WO2007080698A1

WO2007080698A1 - Photosensitive resin composition, photosensitive transfer film, and method for pattern formation

Info

Publication number: WO2007080698A1
Application number: PCT/JP2006/322305
Authority: WO
Inventors: Kazumori Minami; Yasutomo Goto; Morimasa Sato
Original assignee: Fujifilm Corporation
Priority date: 2006-01-13
Filing date: 2006-11-08
Publication date: 2007-07-19
Also published as: KR20080085173A; JPWO2007080698A1

Abstract

This invention provides a photosensitive resin composition, which can realize excellent resist conformation on a substrate, and can simultaneously realize excellent developability and the refinement of peeled pieces upon etching, a photosensitive transfer film comprising a photosensitive layer formed using the photosensitive resin composition, and a method for pattern formation which can form a high-definition pattern using the photosensitive transfer film. The photosensitive resin composition is characterized by comprising a binder, a polymerizable compound, and a photopolymerization initiator and having a melt viscosity of 40,000 to 120,000 Pa·s at 50ºC and 5,000 to 20,000 Pa·s at 70ºC.

Description

Specification

Photosensitive resin composition, photosensitive transfer film and pattern forming method

[0001] The present invention relates to a photosensitive resin composition suitable for forming a photosensitive layer of a dry film resist (DFR), a photosensitive transfer film having a photosensitive layer formed from the photosensitive resin composition, and The present invention relates to a pattern forming method using the photosensitive transfer film.

Background art

Conventionally, when a pattern is formed, a photosensitive transfer film in which a photosensitive layer is formed by applying a photosensitive resin composition on a support and drying it has been used. As a method for forming the pattern, for example, a photosensitive layer is formed using a photosensitive transfer film on a substrate such as a copper clad laminate on which the pattern is formed, and the photosensitive layer is exposed. It is known that after the exposure, the photosensitive layer is developed to form a pattern, further etched, and then the pattern is removed.

[0003] Any layer IVH (ALIVH) method adopting an Interstitial Via Hole (IVH) structure in which a via hole is formed in a necessary portion for each layer as a method for producing a build-up substrate, before forming the pattern. The method is known. In this method, copper is coated on an ultra-thin aramid resin of about 100 m, so in other methods, the irregularity of about 1 to 2 / zm becomes as large as about 12 m, and the obtained substrate Resist trackability is required.

[0004] On the other hand, in the formation of the pattern, contamination of the apparatus due to a peeled piece of the photosensitive layer or the like, and a decrease in resolution are serious problems.

For example, when a photosensitive layer is laminated on a substrate having a plurality of hole portions such as a printed wiring board having a hole portion such as a through hole or a via hole, the photosensitive layer is supported from the photosensitive layer for development after exposure. When an attempt is made to peel the body, the uncured unexposed portion of the photosensitive layer adheres to the support near the hole in the substrate and breaks, and when the substrate is peeled off, so-called unexposed film breakage occurs. There was something to do. For this reason, minute peeling pieces peeled off from the photosensitive layer contaminate the device or reduce the resolution of the pattern. May cause problems such as.

[0005] In order to solve this problem, in order to prevent development scum and improve releasability, a method using a monofunctional monomer as a material for dry film resist (DFR) (see Patent Document 1 and Patent Document 2, etc.), a binder A method for adjusting the acid value, glass transition temperature (Tg), IZO value, etc. of the resin has been proposed. However, according to the methods described in Patent Documents 1 and 2, there is a problem that developability deteriorates. is there.

As described above, there has been a problem that other performance such as developability is deteriorated by improving the peelability of the resist.

[0006] Therefore, a photosensitive resin composition having good resist followability on a substrate and having both excellent developability and finer strips at the time of resist stripping. A photosensitive transfer film having a photosensitive layer formed of a photosensitive resin composition and a pattern forming method capable of forming a high-definition pattern using the photosensitive transfer film have not been provided yet, and further improvements and developments have been made. This is the current situation.

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-330189

Patent Document 2: Japanese Patent Laid-Open No. 2003-345005

Disclosure of the invention

Problems to be solved by the invention

[0008] The present invention has been made in view of the current situation, and it is an object of the present invention to solve the above-described problems and achieve the following objects. That is, the present invention provides a photosensitive resin composition that has good followability of a resist on a substrate, and that can achieve both excellent developability and finer stripping at the time of resist stripping. It is an object of the present invention to provide a photosensitive transfer film having a photosensitive layer formed of a photosensitive resin composition, and a pattern forming method capable of forming a high-definition pattern using the photosensitive transfer film.

Means for solving the problem

[0009] As a result of intensive studies in view of the above problems, the present inventors have obtained the following knowledge. That is, the melt viscosity of a photosensitive resin composition containing a noinder, a polymerizable compound, and a photopolymerization initiator is 50. C is 40,000 to 120,000 Pa, s, 70. By setting C to 5,000 to 20,000 Pa's, the followability of the resist on the substrate is good and excellent development is achieved. It is a finding that a photosensitive layer can be formed which can satisfy both the properties and the miniaturization of the peeled piece when the resist is peeled off.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,

<1> Contains a binder, a polymerizable compound, and a photopolymerization initiator, and has a melt viscosity of 50. C is 40,000-120, OOOPa, s, 70. It is a photosensitive resin composition characterized by having a C of 5,000 to 20, OOOPa, s.

<2> The copolymer includes a copolymer A having a mass average molecular weight of 3,000 to 10,000, and a copolymer B having a mass average molecular weight of 30,000 to 150,000, The photosensitive resin composition according to <1>, wherein a mass ratio of A to the copolymer B is AZB = 10Z90 to 90Z10.

<3> The photosensitive resin composition according to <2>, wherein a mass ratio of the copolymer Α to the copolymer で is A / B = 10Z90 to 40Z60.

<4> The photosensitive resin composition according to <3>, wherein the copolymer を has a structural unit derived from at least one of styrene and a styrene derivative.

<5> The photosensitive resin composition according to any one of <3>, force <4>, wherein the copolymer B contains a butyl monomer having a carboxyl group.

<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the polymerizable compound includes a monomer having at least one of a urethane group and an aryl group.

<7> The photosensitive resin composition according to <6>, wherein the polymerizable compound contains a compound having a polyalkylene oxide chain, and the polyalkylene oxide chain has at least one of an ethylene group and a propylene group. It is a thing.

<8> The photopolymerization initiator is a halogenated hydrocarbon derivative, phosphine oxide, hexaarylbiimidazole, oxime derivative, organic peroxide, thio compound, ketone compound, acyl phosphine oxidoxide compound, The photosensitive resin composition according to any one of <1> to <7>, comprising at least one selected from an aromatic onium salt and a ketoxime ether. [0011] <9> A photosensitive transfer film comprising a photosensitive layer formed of the photosensitive resin composition according to any one of <1> to <8> on a support. .

<10> When the photosensitive layer is exposed and developed with a laser beam having a wavelength of 390 to 420 nm, the thickness of the exposed portion of the photosensitive layer is used for the exposure that is not changed after the exposure and development. The photosensitive transfer film according to <9>, wherein the minimum energy (sensitivity) of light is 0.1 to 20 miZcm ² .

<11> The photosensitive transfer film according to any one of <9> to <10>, wherein the photosensitive layer has a thickness of 1 to: LOO μm.

<12> The photosensitive transfer film according to any one of <9> to <11>, wherein the support contains a synthetic resin and is transparent.

<13> The light-sensitive transfer film according to any one of the above <9> Karaku 12>, wherein the support is long.

<14> The photosensitive transfer film according to any one of <9> to <13>, which is long and wound in a roll shape.

<15> The photosensitive transfer film according to any one of <9>, <14>, which has a protective film on the photosensitive layer.

<16> The photosensitive transfer film according to any one of <9> and 15>, wherein the photosensitive layer is laminated on a substrate to be processed, and then the photosensitive layer is exposed. This is a pattern forming method characterized by this.

<17> Exposure includes light irradiation means, and n (where n is a natural number of 2 or more) two-dimensionally arranged pixel parts that receive and emit light from the light irradiation means, An exposure head provided with a light modulation means capable of controlling the picture element portion according to pattern information, wherein the column direction of the picture element portion is a predetermined set inclination angle Θ with respect to the scanning direction of the exposure head. Using an exposure head arranged to form

For the exposure head, a process of designating the pixel part to be used for N double exposure (where N is a natural number of 2 or more) of the usable pixel parts by means of a used pixel part specifying means;

The exposure head is controlled by the pixel part control unit and the used pixel part specifying unit. Controlling the pixel part so that only the specified pixel part is involved in exposure, and

Performing exposure by moving the exposure head relative to the photosensitive layer in a scanning direction; and

The pattern forming method according to the above item 16>, including: In the pattern forming method described in 17>, the exposure head is subjected to N double exposure (where N is a natural number of 2 or more) of the usable pixel parts by means of the used pixel part specifying means. The pixel part to be used is specified, and the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in the exposure. . By performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction, the exposure head is formed on the exposed surface of the photosensitive layer due to a shift in the mounting position or mounting angle of the exposure head. Variations in resolution and unevenness in density of the pattern are leveled. As a result, the photosensitive layer is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.

<18> The exposure is performed by a plurality of exposure heads, and the used picture element designating unit is configured to perform drawing related to exposure of a head-to-head connection area, which is an overlapping exposure area on an exposed surface formed by the plurality of exposure heads. The pattern forming method according to <17>, wherein among the element parts, the image element part to be used for realizing N double exposure in the inter-head connection region is designated. In the pattern forming method according to <18>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit is an overlapped exposure region on an exposed surface formed by the plurality of exposure heads. Of the picture element parts involved in the exposure of the head-to-head connection area, the position of the exposure head and the mounting position of the exposure head can be determined by specifying the picture element part used for realizing the N-fold exposure in the head-to-head connection area. Variations in the resolution and density unevenness of the pattern formed in the connecting region between the heads on the exposed surface of the photosensitive layer due to the angle deviation are leveled. As a result, the photosensitive layer is exposed with high definition. For example, a high-definition pattern is then formed by developing the photosensitive layer.

<19> Exposure is performed by a plurality of exposure heads, Realizes N-fold exposure in areas other than the head-to-head connection area among the pixel parts involved in exposure other than the head-to-head connection area, which are overlapping exposure areas on the exposed surface formed by the exposure head. The pattern forming method according to <18>, wherein the pixel part to be used for designating is specified. In the pattern forming method according to the above item 19, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit performs overlapping exposure on the exposed surface formed by the plurality of exposure heads. By specifying the pixel part to be used for realizing N double exposure in areas other than the head-to-head connection area among the pixel parts related to exposure other than the head-to-head connection area, the exposure is performed. Variations in the resolution and density unevenness of the pattern formed in areas other than the joint area between the heads on the exposed surface of the photosensitive layer due to deviations in the mounting position and mounting angle of the head are equalized. As a result, the photosensitive layer is exposed with high definition. For example, by developing the photosensitive layer thereafter, a high-definition pattern is formed.

<20> Setting tilt angle Θ force N N number of double exposures, number s of pixel parts in the row direction, interval P of the pixel parts in the row direction, and exposure with the exposure head tilted For the pitch δ in the column direction of the pixel part along the direction orthogonal to the scanning direction of the head, the following equation is given: spsin Θ ≥ Ν δ

Satisfy eal

For ideal, θ≥ Θ

<1 id set to satisfy ideal relationship

The pattern forming method according to any one of 7> Karaku 19>.

<21> The pattern forming method according to any one of <17> to <20>, wherein the N force of N double exposure is a natural number of 3 or more. In the pattern forming method described in 21>, multiple drawing is performed by using a natural number of N force 3 or more in N double exposure. As a result, due to the effect of offsetting, variations in the resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to deviations in the mounting position and mounting angle of the exposure head are more accurately and evenly distributed. Is done.

<22> Use pixel part designation means

A light spot position detecting means for detecting a light spot position as a pixel unit that is generated by the picture element unit and constitutes an exposure area on the exposed surface;

Based on the detection result by the light spot position detecting means, a pixel part selecting means for selecting a picture element part to be used for realizing N double exposure; The pattern forming method according to any one of the above items 17> to 21>.

<23> The pattern forming method according to any one of the above items 17> Karaku 22>, in which the used pixel part designation means designates the used pixel part used to realize N double exposure in units of lines. is there.

[0014] <24> The light spot position detecting means detects the light spot column direction on the surface to be exposed and the exposure head running direction when the exposure head is tilted based on at least two light spot positions detected. The actual inclination angle Θ 'formed by the image is determined, and the pixel part selection means selects the pixel part to be used so as to absorb the error between the actual inclination angle Θ' and the set inclination angle Θ. <23> The pattern forming method described in any of the above.

<25> The actual inclination angle Θ ′ is an average value, a median value, and a plurality of actual inclination angles formed by the row direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is inclined. 24. The pattern forming method according to 24>, wherein the pattern forming method is one of a maximum value and a minimum value.

<26> The pixel part selection means derives a natural number T near t satisfying the relationship of ttan 0 '= Ν (where 表す represents Ν of the double exposure number) based on the actual inclination angle θ Ί. , M rows (where m represents a natural number greater than or equal to 2) The above-mentioned pixel portion from the first row to the T-th row in the arranged pixel portion is selected as the used pixel portion. 25. The pattern forming method according to any one of the above items.

<27> The pixel part selection means derives the natural number T near t satisfying the relationship of ttan 0 '= Ν (where Ν represents Ν of the double exposure number) based on the actual inclination angle θ Ί. , M line (where m represents a natural number greater than or equal to 2), the (T + 1) line power in the arranged pixel part is identified as an unused pixel part, 26. The pattern forming method according to any one of 22> kara 25>, wherein the pixel part excluding the unused pixel part is selected as a used pixel part.

[0015] <28> In the region including at least a double exposure region on the exposed surface formed by a plurality of pixel portion rows, the pixel portion selection means,

(1) Means for selecting a pixel part to be used so that the total area of an overexposed area and an underexposed area is minimized with respect to an ideal N double exposure. (2) Means for selecting a pixel part to be used so that the number of pixel units in an overexposed area is equal to the number of pixel units in an underexposed area for an ideal N double exposure,

(3) Means for selecting a pixel part to be used so that the area of an overexposed area is minimized and an underexposed area does not occur for an ideal N-fold exposure, and

(4) Means for selecting the pixel part to be used so that the area of the underexposed area is minimized and the overexposed area does not occur with respect to the ideal N double exposure.

The pattern forming method according to any one of the above, wherein 22> Karaku 27>.

<29> In the connection area between the heads, which is the overlapping exposure area on the exposed surface formed by the plurality of exposure heads,

(1) For the ideal N double exposure, from the pixel part involved in the exposure of the inter-head connecting area, the total area of the overexposed and underexposed areas is minimized. Means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;

(2) In relation to the ideal N double exposure, the number of pixel units in the overexposed area is equal to the number of pixel units in the underexposed area. A means for identifying an unused pixel part from the pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;

(3) For the ideal N-double exposure, the area of the overexposed area is minimized, and the pixel part involved in the exposure of the connecting area between the heads is used so that the underexposed area does not occur. A means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part; and

(4) For the ideal N-fold exposure, the area of the underexposed area is minimized, and the pixel part involved in the exposure of the connection area between the heads is used so that the overexposed area does not occur. A means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;

of! The pattern forming method according to <22> to <28>, which is a deviation, from!

<30> The pattern shape according to the above <29>, in which unused pixel parts are specified in units of lines. It is a method of creation.

[0016] <31> In order to specify the used pixel part in the used pixel part specifying means, out of the usable picture element parts, N (N−1) column-by-column drawings are used for N of N multiple exposures. The pattern forming method according to any one of <21> to <30>, wherein the reference exposure is performed by using only the drawing element part constituting the element part row. In the pattern forming method described in 31>, in order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, N— 1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of simple single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<32> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, for the N-exposure N, the above-mentioned pixel part row constituting each 1ZN line is configured. The pattern forming method according to any one of the above items 21> Karaku 30>, wherein reference exposure is performed using only the pixel part. In the pattern forming method described in 32>, in order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, 1ZN lines for N of N double exposures. Reference exposure is performed using only the pixel parts constituting each pixel part sequence, and a simple pattern of approximately single drawing is obtained. As a result, the pixel portion in the head-to-head connection region is easily specified.

<33> From the above <17>, the used pixel part specifying means includes a slit and a photodetector as a light spot position detecting means, and an arithmetic unit connected to the photodetector as a pixel part selecting means <32> The pattern forming method according to any one of the above.

<34> N force of N double exposure 3 to 7 natural numbers from <17> to <33>

V is a pattern forming method described in any of the above.

[0018] <35> The light modulation means further includes a pattern signal generation means for generating a control signal based on the pattern information to be formed, and the pattern signal generation means outputs the light emitted from the light irradiation means. <17> to <34> to be modulated according to the generated control signal

V is a pattern forming method described in any of the above.

<36> The pattern information is converted so that the dimension of the predetermined part of the pattern represented by the pattern information matches the dimension of the corresponding part that can be realized by the specified used pixel part. The pattern forming method according to any one of the above items 17> to 35> having a conversion means.

<37> Light modulation means force The pattern forming method according to any one of <17> to <36>, which is a spatial light modulation element.

<38> The pattern forming method according to 37, wherein the spatial light modulator is a digital 'micromirror' device (DMD).

<39> The pattern forming method according to any one of the above <17>, <38>, wherein the picture element portion is a micromirror.

<40> The pattern forming method according to any one of the above items <17> to <39>, wherein the light irradiation means can irradiate by combining two or more lights. In the pattern forming method according to <40>, since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, by developing the photosensitive layer thereafter, an extremely fine pattern can be formed.

<41> The light irradiating means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects the laser beams irradiated with the plurality of laser forces and couples the laser beams to the multimode optical fiber. The pattern forming method according to any one of the above <17> forces <40>. In the pattern forming method according to 41, the laser beam irradiated by each of the plurality of laser forces is collected by the collecting optical system and can be coupled to the multimode optical fiber. By doing so, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, after that, the photosensitive layer is developed to form an extremely fine pattern.

<42> The pattern forming method according to any one of <16> to <41>, wherein the photosensitive layer is developed after the exposure.

The invention's effect

[0022] According to the present invention, the conventional problems can be solved, the followability of the resist on the substrate is good, excellent developability, and finer strips at the time of resist stripping. Both A photosensitive resin composition capable of standing, a photosensitive transfer film having a photosensitive layer formed from the photosensitive resin composition, and a pattern capable of forming a high-definition pattern using the photosensitive transfer film A forming method can be provided.

Brief Description of Drawings

FIG. 1 is a perspective view showing an appearance of an example of a pattern forming apparatus.

FIG. 2 is a perspective view showing an example of the configuration of the scanner of the pattern forming apparatus.

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

FIG. 3B is a plan view showing an arrangement of exposure areas by each exposure head.

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

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

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

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

FIG. 7A is a perspective view for explaining the operation of the DMD.

FIG. 7B is a perspective view for explaining the operation of the DMD.

FIG. 8 is an explanatory view showing an example of unevenness that occurs in a pattern on an exposed surface when there is an attachment head angle error and pattern distortion.

FIG. 9 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit.

FIG. 10 is a top view for explaining a method for measuring the position of a light spot on a surface to be exposed using a slit.

[FIG. 11] FIG. 11 is an explanatory view showing a state in which unevenness generated in a pattern on an exposed surface is improved as a result of using only selected micromirrors for exposure.

[FIG. 12] FIG. 12 is an explanatory view showing an example of unevenness occurring in a no-turn on the exposed surface when there is a relative position shift between adjacent exposure heads.

FIG. 13 is a top view showing a positional relationship between an exposure area by two adjacent exposure heads and a corresponding slit.

[FIG. 14] FIG. 14 illustrates a technique for measuring the position of a light spot on an exposed surface using a slit. It is a top view for doing.

[FIG. 15] FIG. 15 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 12 are actually moved, and unevenness in the pattern on the exposed surface is improved.

FIG. 16 is an explanatory diagram showing an example of unevenness that occurs in a pattern on an exposed surface when there is a relative position shift and a mounting angle error between adjacent exposure heads.

FIG. 17 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG.

FIG. 18A is an explanatory view showing an example of magnification distortion.

FIG. 18B is an explanatory diagram showing an example of beam diameter distortion.

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 plurality of exposure heads.

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

FIG. 21B is an explanatory diagram showing a second example of reference exposure using a single exposure head.

FIG. 22 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads. BEST MODE FOR CARRYING OUT THE INVENTION

[Photosensitive resin composition]

The photosensitive resin composition of the present invention contains at least a solder, a polymerizable compound, and a photopolymerization initiator, and includes other components appropriately selected as necessary.

[0025] The melt viscosity of the photosensitive resin composition is 40, 000-120, OOOPa's at 50 ° C,

45, 000 ~: L 10,000 / pa, s / he is very good! Further, the force S is preferably 5,000 to 20,000 Pa's at 70 ° C and 5,500-18,000. The melt viscosity is 120 at 50 ° C. , If OOOPa's is exceeded or if it exceeds 20, OOOPa's at 70 ° C, the followability of the resist on the substrate will deteriorate. In addition, if the melt viscosity is less than 40, OOOPa's at 50 ° C or less than 5, OOOPa's at 70 ° C, the tentability is insufficient because the strength of the film itself is insufficient. . The melt viscosity is, for example, by repeating lamination of the photosensitive layer surfaces of the photosensitive resin composition, adjusting the sample so that the thickness becomes 150 ± 10 m, and then adjusting the photosensitive layer to 25 ° C 50% RH. After being allowed to stand for 24 hours in this environment, it can be measured using a rheometer (dynamic viscoelasticity measuring device) (REOLO GCA, DynAlyserDAR-100) under the conditions of frequency 1Ηζ and gap 1.5 mm.

[0026] <Binder>

The noinder is not particularly limited and can be appropriately selected according to the purpose. For example, the copolymer A having a mass average molecular weight of 3,000 to 10,000, and a mass average molecular weight of 30, It is preferable that the mass specific force of the copolymer A and the copolymer B is AZB = 10Z90 to 90Z10.

[0027] The mass average molecular weight is a relative value in terms of polystyrene, and can be determined from a calibration curve obtained by measuring a polystyrene standard mixed sample having a known molecular weight, for example.

[0028] The above-mentioned noder is, for example, preferably swellable in an alkaline aqueous solution, more preferably soluble in an alkaline aqueous solution.

As the binder exhibiting swellability or solubility with respect to the alkaline aqueous solution, for example, those having an acidic group are preferably exemplified.

[0029] The acidic group is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyxenore group is preferable. .

Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, polyurethane resin, polyamic acid resin, and modified epoxy resin. Among these, solubility in a coating solvent, Viewpoints such as solubility in alkaline developer, suitability for synthesis, and ease of adjustment of film properties. Vinyl copolymers having a carboxyl group are preferred. From the viewpoint of developability, a copolymer of at least one of styrene and a styrene derivative is also preferable. [0030] The vinyl copolymer having a carboxyl group can be obtained by copolymerization with at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith. Examples of the compounds described in JP-A-2005-258431, [0164] to [0205].

[0031] The content of the binder in the photosensitive layer is not particularly limited. A force that can be appropriately selected according to the purpose. For example, 10 to 90% by mass is preferable, and 20 to 80% by mass is more preferable. 40-80 mass% is especially preferable.

If the content is less than 10% by mass, the alkali developability and the adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. The stability against image time and the strength of the cured film (tent film) may be reduced. The above content may be the total content of the binder and the polymer binder used in combination as necessary.

[0032] When the binder is a substance having a glass transition temperature (Tg), the glass transition temperature is not particularly limited and can be appropriately selected depending on the purpose. For example, the light-sensitive transfer film From at least one of the viewpoints of suppressing tack and edge fusion and improving the peelability of the support, 80 ° C or higher is preferable, 100 ° C or higher is more preferable, and 120 ° C or higher is particularly preferable.

When the glass transition temperature is less than 80 ° C., the tack fusion of the photosensitive transfer film may increase or the peelability of the support may deteriorate.

[0033] The Noinda one acid value, especially the force limit Ru can be appropriately selected depending on the Nag purpose for example, preferably 70~250mgKOHZg force ^{s, 90~200mgKOH} / g and more preferred signaling 100～180MgKOH / g is particularly preferred.

If the acid value is less than 70 mg KOHZg, developability may be insufficient or resolution may be inferior, and permanent patterns such as wiring patterns may not be obtained in high definition. At least the developer resistance and adhesion of the turn may be poor, and a high-definition pattern may not be obtained.

[0034] Monocopolymer A—

As the copolymer A, as long as the mass average molecular weight is 3,000 to 10,000, in particular No restrictions can be selected according to the purpose, and the weight average molecular weight is more preferable than 3,000 to 9,000 force <, 3,000 to 8,000 force is particularly preferable! /, ₀

When the weight average molecular weight of the copolymer A is less than 3,000, the residual film ratio after development may be lowered. If the mass average molecular weight exceeds 10,000, the solubility in the developer is lowered, the resolution is lowered, and the fineness of the peeled piece cannot be achieved, or the melt viscosity is within the range of the present invention. In some cases, the followability of the resist on the substrate may be poor.

[0035] Examples of the monomer constituting the copolymer A include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. , Acrylic acid dimer, monomer having a hydroxyl group (for example, 2-hydroxyethyl (meth) acrylate) and cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride) _Ω —Carboxy-poly-strength prolacton mono (meth) acrylate, (meth) acrylic acid esters, crotonic acid esters, bulle esters, maleic acid diesters, fumaric acid diesters, itacon Acid diesters, (meth) acrylamides, butyl ethers, esters of butyl alcohol, styrenes (eg Styrene, styrene derivatives, etc.), (meth) acrylonitrile, heterocyclic groups substituted with a bur group (for example, bulupyridine, bulupyrrolidone, bur force rubazole, etc.), Ν bureformamide, ビュ buracetoamide, Ν burimidazole , Bicaprolatatone, 2-acrylamido-2-methylpropanesulfonic acid, monophosphate (2-allyloyloxychetyl ester), monophosphate (1-methyl-2-allyloyloxyethyl ester), and Examples thereof include butyl monomers having a functional group (for example, a urethane group, a urea group, a sulfonamide group, a phenol group, an imide group).

[0036] Further, as the copolymer Α, from the viewpoint that a permanent pattern such as a wiring pattern can be formed with high definition and from the viewpoint of improving the tent property, for example, at least styrene and a styrene derivative are used. It is preferable to have a structural unit derived from one of them.

[0037] Examples of the copolymer A include a copolymer of benzyl methacrylate and methacrylic acid, a copolymer of styrene and acrylic acid, a copolymer of methyl methacrylate and methacrylate, and styrene. Copolymer of styrene and methacrylic acid, copolymer of styrene and maleic anhydride, Copolymers of benzyl methacrylate, methacrylic acid, and styrene, copolymers of methyl methacrylate, methacrylate, and styrene, and benzyl methacrylate and methacrylate, methyl methacrylate, and 2-ethylhexyl. Examples thereof include a copolymer with metacryl.

[0038] Monocopolymer B—

The copolymer B is not particularly limited as long as the mass average molecular weight is 30,000 to 150,000, and can be appropriately selected according to the purpose. The mass average molecular weight is 40,000 to 130,000. 000 power more preferred, 40,000 to 120,000 power ^ especially preferred! / ,.

If the weight average molecular weight of the copolymer B is less than 30,000, the strength of the cured film required for tent properties may be insufficient, and if it exceeds 150,000, the developability will be poor. Sometimes.

[0039] Examples of the monomer constituting the copolymer B include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. , Acrylic acid dimer, monomer having a hydroxyl group (for example, 2-hydroxyethyl (meth) acrylate) and cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride) _Ω —Carboxy-poly-prolactonone (meth) acrylate, (meth) acrylic acid esters, crotonic acid esters, bulle esters, maleic acid diesters, fumaric acid diesters, itacon Acid diesters, (meth) acrylamides, butyl ethers, esters of butyl alcohol, styrenes (eg , Styrene, styrene derivatives, etc.), (meth) acrylonitrile, heterocyclic groups substituted with a bur group (for example, bulupyridine, bulupyrrolidone, bur force rubazole, etc.), ビュ buluformamide, ビュ buracetoamide, Ν bulu Imidazole, bicaprolatatone, 2-acrylamido-2-methylpropanesulfonic acid, monophosphate (2- allyloyloxychetyl ester), monophosphate (1-methyl-2- attaroyloxyethyl ester), And a butyl monomer having a functional group (for example, a urethane group, a urea group, a sulfonamide group, a phenol group, an imide group, etc.).

[0040] In addition, as the copolymer を, from the viewpoint that a permanent pattern such as a wiring pattern can be formed with high definition and from the viewpoint of improving the tent property, for example, a butyl monomer having a carboxyl group is used. Preferred to have. [0041] Examples of the copolymer B include a copolymer of benzyl methacrylate and methacrylic acid, a copolymer of styrene and acrylic acid, a copolymer of methyl methacrylate and methacrylate, and styrene. Copolymer of methacrylic acid, styrene, maleic anhydride, benzyl methacrylate, methacrylic acid, styrene, methyl methacrylate, methacrylic acid, and styrene. And polymers and copolymers of benzyl methacrylate, methacrylic acid, methyl methacrylate, and 2-ethylhexyl methacrylate.

[0042] The mass ratio (AZB) between the copolymer A and the copolymer B is not particularly limited as long as AZB = 1θΖ90 to 9θΖ10, and can be appropriately selected according to the purpose. From the viewpoint of reducing unexposed film breakage that is preferably / B = 10Z90 to 80Z20, it is more preferable that で Β = 10Ζ90 to 40Ζ60.

[0043] <Polymerizable compound>

The polymerizable compound is not particularly limited and may be appropriately selected according to the purpose. For example, a monomer or oligomer having at least one of a urethane group and an aryl group is preferably exemplified. These preferably have two or more polymerizable groups.

[0044] Examples of the polymerizable group include an ethylenically unsaturated bond (for example, a (meth) atalyl group, a (meth) acrylamide group, a styryl group, a beryl group such as a butyl ester or a butyl ether, a allylic ether or the like. Aryl groups such as aryl esters) and polymerizable cyclic ether groups (for example, epoxy groups, oxetane groups, etc.), among which ethylenically unsaturated bonds are preferred.

[0045] Monomers having urethane groups

The monomer having a urethane group is not particularly limited as long as it has a urethane group, and can be appropriately selected according to the purpose. For example, [0210] to [0262] in JP-A-2005-258431 And the like.

[0046] A monomer having an aryl group

The monomer having an aryl group is not particularly limited as long as it has an aryl group, and can be appropriately selected according to the purpose. For example, a polyhydric alcohol compound having an aryl group, a polyvalent amine compound. And at least one of polyamino amino alcohol compound Examples thereof include esters or amides of deca and unsaturated carboxylic acids, and examples thereof include compounds described in JP-A-2005-258431, [0264] to [0271].

[0047] Compound having polyalkylene oxide chain

The photosensitive resin composition of the present invention may contain a compound having a polyalkylene oxide chain.

The compound having a polyalkylene oxide chain may be a monofunctional monomer that is not particularly limited, or may be a polyfunctional monomer! /.

As the monofunctional monomer, for example, a compound represented by the following structural formula (i) is preferably exemplified.

[Chemical 1]

~ \ Structural formula (i)

COO- (XO) — R ₂

n

In the structural formula (i), R ¹ represents a hydrogen atom or a methyl group.

X represents an alkylene group having 2 to 6 carbon atoms, and preferably has a chain structure rather than a cyclic structure. The chain alkylene group may have a branch. Examples of the alkylene group include an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Among these, an ethylene group and a propylene group are preferable.

n is an integer of 1 to 30, and when n is 2 or more, a plurality of (—X—O) may be the same or different from each other, and (−X—0-) are When they are different, for example, a combination of an ethylene group and a propylene group is preferably exemplified.

[0048] Examples of R ² include an alkyl group, an aryl group, an aralkyl group, and the like, and these groups may be further substituted with a substituent.

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, a dodecyl group, and a hexadecyl group. Group, octadecyl group, and the like. The alkyl group may have a branch or ring structure which may have a substituent.

Examples of the aralkyl group include a benzyl group and a phenethyl group. . The aralkyl group may have a substituent.

Examples of the aryl group include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, an ethyl file group, a methoxy file group, a propyl file group, a butyl file group, a t-butyl file group, and an octyl file. Groups, norphenyl groups, chlorophenol groups, cyanphenol groups, dibromophenol groups, tribromophenol groups, bibromophenyl groups, benzylphenyl groups, a dimethylbenzylphenyl groups, etc. Can be mentioned. The aryl group may have a substituent.

[0049] Examples of the substituent in the alkyl group, the aralkyl group, and the aryl group include a hydrogen atom, a rogen atom, an aryl group, an alkyl group, an alkoxy group, and a cyan group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. The aryl group preferably has a total carbon number of 6 to 20, more preferably 6 to 14. Examples of the aryl group include a full group, a naphthyl group, an anthracyl group, and a methoxyfur group.

, Etc.

The alkenyl group preferably has a total carbon number of 2 to 10 and more preferably 2 to 6. Examples of the alkenyl group include an ethur group, a propenyl group, a butyryl group, and the like.

The alkoxy group may be branched and the total number of carbon atoms is preferably 1 to 5 and more preferably 1 to 5 times. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a 2-methylpropyloxy group, and a butoxy group.

[0050] Specific examples of the compound represented by the structural formula (i) include compounds represented by the following structural formula. However, in the following formula, R represents a hydrogen atom or a methyl group. n represents an integer of 1 to 30, m and L each represents an integer of 1 or more, and m + L represents an integer of 1 to 30. Me represents a methyl group, and Bu represents a butyl group.

[Chemical 2] (CH ₂ CH ₂ 0) _n -Me

C00- (CH ₂ CH ₂ 0) _n -Bu

, C00- (CH ₂ CH ₂ 0>

, C00- (CH ₂ CH ₂ 0 ^C 9 ^H 19

C00- (CH ₂ CH ₂ 0) _m- (C ₃ H ₆ 0) _L -Me

[Chemical 3]

[0051] In addition, in the compound having a polyalkylene oxide chain, as the compound having at least one of an ethylene group and a propylene group, polyethylene glycol and polypropylene glycol having 10 to 30 ethylene groups or propylene groups are also suitable. Is mentioned.

The compound having a polyalkylene oxide chain may be used alone or in combination of two or more.

[0052] Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate having 2 to 30 ethylene groups (for example, diethylene glycol di (meth)). Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol # 400 dimetatalate, polyethylene glycol # 600 dimetatalate, polyethylene glycol # 100 0 dimetatalate, etc.), propylene Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate with 2 to 18 propylene groups (eg, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetra Ropire glycol di (meth) Atari rate, dodecamethylene glycol di (meth) Atari rate, etc.)

, Ethylene glycol chain Z dialkyl (ethylene) chain di (meth) acrylate (for example, compounds described in WO 01Z98832 pamphlet), polybutylene glycol di (meta) ) Atarirate.

Among these, from the viewpoint of availability, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol chain Z and alkylene glycol chain each having at least one propylene glycol chain. Di (meth) acrylate is preferred.

[0053] The content of the compound having a polyalkylene oxide chain in the polymerizable compound is preferably 40% by mass or less, more preferably 1 to 30% by mass, and even more preferably 1 to 25% by mass. preferable. If the content is less than 0.1% by mass, the effect of improving the peelability and development latitude may be insufficient, and if it exceeds 40% by mass, the resolution, adhesion, tent property, etc. are poor. There is a case to hesitate. [0054] Other polymerizable monomers

In the pattern forming method of the present invention, a polymerizable monomer other than the monomer having a urethane group and the monomer having an aryl group may be used in combination as long as the characteristics as the photosensitive transfer film are not deteriorated. ,.

[0055] As the polymerizable monomer other than the monomer containing a urethane group and the monomer containing an aromatic ring, for example, an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, Examples include esters of maleic acid and the like and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and polyhydric amine compounds, and examples include [0274]-[ [0284] and the like.

[0056] The content of the polymerizable compound in the photosensitive layer is, for example, preferably 5 to 90% by mass, more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass.

If the content is 5% by mass, the strength of the tent film may be reduced, and if it exceeds 90% by mass, edge fusion during storage (extruding failure of the roll end force) may be deteriorated. is there.

In addition, the content of the polyfunctional monomer having two or more polymerizable groups in the polymerizable compound is preferably 5 to: LOO mass% is preferable 20 to: LOO mass% is more preferable 40 to: LOO mass % Is particularly preferred.

[0057] <<Photoinitiator>>

The photopolymerization initiator can be appropriately selected from known photopolymerization initiators that are not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound. Those that have photosensitivity to visible light may have some effect with photo-excited sensitizers, and may be active agents that generate active radicals. Cationic polymerization is performed depending on the type of monomer. It may be an initiator that initiates. The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

[0058] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, triazide). Having skeleton, oxadiazole skeleton, etc.), hexarylbiimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, metaguchines Etc. Among these, from the viewpoints of the sensitivity and storage stability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate, a halogenated hydrocarbon having a triazine skeleton, an oxime derivative, a ketone compound, Hexaarylbiimidazole compounds are preferred, for example, compounds described in [0288] to [0309] of JP-A-2005-258431.

[0059] The content of the photopolymerization initiator in the photosensitive layer is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass, and particularly preferably from 0.5 to 15% by mass.

[0060] <<Other ingredients>>

Examples of the other components include sensitizers, thermal polymerization inhibitors, plasticizers, color formers, colorants, and the like, and adhesion promoters to the substrate surface and other auxiliary agents (for example, pigments). , Conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, chain transfer agents, etc.) Examples thereof include compounds described in JP-A-2005-258431, [0312] to [0336]. By appropriately containing these components, it is possible to adjust properties such as the stability, photographic properties, print-out properties, and film properties of the target photosensitive transfer film.

[0061] (Photosensitive transfer film)

The photosensitive transfer film of the present invention has at least a photosensitive layer formed of the photosensitive resin composition of the present invention on the support, and if necessary, a protective film, and further if necessary. , And other layers such as a cushion layer and an oxygen barrier layer (PC layer). The form of the photosensitive transfer film can be appropriately selected according to the purpose without any particular restriction. For example, the form having the photosensitive layer and the protective film in this order on the support, A form in which the PC layer, the photosensitive layer, and the protective film are provided in this order on a support, and the cushion layer, the PC layer, the photosensitive layer, and the protective film are provided on the support. The form etc. which have in order are mentioned.

The photosensitive layer may be a single layer or a plurality of layers.

[Photosensitive layer] The photosensitive layer is formed by the photosensitive resin composition of the present invention.

As a method for forming the photosensitive layer, a photosensitive composition solution is prepared by dissolving, emulsifying, or dispersing the photosensitive composition of the present invention in water or a solvent on the support, and the solution is used. Examples of the method include a method of directly coating and laminating by drying.

[0063] The solvent of the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec butanol, n —Alcohols such as hexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisoptyl ketone; Ethyl acetate, butyl acetate, n-amyl acetate, methyl ethyl sulfate, ethyl ethyl propionate, phthalic acid Esters such as dimethyl, ethyl benzoate, and methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1, 1, 1-trichloroethane, Such as methylene chloride, monochrome benzene, etc. Rogenated hydrocarbons: Tetrahydrofuran, Jetyl etherenole, Ethylene glycol monomethino ethenore, Ethylene glycol eno monoethinore ether, ethers such as 1-methoxy-2-propanol; Dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane Etc. These may be used alone or in combination of two or more. Also, add a known surfactant.

[0064] The coating method can be appropriately selected according to the purpose without any particular limitation. For example, a spin coater, a slit spin coater, a roll coater, a die = 1 ter, a force tensor coater, or the like is used. And a method of directly applying to the support.

The drying conditions vary depending on each component, the type of solvent, the ratio of use, etc., but are usually 60 to 110 ° C. for 30 seconds to 15 minutes.

[0065] The thickness of the photosensitive layer can be appropriately selected according to the purpose for which there is no particular limitation. For example, 1 to: LOO 111 or more preferably 5 to 70 m force.

[0066] Further, in the case where the photosensitive layer is exposed and developed with a laser beam having a wavelength of 390 to 420 nm, the thickness of the exposed portion of the photosensitive layer is not changed after the exposure and development. The minimum energy (sensitivity) of light used for the light is 0.1 to 20mjZcm ² And are preferred.

[0067] Here, "the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development" is so-called development sensitivity. It can be determined from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for the exposure when exposed and the thickness of the cured layer generated by the development process following the exposure. .

The thickness of the cured layer increases as the exposure amount increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.

Here, when the difference between the thickness of the cured layer and the thickness of the photosensitive layer before the exposure is within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure / development.

A method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and may be appropriately selected depending on the intended purpose. However, a film thickness measuring device, a surface roughness measuring device (for example, Surfcom) 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.

[Support and Protective Film]

The support can be appropriately selected according to the purpose for which there is no particular limitation. However, it is preferable that the photosensitive layer can be peeled off and the light transmittance is good. Further, the surface is smooth. More preferred to have good sex. Specific examples of the support and the protective film are described in Japanese Patent Application Laid-Open No. 2005-258431, [0342] and [0344] to [034 8].

[0069] The thickness of the support can be appropriately selected depending on the purpose for which there is no particular limitation. However, t is preferably 4 to 300 μm force, more preferably 5 to 175 μm force ^. Ms./ !.

[0070] [Other layers]

The other layers can be appropriately selected according to the purpose without any particular limitation, and examples thereof include layers such as a cushion layer, a barrier layer, a release layer, an adhesive layer, a light absorption layer, and a surface protective layer. The photosensitive transfer film may have one of these layers alone. It may have two or more types, and may have two or more layers of the same type.

[0071] It is preferable that the photosensitive transfer film is wound around a cylindrical core, wound into a long roll, and stored. The length of the long photosensitive transfer film is not particularly limited, and can be appropriately selected from the range of 10-20, OOOm, for example. In addition, slitting may be performed for ease of use by the user, and a long body in the range of 100 to 1, OOOm may be rolled. In this case, it is preferable that the support is wound so that the outermost side is the outermost side. The roll-shaped photosensitive transfer film may be slit into a sheet shape. In order to protect the end face and prevent edge fusion during storage, it is preferable to install a separator (especially moisture-proof, with desiccant) on the end face, and the packaging is also low in moisture permeability. I prefer to use

[Pattern Formation Method]

The pattern forming method of the present invention includes at least a laminating step of forming a laminate by transferring the photosensitive layer in the photosensitive transfer material of the present invention to the surface of the base material, and an exposure step, and an appropriately selected developing step and etching step. It includes other processes such as a process and a resist stripping process.

[0073] [Lamination process]

The method for forming the laminate is not particularly limited, and can be appropriately selected according to the purpose. However, the photosensitive transfer film is peeled off from the substrate, and the protective film is peeled off while heating and pressurizing. It is preferable to laminate at least one of them.

The heating temperature is not particularly limited and can be appropriately selected according to the purpose. For example, 15 to 180 ° C is preferable, and 60 to 140 ° C is more preferable.

The pressure of the pressurization is not particularly limited and can be appropriately selected depending on the purpose. However, the column is preferably 0.1 to 1. OMPa force, more preferably 0.2 to 0.8 MPa force ^ I like it!

[0074] The apparatus for performing at least one of the heating and pressurization can be appropriately selected according to the purpose without particular limitation, and examples thereof include a laminator and a vacuum laminator.

[0075] The apparatus for performing at least one of the heating and pressurization can be appropriately selected depending on the purpose, and for example, a laminator (for example, VP- 成 manufactured by Taisei Laminator Co., Ltd.) Are preferable. [0076] << Substrate >>

As the base material, there are no particular restrictions on known materials, those having high surface smoothness, and those having a surface with a rough surface. For each purpose of a photo solder resist, a photoresist for forming a wiring pattern, and a color resist. The plate-like base material (substrate) is preferred, and specifically, a known printed wiring board forming substrate (for example, a copper-clad laminate), a glass plate (for example, Soda glass plate, glass plate sputtered with oxygen and quartz, quartz glass plate, etc.), synthetic resin film, paper, metal plate and the like.

[0077] The laminate is formed by forming the photosensitive layer on a base material, and curing a region exposed by an exposure process described later on the photosensitive layer, and forming a pattern by a development process described later. Can do.

[Exposure process]

The exposure step is a step of exposing the photosensitive layer of the laminate formed in the lamination step.

The exposure can be appropriately selected according to the purpose for which there is no particular limitation, and powers such as digital exposure, analog exposure, etc. Among these, digital exposure is preferable.

[0079] Examples of the digital exposure include, for example, a light irradiating unit and n light (n is a natural number of 2 or more) two-dimensional shape that receives and emits light from the light irradiating unit. An exposure head having light modulation means capable of controlling the drawing portion in accordance with pattern information, wherein the drawing portion of the drawing portion is aligned with respect to a scanning direction of the exposure head. Using an exposure head arranged such that the column direction forms a predetermined inclination angle Θ, the exposure head is designated by the use pixel part designation means, and the N-fold exposure (however, of the usable picture element parts) , N is a natural number greater than or equal to 2) and specifies the pixel part to be used, and for the exposure head, only the pixel part specified by the pixel part specifying unit is used by the pixel part control unit. Control the pixel part so that the Against the optical layer, a method of performing exposure by relatively moving the exposing head in the scanning direction is preferable.

Note that the “N-double exposure” means that a straight line parallel to the scanning direction of the exposure head is formed on the surface to be exposed in almost all regions of the exposure region on the surface to be exposed of the photosensitive layer. This refers to exposure with a setting that intersects the N light spots (pixel array) irradiated on. Where "light spot “Column (pixel column)” refers to an array of light spots (pixels) as pixel units generated by the pixel unit in a direction in which the angle formed with the scanning direction of the exposure head is smaller. Let's say. The arrangement of the picture element portions does not necessarily have to be a rectangular lattice, for example, an arrangement of parallelograms.

Here, the “substantially all areas” of the exposure area is described as a straight line parallel to the scanning direction of the exposure head by tilting the pixel part rows at both side edges of each picture element part. Since the number of picture element parts in the used picture element part decreases, even if it is used to connect multiple exposure heads in such a case, scanning will occur due to errors in the mounting angle and arrangement of the exposure heads. The number of pixel parts in the used pixel part that intersects a straight line parallel to the direction may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is less than the resolution. In the small part, due to errors such as the mounting angle and pixel part placement, the pixel part pitch along the direction perpendicular to the scanning direction does not exactly match the pixel part pitch of the other part, and scanning is not possible. The number of pixel parts in the used pixel part that intersects a straight line parallel to the direction increases or decreases within the range of ± 1. Because there is. In the following description, N multiple exposures where N is a natural number of 2 or more are collectively referred to as “multiple exposure”. Furthermore, in the following description, “N double exposure” and “multiple exposure” are used as terms corresponding to “N double exposure” and “multiple exposure” with respect to an embodiment in which the exposure apparatus or exposure method of the present invention is implemented as a drawing apparatus or drawing method. The term “multiple drawing” shall be used. N in the N-exposure is a natural number of 2 or more, a force that can be appropriately selected according to the purpose for which there is no particular limitation, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is more preferable. .

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

The pattern forming apparatus is a V-flat exposure apparatus of a flat bed type, and as shown in FIG. 1, a laminate 12 (hereinafter referred to as “laminated layer”) in which at least the photosensitive layer in the photosensitive transfer film is stacked. A plate-like moving stage 14 that adsorbs and holds the photosensitive material 12 on the surface (sometimes referred to as “photosensitive material 12” or “photosensitive layer 12”). On the upper surface of the thick plate-shaped installation base 18 supported by the four legs 16, there are two guides extending along the stage moving direction. Id 20 is installed. The stage 14 is arranged so that its longitudinal direction faces the stage moving direction, and is supported by the guide 20 so as to be reciprocally movable. The pattern forming apparatus 10 is provided with a stage driving device (not shown) for driving the stage 14 along the guide 20.

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

[0083] Here, for explanation, an X axis and a Y axis orthogonal to each other are defined in a plane parallel to the surface of the stage 14 as shown in FIG.

[0084] At the upstream edge along the scanning direction of the stage 14 (hereinafter, sometimes simply referred to as "upstream"), a "<" shape that opens in the direction of the X-axis Ten slits 28 are formed at regular intervals. Each slit 28 also has a force with a slit 28a located on the upstream side and a slit 28b located on the downstream side. The slit 28a and the slit 28b are orthogonal to each other, and the slit 28a has an angle of −45 degrees and the slit 28b has an angle of +45 degrees with respect to the X axis.

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

[0086] At the position below each slit 28 in the stage 14, a single cell type as a light spot position detecting means for detecting a light spot as a pixel unit in a used pixel part specifying process to be described later. A photodetector (not shown) is incorporated. In addition, each photodetector is used as a pixel part selection means for selecting the pixel part to be used in the process of specifying the pixel part to be used, which will be described later. Connected to all the arithmetic units (not shown).

[0087] The operation form of the pattern forming apparatus at the time of exposure may be a form in which exposure is continuously performed while the exposure head is constantly moved, or each pattern is moved while the exposure head is moved step by step. The exposure operation may be performed with the exposure head stationary at the destination position.

[0088] << Exposure head>>

Each exposure head 30 is connected to a scanner 24 so that each pixel portion (micromirror) row direction of an internal digital 'micromirror' device (DMD) 36 described later forms a predetermined set inclination angle Θ with the scanning direction. Is attached. Therefore, the exposure area 32 by each exposure head 30 is a rectangular area inclined with respect to the scanning direction. As the stage 14 moves, a strip-shaped exposed region 34 is formed for each exposure head 30 in the photosensitive layer 12. In the example shown in FIGS. 2 and 3B, the scanner 24 includes ten exposure heads arranged in a matrix of 2 rows and 5 columns.

In the following, when the individual exposure heads arranged in the m-th column and the n-th column are indicated, they are represented as exposure heads 30, and the exposure by the individual exposure heads arranged in the m-th row and the n-th column mn

When the light area is indicated, it is expressed as exposure area 32.

mn

In addition, as shown in FIGS. 3A and 3B, the exposure exposure of each row arranged in a line so that each of the strip-shaped exposed regions 34 partially overlaps the adjacent exposed region 34 is performed. Each of the nodes 30 is arranged with a predetermined interval (natural number times the long side of the exposure area, twice in this embodiment) in the arrangement direction. Therefore, the exposure area 32 in the first row and the exposure area

11 The part that cannot be exposed to the rear 32 can be exposed by the exposure area 32 in the second row.

12 21

it can.

As shown in FIGS. 4, 5A, and 5B, each of the exposure heads 30 includes a light modulation unit that modulates incident light for each pixel part according to image data (modulation for each pixel part). DMD36 (made by Texas Instruments Inc., USA) as a spatial light modulator. This DMD 36 is connected to a controller as a pixel part control means having a data processing part and a mirror drive control part. In the data processing unit of this controller, each micromirror in the use area on the DMD 36 is determined for each exposure head 30 based on the input image data. A control signal for controlling the driving of is generated. Further, the mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 36 for each exposure head 30 based on the control signal generated by the image data processing unit.

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

[0092] As shown in detail in Figs. 5A and 5B, the lens system 40 includes a pair of combination lenses 44 that collimate the laser light emitted from the fiber array light source 38 and a collimated laser. It is composed of a pair of combination lenses 46 that correct the light amount distribution of light so that it is uniform, and a condensing lens 48 that condenses the laser light whose light amount distribution has been corrected on the DMD 36.

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

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

-Light modulation means- The light modulation means has n (where n is a natural number of 2 or more) two-dimensionally arranged pixel parts, and according to the pattern information. Any device that can control the picture element portion can be appropriately selected according to the purpose without any particular restriction. For example, a spatial light modulator is preferable.

[0096] Examples of the spatial light modulator include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (S LM), and transmission by an electro-optic effect. Optical element that modulates light (PLZT element), liquid crystal light shatter (FLC), etc., among which DMD is preferred.

[0097] Preferably, the light modulation unit includes a pattern signal generation unit that generates a control signal based on pattern information to be formed. In this case, the light modulating means modulates light according to the control signal generated by the pattern signal generating means.

The control signal can be appropriately selected according to the purpose for which there is no particular limitation. For example, a digital signal is preferably used.

Hereinafter, an example of the light modulation means will be described with reference to the drawings.

As shown in FIG. 6, the DMD 36 has a mirror structure in which a large number of micromirrors 58 are arranged in a lattice pattern as a pixel portion constituting each pixel (pixel). It is a device. In this embodiment, the power to use DMD36 in which micromirrors 58 of 1024 columns x 768 rows are arranged. Of these, micromirrors 58 that can be driven by a controller connected to DMD36, that is usable, are only 1024 columns x 256 rows. Suppose that The data processing speed of DMD36 is limited, and the modulation speed per line is determined in proportion to the number of micromirrors used. Thus, by using only some of the micromirrors in this way, Modulation speed increases. Each micromirror 58 is supported by a support column, and a material having high reflectivity such as aluminum is deposited on the surface thereof. In the present embodiment, the reflectance of each micromirror 58 is 90% or more, and the arrangement pitch thereof is 13.7 m in both the vertical direction and the horizontal direction. The SRAM cell 56 is a silicon gate CMOS manufactured on an ordinary semiconductor memory manufacturing line via a support including a hinge and a yoke, and is configured monolithically (integrated) as a whole.

[0099] 56D SRAM cells (memory cells) of DMD36. When an image signal representing the density of each point constituting the desired two-dimensional pattern is written in binary, each micromirror 58 supported by the column is Inclined to one of ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 36 is disposed with the diagonal line as the center. FIG. 7 (b) shows a state tilted to + α degrees when the micromirror 58 is in the on state, and FIG. 7 (b) shows a state tilted to α degrees when the micromirror 58 is in the off state. In this way, the laser incident on the DMD 36 is controlled by controlling the inclination of the micro mirror 58 in each pixel of the DMD 36 in accordance with the image signal as shown in FIG. Light B is reflected in the tilt direction of each micromirror 58.

[0100] FIG. 6 shows an example of a state in which a part of the DMD 36 is enlarged and each micromirror 58 is controlled to + α degrees or α degrees. The on / off control of each micromirror 58 is performed by the controller connected to the DM D36. In addition, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 58 travels.

[0101] -Light irradiating means- The light irradiating means can be appropriately selected according to the purpose without particular limitation. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copying machine For example, a fluorescent tube, a known light source such as an LED or a semiconductor laser, or a means capable of combining and irradiating two or more lights. Among these, a means capable of combining and irradiating two or more lights is preferable. .

The light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support. In particular, ultraviolet to visible light, electron beams, X-rays, laser light, etc. are mentioned, and among these, laser light is preferred. Laser that combines two or more lights (hereinafter sometimes referred to as “combined laser”) ) Is more preferable. Even when the support is peeled off and the light is irradiated with light, the same light can be used.

[0102] As the wavelength of the visible light, the ultraviolet power is preferably 300 to 1500 nm, more preferably 320 to 800 mn, and particularly preferably 330 to 650 mn.

The wavelength of the laser light is, for example, 200 to 1500 nm force S, preferably 300 to 800 nm force, more preferably 330 to 500 mn force, and 400 to 450 mn force, particularly preferred! /.

[0103] As means capable of irradiating the combined laser, for example, a plurality of lasers, a multimode optical fiber, and a laser beam irradiated with each of the plurality of laser forces are condensed and coupled to the multimode optical fiber. Preferred is a means having a collective optical system.

[0104] Examples of means (fiber array light source) capable of irradiating the combined laser include means described in JP-A No. 20 05 258431 [0109] to [0146].

[0105] <<Used pixel part designation method>> The used pixel part specifying means includes a light spot position detecting means for detecting the position of a light spot as a pixel unit on the exposed surface, and a detection result by the light spot position detecting means. It is preferable to have at least a pixel part selection means for selecting a pixel part to be used for realizing N double exposure.

Hereinafter, an example of a method for designating a pixel part to be used for N double exposure by the used pixel part designation unit will be described.

[0106] (1) Specification method of used pixel part in single exposure head

In the present embodiment (1), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and the variation in resolution and density unevenness due to the mounting angle error of each exposure head 30 are reduced. We will explain how to specify the pixel parts to be used to achieve ideal double exposure.

[0107] The set tilt angle Θ in the column direction of the pixel part (micromirror 58) with respect to the scanning direction of the exposure head 30 can be used as long as there is no mounting angle error of the exposure head 30 etc. From the angle Θ, which is exactly double exposure using a 1024 column x 256 row pixel part

The ideal also uses a slightly larger angle.

This angle Θ is the number of N exposures N, the number of usable micromirrors 58 in the row direction s

ideal

The following formula 1, spsin θ ≥ Ν δ (formula), with respect to the column spacing p of the usable micromirrors 58 and the pitch δ of the scanning lines formed by the micromirrors with the exposure head 30 inclined. 1)

iaeal

Given by. As described above, the DMD 36 in the present embodiment is configured by arranging a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals in a rectangular lattice shape, so that pcos θ = δ (Equation 2)

ideal

And the above equation 1 is

stan Q = N (Formula 3)

ideal

It becomes. In the present embodiment (1), since s = 256 and N = 2 as described above, the angle Θ is about 0.45 degrees according to the equation 3. Therefore, the set tilt angle Θ is, for example, 0.5 ideal

An angle of about 0 degrees should be adopted. The pattern forming apparatus 10 is within an adjustable range so that the mounting angle of each exposure head 30, that is, each DMD 36 is an angle close to the set inclination angle Θ. It is assumed that initial adjustment is performed so that

[0108] FIG. 8 shows unevenness generated in the pattern on the exposed surface due to the effect of the mounting angle error of one exposure head 30 and the pattern distortion in the pattern forming apparatus 10 initially adjusted as described above. It is explanatory drawing which showed the example. In the following drawings and description, the light spot as the pixel unit generated by each pixel part (micromirror) and constituting the exposure region on the exposed surface, the light spot in the m-th row ¾τ (m), the light spot in the nth column is denoted as c (n), and the light spot in the mth row and the nth column is denoted as P (m, n).

[0109] The upper part of FIG. 8 shows the pattern of light spots from the usable micromirror 58 projected onto the exposed surface of the photosensitive material 12 with the stage 14 being stationary, and the lower part is The pattern of the light spot group as shown in the upper part appears, and the state of the exposure pattern formed on the exposed surface is shown when the stage 14 is moved in this state and continuous exposure is performed. Is.

In FIG. 8, for convenience of explanation, the exposure pattern by the odd-numbered columns of the micromirrors 58 that can be used and the exposure pattern by the even-numbered columns are shown separately. However, the actual exposure patterns on the exposed surface are shown in FIG. It is a superposition of two exposure patterns.

[0110] In the example of Fig. 8, the set inclination angle 0 is set to a slightly larger angle than the above angle 0.

ideal

As a result of this, and because it is difficult to finely adjust the mounting angle of the exposure head 30, there is an error between the actual mounting angle and the set inclination angle Θ. Also in FIG. Specifically, in an overlapped exposure area on the exposed surface formed by a plurality of pixel part rows in both an exposure pattern by an odd-numbered micromirror and an exposure pattern by an even-numbered micromirror. In other words, overexposure occurs with double exposure, resulting in redundant drawing areas and uneven density.

Further, the example of FIG. 8 is an example of pattern distortion appearing on the surface to be exposed, and “angular distortion” is generated in which the inclination angle of each pixel column projected on the surface to be exposed is not uniform. The Causes of this angular distortion include various aberrations and alignment deviations of the optical system between the DMD 36 and the exposed surface, distortion of the DMD 36 itself, and micromirror placement errors.

The angular distortion that appears in the example in Fig. 8 indicates that the tilt angle with respect to the scanning direction is It is a distortion of a form that is smaller and larger in the right column of the figure. As a result of this angular distortion, the overexposed area is smaller on the exposed surface shown on the left side of the figure and larger on the exposed surface shown on the right side of the figure.

[0112] In order to reduce density unevenness in the overlapped exposure region on the exposed surface formed by a plurality of pixel part rows as described above, the slit 28 and the photodetector are used as the light spot position detecting means. The actual inclination angle Θ ′ is specified for each exposure head 30, and the arithmetic unit connected to the photodetector is used as the pixel part selection unit based on the actual inclination angle Θ ′. A process of selecting a micromirror to be used for actual exposure is performed. Based on at least two light spot positions detected by the light spot position detecting means until the actual tilt angle θ, the light spot column direction on the surface to be exposed and the exposure head when the exposure head is tilted. It is specified by the angle formed by the scanning direction.

Hereinafter, the actual inclination angle Θ ′ and the used pixel selection process will be described with reference to FIGS.

[0113] Specifying the actual inclination angle

FIG. 9 is a top view showing the positional relationship between the exposure area 32 by one DMD 36 and the corresponding slit 28. The size of the slit 28 is set to sufficiently cover the width of the exposure area 32.

In the example of the present embodiment (1), the angle formed by the 512-th light spot array positioned substantially at the center of the exposure area 32 and the scanning direction of the exposure head 30 is measured as the actual inclination angle Θ ′. The Specifically, the micromirror 58 in the first row and the 512th column on the DMD 36 and the micromirror 58 in the 256th row and the 512th column are turned on, and the light spots on the exposure surface corresponding to each of them are turned on. The positions of P (l, 512) and Ρ (256, 512) are detected, and the angle formed by the straight line connecting them and the scanning direction of the exposure head is specified as the actual tilt angle Θ ′.

FIG. 10 is a top view illustrating a method for detecting the position of the light spot 256 (256, 512).

First, with the micromirror 58 in the 256th row and the 512th column turned on, the stage 14 is slowly moved to move the slit 28 relatively along the axis direction, and the light spot Ρ (256, 512) is The slit 28 is positioned at an arbitrary position between the upstream slit 28a and the downstream slit 28b. At this time, the coordinates of the intersection of slit 28a and slit 28b are (XO, YO) and To do. The value of this coordinate (XO, YO) is determined and recorded by the movement distance of the stage 14 to the above position indicated by the drive signal given to the stage 14 and the known X-direction position force of the slit 28. The

[0115] Next, the stage 14 is moved, and the slit 28 is relatively moved to the right in FIG. Then, as indicated by a two-dot chain line in FIG. 10, the stage 14 is stopped when the light of the light spot 256 (256, 512) passes through the left slit 28b and is detected by the photodetector. The coordinates (XO, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

[0116] Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved along the Y axis to the left in FIG. Then, as indicated by a two-dot chain line in FIG. 10, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the right slit 28a and is detected by the photodetector. The coordinates (XO, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

[0117] From the above measurement results, coordinates indicating the position of the light spot P (256, 512) on the exposed surface

(X, Y) is determined by calculating Χ = ΧΟ + (Υ1—Y2) Z2 and Y = (Y1 + Y2) Z2. By the same measurement, the coordinates indicating the position of P (l, 512) are also determined, and the inclination angle formed by the straight line connecting the coordinates and the scanning direction of the exposure head 30 is derived, and this is the actual inclination angle. It is specified as Θ.

[0118] -Selection of used pixel part- Using the actual inclination angle Θ 'specified in this way, the arithmetic unit connected to the photodetector is represented by the following equation 4

ttan 0 (Equation 4)

A natural number T is derived that is closest to the value t satisfying the above relationship, and the micromirrors in the 1st to Tth rows on the DMD 36 are selected as the micromirrors that are actually used during the main exposure. As a result, in the exposure area near the 512th column, a micromirror that minimizes the total area of the overexposed area and the underexposed area for the ideal double exposure is actually realized. It can be selected as a micromirror to be used for.

[0119] Here, instead of deriving the natural number closest to the above value t, the smallest self value equal to or greater than the value t is used. It is also possible to derive the number. In that case, in the exposure area in the vicinity of the 512th column, a micromirror that minimizes the area of the overexposed area and produces an insufficient exposure area for ideal double exposure. Can be selected as the actual micromirror to be used.

It is also possible to derive the maximum natural number less than the value t. In that case, in the exposure area near the 512th column, a micromirror that minimizes the area of the underexposed area and does not produce an overexposed area with respect to the ideal double exposure. It can be selected as a micromirror to be actually used.

FIG. 11 shows the unevenness on the exposed surface shown in FIG. 8 in the exposure performed using only the light spot generated by the micromirror selected as the micromirror actually used as described above. It is explanatory drawing which showed how it is improved.

In this example, it is assumed that T = 253 is derived as the natural number T and the micromirror on the 253rd line is selected as the first line force. For the micromirrors in the 254th to 256th lines that have not been selected, a signal for setting the angle in the always-off state is sent by the pixel part control means. Is not involved in exposure. As shown in Fig. 11, overexposure and underexposure are almost completely eliminated in the exposure area near the 512th column, and uniform exposure very close to ideal double exposure is realized.

On the other hand, in the left region of FIG. 11 (near c (l) in the figure), the angle distortion of the light spot sequence on the exposed surface is near the center (c (512 in the figure)) due to the angular distortion. It is smaller than the angle of inclination of the ray train in the area of). Therefore, the exposure using only the micromirrors selected based on the actual inclination angle θ Ί measured with c (512) as a reference, is ideal for each of the even-numbered exposure pattern and the odd-numbered exposure pattern. A slight under-exposure area is generated for the double exposure.

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 amount is insufficient are compensated for each other, and the uneven exposure due to the angular distortion is performed. Can be minimized by the effect of offset by double exposure.

[0122] Further, in the region on the right side of FIG. 11 (near c (1024) in the figure), the exposure is caused by the angular distortion. The tilt angle of the light beam on the optical surface is larger than the tilt angle of the light beam in the region near the center (near c (512) in the figure). Therefore, in the exposure with the micromirror selected based on the actual tilt angle θ measured with c (512) as the reference, as shown in the figure, the region is overexposed for the ideal double exposure. Will occur slightly. 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 overlap each other, the overexposed areas are complemented with each other, and the density unevenness due to the angular distortion is It can be minimized by the effect of offset by double exposure.

In the present embodiment (1), as described above, the actual tilt angle Θ ′ of the 512th ray array is measured, and the actual tilt angle Θ is used to calculate T based on the T derived from the equation (4). However, as a method for specifying the actual inclination angle Θ ′, a plurality of image element row directions (light spot rows) and a scanning direction of the exposure head are used. The actual tilt angle is measured, and any one of the average value, median value, maximum value, and minimum value is specified as the actual tilt angle Θ '. As a form to select a mirror.

When the average value or the median value is set to the actual inclination angle Θ ′, it is possible to realize exposure with a good balance between an overexposed area and an underexposed area with respect to an ideal N-fold exposure. For example, the total area of overexposed areas and underexposed areas is minimized, and the number of pixel units (number of light spots) in overexposed areas and underexposed areas It is possible to achieve an exposure that makes the number of pixel units (number of light spots) equal to the maximum number of pixels. It is possible to achieve exposure that places more importance on eliminating excessive regions, for example, to achieve exposure that minimizes the area of underexposed regions and prevents overexposed regions. Is possible.

Furthermore, if the minimum value is the actual inclination angle Θ ′, it is possible to realize exposure that places more emphasis on the exclusion of areas that are insufficient for the ideal N double exposure. Exposure that minimizes the area of the area to be exposed and does not produce underexposed areas. It is possible to realize.

On the other hand, the identification of the actual inclination angle Θ is not limited to the method based on the positions of at least two light spots in the same pixel part row (light spot row). For example, the angle obtained from the position of one or more light spots in the same pixel part sequence c (n) and the position of one or more light spots in a row in the vicinity of c (n), The actual inclination angle Θ ′ may be specified.

Specifically, one light spot position in c (n) and one or a plurality of light spot positions included in a light spot row on the straight line and in the vicinity along the scanning direction of the exposure head are detected. The actual inclination angle Θ ′ can be obtained from these positional information. Furthermore, the angle obtained based on the position of at least two light spots in the light spot array in the vicinity of the c (n) line (for example, two light spots arranged so as to straddle c (n)) is obtained. The actual inclination angle Θ ′ may be specified.

[0125] As described above, according to the specification method of the used pixel portion of the present embodiment (1) using the pattern forming apparatus 10, the variation in resolution due to the effect of the mounting angle error or pattern distortion of each exposure head, Reduces density unevenness and achieves ideal N double exposure.

[0126] (2) Specification method of used pixel part between multiple exposure heads <1>

In this embodiment (2), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and is a head that is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads 30. In the connection area, the solution caused by the deviation of the relative position of the two exposure heads (for example, exposure heads 30 and 30) in the X-axis direction from the ideal state.

12 21

Describes how to specify the pixel part to be used in order to reduce the variation in image density and uneven density, and to realize ideal double exposure.

[0127] The set tilt angle Θ of each exposure head 30, that is, each DMD 36, can be used as long as there is no mounting angle error of the exposure head 30 and can be used. 58 and adopt an angle Θ that is exactly double exposure.

ideal

The

This angle Θ is obtained from the above equations 1 to 3 in the same manner as in the above embodiment (1).

ideal

In the present embodiment (2), it is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DM D 36, becomes this angle Θ.

ideal

FIG. 12 shows two exposures in the pattern forming apparatus 10 initially adjusted as described above. Ideal position relative to the X-axis direction of the head (exposing heads 30 and 30 as an example)

12 21

FIG. 6 is an explanatory view showing an example of density unevenness generated in a pattern on an exposed surface due to the influence of deviation from the state. Deviations in the relative position of each exposure head in the X-axis direction can occur because it is difficult to fine-tune the relative position between exposure heads.

The upper part of FIG. 12 is a micromirror 58 that can be used by the DMD 36 of the exposure heads 30 and 30 that is projected onto the exposed surface of the photosensitive material 12 while the stage 14 is stationary.

12 21

It is the figure which showed the pattern of the light spot group of force. The lower part of Fig. 12 shows the exposure pattern formed on the exposed surface when the stage 14 is moved and continuous exposure is performed with the light spot group pattern shown in the upper part appearing. The state of exposure areas 32 and 32

12 21 is shown here.

In FIG. 12, for convenience of explanation, every other column exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. However, the actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

[0130] In the example of FIG. 12, the relative position between the exposure heads 30 and 30 in the X-axis direction described above.

12 21

As a result of the deviation from the ideal state, the connection between the heads of the exposure areas 32 and 32 in both the exposure pattern by the pixel array group A and the exposure pattern by the pixel array group B is performed.

12 21

In the area, there is an overexposed part than the ideal double exposure state.

[0131] In order to reduce density unevenness appearing in the inter-head connecting region formed on the exposed surface by the plurality of exposure heads as described above, in this embodiment (2), the light spot position detection is performed. Using a set of slit 28 and photodetector as means, exposure head 30 and 30 force

The position (coordinates) of some of the light spots that constitute the inter-head connecting area formed on the exposed surface is detected from among the 12 21 light spot groups. Based on the position (coordinates), processing for selecting a micromirror to be used in actual exposure is performed using an arithmetic unit connected to the photodetector as the pixel part selection means.

[0132] Detection of one position (coordinate)

FIG. 13 shows the positional relationship between the exposure areas 32 and 32 similar to those in FIG. It is the top view which showed engagement. The size of the slit 28 is already exposed by the exposure heads 30 and 30.

12 21

Large enough to cover the width of the overlap between areas 34, i.e. exposure heads 30 and 30

The size from 12 21 is sufficiently large to cover the connecting area between the heads formed on the exposed surface.

[0133] Fig. 14 shows an example when the position of the light spot P (256, 1024) in the exposure area 32 is detected.

twenty one

It is a top view explaining the detection method.

First, with the micromirror in the 256th row and the 1024th column turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 1024) is upstream. The slit 28 is positioned at an arbitrary position between the slit 28a on the side and the slit 28b on the downstream side. At this time, the coordinates of the intersection of the slit 28a and the slit 28b are (XO, Y0). The value of this coordinate (XO, Y0) is determined and recorded by the movement distance of the stage 14 to the above position indicated by the drive signal given to the stage 14 and the known X-direction position force of the slit 28. The

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

[0135] Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved along the Y axis to the left in FIG. Then, as indicated by a two-dot chain line in FIG. 14, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the right slit 28a and is detected by the photodetector. The coordinates (XO, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the light spot P (256, 1024).

[0136] From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 1024) on the exposed surface are: X = X0 + (Y1-Y2) Z2, Υ = (Υ1 + Υ2) Determined by calculation of Ζ2.

[0137] Identification of unused pixel parts

In the example of Fig. 12, first, the position of light spot Ρ (256, 1) in exposure area 32 is

12

Detection is performed by a combination of a slit 28 and a photodetector as a position detection means. Next, exposure area 32

The position of each light spot on the light spot line r (256) of the 256th line of 21 is defined as Ρ (256, 1024), Ρ (256, 10 23) X coordinates larger than light spot P (256, 1) in exposure area 32

12

When the light spot P (256, n) in the exposure area 32 indicating is detected, the detection operation ends.

twenty one

The Then, from the light spot light spot sequence c (n + l) to c (1024) in the exposure area 32

twenty one

The corresponding micromirror is specified as a micromirror (unused pixel part) that is not used during the main exposure.

For example, in FIG. 12, the light spot P (256, 1020) force in the exposure area 32 Exposure area 32

21 Shows an X coordinate larger than light spot P (256, 1) of 1 and light spot P (256, 1) of exposure area 32

2 21

020) is detected, the detection operation ends.In FIG. 15, the 1021 row power in the exposure area 32 corresponding to the portion 70 covered by the diagonal line is also the light spot that forms the 1024th row.

twenty one

The micromirror force corresponding to is specified as a micromirror that is not used during the main exposure. Next, the position of the light spot P (256, N) in the exposure area 32 is detected for the number N of N double exposures.

12

Is done. In this embodiment (2), since N = 2, the position of the light spot P (256, 2) is detected.

Next, exposure area 32

Except for the 21 light spot sequences identified above as the light spot train corresponding to the micromirror that is not used during the main exposure, the positions of the light spots that make up the rightmost 1020th column are represented by P (l , 1020) The force is also detected in order as P (l, 1020), P (2, 1020) ..., and light spot P indicating an X coordinate larger than light spot P (256, 2) in exposure area 32 (m, 1020)

12

When is detected, the detection operation is terminated.

Thereafter, in an arithmetic unit connected to the photodetector, an exposure area 32

12 light spots P (

256, 2) and X of the light spots P (m, 1020) and P (m—1, 1020) in the exposure area 32

twenty one

The X coordinate of the light spot P (m, 1020) in the exposure area 32 is the exposure area 3

twenty one

If the X coordinate of light spot P (256, 2) of 2 is close, light spot P (l, 1020) of exposure area 32

12 21

The micromirror corresponding to the force P (m-1, 1020) is also identified as the micromirror that is not used during the main exposure.

In addition, the X coordinate of the light spot P (m–1, 1020) in the exposure area 32 is the light in the exposure area 32.

21 When close to the X coordinate of 12 point P (256, 2), the light spot P (l, 1020) force of exposure area 32 is also P (m

twenty one

-Micromirror force corresponding to 2, 1020) Specified as a micromirror not used in this exposure. Furthermore, the position of the light spot P (256, N-1) in the exposure area 32, that is, the light spot P (256, 1),

12

The same applies to the position of each light spot that constitutes column 1019, which is the next column of exposure area 32.

twenty one

Detection processing and micromirrors that are not used are identified.

As a result, for example, micromirrors corresponding to the light spots that form the shaded area 72 in FIG. 15 are added as micromirrors that are not used during actual exposure. These micromirrors are always signaled to set their micromirror angle to the off-state angle, and these micromirrors are essentially not used for exposure.

[0140] Thus, by identifying micromirrors that are not used during actual exposure and selecting those that are not used as microphone mirrors during actual exposure, exposure areas 32 and 32 are selected. Ideal double dew in the area between the heads

12 21

The total area of areas that are overexposed and underexposed to light can be minimized, and uniform exposure very close to ideal double exposure is achieved, as shown in the lower part of Fig. 15. can do.

[0141] In the above example, the X coordinate of the light spot P (256, 2) of the exposure area 32 and the exposure area are determined when specifying the light spot that constitutes the shaded area 72 in FIG. 32 of

12 21 Without comparing P (m, 1020) and P (m—1, 1020) with the X-coordinates, the light spot P (l, 1020) force in the exposure area 32 immediately increases P (m— 2, 1020)

twenty one

May be specified as a micromirror that is not used during the main exposure. In that case, a micromirror that minimizes the area of the overexposed region with respect to the ideal double exposure and does not generate an underexposed region in the connecting region between the heads. It can be selected as a micromirror to be actually used.

In addition, the light spot P (l, 1020) force in the exposure area 32 corresponds to P (m— 1, 1020).

twenty one

You may identify a mirror as a micromirror which is not used for this exposure. In that case, in the connecting area between the heads, a micromirror that minimizes the area of the area that is underexposed with respect to the ideal double exposure and that does not cause an overexposed area is actually used. It can be selected as the micromirror to be used.

Furthermore, in the connecting area between the heads, the number of pixel units (number of light spots) in an overexposed area and the number of pixel units (number of light spots) in an underexposed area with respect to an ideal double drawing. The micromirrors that are actually used may be selected so as to be equal.

[0142] As described above, according to the method for designating the used picture element portion of the present embodiment (2) using the pattern forming apparatus 10, the solution caused by the relative position shift in the X-axis direction of the plurality of exposure heads. It reduces image variability and density unevenness, and realizes ideal N double exposure.

[3] (3) How to specify the pixel part to be used between multiple exposure heads <2>

In this embodiment (3), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and is a head that is an overlapped exposure region on the exposed surface formed by a plurality of exposure heads 30. In the connection area, the relative position of the two exposure heads (for example, exposure heads 30 and 30) in the X-axis direction deviates from the ideal state, as well as each exposure.

12 21

Designation of the pixel part to be used to realize ideal double exposure by reducing the variation in resolution and density unevenness caused by the head mounting angle error and the relative mounting angle error between the two exposure heads A method will be described.

[0144] The set tilt angle of each exposure head 30, that is, each DMD 36, can be used as long as there is no mounting angle error of the exposure head 30 and the 1024 columns x 256 rows of usable pixel parts (micrometers). Angle slightly larger than angle Θ, which is exactly double exposure using mirror 58)

ideal

The degree shall be adopted.

This angle Θ is obtained in the same manner as in the above embodiment (1) using the above equations 1-3.

ideal

In this embodiment, since s = 256 and N = 2 as described above, the angle Θ is

ideal About 0.45 degrees. Therefore, for example, an angle of about 0.50 degrees may be adopted as the set inclination angle Θ. It is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle Θ within an adjustable range.

[0145] FIG. 16 shows a mounting angle error between two exposure heads (for example, exposure heads 30 and 30) in the pattern forming apparatus 10 in which the mounting angles of each exposure head 30, that is, each DMD 36 are initially adjusted as described above. And relative mounting angle error between each exposure head 30 and 30

2 21 12 21

FIG. 6 is an explanatory diagram showing an example of unevenness that occurs in a pattern on an exposed surface due to the influence of a shift in relative position.

[0146] In the example of FIG. 16, the phases of the exposure heads 30 and 30 in the X-axis direction are the same as the example of FIG. As a result of the misalignment, the exposure head scanning direction on the exposed surface in the exposure areas 32 and 32 is determined in both the exposure patterns of every other light spot group (pixel array group A and B).

12 21

In the overlapping exposure areas on the orthogonal coordinate axes, there is an area 74 where the amount of exposure is excessive compared to the ideal double exposure state, which causes uneven density.

Further, in the example of FIG. 16, the result of setting the tilt angle Θ of each exposure head slightly larger than the angle Θ satisfying the above equation (1) and fine adjustment of the mounting angle of each exposure head ideal

As a result of the fact that the actual mounting angle has deviated from the above-mentioned set inclination angle 0 because of the difficulty of the exposure, the exposure area other than the overlapping exposure area on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface In this area, both of the exposure patterns of every other light spot group (pixel array groups A and B) and the pixel that is an overlapped exposure region on the exposed surface formed by a plurality of pixel part rows. In the connecting region between sub-rows, a region 76 is formed which is overexposed than the ideal double exposure state, and this causes further density unevenness.

In this embodiment (3), first, the mounting angle error of each of the exposure heads 30 and 30 and the relative position are adjusted.

12 21

Use pixel selection processing is performed to reduce density unevenness due to the influence of the angle difference. Specifically, a set of the slit 28 and the photodetector is used as the light spot position detecting means, and the actual inclination angle Θ ′ is specified for each of the exposure heads 30 and 30, and the actual inclination angle is determined.

12 21

Based on the angle θ, processing for selecting a micromirror used for actual exposure is performed using an arithmetic unit connected to a photodetector as the pixel portion selection means.

[0148] Specifying the real inclination angle 0

The actual inclination angle Θ ′ is specified by the light spot P (l,

12 12

The positions of 1) and P (256, 1) and the light spot P (l

21 21

, 1024) and P (256, 1024) are detected by the combination of the slit 28 and the photodetector used in the above-described embodiment (2), respectively, the inclination angle of the straight line connecting them, and the exposure head This is done by measuring the angle between the running direction.

[0149] Identification of unused pixel parts

The arithmetic device connected to the photodetector using the actual inclination angle Θ ′ thus specified is similar to the arithmetic device in the above-described embodiment (1), as shown in the following equation 4

ttan 0 (Equation 4) The natural number T that is closest to the value t that satisfies this relationship is assigned to each of the exposure heads 30 and 30.

12 21

Then, the (Τ + 1) line force on the DMD 36 is also identified as the micromirror that is not used for the main exposure.

For example, 露光 = 254 for exposure head 30 and Τ = 255 for exposure head 30

12 21

Is derived, the micromirror force corresponding to the light spots constituting the portions 78 and 80 covered with diagonal lines in FIG. 17 is specified as a micromirror that is not used in the main exposure. As a result, in each of the exposure areas 32 and 32 other than the connection area between the heads.

12 21

The total area of the overexposed and underexposed areas with respect to the ideal double exposure can be minimized.

[0150] Here, instead of deriving the natural number closest to the above value t, the smallest natural number equal to or greater than the value t may be derived. In that case, to multiple exposures in exposure areas 32 and 32

12 21

In each area other than the head-to-head connection area, which is the overlapping exposure area on the exposed surface formed by the head, the area where the overexposure is excessive for the ideal double exposure is minimized, and the exposure is insufficient This can be done without creating an area.

Or it is good also as deriving the maximum natural number below value t. In that case, exposure area 32 32

Areas that are underexposed for ideal double exposure in areas 12 and 21 other than the joint area between the heads, which are overlapping exposure areas on the exposed surface formed by multiple exposure heads Therefore, it is possible to prevent an area that is overexposed and has a minimum area.

The number of pixel units in the overexposed area for the ideal double exposure in each area other than the joint area between the heads, which is the overlapping exposure area on the exposed surface formed by multiple exposure heads ( It is also possible to specify a micromirror that is not used during the main exposure so that the number of pixel units (number of light spots) in the underexposed area is equal to the number of light spots!

[0151] Thereafter, with respect to the micromirror corresponding to the light spot other than the light spots constituting the regions 78 and 80 covered by the oblique lines in FIG. 17, this embodiment (3) described with reference to FIGS. The same processing was performed, and micromirrors corresponding to the light spots constituting the shaded area 82 and the shaded area 84 in FIG. 17 were identified and added as micromirrors that are not used during the main exposure. Is done. With respect to the micromirrors identified as not being used at the time of exposure, the pixel unit control means sends a signal for setting the angle of the always-off state, and these microphone mirrors substantially Not involved in exposure.

[0152] As described above, according to the method for designating the used picture element portion of the present embodiment (3) using the pattern forming apparatus 10, the relative position shift in the X-axis direction of the plurality of exposure heads, and Variations in resolution and density unevenness due to the mounting angle error of the optical head and the relative mounting angle error between the exposure heads can be reduced, and ideal N-fold exposure can be realized.

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

[0154] In the above embodiments (1) to (3), as a means for detecting the position of the light spot on the surface to be exposed, a set of the slit 28 and the single cell type photodetector is used. The force that was used is not limited to this, V, or any other form can be used. For example, a two-dimensional detector can be used.

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

It should be noted that there are various forms of pattern distortion that can occur on the exposed surface, in addition to the angular distortion described in the above example.

As an example, as shown in FIG. 18A, there is a form of magnification distortion that reaches the exposure area 32 on the exposure surface at different magnifications from the light power from each micromirror 58 on the DMD 36. As shown in FIG. 18B, there is a form of beam diameter distortion that reaches the exposure area 32 on the exposed surface with different beam diameters, the light power from each micromirror 58 on the DMD 36. These magnification distortion and beam diameter distortion are mainly related to DMD36 and exposure. This is caused by various aberrations and alignment deviation of the optical system between the optical surfaces.

As another example, there is a form of light amount distortion that reaches the exposure area 32 on the surface to be exposed with a different light amount from each micromirror 58 on the DMD 36. In addition to various aberrations and misalignment, this distortion of light intensity includes the positional dependency of the transmittance of the optical element between the DMD 36 and the exposed surface (for example, the single lens 52 and 54 in FIGS. 5A and 5B), This is caused by unevenness in the amount of light due to the DMD 36 itself. These forms of pattern distortion also cause unevenness in resolution and density in the pattern formed on the exposed surface.

[0157] According to the above embodiments (1) to (3), after selecting the micromirrors actually used for the main exposure, the residual elements of the pattern distortion of these forms are also the above-mentioned angular distortion. As with the residual elements, it can be leveled by the effect of multiple exposure, and the unevenness in resolution and density can be reduced over the entire exposure area of each exposure head.

[0158] <<Reference exposure>>

As a modified example of the above embodiments (1) to (3), among available micromirrors, every (N-1) micromirror columns or adjacent to 1ZN rows of all light spot rows The reference exposure is performed using only the group of micromirrors that make up the row, and the microphone mirror that is not used during actual exposure is identified among the micromirrors used for the reference exposure so that uniform exposure can be achieved. You can do it.

The result of the reference exposure by the reference exposure means is output as a sample, and the output reference exposure result is subjected to analysis such as confirmation of resolution variation and density unevenness and estimation of the actual inclination angle. The analysis of the result of the reference exposure is a visual analysis by the operator.

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

In this example, the main exposure is assumed to be double exposure, and therefore N = 2. First, reference exposure is performed using only the micromirrors corresponding to the odd-numbered light spot arrays indicated by solid lines in FIG. 19A, and the reference exposure results are output as samples. Based on the reference exposure result output from the sample, it is possible to specify a micromirror to be used in the main exposure by confirming variations in resolution and uneven density, or estimating the actual tilt angle. For example, a microphone aperture mirror other than the micromirror corresponding to the light spot array shown by hatching in FIG. 19B is designated as actually used in the main exposure among the micromirrors constituting the odd light spot array. Is done. For even-numbered light spot arrays, a separate reference exposure may be performed in the same manner to specify a micromirror to be used during the main exposure, or the same pattern as that for odd-numbered light spot arrays may be applied. Good.

By specifying the micromirrors used during the main exposure in this way, a state close to an ideal double exposure can be realized in the main exposure using both the odd-numbered and even-numbered micromirrors.

FIG. 20 is an explanatory view showing an example of a form in which reference exposure is performed using only a plurality of (N-1) micromirrors using a plurality of exposure heads.

In this example, the main exposure is assumed to be double exposure, and therefore N = 2. First, reference is made by using only micromirrors corresponding to odd-numbered light spot rows of two exposure heads adjacent to each other in the X-axis direction (for example, exposure heads 30 and 30) shown by a solid line in FIG.

12 21

Exposure is performed, and a reference exposure result is output as a sample. Based on the output result of the reference exposure, the two exposure heads check resolution variations and density unevenness in areas other than the head-to-head connection area formed on the exposed surface, and estimate the actual inclination angle. Therefore, it is possible to specify the micromirror to be used during the main exposure.

For example, the micromirror force other than the micromirror corresponding to the light spot array in the area 86 shown by hatching in FIG. Designated as actually used. For even-numbered light spot arrays, a separate reference exposure may be performed in the same manner, and the micromirror used for the main exposure may be designated, or the same pattern as that for the odd-numbered pixel lines may be applied. .

In this way, by specifying the micromirrors that are actually used during the main exposure, in the main exposure using both the odd-numbered and even-numbered micromirrors, the two exposure heads form the surface to be exposed. A state close to ideal double exposure can be achieved in areas other than the head-to-head connection area.

[0161] FIGS. 21A and 21B use a single exposure head and correspond to IZN rows for all light spot rows It is explanatory drawing which showed an example of the form which performs reference exposure using only the micromirror group which comprises an adjacent line.

In this example, the main exposure is assumed to be double exposure, and therefore N = 2. First, reference exposure is performed using only a micromirror corresponding to the light spot in the first to 128 (= 256/2) rows shown by the solid line in FIG. 21A, and the reference exposure result is output as a sample. Based on the reference exposure result outputted from the sample, the micromirror to be used in the main exposure can be specified.

For example, a microphone mouth mirror other than the micromirror corresponding to the light spot group indicated by hatching in FIG. 21B is actually used during the main exposure in the micromirrors in the first to 128th rows. Can be specified as For the micromirrors in the 129th to 256th lines, a separate reference exposure may be performed in the same manner, and the micromirror to be used during the main exposure may be designated, or the first to 128th lines may be designated. You can apply the same pattern as for the micromirror.

By specifying the micromirror to be used during the main exposure in this way, it is possible to achieve a state close to ideal double exposure in the main exposure using the entire micromirror. Used, two adjacent exposure heads in the X-axis direction (for example, exposure heads 30 and 30) are equivalent to 1ZN rows of the total number of light spots

12 21

FIG. 10 is an explanatory diagram showing an example of a form in which reference exposure is performed using only micromirror groups constituting adjacent rows.

In this example, the main exposure is assumed to be double exposure, and therefore N = 2. First, the first line force indicated by the solid line in FIG. 22 is also subjected to reference exposure using only the micromirror corresponding to the light spot of the 128th (= 256Z2) line, and the reference exposure result is output as a sample. Based on the reference exposure result output from the sample, the main exposure can be realized with minimal variation in resolution and density unevenness in areas other than the joint area between the heads formed on the exposed surface by the two exposure heads. In addition, it is possible to specify a micromirror to be used during the main exposure.

For example, in FIG. 22, a light spot array in a region 90 indicated by hatching and a region 92 indicated by shading Micromirror force other than micromirrors corresponding to is designated as the actual one used during the main exposure in the micromirrors in the 1st to 128th lines. For the micromirrors in the 129th to 256th lines, a separate reference exposure may be performed in the same manner to specify the micromirror to be used for the main exposure, and the first to 128th lines are designated. The same pattern as that of the micromirror may be applied.

By specifying the micromirror to be used during the main exposure in this way, a state close to ideal double exposure is realized in areas other than the joint area between the heads formed on the exposed surface by the two exposure heads. it can.

[0163] In the above embodiments (1) to (3) and the modified examples, the power described in the case where the main exposure is double exposure is not limited to this, and any multiple exposure over double exposure is possible. It is good. In particular, by setting the triple exposure power to approximately seven exposures, it is possible to achieve exposure with high resolution and reduced resolution variation and density unevenness.

[0164] In addition, in the exposure apparatus according to the embodiment and the modification example described above, the size of the predetermined portion of the two-dimensional pattern represented by the image data matches the size of the corresponding portion that can be realized by the selected use pixel. It is preferable that a mechanism for converting image data is provided. By converting the image data in this way, it is possible to form a high-definition pattern on the exposed surface according to the desired two-dimensional pattern.

[0165] [Development process]

The developing step exposes the photosensitive layer in the pattern forming material in the exposing step, cures the exposed region of the photosensitive layer, and then removes the uncured region to form an image, thereby forming a no-turn. It is a process.

[0166] The development step can be preferably carried out, for example, by a developing means.

The developing means is not particularly limited as long as it can be developed using a developer, and can be appropriately selected according to the purpose. For example, the means for spraying the developer, and applying the developer And means for immersing in the developer. These may be used alone or in combination of two or more.

In addition, the developing unit may include a developing solution replacing unit that replaces the developing solution, a developing solution supply unit that supplies the developing solution, and the like. [0167] The developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkaline solutions, aqueous developers, organic solvents, etc. Among these, weakly alkaline aqueous solutions are mentioned. preferable. Examples of the basic component of the weak alkaline liquid include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

[0168] The pH of the weak alkaline aqueous solution is more preferably about 9 to 11 force, for example, preferably about 8 to 12. Examples of the weak alkaline aqueous solution include 0.1 to 5% by mass of sodium carbonate aqueous solution or potassium carbonate aqueous solution.

The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and for example, about 25 ° C. to 40 ° C. is preferable.

[0169] The developer is a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) In order to accelerate development, an organic solvent (for example, alcohols, ketones, esters, ethers, amides, latatones, etc.) may be used in combination. The developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or may be an organic solvent alone.

[0170] [Etching process]

The etching step can be performed by a method appropriately selected from among known etching methods.

[0171] The etching solution used for the etching treatment can be appropriately selected according to the purpose without any particular restriction. For example, when the metal layer is formed of copper, cupric chloride is used. Examples thereof include a solution, a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution. Among these, the point of the etching factor salty ferric solution is preferable.

A permanent pattern can be formed on the surface of the substrate by removing the pattern as a strip after the etching process.

The permanent pattern is not particularly limited and can be appropriately selected according to the purpose. For example, a wiring pattern etc. are mentioned suitably.

[Resist stripping step]

The resist stripping step can be performed by a method appropriately selected from known resist stripping methods without particular limitation as long as it is a step of stripping the pattern and then stripping it as strips.

In the photosensitive layer comprising the photosensitive resin composition of the present invention, the strips produced in the resist stripping process are extremely fine, and can prevent stripping failure and the like, and can prevent contamination of the apparatus by the stripping pieces. .

[0173] The stripping solution used for the resist stripping treatment is not particularly limited and may be appropriately selected depending on the purpose. For example, 1 to 10% by mass of sodium hydroxide aqueous solution, 1 to: LO mass inorganic alkali aqueous solution and the like ^_0/0 Mizusani匕aqueous potassium and 1 to 20 mass ^_0/0 Amin organic alkaline aqueous solution. among these,. 1 to: LO wt% of an inorganic Al force Li solution Is preferred.

[0174] The strips produced by the resist stripping step preferably have a maximum side length of 5 cm or less. If the length of the maximum side of the peeling piece exceeds 5 cm, it may cause a peeling failure or cause trouble in the transportation system of the apparatus.

[Manufacturing Method of Printed Wiring Board]

The pattern forming method of the present invention can be suitably used for the production of a printed wiring board, particularly for the production of a printed wiring board having a hole portion such as a through hole or a via hole. Hereinafter, an example of a method for producing a printed wiring board using the pattern forming method of the present invention will be described.

[0176] Method for producing printed wiring board

As a method for producing a printed wiring board having a hole portion such as a through hole or a via hole, (1) the photosensitive transfer film is formed on a substrate for forming a printed wiring board having a hole portion as the base, and the photosensitive layer thereof. Are stacked in a positional relationship on the substrate side, and (2) a desired region is irradiated from the opposite side of the laminate to the substrate to cure the photosensitive layer, (3) The laminate strength The support in the photosensitive transfer film The pattern can be formed by removing the body, cushion layer and barrier layer, (4) developing the photosensitive layer in the laminate, and removing the uncured portion in the laminate.

[0177] Thereafter, in order to obtain a printed wiring board, a method of etching or plating the printed wiring board forming substrate using the formed pattern (for example, a known subtractive method or additive method (for example, Semi-additive method and full additive method)). Among these, the subtractive method is preferable in order to form a printed wiring board with industrially advantageous tenting. After the treatment, the cured resin remaining on the printed wiring board forming substrate is peeled off. In the case of the semi-additive method, the copper thin film portion is further etched after the peeling to produce a desired printed wiring board. can do. A multilayer printed wiring board can also be manufactured in the same manner as the printed wiring board manufacturing method.

[0178] Next, a method for producing a printed wiring board having through holes using the photosensitive transfer film will be further described.

First, a printed wiring board forming substrate having through holes and having a surface covered with a metal plating layer is prepared. As the printed wiring board forming substrate, for example, a copper clad laminated substrate and a substrate in which a copper plating layer is formed on an insulating base material such as glass-epoxy, or an interlayer insulating film is laminated on these substrates, and a copper plating layer is formed. A formed substrate (laminated substrate) can be used.

[0180] Next, when a protective film is provided on the photosensitive transfer film, the protective film is peeled off, and the photosensitive layer in the photosensitive transfer film is in contact with the surface of the printed wiring board forming substrate. In this way, pressure bonding is performed using a pressure roller (lamination process). Thereby, a laminate having the printed wiring board forming substrate and the laminate in this order is obtained.

The lamination temperature of the photosensitive transfer film is not particularly limited, for example, room temperature (15 to 30 ° C.) or under heating (30 to 180 ° C.). Among these, under heating (60 to 140 ° C) is preferred.

The roll pressure of the crimping roll is not particularly limited, for example, 0.1 to lMPa is preferable.

The crimping speed is preferably 1 to 3 mZ, which is not particularly limited. Alternatively, the printed wiring board forming substrate may be preheated or laminated under reduced pressure.

[0181] The laminate may be formed by laminating the photosensitive transfer film on the printed wiring board forming substrate, or a photosensitive resin composition solution for manufacturing the photosensitive transfer film. The photosensitive layer, the barrier layer, the cushion layer, and the support may be laminated on the printed wiring board forming substrate before the coating is applied directly to the surface of the printed wiring board forming substrate and dried.

[0182] Next, the photosensitive layer is cured by irradiating light from the surface of the laminate opposite to the substrate.

After the exposure, the support is peeled from the laminate (peeling step).

[0183] Next, the uncured region of the photosensitive layer on the printed wiring board forming substrate is dissolved and removed with an appropriate developer to cure the hardened layer for forming the wiring pattern and the metal layer for protecting the through hole. A layer pattern is formed to expose the metal layer on the surface of the printed wiring board forming substrate (development process).

[0184] Further, after development, if necessary, post-heating treatment or post-exposure processing may be performed to further accelerate the curing reaction of the cured portion. The development may be a wet development method as described above or a dry development method.

Next, the metal layer exposed on the surface of the printed wiring board forming substrate is removed by dissolution with an etching solution (etching step). Since the opening of the through hole is covered with a cured resin composition (tent film), the metal coating of the through hole prevents the etching solution from entering the through hole and corroding the metal plating in the through hole. Will remain in the prescribed shape. Thereby, a wiring pattern is formed on the printed wiring board forming substrate.

[0186] The etching solution is not particularly limited, and can be appropriately selected according to the purpose. For example, when the metal layer is formed of copper, a cupric chloride solution, salt solution Examples thereof include a ferric solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, and the like. Among these, a salty ferric solution is preferable from the viewpoint of an etching factor.

[0187] Next, the cured layer is removed from the printed wiring board forming substrate with a strong alkaline aqueous solution or the like as a strip (resist stripping step). Stripping in the resist stripping process Although a piece is formed, the peeling piece of the pattern formed by the photosensitive layer having the photosensitive resin composition power of the present invention is extremely small, and therefore, contamination of the apparatus by the peeling piece without peeling failure can be prevented.

[0188] The base component in the strong alkaline aqueous solution is not particularly limited, and examples thereof include sodium hydroxide and potassium hydroxide.

The pH of the strong alkaline aqueous solution is, for example, preferably about 13-14, more preferably about 12-14.

The strong alkaline aqueous solution is not particularly limited, and examples thereof include 1 to 10% by mass of sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

[0189] The printed wiring board may be a multilayer printed wiring board.

The photosensitive transfer film may be used in a plating process that involves only the etching process described above. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard plating. Gold plating such as gold plating and soft gold plating can be used.

[0190] Since the pattern transfer method of the present invention uses the photosensitive transfer film of the present invention, formation of various patterns, formation of permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, It can be suitably used for the production of liquid crystal structural members such as partition walls, the production of holograms, micromachines, proofs, etc., and can be particularly suitably used for the formation of high-definition wiring patterns.

Example

[0191] Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

[0192] (Example 1)

Manufacture of photosensitive transfer film

A 16 μm thick polyethylene terephthalate film as the support is coated with a photosensitive resin composition solution having the following composition and dried to form a 15 m thick photosensitive layer, and then the photosensitive layer. A 20 μm thick polypropylene film as the protective film The photosensitive transfer film was manufactured by laminating.

[Composition of photosensitive resin composition solution]

Binders with the compositional power shown in Table 1 below · · · 20 parts by mass

ΒΡΕ500 (manufactured by Shin-Nakamura) · 10 parts by mass

UAT1 (manufactured by Shin-Nakamura Chemical).. .10 parts by mass

Ν—Methyl Ataridon ····· 11 parts by mass

2, 2, 1 bis (ο black mouth) 1, 4, 4, 5, 5, 1 tetraphenyl imidazole · '· 2.17 parts by mass

2-Mercaptobenzimidazole '·· 0.23 parts by mass

Malachite green oxalate… 0.02 parts by mass

Leuco crystal violet ·····. 26 parts by mass

Methyl ethyl ketone 40 mass parts

1-methoxy 2-propanol '· · 20 parts by mass

*: Including copolymer Α and copolymer Β. The weight average molecular weight, mass ratio, and composition of each copolymer are shown in Table 1 below.

[0194] Next, the protective film of the photosensitive transfer film is peeled off from the surface of a copper-clad laminate (no through-hole, copper thickness: 12 m) whose surface is polished, washed and dried as the substrate. And laminator (MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.) so that the photosensitive layer of the photosensitive transfer film is in contact with the copper-clad laminate, the copper-clad laminate, A laminate in which the photosensitive layer and the polyethylene terephthalate film (support) were laminated in this order was prepared.

The crimping conditions were a crimping roll temperature of 105 ° C, a crimping roll pressure of 0.3 MPa, and a laminating speed of lmZ.

About the photosensitive layer of the photosensitive transfer film in the laminate, the melt viscosity, followability on the substrate, unexposed film breakage, developability, sensitivity, resolution, edge roughness, peeled piece size, and tent property are as follows. evaluated.

[0195] <Melt viscosity>

Repeat the lamination of the photosensitive layer surfaces, and prepare the sample so that the thickness is 150 ± 10 m. After adjustment, the photosensitive layer is allowed to stand in an environment of 25 ° C and 50% RH for 24 hours, and then a rheometer (dynamic viscosity measuring device) (REOLOGCA, DynAlyserDAR-100) is used with a frequency of 1 Hz and a gap of 1.5 mm. It measured on condition of this. The results are shown in Table 2.

[0196] <Developability>

The laminate strength is peeled off, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate, Spray start force The time required for the photosensitive layer on the copper clad laminate to be dissolved and removed was measured, and this was taken as the shortest development time. The shortest development time was evaluated according to the following criteria. The results are shown in Table 3.

[0197] Evaluation criteria

○ · · · 30 seconds or less

△ · · · Over 30 seconds and less than 60 seconds

Χ Over 60 seconds

[0198] <Sensitivity>

The photosensitive layer of the photosensitive transfer film in the laminate described above prepared from said support side, a patterning device, which is described below, the light energy of 0. ImiZcm ² force at 2 ^1/2 times intervals until LOOmiZcm ² Exposure was performed by irradiating light of different amounts, and a part of the photosensitive layer was cured. After standing at room temperature for 10 minutes, the support was peeled from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C was sprayed to the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. In the evaluation of the developability, spraying was performed for twice the minimum development time obtained in the above, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Next, a sensitivity curve was obtained by plotting the relationship between the amount of light irradiation and the thickness of the cured layer. From the sensitivity curve, the light energy amount (sensitivity) required for curing the photosensitive layer was determined as the amount of light energy when the thickness of the cured region was 15 m, which was the same as that of the photosensitive layer before exposure. The results are shown in Table 3.

[0199] <<Pattern forming device>>

As the light irradiating means, a combined laser light source described in JP-A-2005-258431, and as the light modulating means, a micromirror 58 is 1024 in the main scanning direction schematically shown in FIG. Among the 768 array of arrayed micromirrors arranged in the sub-scanning direction, DMD36 controlled to drive only 1024 x 256 6 columns, and the light shown in FIG. 5A and FIG. A pattern forming apparatus 10 provided with an exposure head 30 having an optical system that forms an image on a conductive transfer film was used.

[0200] The tilt angle of each exposure head 30, ie each DMD 36, is slightly larger than the angle Θ that is exactly double exposure using the available 1024 rows x 256 rows micromirror 58

ideal

Adopted the size and angle. This angle 0 is the number of N exposures N, the available micromirrors

ideal

(1) The number s in the column direction of 58, the interval p in the column direction of the usable micromirrors 58, and the pitch δ of the scanning line formed by the micromirrors when the exposure head 30 is tilted, ,

spsin θ ≥Ν δ (Equation 1)

iaeal

ideal

And the above equation 1 is

stan Q = N (Formula 3)

ideal

Since s = 256, N = 2, the angle 0 is about 0.45 degrees. Therefore, the setting

ideal

As the constant inclination angle Θ, for example, 0.50 degrees was adopted.

[0201] First, in order to correct the variation in resolution and uneven exposure in double exposure, the state of the exposure pattern on the exposed surface was examined. The results are shown in FIG. In FIG. 16, the pattern of the light spot group from the micromirror 58 that can be used by the DMD 36 of the exposure heads 30 and 30 projected onto the exposed surface of the photosensitive transfer film 12 with the stage 14 stationary.

12 21

Showed. The state of the exposure pattern formed on the exposed surface when the stage 14 is moved and continuous exposure is performed with the light spot group pattern shown in the upper part appearing in the lower part. Are shown for exposure areas 32 and 32. In Figure 16,

12 21

For convenience of explanation, the exposure pattern for every other column of the micromirrors 58 that can be used is shown separately for the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B. The exposure pattern on the surface overlaps these two exposure patterns. It is

[0202] From the ideal state of the relative position between exposure heads 30 and 30, as shown in FIG.

12 21

As a result of the shift, the coordinates orthogonal to the scanning direction of the exposure head in the exposure areas 32 and 32 in both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B.

12 21

It can be seen that there are overexposed areas in the overlapping exposure areas on the axis than in the ideal double exposure state.

[0203] A set of a slit 28 and a photodetector is used as the light spot position detecting means, and an exposure head 30 is used.

12, the positions of the light spots P (l, 1) and P (256, 1) in the exposure area 32

For 12 21, the positions of light spots P (l, 1024) and P (256, 1024) within the exposure area 32 are detected.

twenty one

The angle formed by the inclination angle of the straight line connecting them and the scanning direction of the exposure head was measured.

[0204] Using the actual inclination angle Θ ', the following equation 4

ttan 0 (Equation 4)

The natural number T that is closest to the value t that satisfies this relationship is assigned to each of the exposure heads 30 and 30.

12 21

Derived. T = 254 for exposure head 30, 、 = 25 for exposure head 30

12 21

5 were derived respectively. As a result, the micromirrors constituting the portions 78 and 80 covered with diagonal lines in FIG. 17 were identified as micromirrors that are not used during the main exposure.

Thereafter, regarding the micromirror corresponding to the light spots other than the light spots constituting the areas 78 and 80 covered by the oblique lines in FIG. 17, the area 82 covered by the oblique lines in FIG. In addition, micromirrors corresponding to the light spots constituting the shaded area 84 were identified and added as micromirrors not used during the main exposure.

For the micromirrors identified as not used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel unit control means, and these microphone mirrors are substantially It was controlled so that it was not involved in exposure.

As a result, the exposure areas formed by a plurality of the exposure heads in the exposure areas 32 and 32.

12 21

Minimize the total area of overexposed and underexposed areas for ideal double exposure in each area other than the head-to-head connection area, which is the overlapping exposure area on the optical surface. It can be.

[0206] <Resolution> The laminate is produced under the same method and conditions as the developability evaluation method, and the room temperature (23 ° C,

(55% RH) for 10 minutes. From the polyethylene terephthalate film (support) of the resulting laminate, using the pattern forming device, exposure of each line width in 1 μm increments from 10 m to 50 μm line width with line Z space = 1Z1. I do. The amount of exposure at this time is the amount of light energy required to cure the photosensitive layer of the photosensitive transfer film obtained by measuring the sensitivity. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate. On the entire surface of the photosensitive layer on the copper clad laminate

1% sodium carbonate aqueous solution at 30 ° C with spray pressure 0.15MPa and the shortest development time

Spray for twice the time to dissolve away uncured areas. The surface of the copper clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, and the cured resin pattern line is free from defects such as toughness and distortion, and is the smallest line that can form a space. The width was measured and used as the resolution. The smaller the numerical value, the better the resolution. The results are shown in Table 3.

[0207] <Edge roughness>

Using the pattern forming apparatus, the laminated body is irradiated and exposed so as to form a horizontal line pattern in a direction perpendicular to the scanning direction of the exposure head, and a partial region of the photosensitive layer is exposed to the resolution. A pattern was formed in the same manner as the above measurement. Of the obtained patterns, any five points on a line with a line width of 30 m were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×), and the edge position in the field of view was observed. Of these, the difference between the most swollen part (mountain peak) and the most constricted part (valley bottom) was obtained as an absolute value, and the average value of the five observed points was calculated, and this was used as edge roughness. As the edge roughness, a smaller value is preferable because good performance is exhibited. The results are shown in Table 3.

[0208] <Tent characteristics>

The laminated body was subjected to the same method and conditions as the developability evaluation method, except that a copper-clad laminate (100 pieces of 4 mm diameter through holes, copper thickness 12 m) was used as the substrate. Was prepared. The entire surface of the laminate was exposed using the pattern forming apparatus and developed. Thereafter, the presence or absence of breakage of the cured resin pattern formed on the through hole was observed with an optical microscope. The results are shown in Table 3.

[0209] <Peeling piece size> Using the laminate having the pattern formed in the measurement of the resolution, on the surface of the exposed copper-clad laminate in the laminate, a salted pig iron etchant (ferric chloride-containing etching solution, 40 ° Baume, Etching was performed by spraying at a liquid temperature of 40 ° C at 0.25 MPa for 36 seconds to dissolve and remove the exposed copper layer not covered with the hardened layer. Next, a 3% by weight aqueous solution of sodium hydroxide and sodium hydroxide (40 ° C.) was sprayed onto the cured resin pattern on the substrate to perform a resist stripping process, and stripped pieces were removed. The size of the peeled piece removed was measured, and the length of the largest side of the largest peeled piece was measured with an optical microscope. The results are shown in Table 3.

[0210] <Trackability on substrate>

As the substrate (substrate), a copper-clad laminate (copper thickness) with a surface polished, washed and dried, with a line Z space = 1Z1, a line width of 50 μm, an etching depth of 8 μm and a no fetch line formed. 16 μm) on the same conditions as in the evaluation method for developability, the laminate was prepared, and the obtained laminate was used on the polyethylene terephthalate film (support). Irradiation was performed so as to form a line with Z space = 30 m perpendicular to the half-etched line, and a pattern was formed in the same manner as the resolution measurement. Next, after performing an etching process in the same manner as the peeling piece size evaluation method, the surface of the substrate was observed with an optical microscope and evaluated according to the following criteria. The results are shown in Table 2.

○ 'No pattern breaks because the resist is also following in the first fetch part X · ·' There is not enough resist tracking in the half-etched part, and there is a pattern break [0211] <Unexposed film breaks>

A laminated body for evaluation of unexposed film breakage was prepared in the same manner as in the laminated body except that the photosensitive layer was laminated on both surfaces under the pressure bonding conditions with respect to the copper clad laminated board in the laminated body. The obtained laminate was stored at room temperature (25 ° C., 50% RH) for 5 days. The substrate was peeled from the layered product after storage, and the number of peeled and broken photosensitive layers in the hole portion was counted, and evaluation of unexposed film breakage was performed. In each hole portion having a diameter of 1 to 6 mm, the diameter of the largest hole portion in which 30 holes were not broken at all was defined as the unexposed film tear value. The results are shown in Table 2. [0212] (Examples 2 to 6)

In Example 1, except that the binder copolymer A and copolymer B were changed to the compositions and mass ratios shown in Table 1, in the same manner as in Example 1, the melt viscosity, the followability on the substrate, unexposed Film tear, developability, sensitivity, resolution, edge roughness, peeled piece size, and tent properties were evaluated. The results are shown in Tables 2 and 3.

[0213] (Example 7)

In Example 1, the exposure apparatus was replaced with an exposure apparatus having an ultra-high pressure mercury lamp as a light source, and the exposure was performed using a photomask. , Unexposed film breakage, developability, sensitivity, resolution, edge roughness, peeled piece size, and tent properties were evaluated. The results are shown in Tables 2 and 3.

[0214] (Example 8)

In the pattern forming apparatus of the first embodiment, the set inclination angle Θ is calculated with N = 1 based on Equation 3 above, and the natural number T closest to the value t satisfying the relationship of ttan 0 ′ = 1 is derived based on Equation 4 above. In the same manner as in Example 1 except that N exposure (N = l) was performed, melt viscosity, followability on substrate, unexposed film breakage, developability, sensitivity, resolution, edge roughness, peeling The piece size and tent property were evaluated. The results are shown in Tables 2 and 3.

The shortest development time is 10 seconds, and the light energy required to cure the photosensitive layer is approximately 3 mj / cm (?

[0215] (Comparative Examples 1 to 5)

In Example 1, except that the copolymer A and the copolymer B of the binder were changed to the compositions shown in Table 1, in the same manner as in Example 1, the melt viscosity, the followability on the substrate, the unexposed film was broken, Image quality, sensitivity, resolution, edge roughness, peeled piece size, and tentability were evaluated. The results are shown in Tables 2 and 3.

[0216] [Table 1] Weight average molecular weight Copolymer A Copolymer B

A / B

AB AA St MAA MMA EHA BzMA Example 1 8000 100000 10/90 37.0 63.0 28.8 55.0 11.7 4.5 Example 2 8000 100000 50/50 37.0 63.0 28.8 55.0 11.7 4.5 Example 3 8000 100000 80/20 37.0 63.0 28.8 55.0 11.7 4.5 Implementation Example 4 4000 100000 10/90 37.0 63.0 28.8 55.0 11.7 4.5 Example 5 8000 100000 10/90 29.0 71.0 28.8 55.0 11.7 4.5 Example 6 8000 100000 10/90 37.0 63.0 30.0 0.0 0.0 70.0 Example 7 8000 100000 10/90 37.0 63.0 28.8 55.0 11.7 4.5 Example 8 8000 100000 10/90 37.0 63.0 28.8 55.0 11.7 4.5 Comparative Example 1-100000 0/100--28.8 55.0 11.7 4.5 Comparative Example 2 8000 100000 5/95 37.0 63.0 28.8 55.0 11.7 4.5 Comparative Example 3 8000 100000 95/5 37.0 63.0 28.8 55.0 11.7 4.5 Comparative Example 4 15000 100000 10/90 37.0 63.0 28.8 55.0 11.7 4.5 Comparative Example 5 8000 20000 10/90 37.0 63.0 28.8 55.0 11.7 4.5

AA: Acrylic acid

St: Styrene

MAA: Methacrylic acid

MMA: Methyl metatalylate

EHT: 2 Ethylhexyl Atarire

BzMA: benzylmetatalylate

[Table 2]

Melt viscosity (Pa-s) Unexposed film break on substrate

50 ° C 70. C followability ^ mm

Example 1 110000 18000 ○ 6 or more

Example 2 55000 8000 o 5

Example 3 50000 6000 〇 4

Example 4 100000 11000 〇 6 or more

Example 5 110000 18000 o 6 or more

Example 6 110000 18000 〇 6 or more

Example 7 110000 18000 o 6 or more

Example 8 110000 18000 ○ 6 or more

Comparative Example 1 180000 45000 X 6 or more

Comparative Example 2 160000 35000 X 6 or more

Comparative Example 3 38000 4000 ○ 2

Comparative Example 4 170000 40000 X 6 or more

Comparative Example 5 20000 1500 O 1 ίΐ

3] Sensitivity Resolution Edge roughness Peeling strip size Developability Ten Μΐ

(mJ / cm ί (iim) (U m) (cm)

Example 1 ○ 10 15 1.0 2 ○ Example 2 ○ 10 15 1.3 2 ○ Example 3 ○ 10 15 1.4 2 ○ Example 4 ○ 10 15 1.2 2 ○ Example 5 ○ 10 15 1.2 2 ○ Example 6 ○ 10 15 1.3 2 ○ Example 7 ○ 5 15 1.5 2 ○ Example 8 ○ 10 15 1.6 2 ○ Comparative Example 1 X 10 30 1.2 5 ○ Comparative Example 2 X 10 30 1.2 5 ○ Comparative Example 3 ○ 10 15 1.6 2 X Comparison Example 4 ○ 10 20 1.2 5 ○ Comparative Example 5 X 10 15 1.3 5 X [0219] From the results of Table 2 and Table 3, Example 1 in which the melt viscosity is 40,000 to 120, OOOPa's at 50 ° C and 5,000-20, OOOPa's at 70 ° C. In ~ 8, it was found that the followability on the substrate was good. In particular, it was found that in Example 1 and Examples 4 to 8 in which the mass ratio of the copolymer A and the copolymer B was AZB = 10Z90 to 40/60, there was little unexposed film breakage. It turned out that Examples 1-8 which formed the photosensitive layer from the photosensitive resin composition of this invention are excellent also in the developability which an etching peeling piece is small compared with Comparative Examples 1-5.

Furthermore, it was found that the wiring patterns of Examples 1 to 6 in which the variation in resolution and the exposure unevenness in the double exposure were corrected were high definition, the edge roughness was small, and the etching property was excellent.

[0220] (Example 9)

A photosensitive transfer film was produced in the same manner as in Example 1 except that the composition of the photosensitive resin composition solution was changed as follows, and a laminate was prepared.

For the photosensitive layer of the photosensitive transfer film in the laminate, as in Example 1, melt viscosity, followability on the substrate, unexposed film breakage, developability, sensitivity, resolution, edge roughness, peeled piece size, And the tent property was evaluated. These results are shown in Tables 6 and 7.

[0221] [Composition of photosensitive resin composition solution]

Binder with compositional power shown in Table 4 below (*)… 139. 6 parts by mass

Compound represented by the following structural formula (1) (Daiichi Kogyo Seiyaku, New Frontier ΒΡΕΜ-10F)---39.7 parts by mass

Compound represented by the following structural formula (2) (Daiichi Kogyo Seiyaku Co., Ltd., New Frontier GX870 2θ ··· 35. 7 parts by mass

Compound represented by the following structural formula (3) (Toagosei, Alonix M270) · · · 4. Mass part

Compound represented by the following structural formula (4) (manufactured by Shin-Nakamura Chemical Co., Ltd., ΝΚester 4G)… 26.

Compound represented by the following structural formula (5) (manufactured by Shin-Nakamura Engineering Co., Ltd. 2, 2, one screw (o black mouth file) one, four, four, five, five, one tetraphenyl

Dozole '18.5 parts by mass

Ν—Butyl-chloroataridon ···· 99 parts by mass

Phenoxazine .... 03 parts by mass

Leuco Crystal Violet. 1.10 parts by mass

Victoria Pure Naphthalenesulfonate '· 0.19 parts by mass

Compound represented by the following structural formula (6): 0.37 parts by mass

Methyl ethyl ketone 248.8 parts by mass

Tetrahydrofuran 72.7 parts by mass

1-methoxy 2-propanol '·· 406 parts by mass

*: Including copolymer Α and copolymer Β. The weight average molecular weight of each copolymer,

The results are shown in Table 4 below.

[Chemical 4]

Structural formula (i)

However, in the structural formula (1), m + n represents 10.

[Chemical 5]

Structural formula (2)

However, m + n represents 20 in the structural formula (2).

[Chemical 6]

Structural formula (3) In the structural formula (3), n represents 12. [Chemical 7]

[Examples 10 to 14 and Comparative Examples 6 to 9]

In Example 9, except that the binder copolymer A and copolymer B were changed to the compositions and mass ratios shown in Table 4, in the same manner as in Example 9, the melt viscosity, followability on the substrate, unexposed Film tear, developability, sensitivity, resolution, edge roughness, peeled piece size, and tent properties were evaluated. The results are shown in Tables 6 and 7.

[Example 15]

In Example 9, the copolymer V of the binder having a mass average molecular weight of 20,000 was used in the same manner as in Example 9 except that the copolymer and mass ratio shown in Table 5 were used. , Unexposed film breakage, developability, sensitivity, resolution, edge roughness, peeled piece size, and tent property were evaluated. The results are shown in Tables 6 and 7.

[Example 16 and Example 18]

In Example 9, except that the binder copolymer A and copolymer B were changed to the compositions and mass ratios shown in Table 5, in the same manner as in Example 9, the melt viscosity, followability on the substrate, unexposed Film tear, developability, sensitivity, resolution, edge roughness, peeled piece size, and tent properties were evaluated. The results are shown in Tables 6 and 7.

[Example 17]

In Example 9, the compound represented by the structural formula (3), the compound represented by the structural formula (4), In the same manner as in Example 9, except that 72 parts by mass of the compound represented by the structural formula (2) was used instead of the compound represented by the structural formula (5), Followability, unexposed film breakage, developability, sensitivity, resolution, edge roughness, peeled piece size, and tent property were evaluated. The results are shown in Tables 6 and 7.

[Table 4]

AA: Acrylic acid

St: Styrene

MAA: Methacrylic acid

MMA: Methyl metatalylate

[Table 5]

AA: Acrylic acid

St: Styrene

MAA: Methacrylic acid

MMA: Methyl metatalylate

BzMA: benzylmetatalylate [0229] [Table 6]

[0230] [Table 7]

Sensitivity Resolution Edge roughness Peeling piece size

Developability Ten Μΐ

(mJ / cm) (m) (U m), cm)

Example 9 ○ 10 15 1.3 2 ○ Example 10 ○ 10 15 1.2 2 ○ Example 11 ○ 10 15 1.4 2 ○ Example 12 ○ 10 15 1.3 2 ○ Example 13 ○ 10 15 1.2 2 ○ Example 14 ○ 10 17 1.2 2 ○ Example 15 ○ 10 15 1.1 2 X Example 16 ○ 10 15 1.1 2 ○ Example 17 ○ 10 15 1.3 2 ○ Example 18 ○ 10 15 1.1 2 ○ Comparative Example 6 X 10 30 1.2 5 ○ Comparison Example 7 X 10 20 1.2 5 〇 Comparative Example 8 X 12 25 1.2 5 〇 Comparative Example 9 〇 13 25 1.3 2 X From the results shown in Table 6 and Table 7, the melt viscosity is 50. Examples 9 to 18, which are 40,000 to 120, OOOPa's at C and 5,000-20, OOOPa's at 70 ° C, have good followability on the substrate, and excellent sensitivity and resolution. understood. In particular, the mass ratio of the copolymer A and the copolymer B is AZB = 10Z90 to 40Z60, and the copolymer C is not used in Example 9, Examples 12 to 14, and Examples 16 to 18. It was also found that there was little tearing of the unexposed film. Moreover, it turned out that Examples 9-18 which formed the photosensitive layer from the photosensitive resin composition of this invention are excellent also in the developability which an etching peeling piece is small compared with Comparative Examples 6-9.

Industrial applicability

The photosensitive resin composition of the present invention can form a photosensitive layer that has good resist followability on the substrate and that has both excellent developability and finer strips during etching. Therefore, the photosensitive transfer film having a photosensitive layer formed of the photosensitive resin composition can be suitably used for forming various high-definition patterns, and particularly a highly precise permanent pattern. It can be used suitably for formation of.

Claims

The scope of the claims

[1] It contains a binder, a polymerizable compound, and a photopolymerization initiator, and has a melt viscosity of 50. C is 40,000-120, OOOPa, s, 70. A photosensitive resin composition characterized by having a C of 5,000 to 20, OOOPa, s.

[2] Binder strength Copolymer A having a weight average molecular weight of 3,000 to 10,000, and copolymer B having a weight average molecular weight of 30,000 to 150,000, the copolymer 2. The photosensitive resin composition according to claim 1, wherein the mass ratio of A to the copolymer B is A / B = 10Z90 to 90Z10.

[3] The photosensitive resin composition according to claim 2, wherein the mass ratio of the copolymer Α to the copolymer Β is AZB = 10Z90 to 40Z60.

[4] The photosensitive resin composition according to any one of [2] to [3], wherein the copolymer has a structural unit derived from at least one of styrene and a styrene derivative.

[5] The photosensitive resin composition according to any one of claims 2 to 4, wherein the copolymer B contains a butyl monomer having a carboxyl group.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the polymerizable compound contains a monomer having at least one of a urethane group and an aryl group.

[7] The photopolymerization initiator is a halogenated hydrocarbon derivative, phosphine oxide, hexyl biimidazole, oxime derivative, organic peroxide, thio compound, ketone compound, acyl phosphine oxidoxide compound, 7. The photosensitive resin composition according to claim 1, comprising at least one selected from an aromatic onium salt and a ketoxime ether power.

[8] A photosensitive transfer film comprising a photosensitive layer formed of the photosensitive resin composition according to any one of claims 1 to 7 on a support.

[9] When the photosensitive layer is exposed and developed with a laser beam having a wavelength of 390 to 420 nm, the thickness of the exposed portion of the photosensitive layer must not be changed after the exposure and development! / The photosensitive transfer film according to claim 8, wherein the minimum energy (sensitivity) of light used for light is 0.1 to 20 mjZcm ² .

[10] The method further comprises exposing the photosensitive layer after laminating the photosensitive layer on the substrate to be processed in the photosensitive transfer film according to any one of claims 8 to 9. Pa Turn formation method.

[11] The exposure includes light irradiation means, and n (where n is a natural number of 2 or more) two-dimensionally arranged pixel parts that receive and emit light from the light irradiation means, An exposure head provided with a light modulation means capable of controlling the picture element portion in accordance with pattern information, wherein the column direction of the picture element portion forms a predetermined set inclination angle Θ with respect to the scanning direction of the exposure head. Using the exposure head

With respect to the exposure head, the used pixel part specifying means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) out of the usable pixel parts, and the exposure head The pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in exposure, and 11. The pattern forming method according to claim 10, wherein the exposure head is relatively moved in the scanning direction.

[12] The exposure is performed by a plurality of exposure heads, and the used pixel portion specifying means is involved in the exposure of the inter-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. 12. The pattern forming method according to claim 11, wherein among the picture element parts, the picture element part used for realizing N double exposure in the inter-head connecting region is designated.

[13] The exposure is performed by a plurality of exposure heads, and the used picture element designation means is involved in exposure other than the inter-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. 13. The pattern forming method according to claim 12, wherein, in the picture element part, the picture element part used for realizing N double exposure in an area other than the inter-head connection area is designated.

[14] Set tilt angle Θ force N N number of double exposures, number s of pixel portions in the row direction, interval p of the pixel portions in the row direction, and the exposure head in a tilted state! For the pitch δ in the column direction of the pixel portion along the direction orthogonal to the scanning direction of the exposure head, the following equation is given: spsin θ ≥Ν δ

Claims 11 to 13 are set so as to satisfy the relationship of 0 for 0 satisfying ideal

iaeal meal

No !, the pattern forming method described in any one of the above.

[15] Use pixel part designation means

Light spot as a pixel unit generated by the pixel unit and constituting the exposure area on the exposed surface A light spot position detecting means for detecting the position on the surface to be exposed, and a picture element selecting means for selecting a picture element part to be used for realizing the N double exposure based on a detection result by the light spot position detecting means. When

The pattern forming method according to claim 11, further comprising:

16. The pattern forming method according to claim 10, wherein the photosensitive layer is developed after the exposure.