JP2007264483A - Pattern forming material and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming material having high resolution, excellent sensitivity and development latitude, and capable of forming a high-definition pattern, since even in the case of a thin-film photosensitive layer, both of excellent uniformity of thickness and adhesion to a substrate can be satisfied, and to provide a pattern forming method using the pattern forming material. <P>SOLUTION: The pattern forming material has at least a support and a photosensitive layer on the support, wherein the photosensitive layer contains at least a binder, a polymerizable compound, a photopolymerization initiator and a fluorochemical surfactant. The binder is a ring-opening addition reaction product of a copolymer containing a carboxyl group within a molecule and a saturated epoxy compound having one epoxy group per molecule, and has a glass transition temperature (Tg) of 300-400 K and a mass average molecular weight of 1,000-10,000. The photosensitive layer has a thickness of 3-10 μm. The pattern forming method using the pattern forming material is also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a pattern forming material suitable for a dry film resist (DFR) or the like in a printed wiring board field including a package substrate, and a pattern forming method using the pattern forming material.

  In the trend of high integration of semiconductors such as IC chips and LSI chips, package substrates are used to mount them on substrates. Until now, package substrates have mainly been manufactured by subtractive and semi-additive processes using liquid resist or dry film resist (DFR), and at most L / S (line / space) = 20 μm / 20 μm resolution. Was the limit.

With the progress of high integration of LSI, a resolution of L / S = 5 μm / 5 μm is currently required. In general, the resolution mainly depends on the thickness of the photosensitive layer, and the limit of practical pattern resolution is equivalent to the thickness. The pattern thickness d after pattern formation and the line width L of the pattern The aspect ratio of d / L = 1 μm / 1 μm is the limit. In addition, a pattern height of 5 μm is necessary in view of the necessity of conductivity of the formed pattern. Therefore, in order to realize L / S = 5 μm / 5 μm, the thickness of the photosensitive layer needs to be around 5 μm.
However, in the conventional liquid resist, the thickness of the photosensitive layer to be formed is effective up to about 0.5 to 3 μm, and in the conventional DFR, the thickness of the photosensitive layer is effective up to about 10 to 50 μm.
The limitation of the thickness of the photosensitive layer in the case of the liquid resist is because there are problems of pattern reproducibility and coating film flatness at a thickness of about 5 μm. In order to solve this problem, a method of applying and drying positive quinonediazide added with water or OH group-containing microcapsules (see Patent Document 1), a thick film resist (thickness 7 μm) applied on a substrate is a rotating roll And a method of forming a photosensitive layer having a thickness of 7 μm by applying and drying a negative photopolymerizable composition using a bar coater (see Patent Document 3), etc. However, even if these methods are used, the above-mentioned problems have not been solved.

On the other hand, the limitation on the thickness of the photosensitive layer in the case of a pattern forming material such as DFR is because there is a problem in substrate adhesion in the lamination process. For example, in Comparative Example 1 of Patent Document 3, it is shown that when a pattern forming material having a photosensitive layer having a thickness of 7 μm is used, line missing or disconnection occurs.
Up to now, various attempts have been made to increase the resolution of the pattern forming material. For example, it is known that a low molecular weight binder is effective for obtaining a high resolution photosensitive layer (see Patent Document 4). However, when a low molecular weight binder is used, development time is shortened and development tolerance is narrow. There was a problem of becoming. For this reason, stable production of high resolution patterns has been difficult. In addition, it is also known to use a binder having a low glass transition temperature (see Patent Document 5). However, when a binder having a low glass transition temperature is used, the adhesion between the layers in contact with the photosensitive layer is increased, so that it is peeled off when it should be peeled off. It becomes difficult. For example, in the case of a pattern forming material of a type in which a photosensitive layer is formed on a support, it is necessary to laminate the pattern forming material on a substrate and expose it, and then peel the support from the photosensitive layer. If the adhesiveness between the photosensitive layers is too high, a sound is generated when the support is peeled off, and a small part of the photosensitive layer may be transferred to the support, resulting in pattern defects.

Further, as a technique for improving the adhesion of a thin film photosensitive layer to a substrate, a pattern forming material in which a cushion layer (alkali insoluble thermoplastic resin layer) is provided between the photosensitive layer and a support has been proposed (Patent Document 6). reference). The presence of the cushion layer improves the followability of the photosensitive layer to the already formed pattern and substrate, and the photosensitive layer can be laminated without generating bubbles. After the lamination, the photosensitive layer is directly exposed after the cushion layer is peeled off, so that there is a problem that the sensitivity is lowered due to the influence of oxygen in the air.
A pattern forming material is also proposed in which an alkali-soluble thermoplastic resin layer (cushion layer) and an intermediate layer having low oxygen permeability are formed in this order on a support, and a photosensitive layer is provided on the intermediate layer ( (See Patent Document 7). Since the photosensitive layer is exposed through the intermediate layer, the effect of the intermediate layer can suppress a decrease in sensitivity. However, the thickness is thick, and the sensitivity, resolution, and adhesion are still insufficient. It was.

  Further, in order to achieve both thickness uniformity of the photosensitive layer and adhesion to the substrate, it has been proposed that the photosensitive layer contains a fluorosurfactant (see Patent Document 8). However, even in the patent literature, the thickness is large and the resolution is insufficient.

  Therefore, even thin film photosensitive layers currently required in the field of package substrate manufacturing can achieve both excellent thickness uniformity and adhesion to the substrate, and are excellent in resolution, sensitivity, and development tolerance. There is still no suitable pattern forming material capable of forming a fine pattern and a pattern forming method using the pattern forming material, and further improvement and development are desired.

JP-A-3-220557 JP-A-7-161721 JP 2003-140335 A JP 2004-341477 A JP 7-281437 A JP 2003-5364 A JP-A-5-173320 JP 2005-258229 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, since the present invention can achieve both excellent thickness uniformity and adhesion to a substrate even in a thin film photosensitive layer, it has high resolution and is excellent in sensitivity and development tolerance. An object is to provide a pattern forming material capable of forming a high-definition pattern and a pattern forming method using the pattern forming material.

Means for solving the problems are as follows.
<1> It comprises at least a support and a photosensitive layer on the support,
The photosensitive layer contains at least a binder, a polymerizable compound, a photopolymerization initiator, and a fluorosurfactant;
The binder is a ring-opening addition reaction product of a copolymer containing a carboxyl group in the molecule and a saturated epoxy compound having one epoxy group in one molecule, and a glass transition temperature (Tg) of 300 to 400K. And the weight average molecular weight is 1,000 to 10,000,
The photosensitive layer has a thickness of 3 to 10 μm.
<2> The pattern forming material according to <1>, wherein the photosensitive layer has a thickness of 5 to 10 μm.
<3> The copolymer containing a carboxyl group in the molecule is a copolymer having a structural unit derived from styrenes and a dibasic unsaturated carboxylic acid compound, and is represented by the following general formula (I) The pattern forming material according to any one of <1> to <2>.
In the general formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted by halogen atom substitution, and an alkoxy group having 1 to 4 carbon atoms. R ³ represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴ represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, a bicycloalkyl group having 6 to 11 carbon atoms, a tricycloalkyl group having 6 to 11 carbon atoms, or 7 carbon atoms. Represents an aralkyl group having ˜11, an aryl group having 6 to 10 carbon atoms, or a (meth) acryloyloxyalkyl group. m represents an integer of 1 to 5.
X and y represent the composition ratio (molar ratio) of the repeating units, x + y = 100, and x: y = 10 to 90:10 to 90.
<4> The pattern forming material according to <3>, wherein the binder is represented by the following general formula (II).
However, in said general formula (II), R < ¹ > represents either a hydrogen atom or a methyl group. R ² represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted by halogen atom substitution, and an alkoxy group having 1 to 4 carbon atoms. R ³ may be the same as or different from each other, and represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴ may be the same as or different from each other, and represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ^{5 s} may be the same as or different from each other, and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, a bicycloalkyl group having 6 to 11 carbon atoms, It represents any of a tricycloalkyl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a (meth) acryloyloxyalkyl group. R ⁶ represents a residue after addition reaction between the epoxy group in the saturated epoxy compound and the carboxyl group in the dibasic unsaturated carboxylic acid compound. m represents an integer of 1 to 5.
Moreover, x, y, and z represent the composition ratio (molar ratio) of a repeating unit, are x + y + z = 100, and are x: y: z = 10-80: 10-80: 10-80.
<5> at least one of a structural unit derived from a monomer represented by the following structural formula (1) and a structural unit derived from a monomer represented by the following structural formula (2), The pattern forming material according to any one of <1> to <4>, which is a copolymer having a structural unit derived from an ethylenically unsaturated monomer having an alkylene group.
However, in the structural formulas (1) and (2), R ¹ and R ² may be the same as or different from each other, and represent either a hydrogen atom or a methyl group. X ¹ and X ² may be the same as or different from each other, and represent either an oxygen atom or NR ⁴ . The R ⁴ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 7 to 7 carbon atoms. Represents one of 24 aralkyl groups. Z ¹ and Z ² may be the same as or different from each other, and represent a substituent having at least one of an oxygen atom, a nitrogen atom and a sulfur atom. R ³ represents either a hydrogen atom or a fluorine atom. l, n, p, and r represent any integer of 0-10. m and q represent any integer of 0 and 1. o, s, and t represent any integer of 1-10.
<6> The pattern forming material according to any one of <1> to <5>, wherein a cushion layer is provided between the support and the photosensitive layer.
<7> The pattern forming material according to <6>, wherein the cushion layer has a thickness of 5 to 20 μm.
<8> The pattern forming material according to any one of <6> to <7>, wherein the cushion layer is either alkali-soluble or alkali-insoluble.
<9> The pattern forming material according to any one of <6> to <8>, further including an intermediate layer capable of suppressing movement of a substance between the cushion layer and the photosensitive layer.
<10> The pattern forming material according to <9>, wherein the intermediate layer has an oxygen barrier property.
<11> The pattern forming material according to any one of <9> to <10>, wherein the intermediate layer has a thickness of 1 to 3 μm.
<12> The pattern forming material according to any one of <9> to <11>, wherein the intermediate layer is alkali-soluble.
<13> The pattern forming material according to <1> to <12>, wherein the support has a center line average surface roughness of 1 to 15 nm.
<14> The photosensitive layer has a protective film on a surface opposite to the support, and the centerline average surface roughness of the protective film is 100 nm or less on the surface in contact with the photosensitive layer, and is in contact with the photosensitive layer. The pattern forming material according to <1> to <13>, which has a thickness of 100 to 800 nm on the surface not to be used.
<15> A photosensitive resin composition solution in which the composition contained in the photosensitive layer is dissolved, emulsified, or dispersed and has a solid content concentration of 5 to 20% by mass with a filter having a diameter of 1 μm or less. The pattern forming material according to <1> to <14>, which is formed by filtering, coating, and drying.
<16> The photosensitive layer according to any one of <1> to <15>, wherein the photosensitive layer is formed by applying the photosensitive resin composition solution with a coating machine including an extrusion type coating head and drying. It is a pattern forming material.

<17> The photosensitive layer in the pattern forming material according to any one of <1> to <16> is laminated on the substrate so that the photosensitive layer and the substrate are in contact with each other by at least one of heating and pressurization. Laminating process to
An exposure step of exposing the photosensitive layer laminated by the laminating step with light irradiated from a light irradiation means;
And a developing step of developing the photosensitive layer exposed in the exposure step.
<18> The pattern forming method according to <17>, wherein the pattern is a wiring pattern, and the wiring pattern is formed by a semi-additive method.
<19> The pattern forming method according to any one of <17> to <18>, wherein the stacking is performed by any one of a hot roll laminator and a vacuum laminator.
<20> It has an alkali-soluble cushion layer between the support and the photosensitive layer, and after the laminating step, it has a peeling step for peeling the support and the cushion layer from the photosensitive layer. It is the pattern formation method in any one of said <17> to <19> which has an exposure process to expose.
<21> The pattern forming method according to any one of <17> to <20>, wherein the exposure is performed using a blue-violet laser beam having a wavelength of 400 to 410 nm.
<22> 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 an exposure head arranged as follows:
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
The pattern forming method according to any one of <17> to <21>, wherein the exposure head is moved relative to the photosensitive layer in a scanning direction. In the pattern forming method according to <22>, the exposure head is subjected to N-exposure (where N is a natural number of 2 or more) among the usable pixel parts by the used pixel part specifying unit. The pixel part to be used is specified, and the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in exposure. By performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction, the exposure head is formed on the exposed surface of the photosensitive layer due to a shift in the mounting position or mounting angle of the exposure head. Variations in the resolution of the pattern and unevenness in density are leveled. As a result, the photosensitive layer is exposed with high definition. For example, a high-definition pattern is formed by developing the photosensitive layer thereafter.
<23> The exposure is performed by a plurality of exposure heads, and the used drawing element specifying means is related to the exposure of the joint area between the heads which is the overlapping exposure area on the exposed surface formed by the plurality of exposure heads. The pattern forming method according to <22>, wherein, among the element parts, the image element part used for realizing N double exposure in the inter-head connection region is designated. In the pattern forming method according to <23>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designation unit is an overlapped exposure region on the 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 picture element part used for realizing the N-fold exposure in the head-to-head connection area is designated, so that the mounting position and attachment of the exposure head are specified. Variations in resolution and density unevenness of the pattern formed in the connecting area between the heads on the exposed surface of the photosensitive layer due to the angle shift 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.
<24> The exposure is performed by a plurality of exposure heads, and the used picture element specifying means is involved in exposure other than the inter-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The pattern forming method according to <22>, wherein the image element portion used for realizing N double exposure in an area other than the inter-head connection area in the image element area is designated. In the pattern forming method according to <24>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designation unit is an overlapped exposure region on the exposed surface formed by the plurality of exposure heads. Of the picture element parts involved in the exposure other than the inter-head connection area, the attachment position of the exposure head is specified by designating the picture element part used for realizing the N-fold exposure in the areas other than the inter-head connection area. Variations in the resolution and density unevenness of the pattern formed in areas other than the head-to-head connection area on the exposed surface of the photosensitive layer due to the mounting angle deviation are equalized. 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.
<25> When the set inclination angle θ is N, the number N of the multiple exposures, the number s of the pixel portions in the column direction, the interval p in the column direction of the pixel portions, and the exposure head tilted. the relative row direction pitch δ of pixel parts in the direction perpendicular to the scanning direction, the following equation with respect to theta _ideal satisfying spsinθ _ideal ≧ Nδ, which is set so as to satisfy the relation of θ ≧ θ _ideal <22> to <24>.
<26> The pattern forming method according to any one of <22> to <25>, wherein N in N-exposure is a natural number of 3 or more. In the pattern forming method according to <26>, multiple drawing is performed when N in N double exposure is a natural number of 3 or more. As a result, due to the effect of filling, variations in the resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to a shift in the mounting position and mounting angle of the exposure head are more precisely leveled.

<27> 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;
<22> to <26>, further comprising: a pixel part selection unit that selects a pixel part to be used for realizing the N-fold exposure based on a detection result by the light spot position detection unit. This is a pattern forming method.
<28> The pattern forming method according to any one of <22> to <27>, wherein the used pixel part specifying unit specifies a used pixel part to be used for realizing N double exposure in units of rows. is there.

<29> The fact that the light spot position detector detects the column direction of the light spot on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted based on the detected at least two light spot positions. The inclination angle θ ′ is specified, and the picture element selection means selects the use picture element part so as to absorb the error between the actual inclination angle θ ′ and the set inclination angle θ. The pattern forming method according to any one of the above.
<30> The average inclination angle θ ′ is an average value, a median value, and a plurality of actual inclination angles formed by the row direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is inclined. The pattern forming method according to <29>, wherein the pattern forming method is one of a maximum value and a minimum value.
<31> The pixel part selection means derives a natural number T close to t that satisfies the relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <29> to <30>, wherein the pixel elements from the first line to the T-th line in the image elements arranged in a row (where m represents a natural number of 2 or more) are selected as used pixel elements. The pattern forming method according to any one of the above.
<32> The pixel part selection means derives a natural number T close to t that satisfies the relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m In the picture element part arranged in a row (where m represents a natural number of 2 or more), the picture element part in the (T + 1) -th line to the m-th line is specified as an unused picture element part, and the unused picture element part is specified. The pattern forming method according to any one of <29> to <30>, wherein the picture element part excluding the element part is selected as a use picture element part.

<33> In a region including at least an overlapped exposure region on an exposed surface formed by a plurality of pixel part rows, the pixel part selection unit,
(1) Means for selecting a used pixel portion so that a total area of an overexposed region and an underexposed region is minimized with respect to an ideal N-fold exposure;
(2) Means for selecting a pixel part to be used so that the number of pixel units in an overexposed area and the number of pixel units in an underexposed area are equal to each other with respect to an ideal N double exposure;
(3) Means for selecting a pixel part to be used so that the area of an overexposed area is minimized and an underexposed area does not occur with respect to an ideal N double exposure, and (4) Ideal From the above <27>, which is one of means for selecting a pixel part to be used so that the area of an underexposed area is minimized and an overexposed area does not occur with respect to typical N double exposure It is the pattern formation method as described in <32>.
<34> In the connection region between the heads, which is an overlapped exposure region on the exposed surface formed by the plurality of exposure heads,
(1) With respect to the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connection region, the total area of the overexposed region and the underexposed region is minimized. Means for identifying a used pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
(2) Involvement in the exposure of the head-to-head connecting region so that the number of pixel units in the overexposed region and the number of pixel units in the underexposed region are equal to the ideal N-double exposure. Means for identifying an unused pixel part from the pixel part to be selected, and selecting the pixel part excluding the unused pixel part as a used pixel part;
(3) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the overexposed region is minimized and the underexposed region is not generated. A means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part; and
(4) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the underexposed region is minimized and the region that is overexposed is not generated. , Means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
The pattern forming method according to any one of <27> to <33>.
<35> The pattern forming method according to <34>, wherein the unused pixel parts are specified in units of rows.

<36> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, N (n-1) pixel part columns for N multiple exposures The pattern forming method according to any one of <22> to <35>, in which the reference exposure is performed using only the image element portion that constitutes. In the pattern forming method according to <36>, in order to specify the used pixel part in the used pixel part specifying unit, among the usable pixel parts, N of N double exposures (N -1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.
<37> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, for each N of N exposures, a pixel part line is formed for each 1 / N line. The pattern forming method according to any one of <22> to <36>, wherein the reference exposure is performed using only the picture element portion. In the pattern forming method according to <37>, in order to designate a used pixel part in the used pixel part designating unit, among the usable picture element parts, 1 / Reference exposure is performed using only the pixel part constituting the pixel part column for every N rows, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<38> From the above <22> to <37>, the used pixel part specifying means includes a slit and a photodetector as light spot position detecting means, and an arithmetic unit connected to the photodetector as a pixel part selecting means. The pattern forming method according to any one of the above.
<39> The pattern forming method according to any one of <22> to <38>, wherein N in N-fold exposure is a natural number of 3 or more and 7 or less.

<40> The light modulation means further includes pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation means is emitted from the light irradiation means. The pattern forming method according to any one of <22> to <39>, wherein modulation is performed according to the method.
<41> From the above <22> to <22> having conversion means for converting the pattern information 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 designated used pixel part 40> The pattern forming method according to any one of the above.

<42> The pattern forming method according to any one of <22> to <41>, wherein the light modulation unit is a spatial light modulation element.
<43> The pattern forming method according to <42>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<44> The pattern forming method according to any one of <22> to <43>, wherein the pixel part is a micromirror.

<45> The pattern forming method according to any one of <22> to <44>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the pattern forming method according to <45>, 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, after that, the photosensitive layer is developed to form an extremely fine pattern.
<46> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects and couples the laser beams irradiated from the plurality of lasers to the multimode optical fiber. The pattern forming method according to any one of <22> to <45>. In the pattern forming method according to <46>, laser beams emitted from the plurality of lasers are condensed by the collective optical system by the light irradiation unit and can be coupled to the multimode optical fiber. Thus, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, after that, the photosensitive layer is developed to form an extremely fine pattern.

  <47> A pattern formed by the pattern forming method according to any one of <17> to <46>.

  According to the present invention, the conventional problems can be solved, and even a thin photosensitive layer can achieve both excellent thickness uniformity and adhesion to a substrate, so that it has high resolution, and It is possible to provide a pattern forming material excellent in sensitivity and development tolerance and capable of forming a high-definition pattern, and a pattern forming method using the pattern forming material.

(Pattern forming material)
The pattern forming material of the present invention comprises a support and a photosensitive layer on the support. If necessary, a cushion layer, an intermediate layer, etc. are provided between the support and the photosensitive layer. It may also have other layers as necessary.
In the pattern forming material, the photosensitive layer needs to have a thickness of 3 to 10 μm, and more preferably 5 to 10 μm. If the thickness is less than 3 μm, the thickness of the resulting plating resist pattern is insufficient, so that the conductivity of the conductor by plating may not be satisfied, and if it exceeds 10 μm, the required resolution may not be obtained. .

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

  There is no restriction | limiting in particular as thickness of the said support body, According to the objective, it can select suitably, For example, 10-30 micrometers is preferable and 12-25 micrometers is more preferable. If the thickness is less than 10 μm, the film is too flexible and inconvenient to handle, and if it exceeds 30 μm, the resolution may be lowered, and the cost is high, which is not preferable.

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

The support preferably has a center line average surface roughness (Ra) of 1 to 15 nm, more preferably 2 to 10 nm. When the center line average surface roughness (Ra) is less than 1 nm, the film surface is likely to be scratched during film formation, and when it exceeds 15 nm, the resist pattern may be jagged, It may cause chipping or disconnection.
Here, the above-mentioned “centerline average surface roughness (Ra)” means that the portion of the measurement length L is extracted from the roughness curve in the direction of the centerline, and the centerline of this extracted portion is defined as the X axis and the vertical magnification. When the direction is represented by the Y-axis and the roughness curve is represented by Y = f (X), the value obtained by the following formula is represented by nanometers (nm).

  As the support having a center line average surface roughness (Ra) in the range of 1 to 15 nm, a commercially available product may be used. For example, T60 type manufactured by Toray Industries, O type manufactured by Teijin Ltd., M62 type, X71 type, etc. A film obtained by subjecting the film to an easy slip treatment is used. The slippery treatment is performed by coating the film surface with a resin such as polyester, acrylic, urethane, silicone, or fluorine.

  The support that has been subjected to the slippery treatment preferably has a coefficient of static friction (μs) between the slippery treated surfaces of 1.0 or less and a coefficient of dynamic friction (μd) of 0.8 or less. Prominently demonstrated. When the static friction coefficient (μs) exceeds 1.0 and the dynamic friction coefficient (μd) exceeds 0.8, it is not preferable because the film surface is easily damaged during film forming. Here, the static friction coefficient (μs) and the dynamic friction coefficient (μd) can be measured based on JISK7125.

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

<Photosensitive layer>
The photosensitive layer contains at least a binder, a polymerizable compound, a photopolymerization initiator, and a fluorosurfactant, and contains other components appropriately selected as necessary.

<< Binder >>
The binder is a ring-opening addition reaction product of a copolymer containing a carboxyl group in the molecule (hereinafter referred to as a carboxyl group-containing copolymer) and a saturated epoxy compound having one epoxy group in one molecule. It is characterized by that.
The glass transition temperature (Tg) of the binder needs to be 300 to 400K, and among these, 320 to 380K is more preferable. When the Tg is less than 300K, when the pattern forming material is a roll-shaped roll, the photosensitive layer oozes out from the end face and is fused to each other (hereinafter referred to as end face fusion), or in the form of a resist powder during use. On the other hand, if it exceeds 400K, the film quality of the photosensitive layer itself becomes stiff, and resist powder may be generated during slit processing and handling.
The glass transition temperature (Tg) can be measured according to ASTM D3418-82. Specifically, after heating the sample from room temperature to 150 ° C. at a rate of temperature increase of 20 ° C./min using an internal heat input compensation type differential scanning calorimeter (DSC-7 manufactured by PerkinElmer), The sample was allowed to stand at 150 ° C. for 10 minutes, cooled to 0 ° C. at a cooling rate of 50 ° C./min, left for 10 minutes, and again heated to 150 ° C. at a heating rate of 20 ° C./min in a nitrogen atmosphere (20 cc / min). It can be determined by measuring and reading the peak rise temperature using analysis software [Tg job].

The mass average molecular weight of the bidder needs to be 1,000 to 10,000, and among these, 2,000 to 8,000 is more preferable. When the mass average molecular weight is less than 1,000, tackiness cannot be sufficiently suppressed, end surface fusion is likely to occur, storage stability is inferior, and the coating film after exposure is poor in moisture resistance during development. There may be a problem that the film is reduced and the resolution is greatly deteriorated. On the other hand, if it exceeds 10,000, problems such as poor embedding at the time of lamination may occur.
The mass average molecular weight can be measured by GPC (gel permeation chromatography). Specifically, the reaction product was sampled in advance, and the solution dissolved in tetrahydrofuran was separated using a column having a structure in which A-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko were connected, It can be determined by measuring the molecular weight distribution using a standard polystyrene resin calibration curve.

-Carboxyl group-containing copolymer-
The carboxyl group-containing copolymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, styrenes and dibasic unsaturated carboxylic acids represented by the following general formula (I) Preferred examples include a copolymer having a structural unit derived from a compound.

In the general formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted by halogen atom substitution, and an alkoxy group having 1 to 4 carbon atoms. R ³ represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴ represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, a bicycloalkyl group having 6 to 11 carbon atoms, a tricycloalkyl group having 6 to 11 carbon atoms, or 7 carbon atoms. Represents an aralkyl group having ˜11, an aryl group having 6 to 10 carbon atoms, or a (meth) acryloyloxyalkyl group. m represents an integer of 1 to 5.
Moreover, x and y represent the composition ratio (molar ratio) of the repeating unit, x + y = 100, and x: y = 10-90: 10-90.

--Styrenes--
There is no restriction | limiting in particular as said styrenes which give the structural unit of the said carboxyl group-containing copolymer, According to the objective, it can select suitably, For example, styrene, o-methylstyrene, m-methylstyrene, p- Methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o- Examples include chloromethyl styrene, m-chloromethyl styrene, p-chloromethyl styrene, m-trichloromethyl styrene, α-methyl styrene, and the like. Among these, styrene is more preferable.

--Dibasic unsaturated carboxylic acid compound--
The dibasic unsaturated carboxylic acid compound that gives the structural unit of the carboxyl group-containing copolymer is not particularly limited as long as it is a compound containing at least one unsaturated group in one molecule. Dibasic unsaturated carboxylic acid and dibasic unsaturated carboxylic acid monoester are preferred.
Specific examples of the dibasic unsaturated carboxylic acid or dibasic unsaturated carboxylic acid monoester include maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoesters, itaconic acid, itaconic acid monoester Glutaconic acid, glutaconic acid monoester, citraconic acid, citraconic acid monoester, mesaconic acid, mesaconic acid monoesters, and the like. Examples of the monoester include alkyl esters having 1 to 12 carbon atoms, aryl esters having 6 to 10 carbon atoms, aralkyl esters having 7 to 11 carbon atoms, and (meth) acryloyloxyalkyl esters.
Among these, maleic acid monomethyl ester is more preferable, and maleic acid mono-2- (meth) acryloyloxyethyl ester is particularly preferable.

  As the binder of the present invention, among the ring-opening addition reaction products of the carboxyl group-containing copolymer represented by the general formula (I) and a saturated epoxy compound having one epoxy group in one molecule, A copolymer represented by the general formula (II) is preferred.

However, in said general formula (II), R < ¹ >, R < ² >, R < ³ >, R < ⁴ > and R < ⁵ > represent the same group as the thing in the said general formula (I). R ⁶ represents a residue after addition reaction between the epoxy group in the saturated epoxy compound and the carboxyl group in the carboxyl group-containing copolymer represented by the general formula (I). m represents an integer of 1 to 5.
Moreover, x, y, z represents the composition ratio (molar ratio) of a repeating unit, it is x + y + z = 100, and is x: y: z = 10-80: 10-80: 10-80.

-Saturated epoxy compound-
The saturated epoxy compound is not particularly limited as long as it is a compound having one epoxy group in one molecule, and examples thereof include compounds represented by the following general formulas (III-1) to (III-19). Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
However, the general formula (III-1) ~ (III -19) , ^{R 1 to} represent hydrogen atom, an alkyl having 1 to 10 carbon atoms, aryl, and any of the aralkyl group, ^{R 2} has a carbon number 1 to 10 represents an alkylene group, R ³ represents a hydrocarbon group having 1 to 10 carbon atoms, and p represents an integer of 0 to 10.
The said saturated epoxy compound may be used individually by 1 type, and may use 2 or more types together. Among these, phenyl glycidyl ether, glycidyl acetate, and 3,4-epoxycyclohexylmethyl acetate are more preferable.

-Binder synthesis method-
The binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the binder can be obtained by further subjecting the saturated epoxy compound to a ring-opening addition reaction after synthesis of the carboxyl group-containing copolymer. .

--Synthesis of carboxyl group-containing copolymer--
The method for synthesizing the carboxyl group-containing copolymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a copolymer of the styrene and the dibasic unsaturated carboxylic acid compound Can be obtained by copolymerization reaction of the styrenes and the dibasic unsaturated carboxylic acid compound, or water or alcohol for the copolymer of the corresponding styrenes and dibasic unsaturated carboxylic acid anhydride. It can also be obtained by an addition reaction.

  There is no restriction | limiting in particular as a polymerization method with styrenes mentioned above and this dibasic unsaturated carboxylic acid compound, Usually used copolymerization reaction methods, such as a block polymerization method and a solution polymerization method, can be used. Among these, the solution polymerization method can easily convert a low molecular weight polymer or a copolymer under mild conditions by utilizing a difference in radical chain transfer caused by a solvent, or by adjusting a polymerization initiator amount and a reaction temperature. Since it can obtain, it is more preferable. The bulk polymerization method is possible by polymerizing at a high temperature to increase the termination reaction rate, but has a problem that the reaction is difficult to control.

The reaction solvent used in the solution polymerization method is not particularly limited and may be appropriately selected depending on the polymer that is a polymerization reaction product. For example, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol, benzene, and the like are preferable. . Among these, when styrene is used as a monomer, any of xylene, toluene, and cumene is more preferable. In this solution polymerization method, it is preferable to carry out by 30 mass parts-400 mass parts of vinyl monomers with respect to 100 mass parts of solvents.
In the solution polymerization method, as a polymerization initiator, di-tert-butyl peroxide, tert-butyl peroxybenzoate, benzoyl peroxide, 2,2′-azobisisobutyronitrile, and 2,2 ′ It is preferable to use at least one of azobis (2,4-dimethylvaleronitrile) at a concentration of 0.05 parts by mass or more (preferably 0.1 to 15 parts by mass) with respect to 100 parts by mass of the vinyl monomer.
The reaction temperature in the solution polymerization varies depending on the solvent to be used, the initiator, and the polymer to be obtained, but is preferably 70 to 230 ° C.
In the solution polymerization method, it is also preferable to mix other polymers in the solution at the end of the polymerization, and a plurality of polymers may be mixed.

On the other hand, as described above, the hinder of the present invention can also be obtained by addition reaction of water or alcohols to the copolymer of the corresponding styrenes and dibasic unsaturated carboxylic acid anhydride.
Examples of alcohols suitable for the addition reaction include saturated alcohols.
Specific examples of the saturated alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, heptanol, octanol, dodecanol, and cyclohexanol. 2-methylcyclohexanol, benzyl alcohol, dicyclopentanyl alcohol, 2-dicyclopentanyloxyethanol, isobornyl alcohol, adamantyl alcohol, and the like.
The ring-opening addition reaction may use phenols, and preferred phenols include phenol, p-cresol, and α-naphthol.

  The reaction temperature in the addition reaction can be usually 50 to 200 ° C., but 80 to 150 ° C. is more preferable in order to prevent formation of diester and gelation.

Specifically, as the addition reaction method, first, a styrene-dibasic unsaturated carboxylic acid anhydride copolymer is used, such as a glycol monoether ester system such as propylene glycol monomethyl ether acetate or ethylene glycol monobutyl ether acetate. Dissolve in a suitable hydrophilic solvent. Next, the water or alcohol is reacted at the above reaction temperature for about 4 to 40 hours. The progress of the reaction and the completion of the reaction can be determined by tracing the decrease in the acid anhydride absorption by the infrared absorption spectrum and disappearing it. On the other hand, when the alcohol is used in excess of the styrene-dibasic unsaturated carboxylic acid anhydride copolymer, the alcohol can also serve as a solvent, so that it can be reacted directly without a solvent.
As reaction accelerators, tertiary amines such as triethylamine, triethanolamine, morpholine, pentamethyldiethylenetriamine, or quaternary ammonium salts can be used. In order to prevent the formation of a polymer during the reaction, known polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylhydroquinone, tert-butylcatechol, benzoquinone, phenothiazine, etc. can also be used. .

  The styrene-dibasic unsaturated carboxylic acid anhydride copolymer is obtained by radical copolymerization of styrenes and dibasic unsaturated carboxylic acid anhydride in an organic solvent not containing active hydrogen. However, commercially available acid anhydride copolymers thereof can be used. For example, SMA1000 (styrene: maleic anhydride (molar ratio) = 50: 50 is used as the styrene-maleic anhydride copolymer. , Tg = 428K, mass average molecular weight = 5,000, SMA2000 (styrene: maleic anhydride (molar ratio) = 67: 33, Tg = 408K, mass average molecular weight = 7,500), SMA3000 (styrene: maleic anhydride) (Molar ratio) = 75: 25, Tg = 398K, mass average molecular weight = 9,500) and the like are available from Satomer.

  The copolymer composition ratio between the styrenes and the dibasic unsaturated carboxylic acid compound is preferably 10 to 90:90 to 10, more preferably 20 to 80:80 to 20, and 40 to 70:60 in terms of molar ratio. ~ 30 is particularly preferred. If the amount of the styrene compounded is too small and the copolymer composition ratio deviates from 10:90, the development time of the photosensitive layer containing the resulting binder may be too short. If the amount is too large and the copolymer composition ratio is out of 90:10, the developability of the photosensitive layer containing the resulting binder may be inferior.

  Among the copolymers of styrenes and dibasic unsaturated carboxylic acid compounds, a particularly preferred specific example is a styrene-maleic acid monomethyl ester copolymer (styrene: maleic acid monomethyl ester (molar ratio) = 50: 50, Tg = 393K, mass average molecular weight = 5,900), styrene-maleic acid monomethyl ester copolymer (styrene: maleic acid monomethyl ester (molar ratio) = 67: 33, Tg = 388 K, mass average molecular weight = 6, 400).

--Reaction between carboxyl group-containing binder and epoxy compound--
The binder can be obtained by synthesizing the carboxyl group-containing copolymer and further subjecting the saturated epoxy compound to a ring-opening addition reaction.
In the ring-opening addition reaction between the carboxyl group-containing binder and the epoxy compound, a reaction solvent is usually used. The reaction solvent used for the ring-opening addition reaction between the carboxyl group-containing copolymer and the saturated epoxy compound is not particularly limited as long as it dissolves the monomer and the polymer. For example, fragrance such as benzene, toluene, xylene, etc. Group hydrocarbons; alcohols such as methanol, ethanol and 2-propanol; glycols such as ethylene glycol and propylene glycol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; diethyl ether, dibutyl ether, dioxane and methyl propylene glycol , Ethers such as methyl dipropylene glycol; ethyl acetate, isobutyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoalkyl acetate, dipropylene glycol Over monoalkyl acetates, esters such as methyl glycol acetate; propylene glycol monomethyl ether acetate, dimethylformamide, amides such as dimethylacetamide; carbon tetrachloride, halogenated hydrocarbons such as chloroform, etc. can be used. Among these, those having a boiling point higher than the reaction temperature and dissolving the raw materials and products are more preferable. These reaction solvents may be used alone or in combination of two or more.
The concentration of the copolymer resin in the reaction solvent is preferably 20 to 60% by mass. When the resin concentration is less than 20% by mass, a sufficient reaction rate may not be obtained, and when it exceeds 60% by mass, a gelled product may be generated during the reaction.

  The reaction temperature in the ring-opening addition reaction of the copolymer of the styrenes and the dibasic unsaturated carboxylic acid compound with the saturated epoxy compound is preferably 60 to 130 ° C, more preferably 90 to 120 ° C. When the reaction temperature is less than 60 ° C., a practically sufficient reaction rate may not be obtained. When the reaction temperature exceeds 130 ° C., the double bond portion may be cross-linked by radical polymerization due to heat, and a gelled product may be generated. is there.

The ring-opening addition reaction between the carboxyl group-containing copolymer and the saturated epoxy compound is preferably performed using a catalyst in order to obtain a sufficient reaction rate. Examples of the catalyst include tertiary amines such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine, and tri-n-octylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and tetrabutylammonium bromide; Alkyl ureas such as urea; alkyl guanidines such as tetramethylguanidine; phosphines such as triphenylphosphine and tributylphosphine; sulfides such as dimethyl sulfide and diphenyl sulfide; and salts thereof. Among these, triphenylphosphine is more preferable. These catalysts may be used individually by 1 type, and may use 2 or more types together.
As content of the said catalyst, 0.01-10 mass% is preferable normally with respect to the said saturated epoxy compound, and 0.5-5.0 mass% is more preferable. When the content is less than 0.01% by mass with respect to the saturated epoxy compound, a sufficient reaction rate may not be obtained. When the content exceeds 10% by mass, various physical properties of the produced resin may be adversely affected. There is.

The acid value of the binder obtained as described above is preferably 50 to 250 mgKOH / g, more preferably 70 to 220 mgKOH / g, and particularly preferably 90 to 190 mgKOH / g. When the acid value is less than 50 mgKOH / g, it may be difficult to remove the uncured film with a dilute alkaline aqueous solution, and when it exceeds 250 mgKOH / g, the development resistance of the photocured film may be inferior.
The acid value of the binder is the mass (g) of potassium hydroxide necessary to neutralize the acidity of the carboxylic acid in 1 g of the resin A, and a normal neutralization titration method according to JIS K0070. Can be measured.

<< polymerizable compound >>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose.For example, a compound having a urethane group, a compound having an aryl group, a compound having a polyalkylene oxide chain, and the like are preferable. Can be mentioned. These polymerizable compounds may be used alone or in combination of two or more. Moreover, you may use together with another polymeric compound.

The polymerizable compound preferably has two or more polymerizable groups.
Examples of the polymerizable group include an ethylenically unsaturated bond (for example, (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester). Etc.) and a polymerizable cyclic ether group (for example, an epoxy group, an oxetane group, etc.) and the like. Among these, an ethylenically unsaturated bond is more preferable.

-Compound having urethane group-
The compound having a urethane group is not particularly limited as long as it has a urethane group, and can be appropriately selected depending on the purpose. For example, JP-B-48-41708 and JP-A-51-37193 And compounds described in JP-B-5-50737, JP-B-7-7208, JP-A-2001-154346, JP-A-2001-356476, and the like. Examples include adducts of a polyisocyanate compound having one or more isocyanate groups and a vinyl monomer having a hydroxyl group in the molecule.

  Examples of the polyisocyanate compound having two or more isocyanate groups in the molecule include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, A diisocyanate such as 3,3′dimethyl-4,4′-diphenyl diisocyanate; a polyaddition product of the diisocyanate with a bifunctional alcohol (in this case, both ends are isocyanate groups); a burette or isocyanurate of the diisocyanate; Trimer; the diisocyanate or diisocyanates and trimethylolpropane, pe Taeritoritoru, polyfunctional alcohols such as glycerin, or the like adducts of other functional alcohol obtained of such these ethylene oxide adducts and the like.

  Examples of the vinyl monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and triethylene. Glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, octaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate , Tetrapropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Chryrate, dibutylene glycol mono (meth) acrylate, tributylene glycol mono (meth) acrylate, tetrabutylene glycol mono (meth) acrylate, octabutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, trimethylolpropane Examples include di (meth) acrylate and pentaerythritol tri (meth) acrylate. Moreover, the one terminal (meth) acrylate body of the diol body which has different alkylene oxide parts, such as a copolymer (random, a block, etc.) of ethylene oxide and propylene oxide, etc. are mentioned.

In addition, as the compound having a urethane group, a compound having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate, di (meth) acrylated isocyanurate, or tri (meth) acrylate of ethylene oxide-modified isocyanuric acid. Is mentioned. Among these, the compound represented by any one of the following structural formula (3) and structural formula (4) is more preferable, and from the viewpoint of tent properties, at least the compound represented by the structural formula (4) is included. Particularly preferred. Moreover, these compounds may be used individually by 1 type, and may use 2 or more types together.
However, in said structural formula (3) and (4), R < ¹ >, R < ² > and R < ³ > represent either a hydrogen atom or a methyl group, respectively. X ₁ , X ₂ , and X ₃ represent alkylene oxide, and may be used alone or in combination of two or more.

  Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, and a group in which these are combined (may be combined in any of random or block). Among these, any of an ethylene oxide group, a propylene oxide group, a butylene oxide group, and a combination thereof is more preferable, and any of an ethylene oxide group and a propylene oxide group is particularly preferable.

In the structural formulas (3) and (4), m ₁ , m ₂ , and m ₃ represent an integer of 1 to 60, preferably an integer of 2 to 30, and any of 4 to 15 Such an integer is more preferable.

Wherein in the structural formula (3) and (4), ^{Y 1} and ^{Y 2} represents a divalent organic group having 2 to 30 carbon atoms, for example, an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group (—CO—), an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group in which the hydrogen atom of the imino group is substituted with a monovalent hydrocarbon group, Preferable examples include a sulfonyl group (—SO ₂ —) and a combination thereof, and among these, any of an alkylene group, an arylene group, and a combination thereof is more preferable.

The alkylene group may have any one of a branched structure and a cyclic structure. For example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a neopentylene group, and hexylene. Preferred examples include a group, trimethylhexylene group, cyclohexylene group, heptylene group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, dodecylene group, octadecylene group, or any of the groups shown below. It is done.

The arylene group may be substituted with a hydrocarbon group, and examples thereof include a phenylene group, a tolylene group, a diphenylene group, a naphthylene group, and the following groups.

  Examples of the group in which these are combined include a xylylene group.

  The alkylene group, arylene group, and a group obtained by combining these may further have a substituent. Examples of the substituent include a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine). Atom), aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group (for example, , Acetoxy group, butyryloxy group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group) and the like.

  In the structural formulas (3) and (4), n represents an integer of 3 to 6, and any one of 3, 4, and 6 is preferable from the viewpoint of raw material supply capability for synthesizing a polymerizable compound.

In the structural formulas (3) and (4), Z represents an n-valent (trivalent to hexavalent) linking group, and examples thereof include any of the groups shown below.
However, _{X 4} represents an alkylene oxide. m ₄ represents an integer of from 1 to 20. n represents an integer of 3 to 6. A represents an n-valent (trivalent to hexavalent) organic group.

  Examples of A include an n-valent aliphatic group, an n-valent aromatic group, and an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group, an oxygen atom, a sulfur atom, an imino group, and an imino group. Preferred is a substituted imino group in which a hydrogen atom of a group is substituted with a monovalent hydrocarbon group, or a group in which a sulfonyl group is combined, an n-valent aliphatic group, an n-valent aromatic group, or an alkylene group thereof, An arylene group or a group in which an oxygen atom is combined is more preferable, and an n-valent aliphatic group or a group in which an n-valent aliphatic group is combined with an alkylene group or an oxygen atom is particularly preferable.

  The number of carbon atoms of A is, for example, preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and particularly preferably an integer of 3 to 30.

The n-valent aliphatic group may have either a branched structure or a cyclic structure.
As a carbon atom number of the said aliphatic group, for example, any integer of 1-30 is preferable, any integer of 1-20 is more preferable, and any integer of 3-10 is particularly preferable.
The number of carbon atoms of the aromatic group is preferably an integer of 6 to 100, more preferably an integer of 6 to 50, and particularly preferably an integer of 6 to 30.

  The n-valent aliphatic group or aromatic group may further have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, Iodine atom), aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group ( Examples thereof include an acetoxy group, a butyryloxy group), an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group), an aryloxycarbonyl group (for example, a phenoxycarbonyl group), and the like.

The alkylene group may have either a branched structure or a cyclic structure.
The number of carbon atoms of the alkylene group is, for example, preferably an integer of 1 to 18, and more preferably an integer of 1 to 10.

The arylene group may be further substituted with a hydrocarbon group.
As the number of carbon atoms of the arylene group, any integer of 6 to 18 is preferable, and any integer of 6 to 10 is more preferable.

  As a carbon atom number of the monovalent hydrocarbon group of the said substituted imino group, the integer in any one of 1-18 is preferable, and the integer in any one of 1-10 is more preferable.

Preferred examples of A are as follows.

Specific examples of the compounds represented by the structural formulas (3) and (4) include compounds represented by the following structural formulas (5) to (24).
However, the structural formula (5) ~ (24), n, n 1, n 2 and m represents an integer of 1 to 60, l represents an integer of from 1 to 20, R represents either a hydrogen atom or a methyl group.

  70 mass% or less is preferable, as for content in the said polymeric compound of the compound which has the said urethane group, 20-60 mass% is more preferable, and 30-50 mass% is still more preferable. When the content exceeds 70% by mass, resolution, adhesion and the like may be deteriorated.

-Compound having an aryl group-
The compound 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. Examples include esters or amides of at least one of amino alcohol compounds and an unsaturated carboxylic acid.

Examples of the polyhydric alcohol compound, polyhydric amine compound or polyhydric amino alcohol compound having an aryl group include polystyrene oxide, xylylene diol, di- (β-hydroxyethoxy) benzene, 1,5-dihydroxy-1, 2,3,4-tetrahydronaphthalene, 2,2-diphenyl-1,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1-phenyl-1,2-ethanediol, 2,3,5,6-tetra Methyl-p-xylene-α, α′-diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1,4- Diol, 1,1′-bi-2-naphthol, dihydroxynaphthalene, 1,1′-methylene-di-2-naphtho 1,2,4-benzenetriol, biphenol, 2,2′-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4- Chlorresorcinol, hydroquinone, hydroxybenzyl alcohol, methyl hydroquinone, methylene-2,4,6-trihydroxybenzoate, phloroglicinol, pyrogallol, resorcinol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, α- ( 1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino-4-hydroxyphenylsulfone, and the like. In addition, compounds obtained by adding α, β-unsaturated carboxylic acid to glycidyl compounds such as xylylene bis (meth) acrylamide, novolac type epoxy resin and bisphenol A diglycidyl ether, phthalic acid, trimellitic acid, etc. Esterified products obtained from vinyl monomers containing a hydroxyl group in the molecule, diallyl phthalate, triallyl trimellitic acid, diallyl benzenedisulfonate, cationically polymerizable divinyl ethers (for example, bisphenol A divinyl ether), epoxy as a polymerizable compound Compound (for example, novolac type epoxy resin, bisphenol A diglycidyl ether, etc.), vinyl ester (for example, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate), styrene Examples of the compound include divinylbenzene, p-allylstyrene, and p-isopropenestyrene. Among these, the compound represented by the following structural formula (25) is more preferable.
In the structural formula (25), R ⁴ and R ⁵ represent either a hydrogen atom or an alkyl group.

In the structural formula (25), X ₅ and X ₆ represent an alkylene oxide group, which may be used alone or in combination of two or more. As the alkylene oxide group, for example, an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, a group combining these (which may be combined in any of random or block), Among them, any of ethylene oxide group, propylene oxide group, butylene oxide group, and a combination thereof is more preferable, and any of ethylene oxide group and propylene oxide group is particularly preferable. .

In the structural formula (25), m ₅ and m ₆ each represent an integer of 1 to 60, more preferably an integer of 2 to 30, and particularly preferably an integer of 4 to 15. .

In the structural formula (25), T represents a divalent linking group, and examples thereof include methylene, ethylene, MeCMe, CF ₃ CCF ₃ , CO, and SO ₂ .

In the structural formula (25), Ar ¹ and Ar ² represent an aryl group which may have a substituent, and examples thereof include phenylene and naphthylene. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, a halogen group, an alkoxy group, and combinations thereof.

  Specific examples of the compound having an aryl group include 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 2,2-bis [4-((meth)). (Acryloxyethoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane (for example, 2 to 20 ethoxy groups substituted with one phenolic OH group) 2,2-bis (4-((meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxy) phenyl) propane, 2,2-bis (4 -((Meth) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecaethoxy) Phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecaethoxy) phenyl) propane), 2,2-bis [4-((meth) acryloxypropoxy) phenyl] propane, phenolic 2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane (for example, 2,2-bis (4- ((Meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentapropoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecapropoxy) phenyl) propyl Pan, 2,2-bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane, etc.), a compound containing both a polyethylene oxide skeleton and a polypropylene oxide skeleton in the same molecule as the polyether moiety of these compounds (For example, the compound described in WO01 / 98832 etc. are mentioned. Moreover, the compound which has the said aryl group is Shin-Nakamura Chemical Co., Ltd. make, BPE-200, BPE-500, BPE-1000 as a commercial item. , Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., BPEM-10, BPE-4, BPE-10, BPE-20), polymerizable compounds having a bisphenol skeleton and a urethane group. These compounds may be compounds obtained by changing the part derived from the bisphenol A skeleton to bisphenol F, bisphenol S, or the like.

  Examples of the polymerizable compound having a bisphenol skeleton and a urethane group include, for example, an adduct of bisphenol and ethylene oxide, propylene oxide and the like, a compound having a hydroxyl group at the terminal obtained as a polyaddition product, an isocyanate group and a polymerizable group. (For example, 2-isocyanatoethyl (meth) acrylate, α, α-dimethyl-vinylbenzyl isocyanate, etc.) and the like.

  70 mass% or less is preferable, as for content in the said polymeric compound of the compound which has the said aryl group, 20-60 mass% is more preferable, and 30-50 mass% is still more preferable. When the content exceeds 70% by mass, resolution, adhesion, tent property and the like may be deteriorated.

--Compound having polyalkylene oxide chain--
There is no restriction | limiting in particular as a compound which has the said polyalkylene oxide chain | strand, A monofunctional monomer may be sufficient and a polyfunctional monomer may be sufficient.
Suitable examples of the monofunctional monomer include compounds represented by the following structural formula (i).
In the structural formula (i), R ¹ represents either 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 more 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 as or different from each other, and (—X—O—) may be When they are different, for example, a combination of an ethylene group and a propylene group is preferably exemplified.

In the structural formula (i), examples of R ² include an alkyl group, an aryl group, and an aralkyl group, 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, a hexadecyl group, and an octadecyl group. Is mentioned. The alkyl group may have a substituent, and may have a branch or a ring structure.
Examples of the aralkyl group include benzyl group and phenethyl group. The aralkyl group may have a substituent.
Examples of the aryl group include phenyl group, naphthyl group, tolyl group, xylyl group, ethylphenyl group, methoxyphenyl group, propylphenyl group, butylphenyl group, t-butylphenyl group, octylphenyl group, nonylphenyl group, Examples include chlorophenyl group, cyanophenyl group, dibromophenyl group, tribromophenyl group, biphenylyl group, benzylphenyl group, α-dimethyl-benzylphenyl group, and the like. The aryl group may have a substituent.

Examples of the substituent in the alkyl group, aralkyl group, and aryl group include a halogen atom, an aryl group, an alkenyl group, an alkoxy group, and a cyano 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, and more preferably 6 to 14. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, and the like.
As said alkenyl group, C2-C10 is preferable and 2-6 are more preferable. Examples of the alkenyl group include ethynyl group, propenyl group, butyryl group and the like.
The alkoxy group may be branched, and the total carbon number is preferably 1 to 10, more preferably 1 to 5. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a 2-methylpropyloxy group, and a butoxy group.

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

In addition, in the compound having a polyalkylene oxide chain, polyethylene glycol and polypropylene glycol having 10 to 30 ethylene groups or propylene groups are also preferable as the compound having at least one of an ethylene group and a propylene group.
The compound having a polyalkylene oxide chain may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, 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 dimethacrylate, polyethylene glycol # 600 dimethacrylate, polyethylene glycol # 1000 dimethacrylate, etc.), propylene glycol di (meth) acrylate, the number of propylene groups is 2 18 polypropylene glycol di (meth) acrylate (eg, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate) Di (meth) acrylate of an alkylene glycol chain having at least one ethylene glycol chain / propylene glycol chain (for example, international publication), tetrapropylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) acrylate, etc.) No. 01/98832 pamphlet), polybutylene glycol di (meth) acrylate and the like.
Among these, from the viewpoint of availability, etc., ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diene of alkylene glycol chain having at least one ethylene glycol chain / propylene glycol chain each ( More preferred is (meth) acrylate.

  The content of the compound having a polyalkylene oxide chain in the polymerizable compound is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, and still more preferably 1 to 25% by mass. If the content is less than 0.1% by mass, the effect of improving peelability and development latitude may be insufficient. If the content exceeds 40% by mass, resolution, adhesion, tent properties, etc. are deteriorated. There is a case.

-Other polymerizable compounds-
For the pattern forming material of the present invention, a polymerizable compound other than the polymerizable compound may be used. For example, an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and an aliphatic polyhydric alcohol compound, an unsaturated carboxylic acid and a polyvalent amine compound Examples include amides.

  As an ester monomer of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound, for example, as a (meth) acrylic acid ester, neopentyl glycol di (meth) acrylate, ethylene oxide-modified neopentyl glycol di (meth) acrylate, Propylene oxide modified neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butane Diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,5-bentanediol (medium) ) Acrylate, pentaerythritol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) ) Acrylate, glycerin di (meth) acrylate, xylenol di (meth) acrylate and the like.

  Among the (meth) acrylic acid esters, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diglycerin di (meth) are used from the viewpoint of easy availability. ) Acrylate, 1,3-propanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,5-pentanediol (meth) acrylate, neopentyl glycol di (meth) acrylate and the like are preferable.

  Examples of the ester (itaconic acid ester) of the itaconic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4- Examples include butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate.

  Examples of the ester (crotonic acid ester) of the crotonic acid and the aliphatic polyhydric alcohol compound include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Can be mentioned.

  Examples of the ester (isocrotonate) of the isocrotonic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diisocrotonate and pentaerythritol diisocrotonate.

  Examples of the ester of maleic acid and the aliphatic polyhydric alcohol compound (maleic acid ester) include ethylene glycol dimaleate, triethylene glycol dimaleate, and pentaerythritol dimaleate.

  Examples of the amide derived from the polyvalent amine compound and the unsaturated carboxylic acid include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, and octamethylene bis ( And (meth) acrylamide, diethylenetriamine bis (meth) acrylamide, and the like.

  In addition to the above, as the polymerizable compound, for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Compounds obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound such as hexanediol diglycidyl ether, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyester acrylates and polyester (meth) acrylate oligomers, epoxy compounds (for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ester, etc. Ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether) and (meth) acrylic acid reacted polyfunctional acrylates and methacrylates, Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308 (1984), photocurable monomers and oligomers, allyl esters (for example, diallyl phthalate, diallyl adipate, diallyl malonate, diallylamide (eg diallylacetamide, etc.), cations Polymerizable divinyl ethers (for example, butanediol-1,4-divinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether) , Dipropylene glycol divinyl ether, hexanediol divinyl ether, etc.), epoxy compounds (eg, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene) Glycol diglycidyl ether, hexanediol diglycidyl ether, etc.), oxetanes (eg, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, etc.), epoxy compounds, oxetanes (eg, WO01 / 2165) Compound, N-β-hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis (β-methacryloxyethyl) acrylamide And compounds having two different ethylenically unsaturated double bonds, such as allyl methacrylate.

Examples of the vinyl esters include divinyl succinate and divinyl adipate.
These polymerizable compounds may be used alone or in combination of two or more.

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 (exudation failure from the end of the roll) may be deteriorated. .

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

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

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, F . C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, a US patent And the compounds described in the specification of No. 42122976.

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

Examples of the compound described in British Patent No. 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4, 6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) ) -4-amino-6-trichloromethyl-1,3,5-triazine and the like.
Examples of the compound described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

  Examples of the compound described in German Patent No. 3333724 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-Methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3 , 5-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloromethyl) ) -1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan) 2-vinylene) -4,6-bis (trichloromethyl) -1,3,5-triazine, and the like.

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

  Examples of the compound described in JP-A-62-258241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Naphtyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropyl) Phenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloro Chill) -1,3,5-triazine.

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

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

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

  Examples of the hexaarylbiimidazole compound include 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-bisimidazole, 2,2′-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4 -Phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6- Lichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5 '-Tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-cyanophenyl) -4,4', 5.5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2 '-Bis (2-cyanophenyl) -4,4', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4 ', 5 , 5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-e Xoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2- Ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis ( 4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis ( 2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenylphenyl) Enyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4 -Phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetra Phenylbiimi Sol, 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-cyanophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dicyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis ( 2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetra Phenylbiimidazole, 2,2′-bis (2,4-dimethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trimethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diethylphenyl) -4,4 ′ , 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis ( 2-phenylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diphenylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2,2′-bis (2,4,6-triphenylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole.

  Examples of the oxime derivative include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane-3-one. 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyl And oximino-1-phenylpropan-1-one.

  Further, as other photopolymerization initiators, acylphosphine oxides are used. For example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO and the like.

Further, as photopolymerization initiators other than the above, N-phenylglycine and other polyhalogen compounds (for example, carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethyl ketone, etc.), amines (for example, 4-dimethylamino) Ethyl benzoate, n-butyl 4-dimethylaminobenzoate, phenethyl 4-dimethylaminobenzoate, 2-phthalimidoethyl 4-dimethylaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentamethylenebis (4 -Dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-di- Tilaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N- Methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylamine, crystal violet lactone, leuco crystal violet, etc.), metallocenes (for example, bis (η ⁵ -2,4-cyclopentadiene- 1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η ⁵ -cyclopentadienyl-η ⁶ -cumenyl-iron (1 +)-hexafluorophosphate (1-) etc.), JP-A-53-133428, Sho 57-1819, JP-the 57-6096 and JP-like compounds described in U.S. Patent No. 3,615,455 and the like.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, fluorenone, 2-benzyl-dimethyl Amino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl- [4- ( 1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, ben Le dimethyl ketal), and the like.

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

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

<< Fluorosurfactant >>
The fluorosurfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a structural unit derived from a monomer represented by the following structural formula (1) and the following structural formula (2). The copolymer which has at least any one of the structural unit derived from the monomer represented, and the structural unit derived from the ethylenically unsaturated monomer which has a polyoxyalkylene group is preferable.
However, in the structural formulas (1) and (2), R ¹ and R ² may be the same as or different from each other, and represent either a hydrogen atom or a methyl group. X ¹ and X ² may be the same as or different from each other, and represent either an oxygen atom or NR ⁴ . The R ⁴ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 7 to 7 carbon atoms. Represents one of 24 aralkyl groups. Z ¹ and Z ² may be the same as or different from each other, and represent a substituent having at least one of an oxygen atom, a nitrogen atom and a sulfur atom. R ³ represents either a hydrogen atom or a fluorine atom. l, n, p, and r represent any integer of 0-10. m and q represent any integer of 0 and 1. o, s, and t represent any integer of 1-10.

Specific examples of the monomer represented by the structural formula (1) or (2) include monomers represented by the following structural formulas (26) to (44).
However, in the structural formulas (42) to (44), R represents either a hydrogen atom or a methyl group.

  Next, the ethylenically unsaturated monomer having the polyoxyalkylene group will be described. In the present specification, the ethylenically unsaturated monomer having a polyoxyalkylene group means a copolymerizable monomer having an ethylenically unsaturated group and a polyoxyalkylene group in the molecule. There are no particular restrictions.

  As the ethylenically unsaturated group, for example, from the viewpoint of availability of raw materials, compatibility with the blend in the photosensitive resin composition, ease of controlling such compatibility, or polymerization reactivity. Any of (meth) acrylic ester groups and related groups thereof may be mentioned.

The polyoxyalkylene group may be represented by (OR) x, and R represents an alkylene group having 2 to 4 carbon atoms, specifically, —CH ₂ CH ₂ —, —CH ₂ CH. ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH (CH ₃ ) — are mentioned. The x represents an integer, preferably an integer of 2 to 50, and more preferably an integer of 3 to 30. Moreover, when said x is an integer greater than or equal to 2, said R may mutually be same or different. That is, the oxyalkylene unit in the polyoxyalkylene group may be composed of only the same oxyalkylene unit, such as polyoxypropylene, and is different such that the oxypropylene unit and the oxyethylene unit are linked. Two or more oxyalkylene units may be connected regularly or irregularly.

The atom or group bonded to the terminal of the polyoxyalkylene group is not particularly limited and may be a hydrogen atom or any other group, but may be a hydrogen atom, an alkyl group (for example, carbon Preferred examples include an alkyl group having 1 to 20 carbon atoms, an aralkyl group (for example, an aralkyl group having 7 to 24 carbon atoms), and an aryl group (for example, an aryl group having 6 to 10 carbon atoms). The aryl group may further have a substituent such as an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms) or a halogen atom.
The polyoxyalkylene group may have one or more chain bonds (for example, —CONH—Ph—NHCO—, —S—, etc .: Ph represents a phenylene group), and In order to make the oxyalkylene group into a branched chain, the chain bond site may have an atom having a valence of 3 or more.

  There is no restriction | limiting in particular as molecular weight of the said polyoxyalkylene group, Although it can select suitably according to the objective, For example, 250-3,000 are preferable.

Examples of the ethylenically unsaturated monomer having a polyoxyalkylene group include a compound represented by the following structural formula (45).
However, in the structural formula (45), R ⁴ represents either a hydrogen atom or a methyl group. X ³ represents either an oxygen atom or NR ⁶ . R ⁶ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 7 to 7 carbon atoms. Represents one of 24 aralkyl groups. Y represents an alkylene group having 1 to 5 carbon atoms which may have a substituent. R ⁵ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 7 to 24 carbon atoms. Represents one of the aralkyl groups. f is an integer, and in the case of an integer of 2 or more, Ys may be the same or different.

  In the structural formula (45), Y is, for example, preferably a linear or branched alkylene group having 2 to 4 carbon atoms, and f is preferably an integer of 2 to 50, 3 to 30 Any integer is more preferable.

  The substituent in the structural formulas (1), (2) and (45) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a hydroxy group, a halogen atom, an alkyl group (for example, carbon number) 1-12 alkyl groups), alkoxy groups (for example, alkoxy groups having 1 to 12 carbon atoms), aryl groups (for example, aryl groups having 6 to 12 carbon atoms), sulfamoyl groups, carboxyl groups, and the like.

  As a preparation method of poly (oxyalkylene) acrylate and methacrylate as the ethylenically unsaturated monomer having a polyoxyalkylene group, for example, a commercially available hydroxypoly (oxyalkylene) material, for example, manufactured by Asahi Denka Kogyo Co., Ltd. Pluronic, Adeka Polyether; Glico Products, Carbowax; Rohm and Haas, Triton; Daiichi Kogyo Seiyaku Co., Ltd. E. The method of making G etc. react with acrylic acid, methacrylic acid, acrylic acid chloride, methacrylic acid chloride, acrylic acid anhydride etc. by a well-known method is mentioned. In addition, poly (oxyalkylene) diacrylate, poly (oxyalkylene) dimethacrylate and the like produced by a known method can also be used.

  As a commercial item of the ethylenically unsaturated monomer which has the said polyoxyalkylene group, for example, as a hydroxyl-terminated polyalkylene glycol mono (meth) acrylate made by NOF Corporation, Blemmer PE-90, Blemmer PE-200, Blemmer PE -350, Blemmer AE-90, Blemmer AE-200, Blemmer AE-400, Blemmer PP-1000, Blemmer PP-500, Blemmer PP-800, Blemmer AP-150, Blemmer AP-400, Blemmer AP-550, Blemmer AP -800, Blemmer 50PEP-300, Blemmer 70PEP-350B, Blemmer AEP series, Blemmer 55PET-400, Blemmer 30PET-800, Blemmer 55PET-800, Blemma AET series, Blemmer 30PPT-800, Blemmer 50PPT-800, Blemmer 70PPT-800, Blemmer APT series, Brenmer 10PPB-500B, and the like Brenmer 10APB-500B.

  Moreover, as a commercial item of the ethylenically unsaturated monomer which has the said polyoxyalkylene group, Blemmer PME-100, Blemmer PME-200, Blemmer is further used as the alkyl terminal polyalkylene glycol mono (meth) acrylate made from NOF Corporation. PME-400, Blemmer PME-1000, Blemmer PME-4000, Blemmer AME-400, Blemmer 50POEP-800B, Blemmer 50AOEP-800B, Blemmer PLE-200, Blemmer ALE-200, Blemmer ALE-800, Blemmer PSE-400, Blemmer PSE-1300, Blemmer ASEP series, Blemmer PKEP series, Blemmer AKEP series, Blemmer AE-300, Blemmer AE-13 0, Blemmer PNEP series, Blemmer PNPE series, Blemmer 43ANEP-500, Blemmer 70ANEP-550, etc .; manufactured by Kyoeisha Chemical Co., Ltd., light ester MC, light ester 130MA, light ester 041MA, light acrylate BO-A, light acrylate EC-A , Light acrylate MTG-A, light acrylate 130A, light acrylate DPM-A, light acrylate P-200A, light acrylate NP-4EA, light acrylate NP-8EA, and the like.

  The above-mentioned ethylenically unsaturated monomer having a polyoxyalkylene group may be used alone or in combination of two or more.

  Preferable examples of the copolymer as the fluorosurfactant include, for example, a monomer represented by the structural formula (1), and at least one of poly (oxyethylene) acrylate and poly (oxyethylene) methacrylate. , A copolymer obtained by copolymerizing three or more monomers with at least one of poly (oxyalkylene) acrylate and poly (oxyalkylene) methacrylate. In this case, the poly (oxyalkylene) acrylate and poly (oxyalkylene) methacrylate are poly (oxyalkylene) acrylate and poly (oxyalkylene) methacrylate other than the poly (oxyethylene) acrylate and poly (oxyethylene) methacrylate. It is.

The copolymer includes a structural unit derived from at least one of the monomers represented by the structural formulas (1) and (2) and a structural unit derived from an ethylenically unsaturated monomer having a polyoxyalkylene group. Further, it may be a copolymer further having a structural unit derived from another monomer copolymerizable therewith.
The copolymerization ratio of the other monomer capable of copolymerization is not particularly limited and may be appropriately selected depending on the purpose. For example, in all monomers, 30% by mass or less is preferable, and 20% by mass or less is preferable. More preferred.

  Examples of the other copolymerizable monomer include Polymer Handbook 2nd ed. , J. et al. Brandrup, Wiley Interscience (1975), Chapter 2, P1-483. Examples include acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers. , Vinyl esters, dialkyl itaconates, dialkyl esters of fumaric acid, monoalkyl esters, and the like, and compounds having at least one addition-polymerizable unsaturated bond.

  Examples of the compound having at least one addition polymerizable unsaturated bond of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, and trimethylolpropane monoacrylate. , Benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, methacrylic acid esters; methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate , Benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate Such as over doors and the like.

  Examples of the compound having at least one addition-polymerizable unsaturated bond of acrylamides include acrylamide, N-alkylacrylamide (for example, one having 1 to 3 carbon atoms as an alkyl group), N, N-dialkylacrylamide (for example, And alkyl groups having 1 to 3 carbon atoms), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, and the like.

  Examples of the compound having at least one addition polymerizable unsaturated bond of methacrylamide include, for example, methacrylamide, N-alkyl methacrylamide (for example, alkyl group having 1 to 3 carbon atoms), N, N-dialkyl. Examples include methacrylamide (for example, alkyl groups having 1 to 3 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide and the like.

  Examples of the compound having at least one addition polymerizable unsaturated bond of the allyl compound include allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, Allyl benzoate, allyl acetoacetate, allyl lactate, etc.) and allyloxyethanol.

  Examples of the compound having at least one addition-polymerizable unsaturated bond of vinyl ethers include alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, Vinyl esters such as 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether : Vinyl butyrate, bi Luisobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate Etc.

  Examples of the compound having at least one addition polymerizable unsaturated bond of the dialkyl itaconate include dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like.

  Examples of the compound having at least one addition polymerizable unsaturated bond of the dialkyl ester or monoalkyl ester of fumaric acid include, for example, dibutyl fumarate, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleilonitrile, Examples include styrene.

  The content of at least one of the monomer represented by the structural formula (1) and the monomer represented by the structural formula (2) is not particularly limited and may be appropriately selected depending on the intended purpose. The amount of the copolymer is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, still more preferably 20 to 70% by mass, and particularly preferably 40 to 70% by mass.

  There is no restriction | limiting in particular as content of the ethylenically unsaturated monomer which has the said polyoxyalkylene group, Although it can select suitably according to the objective, For example, it is 10-10 with respect to the total mass of the said copolymer. 95 mass% is preferable, 15-70 mass% is more preferable, 20-60 mass% is especially preferable.

  There is no restriction | limiting in particular as a mass mean molecular weight of the said copolymer, Although it can select suitably according to the objective, For example, 3,000-100,000 are preferable and 6,000-80,000 are more preferable. . The copolymer may be a block, random, or graft copolymer, but a random copolymer is preferred.

The method for preparing the copolymer is not particularly limited and may be appropriately selected from known methods according to the purpose. Examples thereof include a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, and an anionic polymerization method. Based on the above, it can be prepared by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a dropping polymerization method or the like, and among these, a radical polymerization method is more preferable.
As an example of the preparation method using the radical polymerization method, monomers such as the (meth) acrylate having a fluoroaliphatic group and the (meth) acrylate having a polyoxyalkylene group are used in a general-purpose radical polymerization initiator in an organic solvent. The copolymer can be prepared by adding and polymerizing. In this case, other addition polymerizable unsaturated compounds can be added and prepared by the same method as described above.
Apart from the preparation method, the copolymer can also be prepared by photopolymerization in the presence of a photosensitizer or photoinitiator or by polymerization using radiation or heat as an energy source.

The polymerization initiator used for the preparation of the copolymer is not particularly limited and may be appropriately selected from known polymerization initiators. For example, peroxides such as benzoyl peroxide and diacyl peroxide; Azo compounds such as azobisisobutyronitrile, azobisisovaleronitrile, phenylazotriphenylmethane; metal chelate compounds such as Mn (acac) ₃ ; transition metal catalysts that cause living radical polymerization, and the like.

  In addition, for the preparation of the copolymer, lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, a thiol compound containing a coupling group (for example, γ-mercaptopropyltrimethoxysilane) Etc.) and other additives such as chain transfer agents can be used.

The copolymer may be prepared in the presence of a solvent or in the absence of a solvent, but is preferably in the presence of a solvent from the viewpoint of workability and the like.
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol, tert-butanol, acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone and methyl amyl ketone, esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate and butyl lactate, methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxy Monocarboxylic acid esters such as propyl propionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, dimethylformamide, Polar solvents such as methyl sulfoxide, N-methylpyrrolidone, ethers such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycols such as acetate and propylene glycol monobutyl ether acetate and esters thereof, halogen solvents such as 1,1,1-trichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, aromatics such as benzene, toluene and xylene And further fluorinated inert liquids such as perfluorooctane and perfluorotri-n-butylamine. The

The said copolymer may be used individually by 1 type, and may be used in combination of 2 or more type.
The copolymer is commercially available from Daikin Fine Chemical, Amax, Hydras Chemical, Central Chemical, Wako Pure Chemicals, etc., and these commercial products can also be used.

There is no restriction | limiting in particular as content with respect to the said photosensitive layer of the said copolymer, Although it can select suitably according to the objective, For example, 0.001-10 mass% is preferable.
When the content is less than 0.001% by mass, the surface shape of the photosensitive layer is deteriorated, and the thickness of the photosensitive layer may not be uniform. When the content exceeds 10% by mass, the adhesion of the photosensitive layer is increased. May get worse.

<< Other ingredients >>
Examples of the other components include reducing agents, hydrogen donors, sensitizers, polymerization inhibitors, plasticizers, color formers, colorants, and the like, and further adhesion promoters to the substrate surface and other agents. Auxiliaries (for example, pigments, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, chain transfer agents, etc.) You may use together. By appropriately containing these components, it is possible to adjust properties such as stability, photographic properties, print-out properties, and film properties of the target pattern forming material.

-Reducing agent and hydrogen donor compound-
The reducing agent is not particularly limited as long as it can react with free radicals and can suppress the color development of the color former, and can be appropriately selected according to the purpose. Examples include methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, alkyl-substituted catechol, phenothiazine, pyrogallol, and phenidone. Among these, phenidone is more preferable.
As the hydrogen donor compounds is not particularly limited, for example, a compound having a -SH _{group, -CH 2 X- (X = R} ) group (R is a substituent containing O, N, and one of the S And the like.
As a compound which has the said -SH group, the compound represented by the following structural formula is mentioned, for example.
Examples of the compound having a —CH ₂ X— (X═R) group include N-phenylglycine, dimethylaminocinnamic acid, dimethylaminobenzaldehyde, and the like.
Among these hydrogen donor compounds, N-phenylglycine is preferable from the same viewpoint as the reducing agent.

-Sensitizer-
The sensitizer can be appropriately selected by visible light, ultraviolet light, visible light laser, or the like as a light irradiation means to be described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, , Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, Methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, chloroacrine) Don, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl)- 7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3 '-Carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7- Diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin , 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin and the like, and others such as JP-A-5-19475, JP-A-7-271028, and JP2002. -363206, JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, and the like.

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

As content of the said sensitizer, 0.05-30 mass% is preferable with respect to all the components of a photosensitive layer, 0.1-20 mass% is more preferable, 0.2-10 mass% is especially preferable.
When the content is less than 0.05% by mass, the sensitivity to active energy rays decreases, the exposure process takes time, and the productivity may decrease. When the content exceeds 30% by mass, the photosensitive layer May precipitate during storage.

-Polymerization inhibitor-
There is no restriction | limiting in particular as said polymerization inhibitor, According to the objective, it can select suitably.
The polymerization inhibitor includes hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to the polymerization initiation radical component generated from the photopolymerization initiator by the exposure. The polymerization initiation radical is deactivated and the initiation of polymerization is prohibited.

  Examples of the polymerization inhibitor include compounds having a lone electron pair (for example, compounds having oxygen, nitrogen, sulfur, metal, etc.), compounds having pi electrons (for example, aromatic compounds), and the like. A compound having a phenolic hydroxyl group, a compound having an imino group, a compound having a nitro group, a compound having a nitroso group, a compound having an aromatic ring, a compound having a heterocyclic ring, a compound having a metal atom (complex with an organic compound) Including). Among these, a compound having a phenolic hydroxyl group, a compound having an imino group, a compound having an aromatic ring, and a compound having a heterocyclic ring are more preferable.

  The compound having a phenolic hydroxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a compound having at least two phenolic hydroxyl groups is preferable. In the compound having at least two phenolic hydroxyl groups, at least two phenolic hydroxyl groups may be substituted with the same aromatic ring or may be substituted with different aromatic rings in the same molecule.

The compound having at least two phenolic hydroxyl groups is more preferably a compound represented by the following structural formula (46), for example.
In the structural formula (46), Z represents a substituent, and m represents an integer of 2 or more. n represents an integer of 0 or more. M and n are preferably integers selected so that m + n = 6. Moreover, when n is an integer greater than or equal to 2, said Z may mutually be same or different.
If m is less than 2, the resolution may deteriorate.

  Examples of the substituent in the structural formula Z include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, Methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), aryloxycarbonyl group having 30 or less carbon atoms (for example, phenoxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms (for example, methylsulfonylaminocarbonyl group, Octylsulfonylaminocarbonyl group), arylsulfonylaminocarbonyl group (for example, toluenesulfonylaminocarbonyl group), acylaminosulfonyl group having 30 or less carbon atoms (for example, benzoylaminosulfonyl group, acetylamino) Sulfonyl group, pivaloylaminosulfonyl group), an alkoxy group having 30 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), arylthio group having 30 or less carbon atoms, alkylthio Group (for example, phenylthio group, methylthio group, ethylthio group, dodecylthio group, etc.), aryloxy group having 30 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro Group, alkyl group having 30 or less carbon atoms, alkoxycarbonyloxy group (for example, methoxycarbonyloxy group, stearyloxycarbonyloxy group, phenoxyethoxycarbonyloxy group), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy group, Phenoxycarbonyloxy group), acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl group ( For example, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidino) Sulfonyl group, etc.), alkylsulfonyl groups having 30 or less carbon atoms (for example, methylsulfonyl group, trifluoromethylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, dodecylsulfonyl group), arylsulfonyl groups (for example, benzenesulfonyl group, Ruenesulfonyl group, naphthalenesulfonyl group, pyridinesulfonyl group, quinolinesulfonyl group), aryl group having 30 or less carbon atoms (for example, phenyl group, dichlorophenyl group, toluyl group, methoxyphenyl group, diethylaminophenyl group, acetylaminophenyl group, methoxycarbonyl) Phenyl group, hydroxyphenyl group, t-octylphenyl group, naphthyl group, etc.), substituted amino group (eg, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acylamino group, etc.), substituted phosphono Group (for example, phosphono group, diethylphosphono group, diphenylphosphono group), heterocyclic group (for example, pyridyl group, quinolyl group, furyl group, thienyl group, tetrahydrofurfuryl group, pyrazolyl group, isoxazolyl group, Sothiazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazolyl group, tetrazolyl group, benzoxazolyl group, benzimidazolyl group, isoquinolyl group, thiadiazolyl group, morpholino group, piperidino group, piperazino group , Indolyl group, isoindolyl group, thiomorpholino group), ureido group (eg methylureido group, dimethylureido group, phenylureido group etc.), sulfamoylamino group (eg dipropylsulfamoylamino group etc.), alkoxycarbonyl An amino group (eg, ethoxycarbonylamino group), an aryloxycarbonylamino group (eg, phenyloxycarbonylamino group), an alkylsulfinyl group (eg, methylsulfinyl group), Reel alkylsulfinyl group (e.g., such as phenylsulfinyl group), a silyl group (e.g., trimethoxysilyl group, triethoxysilyl group), silyloxy group (e.g., trimethylsilyloxy group) and the like.

  Examples of the compound represented by the structural formula (46) include alkyl catechol (for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol). 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert -Butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, 3,5-di-tert-butyl catechol, etc.), alkylresorcinol (for example, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol) 4 Ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, 2-n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, 4-tert-butyl resorcinol, etc.), alkylhydroquinone (eg, methylhydroquinone) Ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, etc.), pyrogallol, phloroglucin and the like.

The compound having a phenolic hydroxyl group is also preferably a compound in which aromatic rings having at least one phenolic hydroxyl group are linked to each other by a divalent linking group.
Examples of the divalent linking group include groups having 1 to 30 carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, SO, SO _{2 and the} like. The sulfur atom, oxygen atom, SO, and SO ₂ may be directly bonded.
The carbon atom and oxygen atom may have a substituent, and examples of the substituent include Z in the above structural formula (46).
The aromatic ring may have a substituent, and examples of the substituent include Z in the above structural formula (46).

Specific examples of the compound having a phenolic hydroxyl group include bisphenol A, bisphenol S, bisphenol M, a known bisphenol compound used as a color developer for thermal paper, a bisphenol compound described in JP-A-2003-305945, and an oxidation compound. Examples thereof include hindered phenol compounds used as an inhibitor. In addition, monophenol compounds having a substituent such as 4-methoxyphenol, 4-methoxy-2-hydroxybenzophenone, β-naphthol, 2,6-di-t-butyl-4-cresol, methyl salicylate, diethylaminophenol, etc. Can be mentioned.
A commercial product of the compound having a phenolic hydroxyl group includes a bisphenol compound manufactured by Honshu Chemical.

There is no restriction | limiting in particular as a compound which has the said imino group, Although it can select suitably according to the objective, For example, a thing with a molecular weight of 50 or more is preferable, and a thing with a molecular weight of 70 or more is more preferable.
The compound having an imino group preferably has a cyclic structure substituted with an imino group. The cyclic structure is preferably a condensed at least one of an aromatic ring and a heterocyclic ring, and more preferably a condensed aromatic ring. Moreover, in the said cyclic structure, you may have an oxygen atom, a nitrogen atom, and a sulfur atom.

  Specific examples of the compound having an imino group include phenothiazine, phenoxazine, dihydrophenazine, hydroquinoline, a compound in which these compounds are substituted with Z in the above structural formula (46), and the like.

The compound having a cyclic structure substituted with the imino group is preferably a hindered amine derivative having a hindered amine in part.
Examples of the hindered amine include hindered amines described in JP-A No. 2003-246138.

The compound having the nitro group or the compound having the nitroso group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, those having a molecular weight of 50 or more are preferred, and those having a molecular weight of 70 or more. Is more preferable.
Specific examples of the compound having the nitro group or the compound having the nitroso group include nitrobenzene, a chelate compound of nitroso compound and aluminum, and the like.

The compound having an aromatic ring is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the aromatic ring has a substituent having a lone electron pair (for example, an oxygen atom, a nitrogen atom, a sulfur atom) And the like substituted by a substituent having
Specific examples of the compound having an aromatic ring include, for example, the above-described compound having a phenolic hydroxyl group, the above-mentioned compound having an imino group, and a compound having an aniline skeleton (for example, methylene blue, crystal violet, etc.). It is done.

The compound having a heterocycle is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the heterocycle has an atom having a lone pair of electrons such as nitrogen, oxygen, and sulfur. preferable.
Specific examples of the compound having a heterocyclic ring include pyridine and quinoline.

There is no restriction | limiting in particular as a compound which has the said metal atom, According to the objective, it can select suitably.
The metal atom is not particularly limited as long as it is a metal atom having an affinity for a radical generated from the polymerization initiator, and can be appropriately selected according to the purpose. Examples thereof include copper, aluminum, and titanium. Can be mentioned.

  Among the polymerization inhibitors, a compound having at least two phenolic hydroxyl groups, a compound having an aromatic ring substituted with an imino group, and a compound having a heterocyclic ring substituted with an imino group are preferable, and the imino group has a cyclic structure. Particular preference is given to compounds constituting the part, hindered amine compounds. Specifically, any of catechol, phenothiazine, phenoxazine, hindered amine, and derivatives thereof is preferable.

  The polymerization inhibitor is generally contained in a trace amount in a commercially available polymerizable compound, but in the present invention, from the viewpoint of improving the resolution, separately from the polymerization inhibitor contained in the commercially available polymerizable compound. The above-mentioned polymerization inhibitor is included. Therefore, the polymerization inhibitor is preferably a compound excluding a monophenol compound such as 4-methoxyphenol contained in the commercially available polymerizable compound for imparting stability.

  The polymerization inhibitor may be added in advance to the photosensitive resin composition solution in the manufacturing process of the pattern forming material.

The content of the polymerization inhibitor is preferably 0.005 to 0.5% by mass, more preferably 0.01 to 0.4% by mass, and 0.02 to 0% with respect to the polymerizable compound in the photosensitive layer. .2% by weight is particularly preferred. If the content is less than 0.005% by mass, the resolution may decrease, and if it exceeds 0.5% by mass, the sensitivity to active energy rays may decrease.
In addition, content of the said polymerization inhibitor represents content remove | excluding monophenol type compounds, such as 4-methoxyphenol contained in the said commercially available polymeric compound for stability provision.

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

  As content of the said plasticizer, 0.1-50 mass% is preferable with respect to all the components of the said photosensitive layer, 0.5-40 mass% is more preferable, 1-30 mass% is especially preferable.

-Color former-
The color former is added to give a visible image (printing function) to the photosensitive layer after exposure.
Examples of the color former include tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, tris (4- Diethylamino-2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolylmethane, tris (4-di Aminotriarylmethanes such as propylaminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine, etc. Aminoxanthines; 3,6-bis (diethyl Aminothioxanthenes such as mino) -9- (2-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9- Amino-9,10-dihydroacridine such as phenylacridine, 3,6-bis (benzylamino) -9,10-dividro-9-methylacridine; aminophenoxazine such as 3,7-bis (diethylamino) phenoxazine Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (4-dimethylamino) Aminophenylmethanes such as phenyl) anilinomethane; 4-amino-4 ′ Aminohydrocinnamic acids such as dimethylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis ( Ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; phenethylanilines such as N, N-diethyl-4-phenethylaniline; 10-acetyl-3,7-bis (dimethylamino) ) An acyl derivative of a leuco dye containing basic NH such as phenothiazine; a leuco-like compound which does not have an oxidizable hydrogen such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmentane but can be oxidized to a coloring compound Leucoin digoid pigment; U.S. Pat. Nos. 3,042,515 and 3,042 Organic amines that can be oxidized to a colored form as described in No. 517 (eg, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediamine triphenylamine, N-vinylcarbazole) and the like. Among these, triarylmethane compounds such as leuco crystal violet are more preferable.

Furthermore, it is generally known that the color former is combined with a halogen compound for the purpose of coloring the leuco body.
Examples of the halogen compound include halogenated hydrocarbons (for example, carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, Diphenylmethyl bromide, hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3-tribromopropane 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, 1,1,1-trichloro-2,2-bis (4 -Chlorophenyl) ethane and the like; halogenated alcohol compounds (for example, 2,2,2-trichloroethanol, Libromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribromo-t-butyl alcohol, 2,2,3-trichlorobutane -1,4-diol and the like; halogenated carbonyl compounds (for example, 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1, 1,1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc .; halogenated ether compounds (for example, 2-bromoethyl methyl ether, 2-bromoethyl ethyl) Ether, di (2-bromoethyl) ether, 1,2 Halogenated ester compounds (eg, bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, α, β) Halogenated amide compounds (for example, chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2- Trichloropropionamide, N-chlorosuccinimide, N-bromosuccinimide, etc.); compounds having sulfur or phosphorus (for example, tribromomethylphenylsulfone, 4-ni B phenyl tribromomethyl sulfone, 4-chlorophenyl tribromomethyl sulfone, tris (2,3-dibromopropyl) phosphate, etc.), e.g., 2,4-bis (trichloromethyl) 6- phenyltriazole and the like. As the organic halogen compound, a halogen compound having two or more halogen atoms bonded to the same carbon atom is preferable, and a halogen compound having three halogen atoms per carbon atom is more preferable. The said organic halogen compound may be used individually by 1 type, and may use 2 or more types together. Among these, tribromomethylphenyl sulfone and 2,4-bis (trichloromethyl) -6-phenyltriazole are particularly preferable.

  The content of the color former is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 5% by mass with respect to all components of the photosensitive layer. Moreover, as content of the said halogen compound, 0.001-5 mass% is preferable with respect to all the components of the said photosensitive layer, and 0.005-1 mass% is more preferable.

-Colorant-
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, known pigments or dyes such as red, green, blue, yellow, purple, magenta, cyan, and black may be used. Specifically, Victoria Pure Blue BO (C.I. 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C.I. Pigment Red) 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FB (CI Pigment Red 11), Fastel Pink B Spula (CI Pigment Red 81), Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI pigment black 1) and carbon black.

  Examples of the colorant suitable for producing a color filter include C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 83, C.I. I. Pigment violet 23, and those described in JP-A-2002-162752 (0138) to (0141). There is no restriction | limiting in particular as an average particle diameter of the said coloring agent, Although it can select suitably according to the objective, For example, 5 micrometers or less are preferable and 1 micrometer or less is more preferable. Moreover, when producing a color filter, as said average particle diameter, 0.5 micrometer or less is preferable.

--- Dye--
The dye is preferably added to improve handling properties such as visibility during inspection of the coated surface and does not reduce the coated surface and exposure sensitivity of the photosensitive layer.
As the dye, those having a large difference in absorption wavelength from the absorption wavelength after coloring by the color former and having no absorption with respect to the exposure wavelength are preferable.
Also, the absorption wavelength of the dye preferably has a maximum absorption wavelength in the range of 500 to 650 nm because the photosensitive layer preferably exhibits a green color that is excellent in visibility during inspection and does not irritate the operator's vision. preferable.
The dye is not particularly limited as long as it is a dye having a filtration pressure of 0.35 μm or less in a filter having a pore size of 0.45 μm of 0.5% by mass of a methyl ethyl ketone solution. It is preferable that the compound has a triallylmethane skeleton. The dye is preferably an ionic dye, and the counter anion of the ionic dye particularly preferably has an aromatic acid, carboxylic acid, phosphoric acid or the like.
Examples of the aromatic acid include naphthalene sulfonic acid and phenyl sulfonic acid. Among these, naphthalene sulfonic acid is more preferable from the viewpoint of solubility.
The compound having the triallylmethane skeleton is excellent in solubility in an organic solvent, excellent in handling properties such as visibility during the inspection of the coated surface of the photosensitive layer, and the coated surface and exposure sensitivity of the photosensitive layer. From the viewpoint of not lowering, it is preferable to use an allyl sulfonic acid compound, and a naphthalene sulfonic acid compound is more preferable.
As said naphthalene acid compound, Victoria pure blue NAPS is mentioned suitably, for example.
--Solubility in organic solvents--
The dye preferably has a filtration pressure of 0.3 MPa or less with a 0.45 μm pore size filter of a 0.5% by mass methyl ethyl ketone solution. The filtration pressure can be measured as follows. The filtration pressure was measured at room temperature and atmospheric pressure.
(1) Dissolve 0.5% by mass of the dye in the methyl ethyl ketone solution.
(2) A filter (ADVANTEC, DISMIC; 25HP045AN) having a pore diameter of 0.45 μm is connected to a syringe (Terumo, SS-20ESZ; diameter 1.5 cm, length 9.5 cm), The methyl ethyl ketone solution with 0.5% by mass of the colored dye filled in the syringe is filtered. At this time, the filtration rate is 50 cc / min.
(3) The pressure acting on the syringe at the time of the filtration is measured with a pressure gauge to obtain the filtration pressure of the colored dye 0.5 mass% methyl ethyl ketone solution.
When the filtration pressure is 0.3 MPa or less, the coloring dye is excellent in solubility in an organic solvent, the surface state of the photosensitive layer and the exposure sensitivity are not deteriorated, and an undissolved residue hardly occurs. It will be a thing. When the filtration pressure exceeds 0.3 MPa, the solubility is inferior, and the undissolved material may cause a surface failure of the photosensitive layer, decrease in exposure sensitivity, or may easily cause a colored dye residue.
The content of the dye is preferably 0.001 to 20% by mass, more preferably 0.03 to 3% by mass, and particularly preferably 0.05 to 0.1% by mass with respect to all components of the photosensitive layer. When the content is less than 0.001% by mass, the color developability deteriorates and the visibility at the time of surface inspection becomes poor. When the content exceeds 20% by mass, the color formation by the color former may not be confirmed. .

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

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

  As content of the said adhesion promoter, 0.001 mass%-20 mass% are preferable with respect to all the components of the said photosensitive layer, 0.01-10 mass% is more preferable, 0.1 mass%-5 mass% % Is particularly preferred.

  The photosensitive layer is, for example, J.I. It may contain organic sulfur compounds, peroxides, redox compounds, azo or diazo compounds, photoreducible dyes, organic halogen compounds, etc. as described in Chapter 5 of “Light Sensitive Systems” Good.

  Examples of the organic sulfur compound include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethane sulfenate, and 2-mercaptobenzimidazole. Is mentioned.

  Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.

  The redox compound is a combination of a peroxide and a reducing agent, and examples thereof include ferrous ions and persulfate ions, ferric ions and peroxides.

  Examples of the azo and diazo compounds include α, α'-azobisiributyronitrile, 2-azobis-2-methylbutyronitrile, and diazonium compounds such as 4-aminodiphenylamine.

  Examples of the photoreducible dye include rose bengal, erythrosine, eosin, acriflavine, lipoflavin, and thionine.

<Cushion layer>
Since the cushion layer has a function of softening under a lamination condition at the time of forming a laminated body in which a pattern forming material is laminated on a base material to be described later, and has a function of promoting the unevenness followability of the photosensitive layer, the support body And between the photosensitive layer and the photosensitive layer. As a result of promoting the unevenness followability, bubbles can be prevented from being formed between the substrate and the photosensitive layer, and the substrate adhesion of the photosensitive layer can be improved.

There is no restriction | limiting in particular as said cushion layer, Although it can select suitably according to the objective, For example, what contains a thermoplastic resin is preferable, and what contains the thermoplastic resin whose softening point is 80 degrees C or less is more. preferable.
The cushion layer may be alkali-soluble or alkali-insoluble, but is preferably alkali-soluble.

  When the cushion layer is alkali-soluble, the thermoplastic resin is not particularly limited, and a known one can be used. For example, a resin described in JP-A-5-173320 can be preferably mentioned. it can.

  When the cushion layer is alkali-insoluble, the thermoplastic resin is not particularly limited, and a known one can be used. For example, the resin described in JP-A-2003-5364 can be preferably mentioned. it can.

  In the case of having the cushion layer, the interlayer adhesive force of the pattern forming material is not particularly limited and can be appropriately selected according to the purpose. It is preferable that the adhesive force between the layer and the cushion layer is the smallest. By setting such an interlayer adhesive strength, the support and the cushion layer are peeled from the laminate, and the photosensitive layer is exposed, and then the photosensitive layer can be developed using a developer. Further, after exposing the photosensitive layer while leaving the support, the support and the cushion layer can be peeled off from the laminate, and the photosensitive layer can be developed using a developer.

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected depending on the purpose. For example, various polymers, supercooling substances, adhesion improvers, surfactants in the thermoplastic resin, Examples thereof include a method of adding a release agent and the like, and a method of adjusting the copolymerization ratio of the thermoplastic resin.

There is no restriction | limiting in particular as thickness of the said cushion layer, Although it can select suitably according to the objective, For example, 1-100 micrometers is preferable, 5-50 micrometers is more preferable, and 10-30 micrometers is especially preferable.
When the thickness is less than 1 μm, unevenness on the surface of the substrate and unevenness followability to bubbles and the like may be reduced, and a high-definition pattern may not be formed. May be.

<Intermediate layer>
The intermediate layer is provided between the cushion layer and the photosensitive layer from the viewpoint of suppressing the movement of the substance and improving the temporal stability of the basic properties of the photosensitive resin such as sensitivity and developability. Is preferred.
There is no restriction | limiting in particular as said substance, Although it can select suitably according to the objective, For example, the substance contained in at least any one of oxygen, water, the said photosensitive layer, and a cushion layer is mentioned.

  The intermediate layer is not particularly limited as long as the movement of the substance can be suppressed, and can be appropriately selected according to the purpose. The intermediate layer may be water-soluble or water-insoluble. Therefore, it is preferably water-soluble or water-dispersible, and preferably soluble in an alkaline liquid. In the case where the intermediate layer is insoluble in the alkaline solution, a step of removing the intermediate layer is necessary after the exposure to remove the intermediate layer with the alkaline solution, which increases the number of production steps. There is.

The intermediate layer is preferably oxygen barrier.
The oxygen permeability in the intermediate layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, under conditions of a temperature of 23 ° C. and a relative humidity of 60%, 50 cc / m ² · day · Atm or less is preferable, and 25 cc / m ² · day · atm or less is more preferable.
Here, the oxygen permeability can be measured in accordance with, for example, the method described in ASTM standards D1434-82 (1986).

  The intermediate layer is not particularly limited as long as it can be dispersed or dissolved in water or an aqueous alkali solution to suppress the movement of the substance, and a known one can be used. For example, the composition described in JP-A-5-173320 A thing can be mentioned suitably.

There is no restriction | limiting in particular as thickness of the said intermediate | middle layer, Although it can select suitably according to the objective, For example, 0.1-30 micrometers is preferable, 0.5-10 micrometers is more preferable, 1-5 micrometers is especially preferable. .
When the thickness is less than 0.1 μm, the function of suppressing the movement of the substance is lowered, the movement of components over time may occur between the photosensitive layer and the cushion layer, and the ability to block oxygen is reduced. Deterioration may reduce the sensitivity of the photosensitive layer. On the other hand, when the thickness exceeds 30 μm, the flexibility is inferior and the handleability of the film may be deteriorated.

  When the pattern forming material has the intermediate layer between the cushion layer and the photosensitive layer, the interlayer adhesive force of the pattern forming material is not particularly limited and may be appropriately selected according to the purpose. For example, among the interlayer adhesive strength of each layer, the interlayer adhesive strength between the support and the cushion layer may be the smallest, layer indirect between the cushion layer and the intermediate layer The adhesive force may be the smallest, and the interlayer adhesive force between the intermediate layer and the photosensitive layer may be the smallest, but among these, the interlayer adhesive force between the cushion layer and the intermediate layer is the most. Smaller is more preferable.

<Protective film>
When the protective film is used in the form of a roll of the pattern forming material of the present invention, the photosensitive layer having adhesiveness is transferred to the support and prevents the wall or the like from adhering to the photosensitive layer. Thus, it is used by being laminated on the photosensitive layer.
There is no restriction | limiting in particular as said protective film, Although it can select suitably according to the objective, For example, a polyester film, a polyethylene film, a polypropylene film, a polyvinyl alcohol film, a Teflon (trademark) film etc. are mentioned. it can. Among these, a polyethylene film and a polypropylene film are more preferable.

  Although it can select suitably as thickness of the said protective film according to the objective, For example, 5-50 micrometers is preferable and 10-30 micrometers is more preferable. When the thickness is less than 5 μm, the strength as a protective film is insufficient, and when the protective film is laminated to the photosensitive layer, the film tends to break. When the thickness exceeds 50 μm, the cost load increases, Wrinkles tend to occur when laminating.

Also in the protective film, surface smoothness is important for the surface in contact with the photosensitive layer, like the support. The protective film of the present invention has a center line average surface roughness (Ra) of 100 nm or less on the surface in contact with the photosensitive layer and 100 to 800 nm on the surface not in contact with the photosensitive layer. It is preferably 10 nm or less on the surface in contact with the photosensitive layer, and more preferably 150 to 400 nm on the surface not in contact with the photosensitive layer.
When the centerline average surface roughness (Ra) exceeds 100 nm on the surface in contact with the photosensitive layer, the surface shape of the protective film is transferred to the photosensitive layer side, the photosensitive layer is recessed, and air during lamination May cause voids.
On the other hand, when the center line average surface roughness (Ra) is less than 100 nm on the surface not in contact with the photosensitive layer, wrinkles are generated during winding of the protective film at the time of lamination, and the workability cannot be laminated. When the surface that does not contact the photosensitive layer exceeds 800 nm, the surface shape of the surface that does not contact the photosensitive layer is transferred to the photosensitive layer by the winding tension at the time of coating and drying of the photosensitive layer and at the time of slitting. It may cause air voids when laminating substrates.

In the protective film, the number of fish eyes having a diameter of 80 μm or more contained in the protective film is preferably 5 / m ² or less. Here, the “fish eye” means that when a material is melted and kneaded, and a film is produced by extrusion stretching or casting, foreign materials, undissolved materials, oxidation degradation products, etc. of the material are taken into the film. It is a thing. The “fish eye diameter” means the maximum diameter of the fish eye.

Such a film having a good fish eye level can be produced by selecting a material, optimizing a kneading method, filtering after melting the material, and the like. The diameter of the fish eye varies depending on the material, but is about 10 μm to 1 mm, and the height from the film surface is about 1 to 50 μm.
Here, the size of the fish eye can be measured using, for example, an optical microscope, a contact type surface roughness meter, a non-contact type surface measuring device using laser light, a scanning electron microscope, or the like.

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

  Such protective films are commercially available, for example, polypropylene films such as Alfan MA-410 and E-200 manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., PS-25 manufactured by Teijin Limited, and the like. And polyethylene terephthalate film such as PS series. A commercially available film may be used after sandblasting.

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

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

<< Other layers >>
In addition to the photosensitive layer, the support, the cushion layer, the intermediate layer, and the protective film, the photosensitive solder resist film of the present invention includes other layers such as a release layer, an adhesive layer, a light absorbing layer, and a surface protective layer. You may have a layer.
There is no restriction | limiting in particular in the arrangement | positioning, thickness, etc. in the said photosensitive soldering resist film of the said other layer, According to the objective, it can select suitably.

<Form of pattern forming material>
Below, the example of the pattern formation material of this invention is demonstrated, referring drawings.
The form of the pattern forming material is not particularly limited as long as the photosensitive layer is provided on one surface of the support, and can be appropriately selected according to the purpose. The pattern forming material of 1st to 4th form can be mentioned suitably.

-Pattern forming material of the first form-
FIG. 35 is a cross-sectional view showing an example of a pattern forming material according to the first embodiment.
The pattern forming material according to the first embodiment includes the photosensitive layer and the protective film on one surface of the support.
That is, as shown in FIG. 35, the pattern forming material according to the first embodiment is obtained by laminating a photosensitive layer 503 and a protective film 501 in this order on one surface of a support 502.

-Pattern forming material of second form-
FIG. 36 is a cross-sectional view showing an example of a pattern forming material according to the second embodiment.
The pattern forming material according to the second embodiment includes the cushion layer, the photosensitive layer, and the protective film in this order on one surface of the support.
That is, as shown in FIG. 36, the pattern forming material according to the second embodiment is formed by laminating a cushion layer 504, a photosensitive layer 503, and a protective film 501 in this order on one surface of a support 502. is there.

-Pattern forming material of the third form-
FIG. 37 is a cross-sectional view showing an example of a pattern forming material according to the third embodiment.
The pattern forming material according to the third aspect includes the cushion layer, the intermediate layer, the photosensitive layer, and the protective film in this order on one surface of the support.
That is, as shown in FIG. 37, in the pattern forming material according to the second embodiment, the cushion layer 504, the intermediate layer 505, the photosensitive layer 503, and the protective film 501 are laminated in this order on one surface of the support 502. It will be.

-Pattern forming material of the fourth form-
FIG. 38 is a cross-sectional view showing an example of a pattern forming material according to the fourth embodiment.
The pattern formation material which concerns on a 4th form is equipped with the said intermediate | middle layer, the said photosensitive layer, and the said protective film in this order on the at least one surface of the said support body.
That is, as shown in FIG. 38, the pattern forming material according to the second embodiment is formed by laminating an intermediate layer 505, a photosensitive layer 503, and a protective film 501 in this order on one surface of a support 502. is there.

<Method for producing pattern forming material>
The pattern forming material can be manufactured, for example, as follows.
First, the coating layer is prepared by dissolving, emulsifying, or dispersing materials contained in the photosensitive layer and, if necessary, other layers such as a cushion layer and an intermediate layer in water or a solvent.
Here, when preparing the coating solution for forming the photosensitive layer, the photosensitive resin composition solution in which the components of the photosensitive layer are dissolved, emulsified or dispersed so that the solid content concentration is 5 to 20% by mass. Preferably it is prepared.
Moreover, it is preferable to filter the said coating liquid, especially the said photosensitive resin composition solution with a filter of diameter 1 micrometer or less after preparation. By performing the filtration, foreign materials, undissolved materials, oxidation degradation products, and the like of the materials contained in the coating solution can be removed, and the flatness of each layer after coating and drying can be improved.

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

Next, the said coating liquid is apply | coated on the said support body, and it can be made to dry and form each layer, and a pattern formation material can be manufactured.
For example, the pattern forming material of the first form is formed by applying the photosensitive resin composition solution onto a support, drying to form a photosensitive layer, and forming a protective film thereon. Can be manufactured.

The pattern forming material of the second form is formed by applying a cushion layer coating solution in which components of the cushion layer are dissolved, emulsified or dispersed on the support, and drying to form a cushion layer. The pattern forming material can be produced by applying the photosensitive resin composition solution to the substrate and drying it to form a photosensitive layer and further forming a protective film thereon.
In the case of the pattern forming material of the second form, various treatments may be performed on the support in order to enhance the adhesion between the cushion layer and the support. Examples thereof include coating of an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge treatment, active plasma irradiation treatment, and laser beam irradiation treatment.
In the pattern forming material of the second form, when only the support is peeled off after the laminating step, the unsupported support is suitable. On the other hand, when the support and the cushion layer are peeled off after the lamination step, it is important not to use a solvent that dissolves the cushion layer or a solvent that swells in the photosensitive resin composition solution.

The pattern forming material of the third form is formed by applying the cushion layer coating liquid on the support and drying to form a cushion layer, and dissolving, emulsifying, or dispersing the components of the intermediate layer on the cushion layer The intermediate layer coating solution is applied and dried to form an intermediate layer. The photosensitive resin composition solution is applied onto the intermediate layer and dried to form a photosensitive layer, and a protective film is further formed thereon. By forming the pattern forming material, it is possible to manufacture the pattern forming material.
Also in the pattern forming material of the third form, when only the support is peeled off after the laminating step, the unsupported support is suitable. On the other hand, when the support and the cushion layer are peeled off after the lamination step, it is important not to use a solvent that dissolves the cushion layer or a solvent that swells in the photosensitive resin composition solution.

The pattern forming material of the fourth form is formed by applying an intermediate layer coating solution in which the components of the intermediate layer are dissolved, emulsified or dispersed on the support, and drying to form an intermediate layer. The pattern forming material can be produced by applying the photosensitive resin composition solution to the substrate and drying it to form a photosensitive layer and further forming a protective film thereon.
Also in the pattern forming material of the fourth form, when only the support is peeled off after the laminating step, the support is untreated as in the case of the pattern forming material of the third form. Is suitable.

The method for applying the coating liquid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a spray method, a roll coating method, a spin coating method, a slit coating method, an extrusion coating method, and a curtain coating. Examples thereof include various methods such as a method, a die coating method, a wire bar coating method, and a knife coating method.
Among these methods, when the photosensitive layer is applied, an extrusion method capable of obtaining the smoothness of the applied layer is particularly preferable.

As the drying after the application, the solvent is removed by heating and drying the coating film in a drier while usually carrying the web and blowing hot air. There is no restriction | limiting in particular as direction of this hot air, For example, a vertical upward flow, a vertical downward flow, a horizontal opposing flow, a horizontal parallel flow, etc. can be selected arbitrarily.
In the method of the present invention, the wind speed of the hot air drier used for the drying of the photosensitive layer coating solution can be changed stepwise. For example, after drying at a wind speed of 2 m / sec first, the wind speed is further increased to dry. can do. If the wind speed is less than 2 m / sec, the temperature of the coating film surface does not rise in a short time, so that the required coating film strength may not be obtained.
The drying conditions vary depending on the type of each component, the usage ratio, and the like, but are usually about 50 to 120 ° C. for about 30 seconds to 15 minutes. The drying zone may be divided into a large number, and the temperature and air volume can be set individually in each zone.

(Pattern formation method)
The pattern forming method of the present invention includes at least a laminating step of laminating the photosensitive layer in the pattern forming material of the present invention on the surface of the substrate, an exposure step, and a developing step, and includes other steps selected as appropriate.

[Lamination process]
The laminating step is a step of laminating the pattern forming material such that the photosensitive layer is on the surface side of the substrate by at least one of pressurization and heating.

There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, a hot roll type laminator (For example, Taisei Laminator company make, VP-II), A vacuum laminator (for example, V130 manufactured by Nichigo Morton Co., Ltd.) and the like are preferable.

<Base material>
The substrate is not particularly limited and can be appropriately selected from known materials having high surface smoothness to those having an uneven surface. A plate-like substrate (substrate) is preferred. Specifically, known printed wiring board forming substrates (for example, copper-clad laminates), glass plates (for example, soda glass plates, etc.), synthetic resin films, paper, metal plates and the like can be mentioned.

  Suitable examples of the printed wiring board forming substrate include a glass epoxy substrate, an epoxy-impregnated aramid nonwoven fabric, and a surface of an insulating layer such as polyimide, on which a copper foil layer is provided as a plating foil or a sputtered foil. When the sputter foil is provided, another metal foil (Ni, Cr, etc.) may be provided as a base layer for the purpose of improving the adhesion between the copper foil and the insulating layer.

  The surface of the base material may be formed with irregularities of about 0.5 to 2 μm by a method such as chemical polishing for the purpose of improving adhesion with the pattern forming material to be laminated.

[Exposure process]
The said exposure process is a process of exposing with respect to the photosensitive layer in the pattern formation material of this invention. The pattern forming material of the present invention is as described above.

  The object of exposure is not particularly limited as long as it is the photosensitive layer in the pattern forming material having a photosensitive layer on the support, and can be appropriately selected according to the purpose. It is preferably performed on a laminate in which the pattern forming materials are laminated.

As the exposure to the laminated body, for example, the photosensitive layer may be exposed through the support of the layered pattern forming material, or after the support is peeled off, the photosensitive layer is exposed. However, when there is no other layer such as a cushion layer or an intermediate layer between the support and the photosensitive layer, as shown in FIG. 39, the support is interposed through the support. It is preferred to expose the photosensitive layer.
When the pattern forming material has a cushion layer between the support and the photosensitive layer, as shown in FIG. 40, after peeling the support together with the cushion layer, It is preferred to expose the photosensitive layer.
When the pattern forming material has the cushion layer and the intermediate layer in this order between the support and the photosensitive layer, as shown in FIG. 41, the support is provided with the cushion layer. After peeling together, the photosensitive layer is preferably exposed through the intermediate layer.
In the case where the pattern forming material has an oxygen-blocking intermediate layer between the support and the photosensitive layer, as shown in FIG. It is preferred to expose the photosensitive layer through the layer.

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

The digital exposure includes, for example, a light irradiating 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 irradiating means. An exposure head provided with a light modulation means capable of controlling the picture element unit according to pattern information, wherein the column direction of the picture element part is a predetermined set inclination angle θ with respect to the scanning direction of the exposure head. Using an exposure head arranged to form
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
A method of performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction is preferable.

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

<Pattern forming device>
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 so-called flat bed type exposure apparatus, and as shown in FIG. 1, a sheet-like photosensitive laminate 12 (at least the photosensitive layer in the photosensitive transfer material is laminated). In the following, there is provided a flat plate-like moving stage 14 that adsorbs and holds a “photosensitive material 12” or “photosensitive layer 12” on the surface. Two guides 20 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 18 supported by the four legs 16. The stage 14 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 20 so as to be reciprocally movable. The pattern forming apparatus 10 is provided with a stage driving device (not shown) that drives the stage 14 along the guide 20.

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

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

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

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

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

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

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

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

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

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

  As shown in detail in FIG. 5, the lens system 40 has a pair of combination lenses 44 that collimate the laser light emitted from the fiber array light source 38, and the light quantity distribution of the collimated laser light becomes uniform. A pair of combination lenses 46 to be corrected in this way, and a condensing lens 48 that condenses the laser light whose light quantity distribution has been corrected on the DMD 36.

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

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

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

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

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

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

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

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

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

The wavelength of the ultraviolet to visible light is preferably, for example, 300 to 1,500 nm, more preferably 320 to 800 nm, and particularly preferably 330 nm to 650 nm.
As a wavelength of the said laser beam, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330 nm-500 nm is still more preferable, 400 nm-450 nm is especially preferable.

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

Hereinafter, means (fiber array light source) capable of irradiating the combined laser will be described with reference to the drawings.
As shown in FIG. 8, the fiber array light source 38 includes a plurality of (for example, 14) laser modules 60, and one end of a multimode optical fiber 62 is coupled to each laser module 60. An optical fiber 64 having a cladding diameter smaller than that of the multimode optical fiber 62 is coupled to the other end of the multimode optical fiber 62. As shown in detail in FIG. 9, seven ends of the optical fiber 64 opposite to the multimode optical fiber 62 are arranged along the direction orthogonal to the scanning direction, and these are arranged in two rows to form the laser emitting unit 66. Is configured.

  As shown in FIG. 9, the laser emitting portion 66 constituted by the end portion of the optical fiber 64 is sandwiched and fixed between two support plates 68 having a flat surface. Moreover, it is desirable that a transparent protective plate such as glass is disposed on the light emitting end face of the optical fiber 64 for protection. The light exit end face of the optical fiber 64 has a high light density and is likely to collect dust and easily deteriorate. However, by arranging the protective plate as described above, it is possible to prevent the dust from adhering to the end face and to delay the deterioration. Can do.

  For example, as shown in FIG. 25, such an optical fiber is formed by coaxially connecting an optical fiber 64 having a length of 1 to 30 cm with a small cladding diameter at the tip portion on the laser light emission side of a multimode optical fiber 62 having a large cladding diameter. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 64 is fused and joined to the outgoing end face of the multimode optical fiber 62 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 64 a of the optical fiber 64 is the same as the diameter of the core 62 a of the multimode optical fiber 62.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused with an optical fiber having a small cladding diameter may be coupled to the output end of the multimode optical fiber 62 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 64 may be referred to as an emission end portion of the multimode optical fiber 62.

  The multimode optical fiber 62 and the optical fiber 64 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used. In the present embodiment, the multimode optical fiber 62 and the optical fiber 64 are step index type optical fibers, and the multimode optical fiber 62 has a cladding diameter = 125 μm, a core diameter = 50 μm, NA = 0.2, an incident end face. The transmittance of the coat is 99.5% or more, and the optical fiber 64 has a clad diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2.

  In general, in the laser light in the infrared region, the propagation loss increases as the cladding diameter of the optical fiber is reduced. For this reason, a suitable cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, the cladding thickness {(cladding diameter−core diameter) / 2} is set to an infrared light having a wavelength band of 800 nm. The propagation loss hardly increases even if it is about ½ of the case of propagating infrared light and about ¼ of the case of propagating infrared light in the 1.5 μm wavelength band for communication. Therefore, the cladding diameter can be reduced to 60 μm.

  However, the cladding diameter of the optical fiber is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber array light source is 125 μm. However, the smaller the clad diameter, the deeper the focal depth, so the clad diameter of the optical fiber is preferably 80 μm or less, more preferably 60 μm or less. 40 μm or less is more preferable. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 64 is preferably 10 μm or more.

  The laser module 60 is composed of a combined laser light source (fiber array light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6 arranged on the heat block 110, And LD7, collimator lenses L1, L2, L3, L4, L5, L6, and L7 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 200, and one multimode. And an optical fiber 62. The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

  The GaN-based semiconductor lasers LD1 to LD7 all have the same oscillation wavelength (for example, 405 nm), and the maximum output is also all the same (for example, 100 mW for the multimode laser and 30 mW for the single mode laser). As the GaN-based semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above 405 nm in a wavelength range of 350 nm to 450 nm may be used.

  As shown in FIGS. 27 and 28, the combined laser light source is housed in a box-shaped package 400 having an upper opening together with other optical elements. The package 400 includes a package lid 410 created so as to close the opening. After the degassing process, a sealing gas is introduced, and the package 400 and the package lid are closed by closing the opening of the package 400 with the package lid 410. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by the reference numeral 410.

  A base plate 420 is fixed to the bottom surface of the package 400, and the heat block 110, a condensing lens holder 450 that holds the condensing lens 200, and the multimode optical fiber 62 are disposed on the top surface of the base plate 420. A fiber holder 460 that holds the incident end is attached. The exit end of the multimode optical fiber 62 is drawn out of the package from an opening formed in the wall surface of the package 400.

  A collimator lens holder 440 is attached to the side surface of the heat block 110, and the collimator lenses L1 to L7 are held. An opening is formed in the lateral wall surface of the package 400, and a wiring 470 for supplying a driving current to the GaN semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 28, in order to avoid complication of the drawing, only the GaN semiconductor laser LD7 is numbered among the plurality of GaN semiconductor lasers, and only the collimator lens L7 is numbered among the plurality of collimator lenses. is doing.

  FIG. 29 shows a front shape of a mounting portion of the collimator lenses L1 to L7. Each of the collimator lenses L <b> 1 to L <b> 7 is formed in a shape in which a region including the optical axis of a circular lens having an aspherical surface is cut out in a parallel plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses L1 to L7 are closely arranged in the light emitting point arrangement direction so that the length direction is orthogonal to the light emitting point arrangement direction of the GaN-based semiconductor lasers LD1 to LD7 (left-right direction in FIG. 29).

  On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having a light emission width of 2 μm, and each of the laser beams B1 in a state parallel to the active layer and a divergence angle in a direction perpendicular to the active layer, for example, 10 ° and 30 °. A laser emitting ~ B7 is used. These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.

Therefore, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the divergence angle is small with respect to the elongated collimator lenses L1 to L7 as described above. Incident light is incident in a state where the direction coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses L1 to L7 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2. 6 mm. In addition, each of the collimator lenses L1 to L7 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 200 is formed by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane in parallel planes, and is long in the arrangement direction of the collimator lenses L1 to L7, that is, in the horizontal direction and short in the direction perpendicular thereto. Is formed. The condenser lens 200 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 200 is also formed by molding resin or optical glass, for example.

  In addition, since the light emitting means for illuminating the DMD uses a high-intensity fiber array light source in which the output ends of the optical fibers of the combined laser light source are arranged in an array, it has a high output and a deep depth of focus. A pattern forming apparatus can be realized. Furthermore, since the output of each fiber array light source is increased, the number of fiber array light sources required to obtain a desired output is reduced, and the cost of the pattern forming apparatus can be reduced.

  In addition, since the cladding diameter at the exit end of the optical fiber is smaller than the cladding diameter at the entrance end, the diameter of the light emitting portion is further reduced, and the brightness of the fiber array light source can be increased. Thereby, a pattern forming apparatus having a deeper depth of focus can be realized. For example, even in the case of ultra-high resolution exposure with a beam diameter of 1 μm or less and a resolution of 0.1 μm or less, a deep depth of focus can be obtained, and high-speed and high-definition exposure is possible. Therefore, it is suitable for a thin film transistor (TFT) exposure process that requires high resolution.

  The light irradiating means is not limited to a fiber array light source including a plurality of the combined laser light sources, and for example, emits laser light incident from a single semiconductor laser having one light emitting point. A fiber array light source in which fiber light sources including optical fibers are arrayed can be used.

  Moreover, as a light irradiation means provided with a plurality of light emitting points, for example, as shown in FIG. 30, a laser in which a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 are arranged on a heat block 110. An array can be used. Further, a chip-shaped multi-cavity laser 110 shown in FIG. 31A in which a plurality of (for example, five) light emitting points 111a are arranged in a predetermined direction is known. Since the multicavity laser 111 can arrange the light emitting points with high positional accuracy as compared with the case where the chip-shaped semiconductor lasers are arranged, it is easy to multiplex the laser beams emitted from the respective light emitting points. However, as the number of light emitting points increases, the multi-cavity laser 111 is likely to be bent at the time of laser manufacture. Therefore, the number of light emitting points 111a is preferably 5 or less.

  As the light irradiation means, as shown in FIG. 31B, a plurality of multi-cavity lasers 111 are arranged on the heat block 110 in the same direction as the arrangement direction of the light emitting points 111a of each chip. A multi-cavity laser array can be used as a laser light source.

  The combined laser light source is not limited to one that combines laser beams emitted from a plurality of chip-shaped semiconductor lasers. For example, as shown in FIG. 32, a combined laser light source including a chip-shaped multicavity laser 111 having a plurality of (for example, three) emission points 111a can be used. The combined laser light source includes a multi-cavity laser 111, a single multi-mode optical fiber 62, and a condenser lens 200. The multicavity laser 111 can be composed of, for example, a GaN laser diode having an oscillation wavelength of 405 nm.

  In the above-described configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111 a of the multicavity laser 111 is collected by the condenser lens 200 and enters the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  A plurality of light emitting points 111 a of the multicavity laser 111 are arranged in parallel within a width substantially equal to the core diameter of the multimode optical fiber 62, and a focal point substantially equal to the core diameter of the multimode optical fiber 62 is formed as the condenser lens 200. By using a convex lens of a distance or a rod lens that collimates the outgoing beam from the multicavity laser 111 only in a plane perpendicular to the active layer, the coupling efficiency of the laser beam B to the multimode optical fiber 62 can be increased. it can.

  As shown in FIG. 33, a multi-cavity laser 111 having a plurality of (for example, three) emission points is used, and a plurality of (for example, nine) multi-cavity lasers 111 are equidistant from each other on the heat block 110. A combined laser light source including the laser array 140 arranged in (1) can be used. The plurality of multi-cavity lasers 111 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 111a of each chip.

  This combined laser light source includes a laser array 140, a plurality of lens arrays 114 arranged corresponding to each multi-cavity laser 111, and a single rod arranged between the laser array 140 and the plurality of lens arrays 114. The lens 113, one multimode optical fiber 130, and a condenser lens 120 are provided. The lens array 114 includes a plurality of microlenses corresponding to the emission points of the multicavity laser 110.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111 a of the plurality of multi-cavity lasers 111 is condensed in a predetermined direction by the rod lens 113 and then each microlens of the lens array 114. It becomes parallel light. The collimated laser beam L is condensed by the condenser lens 200 and enters the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  Still another example of the combined laser light source will be described. As shown in FIGS. 34A and 34B, this combined laser light source has a heat block 182 having an L-shaped cross section in the optical axis direction mounted on a substantially rectangular heat block 180 and is housed between two heat blocks. A space is formed. On the upper surface of the L-shaped heat block 182, a plurality of (for example, two) multi-cavity lasers 111 in which a plurality of light emitting points (for example, five) are arranged in an array form the light emitting points 111a of each chip. It is arranged and fixed at equal intervals in the same direction as the arrangement direction.

  A concave portion is formed in the substantially rectangular heat block 180, and a plurality of (for example, two) light emitting points (for example, five) are arranged in an array on the upper surface of the space side of the heat block 180. The multi-cavity laser 110 is arranged such that its emission point is located on the same vertical plane as the emission point of the laser chip arranged on the upper surface of the heat block 182.

  On the laser beam emission side of the multi-cavity laser 111, a collimator lens array 184 in which collimator lenses are arranged corresponding to the light emission points 111a of the respective chips is arranged. In the collimating lens array 184, the length direction of each collimating lens coincides with the direction in which the divergence angle of the laser beam is large (the fast axis direction), and the width direction of each collimating lens is the direction in which the divergence angle is small (slow axis direction). They are arranged to match. Thus, by collimating and integrating the collimating lenses, the space utilization efficiency of the laser light can be improved, the output of the combined laser light source can be increased, and the number of parts can be reduced and the cost can be reduced. .

  Further, on the laser beam emitting side of the collimating lens array 184, there is one multimode optical fiber 62 and a condensing lens 200 that condenses and couples the laser beam to the incident end of the multimode optical fiber 62. Is arranged.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111a of the plurality of multi-cavity lasers 111 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and collected. The light is collected by the optical lens 200 and is incident on the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  As described above, the combined laser light source can achieve particularly high output by the multistage arrangement of multicavity lasers and the array of collimating lenses. By using this combined laser light source, a higher-intensity fiber array light source or bundle fiber light source can be configured, so that it is particularly suitable as a fiber light source constituting the laser light source of the pattern forming apparatus of the present invention.

  A laser module in which each of the combined laser light sources is housed in a casing and the emission end portion of the multimode optical fiber 62 is pulled out from the casing can be configured.

  In addition, the other end of the multimode optical fiber of the combined laser light source is coupled with another optical fiber having the same core diameter as the multimode optical fiber and a cladding diameter smaller than the multimode optical fiber. However, for example, a multimode optical fiber having a cladding diameter of 125 μm, 80 μm, 60 μm or the like may be used without coupling another optical fiber to the emission end.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Thereafter, with respect to the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered with diagonal lines in FIG. 19, the same processing as that of the present embodiment (3) described with reference to FIGS. In FIG. 19, the micromirrors corresponding to the light spots constituting the shaded area 82 and the shaded area 84 are identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. Not involved.

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

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

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

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

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

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

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

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

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

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

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

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

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

[Development process]
The development step is a step of forming a pattern by exposing the photosensitive layer in the pattern forming material by the exposure step, curing the exposed region of the photosensitive layer, and then developing by removing an uncured region. is there.

The developing step can be preferably performed by, for example, 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 the developer are applied. 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 developer replacing unit that replaces the developer, a developer supplying unit that supplies the developer, and the like.

  There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, an alkaline solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline 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.

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

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

[Other processes]
There is no restriction | limiting in particular as said other process, Although selecting suitably from the process in well-known pattern formation is mentioned, For example, an etching process, a plating process, etc. are mentioned. These may be used alone or in combination of two or more.
When the printed wiring board is manufactured by the subtractive method, the etching process is performed after the development process. When the semi-additive method shown in FIG. 43 is used, the plating process and the etching process are performed after the development process. .

-Etching process-
The etching step can be performed by a method appropriately selected from known etching methods.
There is no restriction | limiting in particular as an etching liquid used for the said etching process, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, Examples thereof include a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide-based etching solution. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor.
By removing unnecessary portions (the metal layer other than the pattern portion) by the etching step, a pattern can be formed on the surface of the base material.
There is no restriction | limiting in particular as said pattern, According to the objective, it can select suitably, For example, a wiring pattern etc. are mentioned suitably.

-Plating process-
The plating step can be performed by an appropriately selected method selected from known plating processes.
Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. And gold plating such as soft gold plating.
A pattern can be formed on the surface of the substrate by removing the cured film after plating by the plating step, and further removing unnecessary portions by etching or the like as necessary.

[Method of manufacturing printed wiring board]
The said pattern formation method of this invention can be used conveniently for manufacture of a printed wiring board, especially manufacture of a printed wiring board which has hole parts, such as a through hole or a via hole. Hereinafter, an example of the manufacturing method of the printed wiring board which has a through hole using the pattern formation method of this invention is demonstrated.

(1) Laminating Step 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 laminate 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.

Next, when a protective film is provided on the pattern forming material, the protective film is peeled off so that the photosensitive layer in the pattern forming material is in contact with the surface of the printed wiring board forming substrate. Is used for pressure bonding (lamination process). Thereby, the laminated body which has the said board | substrate for printed wiring board formation and the said laminated body in this order is obtained.
There is no restriction | limiting in particular as lamination | stacking temperature of the said pattern formation material, For example, room temperature (15-30 degreeC) or under heating (30-180 degreeC) is mentioned, Among these, under heating (60-140 degreeC) ) Is more preferable.
There is no restriction | limiting in particular as roll pressure of the said crimping | compression-bonding roll, For example, 0.1-1 Mpa is preferable.
There is no restriction | limiting in particular as the speed | rate of the said crimping | compression-bonding, and 1-3 m / min is preferable.
The printed wiring board forming substrate may be preheated or laminated under reduced pressure.

(2) Exposure step Next, the photosensitive layer is cured by irradiating light from the surface of the laminate opposite to the substrate. At this time, exposure may be performed after peeling the support as necessary (for example, when the light transmittance of the support is insufficient).
Moreover, when the said support body is not yet peeled at the time after exposure, the said support body is peeled from the said laminated body.

(3) Development step Next, the uncured region of the photosensitive layer on the printed wiring board forming substrate is dissolved and removed with an appropriate developer to protect the cured layer for wiring pattern formation and the metal layer of the through hole. A cured layer pattern is formed, and the metal layer is exposed on the surface of the printed wiring board forming substrate.
Moreover, you may perform the process which further accelerates | stimulates the hardening reaction of a hardening part by post-heat processing or post-exposure processing as needed after image development. The development may be a wet development method as described above or a dry development method.

(4) Wiring part forming step Thereafter, using the formed pattern, a method of peeling the cured photosensitive layer after etching the printed wiring board forming substrate (for example, a subtractive method) or a plating process Then, the cured photosensitive layer is peeled off, and an unnecessary copper foil layer may be processed by etching (for example, a semi-additive method shown in FIG. 43).
Among these, in order to form a printed wiring board with industrially advantageous tenting, the subtractive method is preferable, but in order to form a pattern with higher resolution (small line / space), The semi-additive method is more preferable.
In the semi-additive method, for example, as shown in FIG. 43, a cured film 508 is formed on an insulating layer 507 that has been previously subjected to electroless copper plating 509a, and then an electrolytic copper plating 509b is formed between the patterns of the cured film 508. Then, the cured film 508 is stripped and removed using a stripping solution. Finally, quick etching is performed, and the electroless copper plating previously applied on the insulating layer 507 using the pattern of the electrolytic copper plating 509b as a mask. 509a is etched to obtain a wiring pattern (509a + 509b) to manufacture a semiconductor package substrate.

  There is no restriction | limiting in particular as said etching liquid, Although it can select suitably according to the objective, For example, when the said metal layer is formed with copper, a cupric chloride solution, a ferric chloride solution , Alkaline etching solution, hydrogen peroxide etching solution and the like. Among these, a ferric chloride solution is more preferable from the viewpoint of etching factor.

In order to peel off the cured photosensitive layer, it is treated with a strong alkaline aqueous solution or the like and removed as a peeled piece from the printed wiring board. .
There is no restriction | limiting in particular as a base component in the said strong alkali aqueous solution, For example, sodium hydroxide, potassium hydroxide, etc. are mentioned.
As pH of the said strong alkali aqueous solution, about 12-14 are preferable, for example, and about 13-14 are more preferable.
There is no restriction | limiting in particular as said strong alkali aqueous solution, For example, 1-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution etc. are mentioned.

The printed wiring board may be a multilayer printed wiring board.
The pattern forming material may be used not only for the above etching process but also for a plating process. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. And gold plating such as soft gold plating.

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

  As binders contained in the photosensitive resin compositions of Examples, Polymers P1 to P6 (Synthesis Examples 1 to 6), Polymers P7 to P13 (Comparative Synthesis Example 1) which are binders contained in the photosensitive resin compositions of Comparative Examples ~ 7) were synthesized as follows. The physical properties of the obtained polymers P1 to P13 are shown in Tables 1 to 3.

(Synthesis Example 1)
-Synthesis of polymer P1-
In a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, SMA2000 (manufactured by Sartomer, styrene-maleic anhydride copolymer) in a mixed atmosphere with an oxygen concentration of 7% (Copolymerization composition molar ratio: styrene / maleic anhydride = 67/33, mass average molecular weight = 7,500, Tg = 408K)) 102.1 g and 3.2 g of water were dissolved in 205 g of dioxane as a solvent. , And stirred at 100 ° C. for about 8 hours. Thereafter, 16.2 g of benzyl alcohol was added, and the mixture was further stirred at 100 ° C. for 4 hours until the absorption of the acid anhydride group disappeared while sequentially measuring the infrared absorption spectrum of the reaction product. Thereafter, 15.0 g of phenylglycidyl ether and 2.0 g of benzyltriethylammonium chloride were mixed and stirred at 70 ° C. for 6 hours and then cooled to room temperature to obtain a polymer P1 solution having a solid concentration of 40% by mass.
A part of the obtained polymer P1 solution was precipitated in n-hexane, and the solid content acid value and the mass average molecular weight were measured, which were 168 mgKOH / g and 7,700, respectively. The glass transition temperature (Tg) was 365K. Therefore, it was found that the obtained polymer P1 was a copolymer represented by the following structural formula (P1).
However, in the structural formula (P1), the number represents the molar ratio of repeating units.

(Synthesis Example 2)
-Synthesis of polymer P2-
In a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 102.1 g of the above SMA2000 and 4.1 g of water in a mixed atmosphere with an oxygen concentration of 7% Was dissolved in 209 g of dioxane as a solvent and stirred at 100 ° C. for about 8 hours. Thereafter, 10.8 g of benzyl alcohol was added and the mixture was further stirred at 100 ° C. for 4 hours until the absorption of the acid anhydride group disappeared while sequentially measuring the infrared absorption spectrum of the reaction product. Thereafter, 22.5 g of phenylglycidyl ether and 2.0 g of benzyltriethylammonium chloride were mixed and stirred at 70 ° C. for 6 hours, and then cooled to room temperature to obtain a polymer P2 solution having a solid content concentration of 40% by mass.
A part of the obtained polymer P2 solution was precipitated in n-hexane, and the solid content acid value and the mass average molecular weight were measured, and they were 165 mgKOH / g and 7,840, respectively. The glass transition temperature (Tg) was 339K. Therefore, it was found that the obtained polymer P2 was a copolymer represented by the following structural formula (P2).
However, in the structural formula (P2), the number represents the molar ratio of repeating units.

(Synthesis Example 3)
-Synthesis of polymer P3-
In a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 102.1 g of the above SMA2000 and 5.0 g of water in a mixed atmosphere with an oxygen concentration of 7% Was dissolved in 209 g of dioxane as a solvent and stirred at 100 ° C. for about 8 hours. Thereafter, 5.4 g of benzyl alcohol was added, and the mixture was further stirred at 100 ° C. for 4 hours until the absorption of the acid anhydride group disappeared while sequentially measuring the infrared absorption spectrum of the reaction product. Thereafter, 27.0 g of phenyl glycidyl ether and 2.0 g of benzyltriethylammonium chloride were mixed and stirred at 70 ° C. for 6 hours and then cooled to room temperature to obtain a polymer P3 solution having a solid concentration of 40% by mass.
A part of the obtained polymer P3 solution was precipitated in n-hexane, and the solid content acid value and the mass average molecular weight were measured, and they were 173 mgKOH / g and 7,840, respectively. The glass transition temperature (Tg) was 393K. Therefore, it was found that the obtained polymer P3 was a copolymer represented by the following structural formula (P3).
However, in the structural formula (P3), the number represents the molar ratio of repeating units.

(Synthesis Example 4)
-Synthesis of polymer P4-
SMA1000 (manufactured by Sartomer, styrene-maleic anhydride copolymer) in a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube under a mixed atmosphere with an oxygen concentration of 7%. (Copolymerization composition molar ratio: styrene / maleic anhydride = 50/50, mass average molecular weight = 5,000, Tg = 428K) 101.1 g and water 3.6 g were dissolved in 251 g of dioxane as a solvent, The mixture was stirred for about 5 hours at 100 ° C. Thereafter, 32.4 g of benzyl alcohol was added, and the infrared absorption spectrum of the reaction product was sequentially measured until the absorption of the acid anhydride group disappeared. After that, 30 g of phenylglycidyl ether and 2.0 g of benzyltriethylammonium chloride were mixed and stirred at 70 ° C. for 6 hours. To cool, the solid content concentration to obtain a 40 wt% polymer P4 solution.
A part of the obtained polymer P4 solution was precipitated in n-hexane, and the solid content acid value and the weight average molecular weight were measured, which were 168 mgKOH / g and 6,250, respectively. The glass transition temperature (Tg) was 374K. Therefore, it was found that the obtained polymer P4 was a copolymer represented by the following structural formula (P4).
However, in the structural formula (P4), the number represents the molar ratio of repeating units.

(Synthesis Example 5)
-Synthesis of polymer P5-
In a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 101.1 g of the above SMA1000 and 1.8 g of water in a mixed atmosphere with an oxygen concentration of 7% Was dissolved in 246 g of dioxane as a solvent and stirred at 100 ° C. for about 5 hours. Thereafter, 43.3 g of benzyl alcohol was added, and the mixture was further stirred at 100 ° C. for about 8 hours until the absorption of the acid anhydride group disappeared while sequentially measuring the infrared absorption spectrum of the reaction product. Then, 17.8 g of glycidyl benzoate and 2.0 g of benzyltriethylammonium chloride were mixed and stirred at 70 ° C. for 6 hours and then cooled to room temperature to obtain a polymer P5 solution having a solid concentration of 40% by mass.
A part of the obtained polymer P5 solution was precipitated in n-hexane, and the solid content acid value and the mass average molecular weight were measured. As a result, they were 171 mgKOH / g and 6,140, respectively. The glass transition temperature (Tg) was 350K. Therefore, it was found that the obtained polymer P5 was a copolymer represented by the following structural formula (P5).
However, in the structural formula (P5), the number represents the molar ratio of repeating units.

(Synthesis Example 6)
-Synthesis of polymer P6-
In a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 101.1 g of the above SMA1000 and 54.1 g of benzyl alcohol in a mixed gas atmosphere with an oxygen concentration of 7%. Was dissolved in 260 g of dioxane as a solvent and stirred at 100 ° C. for about 10 hours. Thereafter, 17.8 g of glycidyl benzoate and 2.0 g of benzyltriethylammonium chloride were mixed and stirred at 70 ° C. for 6 hours and then cooled to room temperature to obtain a polymer P6 solution having a solid concentration of 40% by mass.
A part of the obtained polymer P6 solution was precipitated in n-hexane, and the solid content acid value and the weight average molecular weight were measured, and they were 130 mgKOH / g and 6,470, respectively. The glass transition temperature (Tg) was 343K. Therefore, it was found that the obtained polymer P6 was a copolymer represented by the following structural formula (P6).
However, in the structural formula (P6), the number represents the molar ratio of repeating units.

(Comparative Synthesis Example 1)
-Synthesis of polymer P7-
25 g of methacrylic acid, 50 g of methyl methacrylate and 25 g of styrene were mixed with toluene / methyl cellosolve using 0.02 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemicals, V-65) as an initiator. In 150 g of a solvent (mass ratio: 4/6), the mixture was stirred at 80 ° C. for 10 hours under a nitrogen stream, and then cooled to room temperature to obtain a polymer P7 solution having a solid content concentration of 40 mass%.
When the solid content acid value and the weight average molecular weight of the obtained polymer P7 solution were measured, they were 163 mgKOH / g and the weight average molecular weight was 25,000. The glass transition temperature (Tg) was 401K. Therefore, it was found that the obtained polymer P7 was a copolymer represented by the following structural formula (P7).
However, in the structural formula (P7), the number represents the molar ratio of repeating units.

(Comparative Synthesis Example 2)
-Synthesis of polymer P8-
100 g of methacrylic acid, 160 g of methyl methacrylate and 100 g of styrene were started with 4 g of azobisisobutyronitrile, stirred in 750 g of methyl ethyl ketone for 8 hours at 80 ° C. in a nitrogen stream, and 3 g of azobisisobutyronitrile was obtained. The resultant was added as a methyl ethyl ketone solution, further heated and stirred for 12 hours, and then cooled to room temperature. 278 g of methyl ethyl ketone was added to obtain a polymer P8 solution having a solid content concentration of 35% by mass.
When the solid content acid value and the mass average molecular weight of the obtained polymer P8 solution were measured, they were 171 mgKOH / g and the mass average molecular weight was 50,000. The glass transition temperature (Tg) was 403K. Therefore, it was found that the obtained polymer P8 was a copolymer represented by the following structural formula (P8).
However, in the structural formula (P8), the number represents the molar ratio of repeating units.

(Comparative Synthesis Example 3)
-Synthesis of polymer P9-
208.4 g of styrene and 196 g of maleic anhydride were started with 16 g of azobisisobutyronitrile, and the mixture was stirred in 1,420 g of methyl ethyl ketone under a nitrogen stream at 80 ° C. for 8 hours, and 12 g of azobisisobutyronitrile was methyl ethyl ketone. The solution was added as a solution, heated and stirred for 12 hours, cooled to room temperature, 1,600 g of methyl ethyl ketone was added, and a styrene / maleic anhydride copolymer having a solid concentration of 35% by mass was obtained. The obtained polymer was precipitated in a large amount of n-hexane, the solid was vacuum-dried, and the molecular weight was measured by NMR analysis and GPC. The copolymerization ratio was 1/1, and the mass average molecular weight was 43,000 in terms of polystyrene. It turns out that. (Hereinafter, this polymer is referred to as SMA-1.)
In a 2 L separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 101.1 g of the above SMA-1 and water 1. 8 g was dissolved in 261 g of dioxane as a solvent, and the mixture was stirred at 100 ° C. for about 8 hours until the absorption of the acid anhydride group disappeared while sequentially measuring the infrared absorption spectrum of the reaction product. Thereafter, 71.3 g of glycidyl benzoate and 2.0 g of benzyltriethylammonium chloride were mixed and stirred at 70 ° C. for 6 hours and then cooled to room temperature to obtain a polymer P9 solution having a solid concentration of 40% by mass.
When the solid content acid value and the weight average molecular weight of the obtained polymer P9 solution were measured, they were 186 mgKOH / g and the weight average molecular weight was 58,400, respectively. The glass transition temperature (Tg) was 406K. Therefore, it was found that the obtained polymer P9 was a copolymer represented by the following structural formula (P9).
However, in the structural formula (P9), the number represents the molar ratio of repeating units.

(Comparative Synthesis Example 4)
-Synthesis of polymer P10-
In a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 101.1 g of the above SMA-1 and water 9. 0 g was dissolved in 278 g of dioxane as a solvent, and the mixture was stirred at 100 ° C. for about 8 hours until the absorption of the acid anhydride group disappeared while sequentially measuring the infrared absorption spectrum of the reaction product. Thereafter, 75.1 g of phenyl glycidyl ether and 2.0 g of benzyltriethylammonium chloride were mixed and stirred at 70 ° C. for 6 hours and then cooled to room temperature to obtain a polymer P10 solution having a solid concentration of 40% by mass.
When the solid content acid value and the weight average molecular weight of the obtained polymer P10 solution were measured, they were 151 mgKOH / g and the weight average molecular weight was 59,600, respectively. The glass transition temperature (Tg) was 295K. Therefore, it was found that the obtained polymer P10 was a copolymer represented by the following structural formula (P10).
However, in the structural formula (P10), the number represents the molar ratio of repeating units.

(Comparative Synthesis Example 5)
-Synthesis of polymer P11-
208.4 g of styrene and 196 g of maleic anhydride were used as an initiator with 120 g of azobisisobutyronitrile, and 1,420 g of methyl ethyl ketone was added with a 20 mass% methyl ethyl ketone solution of azobisisobutyronitrile in a nitrogen stream. Stir at 80 ° C. for 8 hours, then add 12 g of azobisisobutyronitrile as a methyl ethyl ketone solution, heat and stir for another 12 hours, cool to room temperature, add 1,600 g of methyl ethyl ketone, and the solid content concentration is 35% by mass. A styrene / maleic anhydride copolymer was obtained. The obtained polymer was precipitated in a large amount of n-hexane, the solid was vacuum-dried, and the molecular weight was measured by NMR analysis and GPC. The copolymerization ratio was 1/1 and the mass average molecular weight was 700 in terms of polystyrene. I understood that. (Hereinafter, this polymer is referred to as SMA-2)
In a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 101.1 g of the above SMA-2 and 9 g of water in a mixed gas atmosphere with an oxygen concentration of 7% Was dissolved in 261 g of dioxane as a solvent and stirred at 100 ° C. for about 8 hours until the absorption of the acid anhydride group disappeared while sequentially measuring the infrared absorption spectrum of the reaction product. Thereafter, 71.3 g of glycidyl benzoate and 2.0 g of benzyltriethylammonium chloride were mixed and stirred at 70 ° C. for 6 hours and then cooled to room temperature to obtain a polymer P11 solution having a solid content concentration of 40% by mass.
When the solid content acid value and the weight average molecular weight of the obtained polymer P11 solution were measured, they were 186 mgKOH / g and the weight average molecular weight was 950, respectively. The glass transition temperature (Tg) was 405K. Therefore, it was found that the obtained polymer P11 was a copolymer represented by the following structural formula (P11).
However, in the structural formula (P11), the number represents the molar ratio of repeating units.

(Comparative Synthesis Example 6)
-Synthesis of polymer P12-
In a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 101.1 g of the above SMA-2 and water 9. 0 g was dissolved in 278 g of dioxane as a solvent, and the mixture was stirred at 100 ° C. for about 8 hours until the absorption of the acid anhydride group disappeared while sequentially measuring the infrared absorption spectrum of the reaction product. Thereafter, 75.1 g of phenyl glycidyl ether and 2.0 g of benzyltriethylammonium chloride were mixed and stirred at 70 ° C. for 6 hours and then cooled to room temperature to obtain a polymer P12 solution having a solid concentration of 40% by mass.
When the solid content acid value and the weight average molecular weight of the obtained polymer P12 solution were measured, they were 150 mgKOH / g and the weight average molecular weight was 970, respectively. The glass transition temperature (Tg) was 293K. Therefore, it was found that the obtained polymer P12 was a copolymer represented by the following structural formula (P12).
However, in the structural formula (P12), the number represents the molar ratio of repeating units.

(Comparative Synthesis Example 7)
-Synthesis of polymer P13-
In a 2 L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 101.1 g of the above SMA1000 and 54.1 g of benzyl alcohol were mixed in an atmosphere with an oxygen concentration of 7%. Was dissolved in dioxane (246 g) as a solvent, and the mixture was stirred at 100 ° C. for about 8 hours until the absorption of the acid anhydride group disappeared while sequentially measuring the infrared absorption spectrum of the reaction product. Then, it cooled to room temperature and obtained the polymer P13 solution whose solid content concentration is 40 mass%.
When the solid content acid value and the weight average molecular weight of the obtained polymer P13 solution were measured, they were 180 mgKOH / g and the weight average molecular weight was 5,800. The glass transition temperature (Tg) was 385K. Therefore, it was found that the obtained polymer P13 was a copolymer represented by the following structural formula (P13).
However, in the structural formula (P13), the number represents the molar ratio of repeating units.

The physical properties of the polymers P1 to P13 obtained in Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 to 7 are shown in Tables 1 to 3.

Example 1
Using the pattern forming method of the present invention, a printed circuit board was manufactured by a subtractive method, and its performance was evaluated.
<Manufacture of laminates>
-Production of pattern forming material-
As the support, a polyethylene terephthalate film (trade name: 16QS52, centerline average surface roughness = 12 nm, manufactured by Toray Industries, Inc.) having a width of 30 cm and a thickness of 16 μm was used. A photosensitive resin composition solution F1 (solid content concentration = 15% by mass, viscosity = 15 mPa · s) having the following composition was prepared, in-line filtered through a 1 μmφ filter, and equipped with a horizontal countercurrent hot air dryer. The film was guided to a rouge-type coating head, applied to the surface of the support, and sequentially passed through a drying zone having a temperature of 50 ° C. to 120 ° C. for drying to form a photosensitive layer having a thickness of 7 μm on the support.

[Composition of photosensitive resin composition solution F1]
――――――――――――――――――――――――――――――――――――――――
Polymer P1 solution: 349 parts by mass Polymerizable compound represented by the following structural formula (46) (Daiichi Kogyo Seiyaku Co., Ltd., GX8702c): 4.33 parts by mass Polymerization represented by the following structural formula (47) Compound (Daiichi Kogyo Seiyaku Co., Ltd., BPEM-10F): 44.33 parts by mass. Polymerizable compound represented by the following structural formula (48) (Aronix M270, manufactured by Toagosei Co., Ltd.): 6.4 parts by mass Polyethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester 23G): 16.8 parts by mass. 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′- as a photopolymerization initiator Tetraphenylbiimidazole: 18.5 parts by mass 10- (n-butyl) -2-chloroacridone as a sensitizer: 1.0 part by mass Phenoxazine as a polymerization inhibitor: 0.032 parts by mass Departure Leuco crystal violet as an agent: 1.1 parts by mass. Victoria pure blue naphthalene sulfonate as a dye: 0.186 parts by mass. Phenidone as a reducing agent: 0.022 parts by mass. N as a hydrogen donor compound. -Phenylglycine: 0.370 parts by mass Fluorosurfactant A (monomer of the following structural formula (49) / copolymer of the monomer of the following structural formula (50) (copolymerization composition (mass ratio): 60/40) )): 0.78 parts by mass Methyl ethyl ketone as solvent: 604 parts by mass Propylene glycol monomethyl ether as solvent: 562 parts by mass Cyclohexanone as solvent: 107 parts by mass Methanol as solvent: 67 parts by mass ―――――――――――――――――――――――――――――――――――――
The residual amount of the organic solvent in the obtained photosensitive layer was 0.30% by mass.

However, m + n represents 20 in the structural formula (46). The compound represented by the structural formula (46) is an example of a polymerizable compound having a urethane group.

However, m + n represents 10 in the structural formula (47). The compound represented by the structural formula (47) is an example of a polymerizable compound having an aryl group.

However, n represents 12 in the structural formula (48). The compound represented by the structural formula (48) is an example of a compound having a polyalkylene oxide chain.

  For the photosensitive layer formed on the support, the centerline average surface roughness was measured by the following method.

(1) Centerline average surface roughness of photosensitive layer Next, the centerline average surface roughness of the surface of the photosensitive layer obtained above was measured.
For the centerline average surface roughness Ra (nm), Ra with an area of 368 μm × 238 μm was measured using a non-contact three-dimensional surface analyzer (WYKO, trade name: RST / PLUS). In addition, the definition of Ra followed JIS surface roughness (B0601). The measurement was performed by dividing each sample of 30 cm × 30 cm into 100 grids at intervals of 3 cm, measuring the center of each square region, and calculating the average value and standard deviation from 100 measurements. For the centerline average surface roughness (Ra), a portion of the measurement length L is extracted from the obtained roughness curve in the direction of the centerline, the centerline of this extracted portion is the X axis, and the direction of the vertical magnification is the Y axis. When the roughness curve is represented by Y = f (X), the value obtained by the following formula is represented in nanometers (nm). The average roughness of the photosensitive layer is preferably as low as possible, but is preferably 5% or less of the thickness, more preferably 3% or less, and particularly preferably 2% or less.

On the photosensitive layer on the support, as the protective film, a polypropylene film having a thickness of 12 μm and a fish eye number of 3 / m ² (made by Oji Paper Co., Ltd., trade name: Alphan E-200, contacting with the photosensitive layer) The center line average surface roughness of the non-contact surface = 480 nm and the center line average surface roughness of the surface in contact with the photosensitive layer = 452 nm) were laminated to produce a pattern forming material.
About the manufactured pattern formation material, the peelability of the protective film was evaluated by the following method.

(2) Protective film peelability In the step of peeling the protective film from the pattern forming material, the peel force was measured.
The measurement of the peeling force of the protective film is in accordance with JIS K-6854-2. Specifically, a sample cut out from the pattern forming material into a width of 4.5 cm and a length of 8 cm is used. The peel strength between the photosensitive layer and the protective film when the protective film is peeled off from the sample at a pulling speed of 160 cm / min using a force gauge is measured. Asked. The measurement was performed 5 times and expressed as an average value. The results are shown in Table 7. If it is 10-50 gf, peelability will be favorable.

-Manufacture of laminates-
Next, a single-sided copper-clad laminate for flexible wiring plates (FCCL), the surface of which was prepared by chemical polishing with a 10% by mass aqueous solution of METALIP SP100 (trade name, manufactured by Nippon Surface Chemical Co., Ltd.), washed with water and dried as the base material. (Made by Nikko Materials Co., Ltd., trade name: Machinus, copper foil thickness 5 μm, centerline average surface roughness 0.1 μm). A hot roll laminator (manufactured by Taisei Laminator Co., Ltd.) is made so that the photosensitive layer of the pattern forming material is in contact with the copper foil surface of the copper-clad laminate while peeling off the protective film of the pattern forming material on the copper-clad laminate. , Trade name: MODEL8B-720-PH) to prepare a laminate in which the copper-clad laminate, the photosensitive layer, and the support were laminated in this order.
The pressure bonding conditions were a pressure roll temperature of 105 ° C., a pressure roll pressure of 0.3 MPa, and a laminating speed of 2 m / min. In the case of a 600 mm × 600 mm size substrate, it took about 30 seconds.
The manufactured laminate was evaluated for the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness by the following methods. The results are shown in Table 7.

(3) Support peelability In the step of peeling the support from the laminate, the peel strength was measured after forming the laminate and cooling to room temperature without pattern exposure.
The peel strength of the support is measured according to JIS K-6854-2. Specifically, a sample cut into a width 4.5 cm × length 8 cm from a laminate sample of a pattern forming material and a copper-clad laminate is used. The photosensitive layer and the support when the support is fixed on a pedestal with a double-sided tape so that the support is on the surface side, and the support is peeled off from the sample at a pulling speed of 160 cm / min using a force gauge. The peel force from the body was measured and determined. The measurement was performed 5 times and expressed as an average value. If it is 30gf-200gf, peelability is favorable.

<Development process>
The support was peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed at a pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate to dissolve and remove uncured regions. . Thereafter, it was washed with water and dried to form a resist pattern.
The time required from the start of spraying of the aqueous sodium carbonate solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time.
As a result, the shortest development time was 8 seconds. The shorter the shortest development time, the better the developability.

(4) Development tolerance When the photosensitive layer on the support is developed under the conditions in the development step, the resist pattern line width and pattern shape do not change from 1.5 to 3 times the shortest development time. Is required. The time during which these performances do not change is defined as “development tolerance”. Whether or not the development tolerance was good was visually observed using a microscope and judged according to the following criteria.
-Evaluation criteria-
○: No change in line width and shape when developed at 1.5 times and 3 times the shortest development time △: Although there is a change in line width and shape when developed at 1.5 and 3 times the shortest development time , No change until 1.5 and 2 times development ×: Line width and shape change when developed at 1.5 and 3 times the shortest development time

(5) Exposure sensitivity With respect to the photosensitive layer of the pattern forming material in the laminate, from the support side, using a pattern forming apparatus having a 405 nm laser light source as the light irradiation means, from 0.1 mJ / cm ² The exposure was performed by irradiating with different light energy amounts of up to 100 mJ / cm ² at 2 ¹ / ^2- fold intervals (hereinafter referred to as sensitivity test pattern), and a part of the photosensitive layer was cured. After standing at room temperature for 10 minutes, the support was peeled off from the laminate, and an aqueous sodium carbonate solution (30 ° C., 1% by mass) was sprayed to a spray pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate. Then, spraying was performed twice as long as the shortest development time obtained in the developing step, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Next, a sensitivity curve is obtained by plotting the relationship between the light irradiation amount and the thickness of the cured layer. From the sensitivity curve thus obtained, the amount of light energy when the thickness of the cured region was 95% (6.7 μm) or more of the coating thickness was determined as the amount of light energy necessary for curing the photosensitive layer.

(6) Resolution After allowing the laminate to stand at room temperature (23 ° C., 55% RH) for 10 minutes, line / space (L / S) = 1 from above the support using the pattern forming apparatus. / 1, the line width was exposed in increments of 1 μm from 3 μm to 20 μm (hereinafter referred to as a resolution test pattern). The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the pattern forming material obtained by measuring the exposure sensitivity. After leaving still at room temperature for 10 minutes, the support body was peeled off from the said laminated body. Spray the entire surface of the photosensitive layer on the copper clad laminate with a sodium carbonate aqueous solution (30 ° C., 1% by mass) as the developer at a spray pressure of 0.15 MPa for a time twice the shortest development time obtained in the development step. Then, the uncured region was dissolved and removed. The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twisting was measured on the cured resin pattern line. did. The smaller the numerical value, the better the resolution.

(7) Adhesion degree After the laminate is allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes, line / space (L / S) = from above the support using the pattern forming apparatus. = 1/5, line widths of 3 μm to 20 μm were exposed at each line width in 1 μm increments. The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the pattern forming material obtained by measuring the exposure sensitivity. After leaving still at room temperature for 10 minutes, the support body was peeled off from the said laminated body. Spray the entire surface of the photosensitive layer on the copper clad laminate with a sodium carbonate aqueous solution (30 ° C., 1% by mass) as the developer at a spray pressure of 0.15 MPa for a time twice the shortest development time obtained in the development step. Then, the uncured region was dissolved and removed. The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, and the minimum line width with no abnormalities such as tsumari and twist is measured on the cured resin pattern line. It was. The lower the numerical value, the better the degree of adhesion.

(8) Etchability A copper-clad laminate having a resist pattern produced by irradiating the resolution test pattern with the amount of light energy required to cure the photosensitive layer of the pattern forming material obtained by measuring the exposure sensitivity. Was etched using a 35Be (Baume) aqueous ferric chloride solution, and the edges of the resulting metal pattern were visually observed using a microscope and judged according to the following criteria. When the etching resistance of the resist is inferior, the shoulder of the copper pattern becomes round, and in the worst case, disconnection occurs.
-Evaluation criteria-
○: There is no disconnection and the shoulder of the copper pattern is not rounded.
X: The shoulder of the copper pattern is rounded or disconnected.

(9) Plating resistance The resolution test pattern is exposed with an amount of light energy necessary for curing the photosensitive layer of the pattern forming material obtained by the measurement of the exposure sensitivity, and a 1% by mass aqueous sodium carbonate solution is used. Developed. This sample was degreased, washed with water, plated with copper sulfate at 3.0 A / dm ² for 30 minutes, washed with water and immersed in borohydrofluoric acid, soldered at 1.5 A / dm ² for 10 minutes, and washed with water. Moisture was removed with an air brush, and a cellophane tape (registered trademark, manufactured by Sekisui Chemical Co., Ltd., 24 mm width) was adhered and peeled off rapidly, and the plating resistance was evaluated by the presence or absence of peeling. The evaluation criteria are as follows. If the resist plating resistance is poor, peeling occurs.
-Evaluation criteria-
○: No peeling △: Partial peeling ×: Most peeling

(10) Peeling time After the laminate was allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes, the entire surface was exposed from above the support using the pattern forming apparatus. The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the pattern forming material obtained by measuring the exposure sensitivity. After leaving still at room temperature for 10 minutes, the support body was peeled off from the said laminated body. Spray the entire surface of the photosensitive layer on the copper clad laminate with a sodium carbonate aqueous solution (30 ° C., 1% by mass) as the developer at a spray pressure of 0.15 MPa for a time twice the shortest development time obtained in the development step. did. After drying this, the substrate was immersed in a 3% by mass aqueous sodium hydroxide solution so as to stand up, and the time until the film completely peeled was measured. The shorter this time, the better.

(11) Measurement of edge roughness The pattern is formed in the same manner as the measurement of the resolution except that the pattern forming apparatus is used to perform exposure so that a horizontal line pattern in a direction orthogonal to the scanning direction of the exposure head is formed. Formed. Among the obtained patterns, any five points of a line having a line width of 30 μm were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×), and among the edge positions in the field of view Then, the difference between the most swollen portion (mountain peak portion) and the most constricted portion (valley bottom portion) was obtained as an absolute value, and an average value of five observed positions was calculated, and this was defined as edge roughness. The edge roughness is preferably as the value is small because it exhibits good performance.

(Example 2)
As shown in Table 6, in Example 1, the pattern forming material and the photosensitive laminate were obtained in the same manner as in Example 1 except that the thickness of the photosensitive layer was changed to 5 μm by changing the supply amount of the coating solution. Manufactured.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 6 seconds.

(Example 3)
As shown in Table 6, in Example 1, the pattern forming material and the photosensitive laminate were obtained in the same manner as in Example 1 except that the thickness of the photosensitive layer was changed to 3 μm by changing the supply amount of the coating solution. Manufactured.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 4 seconds.

Example 4
As shown in Table 6, in Example 1, the pattern forming material and the photosensitive laminate were obtained in the same manner as in Example 1, except that the thickness of the photosensitive layer was changed to 10 μm by changing the supply amount of the coating solution. Manufactured.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 13 seconds.

(Example 5)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was replaced with the photosensitive resin composition solution F2 shown in Table 4 (solid content concentration = 15 mass%, viscosity = 15 mPa · s). Except for the above, a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 8 seconds.

(Example 6)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was replaced with the photosensitive resin composition solution F3 (solid content concentration = 15 mass%, viscosity = 16 mPa · s) shown in Table 4. Except for the above, a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 8 seconds.

(Example 7)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was replaced with the photosensitive resin composition solution F4 shown in Table 4 (solid content concentration = 15 mass%, viscosity = 18 mPa · s). Except for the above, a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 8 seconds.

(Example 8)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was replaced with the photosensitive resin composition solution F5 (solid content concentration = 15 mass%, viscosity = 19 mPa · s) shown in Table 4. Except for the above, a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 8 seconds.

Example 9
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was replaced with the photosensitive resin composition solution F6 shown in Table 4 (solid content concentration = 15 mass%, viscosity = 18 mPa · s). Except for the above, a pattern forming material and a photosensitive laminate were produced in the same manner as Example 1.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 8 seconds.

(Example 10)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was replaced with the photosensitive resin composition solution F7 shown in Table 4 (solid content concentration = 15 mass%, viscosity = 15 mPa · s). Except for the above, a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1. However, the fluorosurfactant B used in the photosensitive resin composition solution F7 is a copolymer of the monomer of the following structural formula (51) / monomer of the following structural formula (52) (copolymerization composition (mass ratio): 40. / 60, mass average molecular weight 60,000).
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 8 seconds.

(Example 11)
As shown in Table 6, in Example 2, a vacuum laminator (manufactured by Nichigo Morton, trade name: V130) was used as a laminator instead of a hot roll laminator when the photosensitive layer was pressed onto the copper-clad laminate. Pattern formation in the same manner as in Example 2 except that after vacuum degassing, pressurizing at 0.2 MPa, heating at 70 ° C. at normal pressure, and then cooling to room temperature to produce a laminate. Materials and photosensitive laminates were produced.
When the substrate size is 600 mm × 600 mm, the time required for deaeration of the vacuum laminator is 40 seconds. After returning to atmospheric pressure, heating is performed for 10 seconds, and the time required for the entire lamination process on the substrate is about 60 seconds. Second.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 6 seconds.

(Example 12)
As shown in Table 6, in Example 2, an alkali-soluble cushion layer composition coating solution C1 having the following composition was prepared, filtered using a 1 μmφ filter, and coated with the extrusion coating head. A 14.6 μm thick cushion layer is formed on the support using a machine, and further an intermediate layer composition coating solution I1 having the following composition is prepared and filtered using a 1 μmφ filter, A pattern forming material and a laminate were prepared in the same manner as in Example 2 except that an intermediate layer having a thickness of 1.6 μm was formed on the cushion layer using a coating machine equipped with an extrusion type coating head. .
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7.
In each evaluation, after peeling off the support, the photosensitive layer was exposed through the cushion layer and the intermediate layer. The shortest development time was 11 seconds.

[Composition of cushion layer coating liquid C1]
――――――――――――――――――――――――――――――――――――――――
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 28.8 / 11.7 / 4.5, mass average molecular weight = 90,000): 150 parts by mass-polymerizable compound represented by the structural formula (47): 65 parts by mass-tetraethylene glycol dimethacrylate: 15 parts by mass-p-toluenesulfonamide: 5 parts by mass-benzophenone: 10 parts by mass-methyl ethyl ketone: 300 parts by mass ――――――――――――――――――――――――――――――――――――――――

[Composition of Intermediate Layer Coating Liquid I1]
―――――――――――――――――――――――――――――――――――――――
Polyvinyl alcohol (Kuraray Co., Ltd., trade name: PVA205, saponification rate = 88%): 130 parts by mass Polyvinylpyrrolidone (trade name: K-90, manufactured by GAF Corporation): 60 parts by mass Copolymer of monomer of structural formula (49) / monomer of structural formula (50) as agent A (copolymerization composition (mass ratio): 60/40): 10 parts by mass / distilled water: 3,350 masses Department ――――――――――――――――――――――――――――――――――――――――
The oxygen permeability in the obtained intermediate layer was 20 cc / m ² · day · atm.

(Example 13)
As a support, the surface of a polyethylene terephthalate film (product name: support 16QS52, manufactured by Toray Industries, Inc.) having a thickness of 16 μm and a width of 30 cm is corona-treated, and further, an aqueous gelatin solution is applied to the corona-treated surface and dried to obtain a dry film thickness. In the same manner as in Example 12, a cushion layer coating solution C1 was applied and dried on the surface of the gelatin undercoat layer using a gelatin layer having a 0.08 μm-thick gelatin undercoat layer. Further, an intermediate layer coating solution I2 having the following composition is applied and dried on the cushion layer, and further a photosensitive layer composition coating solution F1 is applied and dried thereon to form a photosensitive resin layer with a thickness of 7 μm. Thus, a pattern forming material was prepared. A substrate laminate was formed in the same manner as in Example 12.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7.
In each evaluation, after peeling off the support, the photosensitive layer was exposed through the cushion layer and the intermediate layer. The shortest development time was 9 seconds.

[Composition of Intermediate Layer Coating Liquid I2]
―――――――――――――――――――――――――――――――――――――――
Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA105, saponification rate = 98.5%): 130 parts by mass Copolymer of monomer of structural formula (49) / monomer of structural formula (50) as surfactant A (copolymerization composition (mass ratio): 60/40): 10 parts by mass / distilled water: 3, 350 parts by mass ――――――――――――――――――――――――――――――――――――――――
The oxygen permeability in the obtained intermediate layer was 10 cc / m ² · day · atm.

(Example 14)
As shown in Table 6, in Example 2, the support used was a corona-treated surface of a polyethylene terephthalate film having a thickness of 16 μm and a width of 30 cm (trade name: support 16QS52, manufactured by Toray Industries, Inc.). A coating solution C2 having an alkali-insoluble cushion layer composition having the following composition was prepared, filtered using a filter of 1 μmφ, and coated on the support using a coating machine equipped with the extrusion-type coating head. A pattern forming material and a laminate were prepared in the same manner as in Example 2 except that a 6 μm cushion layer was formed.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7.
In each evaluation, after the cushion layer was peeled off together with the support, the photosensitive layer was exposed. Moreover, evaluation of the peelability of a support body evaluated the peelability between a cushion layer and a photosensitive layer. The shortest development time was 6 seconds.

[Composition of cushion layer coating liquid C2]
――――――――――――――――――――――――――――――――――――――――
・ Ethylene / vinyl acetate copolymer solution (Mitsui DuPont Polychemical Co., Ltd., trade name: Everflex 45X, vinyl acetate content: 46 mass%): 17 parts by mass Toluene: 83 parts by mass ―――――――――――――――――――――――――――――――――――

(Example 15)
As shown in Table 6, in Example 1, a 4% aqueous solution of hydroxypropylmethylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: TC-5S, polymerization degree 340) was prepared as the oxygen barrier intermediate layer coating solution I3. The same procedure as in Example 1 was conducted except that an intermediate layer having a thickness of 1.6 μm was formed on the support using a coating machine equipped with the extrusion type coating head after filtration using a 1 μmφ filter. A pattern forming material and a laminate were prepared. The obtained intermediate layer had an oxygen permeability of 20 cc / m ² · day · atm.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7.
In each evaluation, after peeling off the support, the photosensitive layer was exposed through the intermediate layer. The shortest development time was 8 seconds.

(Example 16)
As shown in Table 6, in Example 15, a vacuum laminator (manufactured by Nichigo Morton, trade name: V130) was used as a laminator instead of a hot roll laminator when the photosensitive layer was pressed onto the copper-clad laminate. Pattern formation in the same manner as in Example 2 except that after vacuum degassing, pressurizing at 0.2 MPa, heating at 70 ° C. at normal pressure, and then cooling to room temperature to produce a laminate. Materials and photosensitive laminates were produced.
When the substrate size is 600 mm × 600 mm, the time required for deaeration of the vacuum laminator is 40 seconds. After returning to atmospheric pressure, heating is performed for 10 seconds, and the time required for the entire lamination process on the substrate is about 60 seconds. Second.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7.
In each evaluation, after peeling off the support, the photosensitive layer was exposed through the intermediate layer. The shortest development time was 8 seconds.

(Example 17)
A printed circuit board was manufactured by a semi-additive method using the pattern forming method of the present invention, and its performance was evaluated.
<Manufacture of laminates>
-Preparation of substrate-
A carbon dioxide impact laser is formed by forming an interlayer insulation layer on both sides of a 600 mm × 600 mm size internal circuit board on which a copper circuit has been formed with a commercially available insulation layer forming film (Ajinomoto Fine Techno Co., Ltd., trade name: ABF-45SH). A through-hole having a diameter of 80 μm was opened by a punching machine (trade name: SLR-210T, manufactured by Sumitomo Heavy Industries, Ltd.), and the mixture was heated to a mixed aqueous solution of potassium permanganate 65 g / L and sodium hydroxide 40 g / L. It was immersed at 20 ° C. for 20 minutes for desmearing.
Thereafter, an electroless copper plating layer was formed by the following steps (1) to (5) using the following treatment agent to prepare a substrate.
(1) The substrate was immersed in a pretreatment agent (trade name: PC236, manufactured by Meltex Co., Ltd.) at 25 ° C. for 2 minutes, and then washed with pure water for 2 minutes.
(2) The substrate was immersed in a catalyst-imparting agent (trade name: Activator 444, manufactured by Meltex Co., Ltd.) at 25 ° C. for 6 minutes, and then washed with pure water for 2 minutes.
(3) The substrate was immersed in an activation treatment agent (trade name: PA491, manufactured by Meltex Co., Ltd.) at 25 ° C. for 10 minutes, and then washed with pure water for 2 minutes.
(4) The substrate was immersed in an electroless copper plating solution (Meltex, trade name: CU390) at 25 ° C. and pH 12.8 for 20 minutes, and then washed with pure water for 5 minutes.
(5) It was dried at 100 ° C. for 15 minutes. As a result, an electroless copper plating film having a thickness of 0.3 μm was formed on the insulating substrate.

-Manufacture of laminates-
Using the pattern forming material produced in the same manner as in Example 12, while peeling the protective film of the pattern forming material on the substrate, the photosensitive layer of the pattern forming material is the electroless copper plating film surface of the substrate The base material, the cushion layer, the intermediate layer, the photosensitive layer, and the support are bonded to each other by using the hot roll laminator so as to be in contact with the substrate at a laminating speed of 2 m / min. The laminated body laminated | stacked in order was prepared. In the case of a substrate having a size of 600 mm × 600 mm, the time taken for the laminating process was 30 seconds.
Using the obtained photosensitive laminate, as in Example 1, evaluation of peelability of the support, development tolerance, exposure sensitivity, resolution, adhesion, etching resistance, plating resistance, and edge roughness was performed. went. The results are shown in Table 7. The shortest development time was 11 seconds.

<Exposure and development>
Using the laminate manufactured in the same manner as described above, after peeling the support from the laminate, the pattern was formed using the 405 nm light laser irradiation apparatus having the resolution pattern via the cushion layer and the intermediate layer. Exposure was performed (exposure amount = 8 mJ / cm ² ). Then, it developed with 1 mass% sodium carbonate aqueous solution as mentioned above.

<Plating process>
Subsequently, it is immersed in a degreasing agent (trade name: PC455, manufactured by Meltex Co., Ltd.) at 25 ° C. for 30 seconds, washed with water for 2 minutes, and then using an electrolytic copper plating solution having the following composition at 25 ° C., 2.4 A / 100 cm. ² Electrolytic copper plating was performed for 10 minutes. As a result, about 5 μm of copper was precipitated.
[Composition of electrolytic copper plating solution]
――――――――――――――――――――――――――――――――――――――――
· CuSO ₄ · _5H 2 O (copper sulfate pentahydrate, powder): 75 g / L
・ H ₂ SO ₄ (sulfuric acid): 190 g / L
・ Cl ⁻ (HCl aqueous solution): 50 mg / L
Cover grime (Meltex, product name: PCM): 5 ml / L
――――――――――――――――――――――――――――――――――――――――

<Hardened film peeling>
Next, after removing the resist with a 3% by mass aqueous sodium hydroxide solution, copper other than the pattern portion was removed by etching using an etching solution having a composition of 20 g / L sulfuric acid and 10 g / L hydrogen peroxide. The minimum circuit body width / circuit conductor interval (L / S) of the pattern after the etching treatment was 5 μm / 5 μm.

(Example 18)
In Example 1, a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1 except that the pattern forming apparatus was subjected to double exposure instead of the one described below.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 8 seconds.

<< Pattern Forming Apparatus >>
8-9 and 25-29 as the light irradiating means, and 1024 micromirrors 58 arranged in the main scanning direction schematically shown in FIG. 6 as the light modulating means. DMD 36 controlled to drive only 1024 × 256 rows among 768 pairs of mirror rows arranged in the sub-scanning direction, and optical for imaging the light shown in FIG. 5A or FIG. 5B on the pattern forming material A pattern forming apparatus 10 including an exposure head 30 having a system was used.

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

First, the state of the exposure pattern on the exposed surface was examined in order to correct the variation in resolution and uneven exposure in double exposure. The results are shown in FIG. In FIG. 18, the pattern of light spots from the micromirror 58 that can be used by the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the laminate 12 with the stage 14 being stationary. showed that. The state of the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part. Are shown for exposure areas 32 ₁₂ and 32 ₂₁ . In FIG. 18, for convenience of explanation, every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

As shown in FIG. 18, as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ from the ideal state, both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B are both. Thus, it can be seen that, in the exposure areas overlapping on the coordinate axes orthogonal to the scanning direction of the exposure head in the exposure areas 32 ₁₂ and 32 ₂₁ , an overexposed area is generated as compared with the ideal double exposure state.

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

Using the actual inclination angle θ ′, the following equation 4
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ . T = 254 for the exposure head _{30 12,} the exposure head _{30 21} T = 255 was derived respectively. As a result, the micromirrors constituting the portions 78 and 80 covered with diagonal lines in FIG. 19 were identified as micromirrors that are not used during the main exposure.

Thereafter, the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered by the oblique lines in FIG. 19 were similarly covered by the shaded areas 82 and the shaded areas in FIG. Micromirrors corresponding to the light spots constituting the region 84 were identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. It was controlled not to be involved.
As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ , an ideal double exposure is performed in each area other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. Thus, the total area of the overexposed region and the underexposed region can be minimized.

(Comparative Example 1)
As shown in Table 3, in Example 1, the photosensitive resin composition solution F1 was changed to the photosensitive resin composition solution F8 shown in Table 4 (containing polymer P1 of Comparative Synthesis Example 1, solid content concentration = 15% by mass, A pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1 except that the viscosity was changed to 15 mPa · s (but not including a fluorosurfactant).
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 4. The shortest development time was 8 seconds.

(Comparative Example 2)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was changed to the photosensitive resin composition solution F9 shown in Table 5 (containing polymer P7 of Comparative Synthesis Example 1, solid content concentration = 48.1 mass). %, Viscosity = 140 mPa · s, except that the fluorosurfactant is not included), in the same manner as in Example 1, an attempt was made to produce a pattern forming material and a photosensitive laminate. In addition, the photosensitive layer could not be applied.

(Comparative Example 3)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was changed to the photosensitive resin composition solution F10 shown in Table 5 (containing polymer P7 of Comparative Synthesis Example 1, solid content concentration = 15% by mass, A pattern forming material and a photosensitive laminate having a photosensitive layer thickness of 5.0 μm were produced in the same manner as in Example 1 except that the viscosity was changed to 25 mPa · s (but not including a fluorosurfactant).
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 8 seconds.

(Comparative Example 4)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was changed to the photosensitive resin composition solution F11 shown in Table 5 (containing polymer P8 of Comparative Synthesis Example 2, solid content concentration = 50.1 mass). %, Viscosity = 142 mPa · s, except that a fluorosurfactant is not included), and a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 5 seconds.

(Comparative Example 5)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was changed to the photosensitive resin composition solution F12 shown in Table 5 (containing polymer P8 of Comparative Synthesis Example 2, solid content concentration = 15% by mass, A pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1 except that the viscosity was changed to 25 mPa · s (but not including a fluorosurfactant).
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 10 seconds.

(Comparative Example 6)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was changed to the photosensitive resin composition solution F11 shown in Table 5 (containing polymer P8 of Comparative Synthesis Example 2, solid content concentration = 50.1 mass). %, Viscosity = 142 mPa · s, but does not include a fluorine-based surfactant), the photosensitive layer coating solution F10 is directly applied with a bar coater on a copper-clad laminate that has been chemically polished, A pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1 except that a photoresist layer having a thickness of 7 μm was formed by drying at 80 ° C. for 4 minutes.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 8 seconds.

(Comparative Example 7)
As shown in Table 6, on the copper-clad laminate obtained by chemically polishing the surface, a commercially available positive photoresist (manufactured by Fuji Film Electronics Material, trade name: FH-2413F, solid content concentration = 22% by mass, Viscosity = 13 mPa · s, and this coating solution is F13.) Was applied with a bar coater so that the dry thickness was 5 μm, dried and then pre-baked at 120 ° C. for 2 minutes to produce a photosensitive laminate. .
Using the obtained photosensitive laminate, evaluation of development tolerance, exposure sensitivity, resolution, adhesion, etching resistance, plating resistance, and edge roughness was performed in the same manner as in Example 1. The results are shown in Table 4. The shortest development time was 10 seconds. Further, using the positive photoresist, the center line average surface roughness of the photosensitive layer was evaluated in the same manner as in Example 1. The results are shown in Table 7. In addition, since the comparative example 7 did not have a support body and a protective film, evaluation of support body peelability and the peelability of a protective film was not performed.
In Comparative Example 7, a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution was used as a developing solution, and a monoethanolamine / dimethylsulfoxide mixed solution (mass mixing ratio = 7 / 3) was used.

(Comparative Example 8)
As shown in Table 6, in Example 1, the pattern forming material and the photosensitive laminate were obtained in the same manner as in Example 1 except that the thickness of the photosensitive layer was changed to 1 μm by changing the supply amount of the coating solution. Manufactured.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 3 seconds.

(Comparative Example 9)
As shown in Table 6, in Example 1, the pattern forming material and the photosensitive laminate were obtained in the same manner as in Example 1 except that the thickness of the photosensitive layer was changed to 12 μm by changing the supply amount of the coating solution. Manufactured.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 17 seconds.

(Comparative Example 10)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was changed to the photosensitive resin composition solution F14 shown in Table 5 (containing polymer P9 of Comparative Synthesis Example 3, solid content concentration = 15% by mass, A pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1 except that the viscosity was changed to 23 mPa · s.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 10 seconds.

(Comparative Example 11)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was changed to the photosensitive resin composition solution F15 shown in Table 5 (containing polymer P10 of Comparative Synthesis Example 4, solid content concentration = 15% by mass, A pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1 except that the viscosity was changed to 25 mPa · s.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 12 seconds.

(Comparative Example 12)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was changed to the photosensitive resin composition solution F16 shown in Table 5 (containing polymer P11 of Comparative Synthesis Example 5, solid content concentration = 15% by mass, A pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1 except that the viscosity was changed to 10 mPa · s.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 5 seconds.

(Comparative Example 13)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was changed to the photosensitive resin composition solution F17 shown in Table 5 (containing polymer P12 of Comparative Synthesis Example 6, solid content concentration = 15 mass, viscosity) = 8 mPa · s) A pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1, except that the value was changed to 8 mPa · s).
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 6 seconds.

(Comparative Example 14)
As shown in Table 6, in Example 1, the photosensitive resin composition solution F1 was changed to the photosensitive resin composition solution F18 shown in Table 5 (containing polymer P13 of Comparative Synthesis Example 7, solid content concentration = 15% by mass, A pattern forming material and a photosensitive laminate were produced in the same manner as in Example 1 except that the viscosity was changed to 15 mPa · s.
Using the obtained pattern forming material, the center line average surface roughness of the photosensitive layer and the peelability of the protective film were evaluated in the same manner as in Example 1. Further, using the obtained photosensitive laminate, as in Example 1, the peelability of the support, the development tolerance, the exposure sensitivity, the resolution, the adhesion, the etching resistance, the plating resistance, and the edge roughness. Evaluation was performed. The results are shown in Table 7. The shortest development time was 8 seconds.

* BPE500: New Nakamura Chemical Co., Ltd. trade name, polymerizable compound * BPE200: Shin Nakamura Chemical Co., Ltd. trade name, polymerizable compound * UA-21: Shin Nakamura Chemical Co., Ltd. trade name, represented by the structural formula shown below Compound (mean value of n is 4)

* The photosensitive layer coating solution F13 is a commercially available positive photoresist.

From the results shown in Table 7, the pattern forming materials of Examples 1 to 18 achieve both excellent thickness uniformity and adhesion to the substrate without affecting the etching resistance, plating resistance, resist peelability, and the like. It was also found that the resolution, sensitivity, and development tolerance were excellent.
Moreover, since the pattern obtained from the pattern forming material of Example 18 corrected the variation in resolution and the exposure unevenness by double exposure, the edge compared with the pattern obtained from the pattern forming material of Examples 1 to 17 It was found that roughness was small and high definition.

Even if the pattern forming material of the present invention is a thin-film photosensitive layer, it can achieve both excellent thickness uniformity and adhesion to a substrate, so that it has high resolution and sensitivity and development tolerance. Excellent for forming various patterns, for forming permanent patterns such as wiring patterns, for manufacturing liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, and for forming patterns for holograms, micromachines, proofs, etc. However, it can be preferably used for forming a high-definition wiring pattern. Moreover, it can use suitably for the pattern formation method and pattern formation apparatus of this invention.
Since the pattern forming method of the present invention uses the pattern forming material of the present invention, liquid crystal structures such as various patterns, formation of permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, partition walls, etc. It can be suitably used for the production of members, holograms, micromachines, proofs, etc., and can be particularly suitably used for the formation of high-definition wiring patterns.

FIG. 1 is a perspective view showing an appearance of an example of a pattern forming apparatus. FIG. 2 is a perspective view showing an example of the configuration of the scanner of the pattern forming apparatus. FIG. 3A is a plan view showing an exposed region formed on the exposed surface of the photosensitive layer. FIG. 3B is a plan view showing an arrangement of exposure areas by each exposure head. FIG. 4 is a perspective view showing an example of a schematic configuration of the exposure head. FIG. 5A is a top view showing an example of a detailed configuration of the exposure head. FIG. 5B is a side view showing an example of a detailed configuration of the exposure head. FIG. 6 is a partially enlarged view showing an example of the DMD of the pattern forming apparatus of FIG. FIG. 7A is a perspective view for explaining the operation of the DMD. FIG. 7B is a perspective view for explaining the operation of the DMD. FIG. 8 is a perspective view showing an example of the configuration of the fiber array light source. FIG. 9 is a front view showing an example of the arrangement of light emitting points in the laser emitting section of the fiber array light source. FIG. 10 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is an exposure head mounting angle error and pattern distortion. FIG. 11 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit. FIG. 12 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 13 is an explanatory diagram showing a state in which unevenness generated in a pattern on an exposed surface is improved as a result of using only selected micromirrors for exposure. FIG. 14 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift between adjacent exposure heads. FIG. 15 is a top view showing the positional relationship between the exposure areas by two adjacent exposure heads and the corresponding slits. FIG. 16 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 17 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 14 are actually moved and the unevenness in the pattern on the exposed surface is improved. FIG. 18 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift and a mounting angle error between adjacent exposure heads. FIG. 19 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG. FIG. 20A is an explanatory diagram showing an example of magnification distortion. FIG. 20B is an explanatory diagram showing an example of beam diameter distortion. FIG. 21A is an explanatory view showing a first example of reference exposure using a single exposure head. FIG. 21B is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 22 is an explanatory diagram showing a first example of reference exposure using a plurality of exposure heads. FIG. 23A is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 23B is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 24 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads. FIG. 25 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 26 is an example of a plan view showing the configuration of the combined laser light source. FIG. 27 is an example of a plan view showing the configuration of the laser module. FIG. 28 is an example of a side view showing the configuration of the laser module shown in FIG. FIG. 29 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 30 is an example of a perspective view showing a configuration of a laser array. FIG. 31A is an example of a perspective view showing a configuration of a multi-cavity laser. FIG. 31B is an example of a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. 31A are arranged in an array. FIG. 32 is an example of a plan view showing another configuration of the combined laser light source. FIG. 33 is an example of a plan view showing another configuration of the combined laser light source. FIG. 34A is an example of a plan view showing another configuration of the combined laser light source. FIG. 34B is an example of a cross-sectional view along the optical axis of FIG. 34A. FIG. 35 is a cross-sectional view showing an example of the pattern forming material of the first form. FIG. 36 is a cross-sectional view showing an example of the pattern forming material of the second form. FIG. 37 is a cross-sectional view showing an example of the pattern forming material of the third form. FIG. 38 is a cross-sectional view showing an example of the pattern forming material of the fourth embodiment. FIG. 39 is an explanatory diagram showing a method of forming a pattern on a substrate using the pattern forming material of the first form. FIG. 40 is an explanatory diagram showing a method of forming a pattern on a substrate using the pattern forming material of the second form. FIG. 41 is an explanatory diagram showing a method of forming a pattern on a substrate using the pattern forming material of the third form. FIG. 42 is an explanatory view showing a method of forming a pattern on a substrate using the pattern forming material of the fourth embodiment. FIG. 43 is an example of a process chart for explaining the pattern forming method of the present invention in the semi-additive method.

Explanation of symbols

B1 to B7 Laser beam L1 to L7 Collimator lens LD1 to LD7 GaN-based semiconductor laser 10 Pattern forming device 12 Photosensitive layer (photosensitive material)
DESCRIPTION OF SYMBOLS 14 Moving stage 18 Installation stand 20 Guide 22 Gate 24 Scanner 26 Sensor 28 Slit 30 Exposure head 32 Exposure area 36 Digital micromirror device (DMD)
38 Fiber array light source 58 Micro mirror (picture element)
60 laser module 62 multimode optical fiber 64 optical fiber 66 laser emitting unit 110 heat block 111 multicavity laser 113 rod lens 114 lens array 140 laser array 200 condensing lens 501 protective film 502 support 503 photosensitive layer 504 cushion layer 505 intermediate layer 506 Copper foil layer 507 Insulating layer 508 Cured film 509a Electroless copper plating 509b Electrolytic copper plating

Claims (10)

Comprising at least a support and a photosensitive layer on the support;
The photosensitive layer contains at least a binder, a polymerizable compound, a photopolymerization initiator, and a fluorosurfactant;
The binder is a ring-opening addition reaction product of a copolymer containing a carboxyl group in the molecule and a saturated epoxy compound having one epoxy group in one molecule, and a glass transition temperature (Tg) of 300 to 400K. And the weight average molecular weight is 1,000 to 10,000,
The pattern forming material, wherein the photosensitive layer has a thickness of 3 to 10 μm.   The pattern forming material according to claim 1, wherein the photosensitive layer has a thickness of 5 to 10 μm. The copolymer having a carboxyl group in the molecule is a copolymer having a structural unit derived from styrenes and a dibasic unsaturated carboxylic acid compound, and is represented by the following general formula (I): 3. The pattern forming material according to any one of 2 to 3.
In the general formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 1 to 4 carbon atoms. R ³ represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴ represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, a bicycloalkyl group having 6 to 11 carbon atoms, a tricycloalkyl group having 6 to 11 carbon atoms, or 7 carbon atoms. Represents an aralkyl group having ˜11, an aryl group having 6 to 10 carbon atoms, or a (meth) acryloyloxyalkyl group. m represents an integer of 1 to 5.
Moreover, x and y represent the composition ratio (molar ratio) of a repeating unit, it is x + y = 100, and is x: y = 10-90: 10-90. The pattern forming material according to claim 3, wherein the binder is represented by the following general formula (II).
However, in said general formula (II), R < ¹ > represents either a hydrogen atom or a methyl group. R ² represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted by halogen atom substitution, and an alkoxy group having 1 to 4 carbon atoms. R ³ may be the same as or different from each other, and represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴ may be the same as or different from each other, and represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ^{5 s} may be the same as or different from each other, and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, a bicycloalkyl group having 6 to 11 carbon atoms, It represents any of a tricycloalkyl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a (meth) acryloyloxyalkyl group. R ⁶ represents a residue after addition reaction between the epoxy group in the saturated epoxy compound and the carboxyl group in the dibasic unsaturated carboxylic acid compound. m represents an integer of 1 to 5.
Moreover, x, y, and z represent the composition ratio (molar ratio) of a repeating unit, are x + y + z = 100, and are x: y: z = 10-80: 10-80: 10-80. The fluorosurfactant comprises at least one of a structural unit derived from a monomer represented by the following structural formula (1) and a structural unit derived from a monomer represented by the following structural formula (2), and a polyoxyalkylene group. The pattern forming material according to claim 1, which is a copolymer having a structural unit derived from an ethylenically unsaturated monomer.
However, in the structural formulas (1) and (2), R ¹ and R ² may be the same as or different from each other, and represent either a hydrogen atom or a methyl group. X ¹ and X ² may be the same as or different from each other, and represent either an oxygen atom or NR ⁴ . The R ⁴ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 7 to 7 carbon atoms. Represents one of 24 aralkyl groups. Z ¹ and Z ² may be the same as or different from each other, and represent a substituent having at least one of an oxygen atom, a nitrogen atom and a sulfur atom. R ³ represents either a hydrogen atom or a fluorine atom. l, n, p, and r represent any integer of 0-10. m and q represent any integer of 0 and 1. o, s, and t represent any integer of 1-10.   The pattern forming material according to claim 1, further comprising a cushion layer between the support and the photosensitive layer.   The pattern forming material according to claim 6, further comprising an intermediate layer capable of suppressing movement of a substance between the cushion layer and the photosensitive layer.   The pattern forming material according to claim 7, wherein the intermediate layer has an oxygen barrier property. A laminating step of laminating the photosensitive layer in the pattern forming material according to claim 1 on the substrate such that the photosensitive layer and the substrate are in contact with each other by at least one of heating and pressurization,
An exposure step of exposing the photosensitive layer laminated by the laminating step with light irradiated from a light irradiation means;
And a development step of developing the photosensitive layer exposed in the exposure step. The pattern forming method according to claim 9, wherein the pattern is a wiring pattern, and the wiring pattern is formed by a semi-additive method.