the heads, a state close to the ideal two exposures is achieved.

21A and 21B are explanatory views showing an example in which a single exposure head is used and only a microlens group constituting an adjacent row corresponding to 1/N of the total number of lines is used for reference exposure.

In this example, since this exposure is performed twice, N=2. First, the reference exposure is performed using only the microlenses corresponding to the light spots of the 1st line to the 128th (=256/2) lines indicated by the solid line in Fig. 21A, and the reference exposure result is output as a sample. Based on the aforementioned reference exposure result by the sample output, the microlens used in the present exposure can be specified.

For example, microlenses other than the microlenses corresponding to the spot group indicated by oblique lines in Fig. 21B can be designated as the actual use of the present in the microlenses of the first to 128th rows. For the microlenses of the 129th line to the 256th line, the reference exposure can be similarly performed by other methods, and the microlens used for the exposure can be specified, and can also be applied to correspond to the 1st to 128th lines. The pattern of the microlenses is the same pattern.

In such a manner, by designating the microlens used in the present exposure, it is possible to achieve a state close to the ideal two exposures in the present exposure using all of the microlenses.

Fig. 22 is a view showing that a plurality of exposure heads are used, and two exposure heads adjacent to each other in the X-axis direction (for example, one of the exposure heads 30 ₁₂ and 30 ₂₁ ) are respectively used to constitute the equivalent light spot. An explanatory diagram of an example of a form in which a microlens group of adjacent rows of 1/N rows is subjected to reference exposure.

In this example, since this exposure is performed twice, N=2. First, the reference exposure is performed using only the microlenses corresponding to the light spots of the 1st line to the 128th (=256/2) lines indicated by the solid line in Fig. 22, and the reference exposure result is output as a sample. Based on the reference exposure result by the sample output, it is possible to minimize the variation in the resolution and the concentration deviation in the range other than the inter-head contact region formed on the exposed surface by the two exposure heads. In this way, the microlenses used in the present exposure can be specified.

For example, microlenses other than the microlenses corresponding to the range 90 indicated by the oblique line and the spot array in the range 92 indicated by the halftone dots in the microlens of the first row to the 128th row are Can be specified as the actual use of this exposure. For the microlenses of the 129th line to the 256th line, the reference exposure can be similarly performed by other methods, and the microlens used for the exposure can be specified, and can also be applied to correspond to the 1st to 128th lines. The pattern of the microlenses is the same pattern.

In such a manner, by designating the microlens used in the present exposure, it is possible to achieve near-ideal 2 times in a range other than the inter-head contact region formed on the exposed surface by the two exposure heads. The state of exposure.

In the above embodiments (1) to (3) and the modified examples, the case where the exposure is performed by the secondary exposure is separately described. However, the present invention is not limited thereto, and may be any multiple exposure of the secondary exposure or more. In particular, by three exposures to seven exposures, it is possible to ensure high resolution and to achieve exposure which reduces the variation of the resolution and the concentration deviation.

Further, in the exposure apparatus according to the above-described embodiments and modifications, it is preferable to provide an image pattern changing mechanism which is capable of changing the size of a predetermined portion of the 2-dimensional pattern representing the image pattern so as to be The selected mechanism that uses the corresponding parts of the pixel to achieve the same size. By using an image pattern changing mechanism like this, it is possible to form a high-definition pattern of a desired quaternary pattern on the exposure surface.

[development step]

The foregoing development is developed by removing the unexposed portions of the photosensitive layer.

The method for removing the unhardened region is not particularly limited, and may be appropriately selected according to the purpose, and for example, a method in which it can be removed using a developing solution, or the like.

The above-mentioned developing liquid is not particularly limited, and may be appropriately selected according to the purpose of the object. For example, it may be an alkaline aqueous solution, a water-based developing liquid, an organic solvent or the like; among these, it is preferably weak. Alkaline aqueous solution. The base component of the weak alkaline aqueous solution may be, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate or potassium hydrogencarbonate. Sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, borax, and the like.

The pH of the aforementioned weakly alkaline aqueous solution is, for example, preferably from about 8 to 12, more preferably from about 9 to 11. The weakly alkaline aqueous solution may be, for example, 0.1 to 5% by mass of an aqueous sodium carbonate solution or an aqueous potassium carbonate solution.

The temperature of the developing solution may be appropriately selected from those of the photosensitive layer. However, for example, it is preferably about 25 to 40 °C.

The above-mentioned developing solution may also be used in combination with a surfactant, an antifoaming agent, and an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethyleneamine, morpholine, triethanolamine). Or an organic solvent (for example, alcohols, ketones, esters, ethers, guanamines, lactones, etc.) for promoting development. Further, the developing solution may be a water-based developing solution formed by mixing water or an aqueous alkali solution with an organic solvent, or may be a single organic solvent.

[hardening treatment step]

The aforementioned hardening treatment step is a step of performing a hardening treatment on the photosensitive layer in the formed pattern after performing the above-described developing step.

The hardening treatment described above is not particularly limited and may be appropriately selected according to the purpose of the object. For example, for example, a suitable exposure treatment, a total heat treatment, or the like may be employed.

For example, the treatment method for the overall exposure may be, for example, a method of exposing the entire laminated body in which the permanent pattern has been formed after the development step. By the overall exposure, the hardening of the resin in the photosensitive composition forming the photosensitive layer can be promoted, and the surface of the permanent pattern can be hardened.

The apparatus for performing the above-described overall exposure is not particularly limited, and may be appropriately selected according to the needs of the object. For example, for example, a UV exposure machine such as an ultrahigh pressure mercury lamp or the like is suitable.

The above-described overall heating treatment method may be, for example, a method of performing overall heating on the laminated body on which the permanent pattern has been formed after the development step. By this overall heating, the film strength of the surface of the aforementioned permanent pattern can be improved.

The heating temperature of the above comprehensive heating is preferably 120 to 250 ° C, more preferably 120 to 200 ° C. When the heating temperature is less than 120 ° C, the effect of increasing the film strength by heat treatment is not obtained; and when it exceeds 250 ° C, the resin in the photosensitive composition is decomposed and the film quality is changed. Weak and brittle.

The heating time of the above-mentioned overall heating is preferably 10 to 120 minutes, more preferably 15 to 60 minutes.

The apparatus for performing the above-described overall heating is not particularly limited. For example, it can be appropriately selected from known apparatuses according to the purpose, and for example, it may be a drying oven, a heating plate, an IR heater or the like.

- Protective film, interlayer insulating film, solder resist permanent pattern forming method -

In the case where the pattern forming method is a permanent pattern forming method of forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, a permanent pattern can be formed on the printed wiring substrate by the above-described permanent pattern forming method. Further, soldering addition (welding) is performed in the following manner.

That is, the hardened layer of the permanent pattern is formed by the above-described development, and the metal layer is exposed on the surface of the printed wiring board. After gold plating is applied to the metal layer portion exposed on the surface of the printed wiring board, soldering is performed. Then, a semiconductor or a part or the like is mounted on the portion where the soldering has been performed. At this time, the function as a protective film or an insulating film (interlayer insulating film) can be exhibited by the permanent pattern of the hardened layer described above, and the impact from the outside and the conduction between the adjacent electrodes can be prevented.

In the above-described pattern forming apparatus and permanent pattern forming method, when the permanent pattern formed by the above-described permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from external impact and The bending, particularly in the case of the above-mentioned interlayer insulating film, can be effectively used, for example, in a high-density mounting of a semiconductor or a component such as a multilayer wiring substrate, a stacked wiring substrate or the like.

In the above-described permanent pattern forming method of the present invention, since the photosensitive composition of the present invention is used, it can be suitably used for forming various patterns such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern. The manufacture of liquid crystal structural components such as color filters, pillars, ribs, spacers, partition walls, etc., manufacturing of holograms, micromachines, verification, etc., can be suitably used for permanent pattern formation of printed substrates.

[Examples]

Hereinafter, the present invention will be further specifically described by way of examples, but the invention is not limited thereto.

(Synthesis Example 1)

159 g of 1-methoxy-2-propanol was placed in a 1,000 ml three-necked flask and heated to 85 ° C under a nitrogen stream. Thereto, 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of V-601 (Wako Pure Chemical Industries, Ltd.) of 159 g of 1-methoxy-2-propanol solution were added dropwise over 2 hours. When the dropping was completed, it was further heated for 5 hours to cause a reaction. Then, the heating was stopped to obtain a copolymer of benzyl methacrylate/acrylic acid (30/70 mol%).

Next, 120.0 g of the above copolymer solution was transferred into a 300 ml three-necked flask, and 16.6 g of benzyl methacrylate and 0.16 g of p-methoxyphenol were added and stirred to dissolve. After the dissolution, 2.4 g of triphenylphosphine was added, and the addition reaction was carried out under heating at 100 °C. When it was confirmed that the glycidyl methacrylate disappeared, the heating was stopped. 1-methoxy-2-propanol was added to prepare a solution of the polymer compound 1 shown in Table 1 below in a solid content of 30% by mass.

The mass average molecular weight (Mw) of the obtained polymer compound was measured by gel dialysis chromatography (GPC) using polyethylene as a standard material, and it was 15,000.

Further, the acid value (the content of the carboxyl group) per unit solid content obtained by titration with sodium hydroxide was 2.2 meq/g.

Further, the content of the ethylenically unsaturated bond (C=C valence) per unit solid content determined by titration of iodine was 2.1 meq/g.

(Synthesis Example 2~27)

In order to obtain the target polymer compound, in the same manner as in Synthesis Example 1, except that benzyl methacrylate, methacrylic acid, and glycidyl methacrylate in Synthesis Example 1 were appropriately changed to an arbitrary monomer. Polymer compounds 2 to 27 were prepared as shown in Tables 1 to 5, respectively.

In Tables 1 to 5, * 1 represents a mixture of the structure represented by the following structural formula (a) and the structure represented by the structural formula (b); * 2 represents the following structural formula (c) A representative construction and a mixture of constructions represented by structural formula (d).

(Synthesis Example 28)

159 g of 1-methoxy-2-propanol was placed in a 1,000 ml three-necked flask and heated to 85 ° C under a nitrogen stream. Thereto, a solution of 36 g of methyl methacrylate, 72.3 g of methacrylic acid, 4.15 g of V-601 (Wako Pure Chemical Industries, Ltd.) of 159 g of 1-methoxy-2-propanol was added dropwise over 2 hours. When the dropping was completed, it was further heated for 5 hours to cause a reaction. Then, the heating was stopped to obtain a copolymer of methyl methacrylate/acrylic acid (30/70 mol%).

Next, 120.0 g of the above copolymer solution was transferred into 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 the dissolution, 2.4 g of triphenylphosphine was added, and the addition reaction was carried out under heating at 100 °C. When it was confirmed that the glycidyl methacrylate disappeared, the heating was stopped. A solution of the polymer compound 28 represented by the following structural formula was prepared by adding 1-methoxy-2-propanol to a solid content of 30% by mass.

The mass average molecular weight (Mw) of the obtained polymer compound was measured by gel dialysis chromatography (GPC) using polyethylene as a standard material, and it was 15,000.

Further, the acid value (the content of the carboxyl group) per unit solid content obtained by titration with sodium hydroxide was 2.3 meq/g.

Further, the content of the ethylenically unsaturated bond (C=C valence) per unit solid content determined by iodine titration was 2.6 meq/g.

(Example 1)

- Preparation of Photosensitive Composition - Each component was blended in the following amounts to prepare a photosensitive composition solution.

[Amount of each component of the photosensitive composition solution]

. The above polymer compound 1 (the solid content of the above 1-methoxy-2-propanol solution is 30% by mass). . . . . . . 87.4 parts by mass. Dipentaerythritol hexaacrylate (polymeric compound). . . 14 parts by mass. Luciferin-TPO (fluorenyl phosphine oxide compound, photopolymerization initiator.........................6 parts by mass. Apodot YD -8125 (epoxy equivalent 170g/eq., bisphenol A epoxy resin) alkali insoluble thermal crosslinking agent..............7.8 parts by mass. Thermal hardener (cyanide)... ..........0.77 parts by weight. Fluorine-based surfactant (Megafak F-176, manufactured by Dainippon Ink Chemical Industry Co., Ltd., 30% by mass 2-butanone solution). ...0.2 parts by mass. Barium sulfate dispersion (manufactured by Dai Chemical Industry Co., Ltd., B-30): 80 parts by mass. Methyl ethyl ketone...............15 mass Share

In addition, 30 parts by mass of barium sulfate (B30), and 29.2 parts by mass of the above-mentioned polymer compound 1 (in the above 1-methoxy-2-propanol), are used in advance. The mass of the solid component in the solution is 30% by mass), 0.2 parts by mass of CI Pigment Blue 15:3, 0.05 parts by mass of CI Pigment Yellow 185, and 40.55 parts by mass of methyl ethyl ketone are mixed, and then a motor grinder M-200 (manufactured by Aga Co., Ltd.) was prepared by dispersing zirconium beads having a diameter of 1.0 mm at a peripheral speed of 9 m/sec for 3.5 hours.

Further, in the first embodiment, the molar ratio of the molar ratio of the crosslinking group of the thermal crosslinking agent to the acidic group of the binder is (7.8/170)/(87.4*0.3*0.002+29.2). *0.3*0.8*0.0022)=0.63.

Further, the total amount of the solvent-soluble component having a basic substituent in a partial structure was 0%, and the component amount of all the bases having a basic substituent in a partial structure was 0.9%.

-Production of Photosensitive Film - The obtained photosensitive composition solution was applied by bar coating to a 16 μm thick, 300 mm wide, 200 m long PET (polyethylene terephthalate) as the support. The diester film (manufactured by Toray Industries, Inc., 16FB50) was dried in a hot air circulating dryer at 80 ° C to form a photosensitive layer having a thickness of 30 μm. Then, on the photosensitive layer, a 20 μm film thickness, a 310 mm wide, and a 210 m long polypropylene film (E-200, manufactured by Oji Paper Co., Ltd.) was used as a protective film to form a photosensitive film. film.

- Preparation of Photosensitive Film Roller (Cylinder) - The above-mentioned photosensitive film was crimped by a winder to produce an initial roll (cylinder) of a photosensitive film.

The initial cylinder of the obtained photosensitive film was slit by a coaxial roller, and was 250 mm wide on a cylindrical core of ABS resin having a length of 30 mm and an inner diameter of 76 mm. The coil was taken up to 150 meters to form a photosensitive film cylinder.

The photosensitive film cylinder thus obtained was packed in a tubular bag made of black polyethylene (film thickness: 80 μm, water vapor permeability: 25 g/m 2 .24 hours or less), and polypropylene was obtained. The brush is pushed into both ends of the core.

- Formation of permanent pattern - Modulation of photosensitive laminate - Next, chemical polishing is performed on the surface of a printed substrate, a so-called copper-clad laminate (without through holes, copper thickness of 12 μm) Processed and modulated as the substrate described above. The photosensitive layer of the photosensitive film was bonded to the copper-clad laminate, and the protective film of the photosensitive film was peeled off, and a vacuum laminator (VP130, VP130) was used for lamination. Further, a laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) are laminated in this order is prepared.

The pressing conditions were as follows: vacuum suction time was 40 seconds, pressing temperature was 70 ° C, pressing pressure was 0.2 Mpa, and pressing time was 10 seconds.

The shortest development time, sensitivity, resolution, storage stability, and edge roughness were evaluated for the photosensitive laminate described above. The results are shown in Table 6.

<Evaluation of the resolution> (1) Evaluation method of the shortest development time When the polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, the photosensitive layer on the copper clad laminate is In general, a 30 ° C, 1% by mass aqueous sodium carbonate solution is sprayed at a pressure of 0.15 MPa, and the time required from the spraying of the sodium carbonate aqueous solution until the dissolution of the photosensitive layer on the copper clad laminate is measured, and the shortest time is taken as the shortest Development time.

(2) Evaluation method of sensitivity The photosensitive layer of the photosensitive film in the photosensitive layered body prepared above was irradiated from 0.1 mJ/cm ² at intervals of 2 ^1/2 times using the pattern forming apparatus described below. Exposure is performed by light of different light energies up to 100 mJ/cm ² to harden a part of the photosensitive layer. After standing at room temperature for 10 minutes, a 1% by mass aqueous solution of sodium carbonate at 30 ° C was sprayed on the copper-clad laminate at a pressure of 0.15 MPa at twice the shortest development time obtained in the above (1). The photosensitive layer on the plate was entirely removed to dissolve and remove the unhardened region, and the thickness of the remaining hardened region was measured. Next, the relationship between the amount of irradiation of light and the thickness of the hardened layer is plotted to obtain a sensitivity curve. From the sensitivity curve, the light energy at a thickness of 30 μm which is the same as the thickness of the photosensitive layer before exposure was obtained as the exposure energy necessary for hardening the photosensitive layer.

<<Pattern forming apparatus>> The pattern forming apparatus 10 which has the exposure head 30 which has the composite-wave laser light source which is described in the Unexamined-Japanese-Patent No. 2005-258431. The light modulation mechanism can be controlled to drive only the microlens array of 1024 microlenses 58 arranged in the main scanning direction as shown in the schematic diagram of FIG. 6, and the 768 microlens arrays are arranged in the sub-scanning direction. 1024 x 256 columns of DMDs 36, and an optical system as shown in Figs. 5A and 5B in which light is imaged on the photosensitive film.

For each of the exposure heads 30, i.e., the set tilt angle of each of the DMDs 36, the available microlens 58 of 1024 columns x 256 rows can be used at an angle slightly larger than the angle θ _{ideal of} exactly two exposures. The angle θ _ideal is the number N of N exposures, the number s of directions of the microlenses 58 that can be used, the interval p of the available microlenses, and the tilting state of the exposure head 30. Due to the scanning line pitch δ formed by the microlens, it has a relationship of the following formula 1: sp sin θ _ideal ≧N δ (Formula 1)

In the DMD 36 of the present embodiment, as described above, since the plurality of microlenses 58 having the same vertical and horizontal arrangement intervals are arranged in a rectangular lattice shape, p cos θ _ideal = δ (Expression 2) Therefore, the above formula 1 becomes: s tan θ _ideal = N (Formula 3)

Since s = 256 and N = 2, the angle θ _Ideal is about 0.45 degrees. Thereby, the inclination angle θ is set, for example, 0.50 degrees can be employed.

First, in order to correct the variation of the resolution and the unevenness of the exposure in the two exposures, the state of the exposure pattern of the exposed surface is adjusted. The result is shown in Figure 16. In Fig. 16, a projection of the microlens 58 of the DMD 36 having the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the laminated body 12 in a state where the stage 14 is stationary is shown. The pattern of light spots. Further, in the state in which the pattern of the spot group shown in the lower half and the upper half appears, the exposure stage 32 ₁₂ and 32 ₂₁ are exposed to the exposed surface when the moving stage 14 performs continuous exposure. The state of the pattern. In addition, in FIG. 16, the exposure pattern of one row of the microlenses 58 that can be used is divided into the exposure pattern of the pixel group A and the exposure pattern of the pixel group B for convenience of explanation. In addition, the actual pattern on the exposed surface is formed by superimposing two kinds of exposure patterns.

As shown in Fig. 16, it can be understood that the exposure pattern of the pixel group A and the exposure pattern of the pixel group B are both due to the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ as a result of the ideal state. Among the repeated exposure ranges on the coordinate axes in which the scanning directions of the exposure heads 32 ₁₂ and 32 _{21 are} perpendicular to each other, a range in which the exposure is more exposed than the ideal two exposure states is excessive.

Using the combination of the slit 28 and the photodetector as the aforementioned spot position detecting mechanism, the spot P(1, 1) and P (256, in the exposure region 32 ₁₂ are detected for the exposure heads 30 ₁₂ and 30 ₂₁ , 1) The position, the positions of the light spots P (1, 1024) and P (256, 1024) in the exposure area 32 ₁₂ , and the angle formed between the inclination angle of the line connecting them and the scanning direction of the exposure head are measured.

Using the substantial inclination angle θ ', the natural number T about the value t of the exposure heads 30 ₁₂ and 30 ₂₁ which is closest to the relationship 4: t tan θ ' = N (Expression 4) which follows is derived, respectively. Derived separately as follows: T = 254 for exposure head 30 ₁₂ and T = 255 for exposure head 30 ₂₁ . As a result, the microlenses constituting the portions 78 and 80 covered with oblique lines in Fig. 17 are defined as microlenses which are not used at the time of exposure.

Then, with respect to the microlens corresponding to the light spot other than the spot constituting the portions 78 and 80 covered with oblique lines in Fig. 17, the same is defined and the range 82 which is covered by the oblique line in Fig. 17 and The microlens corresponding to the spot of the range 84 covered by the dot is added as a microlens which is not used in the present exposure. It is defined as a microlens that is not used during this exposure.

For the defined microlenses that are not used during such exposure, the micro-lens is controlled by the pixel control mechanism to send an angle of the angle that is normally set to the OFF state, so that the microlenses are substantially independent of exposure.

Thereby, it is possible to make each of the exposure regions 32 ₁₂ and 32 ₂₁ in a range other than the connection region between the heads of the repeated exposure ranges on the exposed surface formed by the plurality of exposure heads, with respect to the ideal In the case of the secondary exposure, the total area of the area that is excessively exposed and the area that is underexposed is minimized.

(3) Evaluation method of the resolution The photosensitive laminate was produced in the same manner and under the same conditions as the evaluation method of the shortest development time of the above (1), and allowed to stand at room temperature (23 ° C, 55% RH) for 10 minutes. From the above-mentioned pattern forming apparatus, the above-described pattern forming apparatus was used to form a line width of 10 μm on a 1 μm scale from the polyethylene terephthalate film (support) of the obtained photosensitive laminate. Exposure of each line width up to 100 microns. The exposure amount at this time is the light energy required to harden the photosensitive layer of the above (2). After standing at room temperature for 10 minutes, a polyethylene terephthalate film (support) was peeled off from the photosensitive laminate. On the entire surface of the photosensitive layer on the copper clad laminate, 30 ° C and 1% by mass of the developing solution were sprayed at a pressure of 0.15 MPa and twice the shortest development time obtained by the above (1). An aqueous solution of sodium carbonate is dissolved to remove the unhardened area. Observing the surface of the thus obtained copper-clad laminate having the cured resin pattern with an optical microlens, and measuring the minimum column width of the hardened resin pattern without abnormalities such as clogging, wavy, and the like, and forming a space For resolution. The smaller the resolution coefficient value, the better. The results are shown in Table 1.

<Evaluation of storage stability (change over time of development time)> - Measurement of development time - (Measurement of development time T ₁ ) The above-mentioned laminated body was placed in a dark place at 25 ° C for 20 minutes, and then peeled off. A polyethylene terephthalate film (support) was taken, and the above-mentioned photosensitive layer was subjected to development processing. The development process described above is carried out by using a sodium carbonate aqueous solution of 30° C. and 1% by mass as an alkali developing solution, and rinsing the entire photosensitive layer on the copper clad laminate to measure the aforementioned layer on the copper clad laminate. The time required until the photosensitive layer is completely removed, and is taken as the development time T ₁ .

(Measurement of development time T ₂ ) The photosensitive laminate was placed in a moisture-proof bag (barrel bag made of black polyethylene, film thickness: 80 μm, water vapor permeability: 25 g/m 2 .24 hours) below), in an environment of 40 ℃ allowed to stand for 72 hours and then measured by the above-described developing time T ₁ of the same method to determine the developing time T _2.

(Measurement of Change Rate of Development Time) The change rate (T ₂ /T ₁ ) of the development time is calculated from the measured development time T ₂ and the aforementioned development time T ₁ , and is based on the following evaluation criteria. To evaluate the preservation stability.

[Evaluation criteria] ◎. . . The change of imaging time satisfies 0.5<(T ₂ /T ₁ )<2.5; ○. . . The change of imaging time satisfies 0.5<(T ₂ /T ₁ )<3;×. . . The change in development time did not satisfy 0.5 < (T ₂ / T ₁ ) <3; T ₁ , T ₂ , (T2/T1) and evaluations obtained in this manner are shown in Table 6.

(Example 2 to Example 7 and Comparative Examples 1 to 3)

In the first embodiment, the photosensitive thin film photosensitive laminate was prepared in the same manner as in Example 1 except that the polymer compound shown in the following Table 6 was used instead of the polymer compound described above, and Example 1 was prepared. The evaluation of sensitivity, resolution, and preservation stability was performed in the same manner. The results are shown in Table 6.

In the following Table 6, the polymer compound (B-1) used in Comparative Example 1 and the polymer compound (B-2) used in Comparative Example 2 were each synthesized according to the following method.

In the polymer compound (B-3) used in Comparative Example 3, a polymer compound (Mw: 8,000, acid value: 80 mg KOH/g) represented by the following structure was used.

(Synthesis Example 29)

The polymer compound (B-1) was obtained by the same procedure except that 2.4 g of triphenylphosphine in Synthesis Example 1 was changed to 2.4 g of tetraethylammonium chloride.

(Synthesis Example 30)

The polymer compound (B-2) was obtained by the same procedure except that 2.4 g of triphenylphosphine in Synthesis Example 28 was changed to 2.4 g of tetraethylammonium chloride.

(Example 8)

A photosensitive film and a photosensitive laminate were produced in the same manner as in Example 1 except that the components were blended in the following amounts to prepare a photosensitive composition solution.

[Amount of each component of the photosensitive composition solution] . The above polymer compound 1 (the solid content of the above 1-methoxy-2-propanol solution is 30% by mass). . . . . . 87.4 parts by mass. Dipentaerythritol hexaacrylate (polymeric compound). . . 14 parts by mass. Irgacure 819 (sulfonyl phosphine oxide compound, Ciba Specialty Chemicals Co., Ltd., photopolymerization initiator). . . . . . . . . . . . . 4 parts by mass. Apodox YD-8170C (epoxy equivalent 155 g / eq., bisphenol F epoxy resin, alkali insoluble thermal crosslinker). . . . . . . 11.3 parts by mass. Thermal hardener (cyanide). . . . . . . . . . . . . 0.77 parts by weight. Fluorine-based surfactant (Megafak F-176, manufactured by Dainippon Ink Chemicals Co., Ltd., 30% by mass 2-butanone solution). . . . 0.2 parts by mass. Barium sulfate dispersion (manufactured by Dai Chemical Industry Co., Ltd., B-30). . 80 parts by mass. Methyl ethyl ketone. . . . . . . . . . . . . . . 15 parts by mass

Further, the above-described barium sulfate dispersion was prepared in the same manner as in Example 1.

In the eighth embodiment, "the molar ratio of the molar ratio of the crosslinking group of the thermal crosslinking agent / the acidic group of the binder" is (11.3/155) / (87.4 * 0.3 * 0.0022 + 29.2 * 0.3) *0.8*0.0022)=1.0.

Further, the total amount of the solvent-soluble component having a basic substituent in a partial structure was 0%, and the component amount of all the bases having a basic substituent in a partial structure was 0.9%.

Further, in the photosensitive film and the photosensitive laminate, the sensitivity, the resolution, and the storage stability were evaluated in the same manner as in Example 1. After the development, the full exposure was performed with an ultrahigh pressure mercury lamp at 50 mJ/cm ² . Moreover, the evaluation of the electroless metal plating resistance was performed by the following method. The results of these are shown in Table 7.

<Evaluation of Electroless Metal Plating Resistance> Electrolytic metal plating was performed on the test substrate described above, and the test substrate was subjected to an appearance change and a peeling test using a cellophane (cellophane) adhesive tape. The peeling state of the photoresist film was evaluated in accordance with the following criteria.

- Evaluation criteria - ○: No change in appearance, no peeling of the photoresist film; △: Although the appearance did not change, the photoresist film was slightly peeled off; ×: Visible film edema was observed, and plating subsidence was observed, and peeling was observed. The photoresist film was largely peeled off during the test.

-- Electroless metal plating project -- A test substrate in which a solder resist pattern (permanent pattern) is formed, and immersed in an acidic degreasing liquid at 30 ° C (20% by mass aqueous solution of Metex L-5B, manufactured by KK Damit, Japan) After 3 minutes, it was immersed in running water for 3 minutes.

Next, it was immersed in a 14.3 mass% aqueous solution of barium persulfate for 3 minutes at room temperature, and then immersed in running water for 3 minutes; and the test substrate was immersed in a 10 mass% sulfuric acid aqueous solution at room temperature. After 1 minute, it was immersed in running water and washed with water for 30 seconds to 1 minute.

Next, the substrate was immersed in a catalyst at 30 ° C (manufactured by Merlot Co., Ltd., a 10% by mass aqueous solution of a metal plate activator 350) for 7 minutes, and then immersed in running water for 3 minutes; then, at 85 The nickel plating solution (manufactured by Merut Couss Co., Ltd., metal plate Ni-865M, 20% by volume aqueous solution, pH: 4.6) was immersed for 20 minutes, and subjected to electroless nickel plating at room temperature at 10 mass. After immersing in a % sulfuric acid aqueous solution for 1 minute, it was immersed in running water and washed with water for 30 seconds to 1 minute.

Next, the test substrate was immersed in a metal plating solution (manufactured by Okuno Pharmaceutical Co., Ltd., OPC electroless mother liquid, pH: 12 to 13, metal plating thickness: 0.3 μm) at 75 ° C for 4 minutes to carry out electroless metal plating. Thereafter, the mixture was immersed in running water for 3 minutes, and further immersed in warm water of 60 ° C for 3 minutes to be sufficiently washed with water, and then dried to obtain a test substrate subjected to electroless metal plating.

(Examples 9 to 13)

In the same manner as in Example 8, except that the polymer compound described above was changed to the polymer compound shown in Table 7 below, a photosensitive film and a photosensitive laminate were produced.

Further, in the photosensitive film and the photosensitive laminate, the sensitivity, the resolution, the electroless metal plating resistance, and the storage stability were evaluated in the same manner as in Example 8. The results are shown in Table 7.

(Comparative Example 4)

In the eighth embodiment, the polymer compound (B-4, Mw: 30,000, acid value: 2.0 meq/g) represented by the following structural formula (f) is replaced by the polymer compound described above. Further, a photosensitive film and a photosensitive laminate were produced in the same manner as in Example 8.

(Example 14)

A photosensitive film and a photosensitive laminate were produced in the same manner as in Example 1 except that the components were blended in the following amounts to prepare a photosensitive composition solution.

[Amount of each component of the photosensitive composition solution] . The above polymer compound 1 (the solid content of the above 1-methoxy-2-propanol solution is 30% by mass). . . . . . 87.4 parts by mass. Dipentaerythritol hexaacrylate (polymeric compound). . . 14 parts by mass. The sensitizer shown in the following structural formula (g). . . . . . . 0.6 parts by mass. Irgacure 907 (base-based photopolymerization initiator containing aminoalkyl group, manufactured by Ciba Specialty Chemicals Co., Ltd. 1.5 parts by mass. TEPIC-S (epoxy equivalent 99 g/ Eq., poorly soluble epoxy resin, alkali-insoluble thermal crosslinking agent)..............3.73 parts by mass. Thermal hardener (cyanide)......... ....0.77 parts by weight. Fluorine-based surfactant (Megafak F-176, manufactured by Dainippon Ink Chemicals Co., Ltd., 30% by mass of 2-butanone solution)....0.2 parts by mass . Barium sulfate dispersion (B-30, manufactured by Seiko Chemical Co., Ltd.): 80 parts by mass. Methyl ethyl ketone...15 parts by mass

Further, the above-described barium sulfate dispersion was prepared in the same manner as in Example 1.

In the present Example 14, "the molar ratio of the molar ratio of the crosslinking agent of the thermal crosslinking agent / the molar ratio of the binder" (3.73/99) / (87.4 * 0.3 * 0.0022 + 29.2 * 0.3) *0.8*0.0022)=0.52.

Further, the total amount of the solvent-soluble component having a basic substituent in a partial structure was 1.9%, and the component amount of all the bases having a basic substituent in a partial structure was 2.8%.

The photosensitive film and the photosensitive laminate were evaluated for sensitivity, resolution, and storage stability in the same manner as in Example 1. The results are shown in Table 8.

(Example 15 and Comparative Example 15)

In the same manner as in Example 14, except that the type of the polymer compound was changed to that shown in Table 8 below, a photosensitive laminate was produced.

Further, in the same manner as in Example 14, the photosensitive film and the photosensitive laminate were evaluated for the sensitivity, the resolution, and the storage stability. The results are shown in Table 8.

(Embodiment 16)

In the eighth embodiment, 4 parts by mass of the photopolymerization initiator "Irgacure 819 (manufactured by sulfhydryl phosphine compound, manufactured by Ciba Specialty Chemicals Co., Ltd.)" was changed to 3 parts by mass of Irgacure 651 (alkyl benzophenone). Type, Ciba Specialty Chemicals Co., Ltd.), and further, 11.3 parts by mass of the alkali-insoluble thermal crosslinking agent "Apodote YD-8170C (epoxy equivalent 155 g / eq., bisphenol F-based epoxy) In the same manner as in Example 8, except that the resin was changed to 11.3 parts by mass of "Apotox YDCN-701 (epoxy equivalent: 195 g/eq., novolak type epoxy resin)". Film and photosensitive laminate.

For the photosensitive laminate, a glass negative mask having the same pattern as in Example 1 was separately prepared, and the negative mask was brought into contact with the laminate to expose the ultrahigh mercury lamp to 100 mJ/cm ² . The amount is exposed. Then, development and evaluation of the resolution were carried out in the same manner as in Example 1, and the storage stability of the photosensitive film was evaluated in the same manner as in Example 1. The results are shown in Table 9.

(Example 17 and Comparative Example 16)

In the same manner as in Example 16, except that the type of the polymer compound was changed to the one shown in the following Table 9, a photosensitive laminate was produced.

Further, in the same manner as in Example 16, the photosensitive film and the photosensitive laminate were evaluated for sensitivity, resolution, and storage stability. The results are shown in Table 9.

From the results of Tables 6 to 9, it is understood that the photosensitive film formed by using the photosensitive layer of the photosensitive compositions of Examples 1 to 17 containing the polymer compound of the present invention has high storage stability; The permanent pattern formed by the exposure methods of Examples 1 to 17 can efficiently form a high-definition permanent pattern (a protective film, an interlayer insulating film, a solder resist pattern, etc.) without impairing the sensitivity and the resolution.

Further, it can be judged from Examples 8 to 13 that in addition to the above properties, electroless metal plating resistance can be provided.

Further, since the above effects are achieved by using a common and inexpensive thermal crosslinking agent, the cost required for the thermal crosslinking agent can be alleviated, and the selection range of the thermal crosslinking agent can be expanded.

[Industrial Availability]

The photosensitive composition and the photosensitive film of the present invention can be suitably used because they can form a high-definition pattern which is excellent in sensitivity, resolution, and storage stability by efficiently containing a predetermined polymer compound. Manufacturing of liquid crystal structural components such as various patterns such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a pillar, a rib, a spacer, and a partition, a hologram, a micromachine, For pattern formation such as verification, it is particularly suitable for use in permanent pattern forming applications of printed substrates.

Since the permanent pattern forming method of the present invention uses the photosensitive composition of the present invention, it can be suitably used for various pattern formation, color filters, and permanent patterns such as a protective film, an interlayer insulating film, and a solder resist pattern. For the formation of liquid crystal structural components such as pillars, ribs, separators, partition walls, etc., for the formation of patterns such as holograms, micromachines, and verification, it is particularly suitable for use in permanent pattern formation of printed substrates.

B. . . Laser beam

P. . . light spot

10. . . Pattern forming device

12. . . Photosensitive material, photosensitive layer

14. . . mobile platform

16. . . Foot

18. . . Setting table

20. . . Guide

twenty two. . . brake

twenty four. . . scanner

26. . . sensor

28. . . Slit

28a. . . Slot on the upstream side

28b. . . Slit on the downstream side

30. . . Exposure head

30 ₁₂ . . . Exposure head

30 ₂₁ . . . Exposure head

32. . . Exposure area

32 ₁₂ . . . Exposure area

32 ₂₁ . . . Exposure area

34. . . Exposure completion area

36. . . Digital microlens device (DMD)

38. . . Fiber array light source

40. . . Lens system

42. . . lens

44, 46. . . Combined lens

48. . . Condenser lens

50. . . Lens system

52, 54. . . lens

56. . . SRAM unit (memory)

58. . . Microlens

78, 80, 82. . . Slash coverage

72, 84, 88, 92. . . Dot coverage

Fig. 1 is a perspective view showing an appearance of an example of a pattern forming device.

Fig. 2 is a perspective view showing the configuration of a scanner of the pattern forming apparatus.

Fig. 3A is a plan view showing an exposure completion region formed on the exposed surface of the photosensitive layer.

Fig. 3B is a plan view showing the arrangement of the exposed areas of the respective exposure heads.

Fig. 4 is a perspective view showing an example of a schematic configuration of an exposure head.

Fig. 5A is a top view showing an example of the detailed configuration of the exposure head.

Fig. 5B is a side view showing an example of a detailed configuration of an exposure head.

Fig. 6 is a partially enlarged view showing an example of a DMD of the pattern forming apparatus of Fig. 1.

Fig. 7A is a perspective view for explaining the action of the DMD.

Fig. 7B is a perspective view for explaining the action of the DMD.

Fig. 8 is an explanatory view showing an example in which the pattern on the exposed surface is deviated when the mounting angle error of the exposure head and the pattern are distorted.

Fig. 9 is a top view showing the positional relationship between the exposure region of one DMD and the corresponding slit.

Figure 10 is a top view showing the use of a slit to measure the position of a spot on an exposed surface.

Fig. 11 is an explanatory view showing a state in which only the selected microlenses are used for exposure, and as a result, the state of the deviation of the pattern generated on the exposed surface is improved.

Fig. 12 is an explanatory view showing an example in which a pattern on the surface to be exposed is deviated when there is a deviation in relative position between adjacent exposure heads.

Fig. 13 is a top view showing the positional relationship between the exposure regions of the adjacent two exposure heads and the corresponding slits.

Fig. 14 is a view showing a top view of a method of measuring the position of a light spot on an exposure surface using a slit.

Fig. 15 is an explanatory view showing a state in which the deviation of the pattern generated on the exposed surface is improved only by the selected actual operation using the pixel in the example of Fig. 12.

Fig. 16 is an explanatory view showing an example in which the pattern on the surface to be exposed is deviated when there is a deviation in the relative position between the adjacent exposure heads and an error in the mounting angle.

Fig. 17 is an explanatory view showing the exposure using only the selected pixel portion in Fig. 16.

Fig. 18A is an explanatory diagram showing an example of the magnification deviation.

Fig. 18B is an explanatory diagram showing an example of the deviation of the beam diameter.

Fig. 19A is an explanatory view showing a first example of reference exposure using a single exposure head.

Fig. 19B is an explanatory view showing a first example of reference exposure using a single exposure head.

Fig. 20 is an explanatory view showing a first example of reference exposure using a complex exposure head.

Fig. 21A is an explanatory view showing a second example of the reference exposure using a single exposure head.

Fig. 21B is an explanatory view showing a second example of the 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.

Claims (20)

A photosensitive composition characterized by comprising at least a photosensitive composition of a binder, a polymerizable compound, a photopolymerization-initiating compound, and a thermal crosslinking agent; when the photosensitive composition is laminated on a substrate After 20 minutes in the dark at 25 ° C, the time required for removing the unexposed portion of the photosensitive composition deposited on the substrate by the developing solution (the shortest development time) is expressed as T ₁ ; The photosensitive composition deposited on the substrate was placed in a dark portion at 40 ° C for 72 hours, and the photosensitive composition deposited on the substrate was removed by a developing solution. The time required for the exposed portion (the shortest development time) is expressed as T ₂ , which satisfies the relationship of 0.5 < T ₂ / T ₁ < 3, wherein the binder is derived from a cyclic ether group in the presence of a catalyst. The polymerizable compound is added to an acidic group of a part of the polymer compound, and a polymerizable compound containing a carboxyl group is added to a part or all of the cyclic ether group of the polymer compound in the presence of a catalyst. Any choice The polymer compound; and the aforementioned catalyst is arbitrarily selected from the group consisting of an acidic compound and a neutral compound. The photosensitive composition of claim 1, wherein the binder comprises a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain. The photosensitive composition of claim 1, wherein the binder comprises a polymer compound having an acidic group in a side chain, an aromatic group which may contain a hetero ring, and an ethylenically unsaturated bond. The photosensitive composition of claim 2, wherein the polymer compound contains an ethylenically unsaturated bond of 0.5 to 3.0 meq/g. The photosensitive composition of claim 2, wherein the polymer compound has a carboxyl group in a side chain, and the content of the carboxyl group in the polymer compound is 1.0 to 4.0 meq/g. The photosensitive composition of claim 2, wherein the polymer compound has an average molecular weight of 10,000 or more and less than 100,000. The photosensitive composition of claim 2, wherein the polymer compound contains 20 mol% or more of a structural unit represented by the following structural formula (I); However, in the above structural formula (I), R ₁ , R ₂ and R ₃ represent a hydrogen atom or a monovalent organic group; L represents an organic group, if not, and Ar represents a heterocyclic ring. Aromatic group. The photosensitive composition of claim 1, wherein the polymerizable compound is a compound having one or more ethylenically unsaturated bonds. The photosensitive composition of claim 1, wherein the thermal crosslinking agent It is at least one selected from the group consisting of an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a block agent, and a melamine derivative. The photosensitive composition of claim 1, wherein the thermal crosslinking agent is alkali-insoluble. The photosensitive composition of claim 1, wherein the molar ratio of the molar ratio of the crosslinking agent of the thermal crosslinking agent to the binder is 0.1 to 1.5. The photosensitive composition of claim 1, wherein at least one of the following components is present in the photosensitive composition: a total amount of solvent-soluble components having a partial structural substituent is 5%. The component amount of all bases having a base substituent in the following structures and partial structures is 7% or less. The photosensitive composition of claim 12, wherein the base substituent is from a grade 1 to a grade 3 amine group, a grade 4 ammonium group, an amine group III The base group, the imidazole group, and the guanamine group are optionally selected. The photosensitive composition of claim 1, wherein T ₁ is 5 to 120 seconds, and T ₂ is 5 to 240 seconds. The photosensitive composition of claim 1, wherein the photopolymerization initiator is arbitrarily selected from the group consisting of a fluorenylphosphine oxide compound and a ketone compound. A photosensitive film comprising a support and a photosensitive layer formed on the support by the photosensitive composition of claim 1 of the patent application. The photosensitive film of claim 16 of the patent application is formed into a long shape and rolled into a cylindrical shape. A permanent pattern forming method is characterized in that a photosensitive composition as described in claim 1 is applied onto a surface of a substrate and dried to form a photosensitive layer, followed by exposure and development. A permanent pattern forming method, characterized in that, after at least one of heating and pressurization, a photosensitive film as disclosed in claim 16 is laminated on a surface of a substrate, and then exposure and development are performed. . A printed substrate characterized by forming a permanent pattern by a permanent pattern forming method as in claim 18 of the patent application.