KR101357733B1 - Photopolymerization initiator, photosensitive composition, photosensitive film, photosensitive laminate, method of forming permanent pattern and printed board - Google Patents

Abstract

In order to make it possible to cope with laser exposure, the present invention can further improve the sensitivity in the photosensitive composition, and furthermore, a photopolymerization initiator capable of satisfactorily maintaining the resolution, storage stability, surface hardness, and dielectric properties, and photosensitive using the same. A printed substrate on which a pattern is formed by a composition, a photosensitive film, a photosensitive laminate, a method of forming a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) using the photosensitive laminate, and the permanent pattern forming method. The purpose is to provide.

To this end, by the photopolymerization initiator which is an oxime ester compound which has a specific unsaturated group, and the photosensitive composition containing the said photoinitiator, the photosensitive film, the photosensitive laminated body, the permanent pattern formation method using the said photosensitive laminated body, and the said permanent pattern formation method Provided is a printed board on which a pattern is formed.

Photoinitiator, photosensitive, composition, film, laminate, permanent pattern, printed board

Description

Photopolymerization Initiator, Photosensitive Composition, Photosensitive Film, Photosensitive Laminate, Permanent Pattern Formation Method, and Printed Substrate

In order that this invention can respond to laser exposure, the photoinitiator which can further improve the sensitivity in a photosensitive composition, the photosensitive composition using this, the photosensitive film, the photosensitive laminated body, the high definition permanent pattern (protective film) , An interlayer insulating film, a solder resist pattern and the like), and a printed circuit board on which a permanent pattern is formed by the permanent pattern forming method.

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

Here, in the formation of a permanent pattern, laser exposure is considered to be an excellent method for recent digitalization and miniaturization of a pattern. However, in order to cope with laser exposure, it is required that the current liquid type is more sensitive than the mainstream solder resist.

On the other hand, oxime ester is conventionally known as a photoinitiator, and has been used for the photosensitive composition (refer patent documents 1-4).

However, only by simply changing the oxime ester used in these conventional photosensitive compositions to the photosensitive composition for soldering resists, the photosensitive composition which has high sensitivity and high resolution and has desired storage stability was not obtained. It is also necessary to maintain good surface hardness and dielectric properties of the formed pattern.

Therefore, in order to be able to cope with laser exposure, by using an oxime ester, the sensitivity of the photosensitive composition can be further improved, and the resolution, storage stability, surface hardness, and dielectric properties can be maintained well. Photopolymerization initiator, a photosensitive composition using the same, a photosensitive film, a photosensitive laminate, a method of forming a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) using the photosensitive laminate, and the permanent pattern forming method. The printed circuit board in which a pattern is formed is not yet provided, and further improvement is calculated | required.

Patent Document 1: Japanese Patent Application Laid-Open No. 60-166306

Patent Document 2: Japanese Patent Application Laid-Open No. 2001-233842

Patent Document 3: International Publication No. 05/080337

Patent Document 4: Japanese Patent Application Laid-Open No. 2000-80068

This invention solves all the said problems in the past, and makes it a subject to achieve the following objectives. That is, the present invention can further improve the sensitivity in the photosensitive composition in order to be able to cope with laser exposure, and can also maintain a resolution, storage stability, surface hardness, and dielectric properties with good photopolymerization initiator. The pattern is formed by a method of forming a photosensitive composition, a photosensitive film, a photosensitive laminate using the same, a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) using the photosensitive laminate, and the permanent pattern forming method. It is an object to provide a printed substrate to be formed.

MEANS TO SOLVE THE PROBLEM The present inventors obtained the following knowledge as a result of earnestly examining in view of the said subject. That is, the compound represented by any one of the following general formulas (1) to (5) can further improve the sensitivity in the photosensitive composition so as to cope with laser exposure, and furthermore, resolution, surface hardness, and dielectric It is a finding that a characteristic can be maintained favorable and a high-definition permanent pattern (protective film, an interlayer insulation film, a soldering resist pattern, etc.) can be formed.

This invention is based on the said knowledge of the present inventors, As a means for solving the said subject, it is as follows. In other words,

<1> It is a compound represented by either of following General formula (1)-(5), It is a photoinitiator characterized by the above-mentioned.

However, in said general formula (1)-(5), a dashed double line represents either a single bond or a double bond. R ¹ represents any ^one of a hydrogen atom, an aliphatic group which may have a substituent, and an aryl group which may have a substituent, and R ² represents a hydrogen atom, = O, = NOCOY, an aliphatic group which may have a substituent, and a substituent Any one of the aryl groups which may have is shown. R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁸ , R ¹⁹ , and R ²⁰ have the same meanings as R ¹ , R ⁵ , R ⁸ , R ¹³ , and R ¹⁷ have the same meaning as R ² . At least ^one of R ¹ and R ² and R ³ , R ⁴ and R ⁵ and R ⁶ , and R ⁷ and R ⁸ and R ⁹ may be bonded to each other to form a ring, and R ¹² and R ¹³ , and R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring. A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , and A ⁸ independently represent any one of a single bond, an oxygen atom, a sulfur atom, NHCO, and CONH. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ independently represent a hydrogen atom and any of the groups shown below, and X ¹ and X ² and X ³ , and X ⁴ and X ⁵ are all hydrogen atoms Except when Y ¹ , Y ² , and Y ³ independently represent any of the groups shown below. G represents either the aliphatic group which may have a substituent, and the aryl group which may have a substituent. J has the same meaning as R ¹ .

<2> is a photoinitiator which is a compound represented by General formula (1) in said <1>.

<3> In said <1> or <2>, the compound represented by General formula (1) is a photoinitiator further represented by following General formula (6).

However, in said general formula (6), R <^21> , R <^22> , R <^23> , R <^24> , R <^25> and R <^26> represent the same meaning as R <^1> in General formula (1)-(5), A ⁹ represents the same meaning as a ¹ in the formula (1) to (5), Y ⁴ represents the same meaning as Y ¹ in the formula (1) to (5). R ²¹ and R ²² , R ²³ and R ²⁴ , and R ²⁵ and R ²⁶ may be bonded to each other to form a ring.

It is a photosensitive composition containing <4> (A) binder, (B) polymeric compound, (C) photoinitiator in any one of said <1>-<3>, and (D) thermal crosslinking agent. .

<5> The photosensitive composition according to the above <4>, wherein the content of the (C) photopolymerization initiator is 0.1 to 15% by mass.

<6> The photosensitive composition as described in <4> or <5>, wherein the (A) binder is an epoxy acrylate compound.

<7> In <4> or <5>, (A) binder is the photosensitive composition containing 1 or more types of vinyl copolymer which has a (meth) acryloyl group and an acidic group in a side chain.

<8> The said (4) or <5> WHEREIN: The (A) binder is a photosensitive composition containing 1 or more types of an epoxy acrylate compound and the vinyl copolymer which has a (meth) acryloyl group and an acidic group in a side chain. .

<9> The photosensitive composition in any one of said <4>-<8> in which (B) polymeric compound contains 1 or more types chosen from the monomer which has a (meth) acryl group.

<10> The compound according to any one of <4> to <9>, wherein the (D) thermal crosslinking agent is a compound obtained by reacting a blocking agent with an epoxy compound, an oxetane compound, a polyisocyanate compound, a polyisocyanate compound, and a melamine derivative. It is 1 or more types of photosensitive compositions chosen.

<11> The photosensitive composition according to any one of <4> to <10>, which contains (E) a thermosetting accelerator.

It has a <12> support body and the photosensitive layer which consists of a photosensitive composition in any one of said <4>-<11> on the said support body, It is a photosensitive film characterized by the above-mentioned.

<13> In the above <12>, when exposing and developing a photosensitive layer, the minimum energy of the light used for the said exposure which does not change the thickness of the part to be exposed of the said photosensitive layer after the said exposure and image development is O It is a photosensitive film which is .1-50000mJ / cm <^2> .

<14> The said <12> or <13> WHEREIN: A support body contains a synthetic resin and is a transparent photosensitive film.

<15> In any one of said <12> to <14>, a support body is a elongate photosensitive film.

<16> The film-sensitive film in any one of said <12> to <15> which is long and wound in roll shape.

<17> The photosensitive film in any one of said <12> to <16> which has a protective film on the photosensitive layer.

It is a photosensitive laminated body which has a photosensitive layer which consists of a photosensitive composition in any one of said <4>-<11> on a <18> base | substrate.

<19> The said photosensitive layer in said <18> is a photosensitive laminated body formed with the photosensitive film in any one of said <12> to <17>.

<20> The photosensitive laminate according to <18> or <19>, wherein the photosensitive layer has a thickness of 1 to 100 µm.

<21> The photosensitive laminated body in any one of said <18>-<20> is equipped with the photosensitive layer,

And at least light modulating means for modulating light from the light irradiating means and exposing the photosensitive layer of the photosensitive laminate to light. In the pattern formation apparatus as described in said <21>, the said light irradiation means irradiates light toward the said light modulation means. The light modulation means modulates the light received from the light irradiation means. Light modulated by the light modulating means is exposed to the photosensitive layer. For example, after developing the said photosensitive layer, a high-definition pattern is formed.

&Lt; 22 > < 21 >, wherein the light modulating means further comprises a pattern signal generating means for generating a control signal based on the pattern information to be formed, wherein the pattern signal generating means transmits the light irradiated from the light irradiation means. It is a pattern forming apparatus which modulates according to the generated control signal. In the pattern forming apparatus according to the above <22>, the light modulating means includes the pattern signal generating means so that the light irradiated from the light irradiating means is modulated in accordance with the control signal generated by the pattern signal generating means. .

&Lt; 23 > The pattern information according to < 21 > or < 22 >, wherein the light modulating means has n drawing parts, and forms any fewer than n drawing parts continuously arranged among the n drawing parts. The pattern forming apparatus is controllable according to the present invention. In the pattern forming apparatus as described in said <23>, the light from the said light irradiation means is controlled by controlling less than n arbitrary drawing parts arrange | positioned continuously among the n drawing parts in the said optical modulation means according to pattern information. This is modulated at high speed.

<24> The pattern forming apparatus according to any one of <21> to <23>, wherein the light modulating means is a spatial light modulating element.

<25> The pattern forming apparatus according to <24>, wherein the spatial light modulator is a digital micro mirror device (DMD).

<26> The pattern forming apparatus in any one of <23> to <25>, wherein the drawing portion is a micromirror.

<27> The pattern forming apparatus in any one of the above <21> to <26>, wherein the light irradiation means is capable of combining two or more lights and irradiating them. In the pattern formation apparatus as described in said <27>, since the said light irradiation means synthesize | combines and irradiates two or more lights, exposure is performed by exposure light with a depth of focus. As a result, exposure to the said photosensitive layer is performed very highly. For example, when the said photosensitive layer is developed after that, a very high definition pattern will be formed.

&Lt; 28 > The light irradiation means according to any one of < 21 > It is a pattern forming apparatus which has an aggregation optical system to make. In the pattern forming apparatus according to <28>, in the light irradiation means, the laser light irradiated from the plurality of lasers is focused by the collective optical system, and the exposure can be combined with the multi-mode optical fiber. It is performed with deep exposure light. As a result, exposure to the said photosensitive layer is performed very highly. For example, when the said photosensitive layer is developed after that, a very high definition pattern will be formed.

<29> It is a permanent pattern formation method including exposing to the photosensitive layer in the photosensitive laminated body in any one of said <18>-<20>.

<30> The <29> method is a permanent pattern formation method in which exposure is performed using the laser beam of 350-415 nm wavelength.

<31> The <29> or <30> method is a permanent pattern formation method performed with an image based on the pattern information which exposure forms.

&Lt; 32 > The two-dimensional exposure of any one of < 29 > to < 31 >, wherein the exposure receives light from the light irradiation means and the light irradiation means and emits the light; An exposure head having a drawing section arranged in a shape and having light modulating means capable of controlling the drawing section in accordance with pattern information, wherein the column direction of the drawing section has a predetermined set inclination angle θ with respect to the scanning direction of the exposure head. Using the placed exposure head,

About the said exposure head, the drawing part used for designating designates the said drawing part used for exposure among N (except N is a natural number of 2 or more) among the available drawing parts,

The drawing head control means controls the drawing head so that only the drawing part designated by the drawing head designation means is involved in the exposure by the drawing part control means.

It is a permanent pattern formation method performed by making the said exposure head relatively move with respect to the said photosensitive layer. In the method for forming a permanent pattern according to the above <32>, in the above-described drawing part that is usable by the use drawing part designation means with respect to the exposure head, N is used for exposure (N is a natural number of 2 or more). A drawing part is designated and the drawing part is controlled by the drawing part control means so that only the drawing part specified by the use drawing part designation means participates in exposure. The exposure is performed by moving the exposure head relatively in the scanning direction with respect to the photosensitive layer, whereby the resolution of the pattern formed on the exposed surface of the photosensitive layer due to the deviation of the installation position or the installation angle of the exposure head. Deviation and unevenness of concentration are even. As a result, exposure to the said photosensitive layer is performed with high definition, and a high definition pattern is formed by developing the said photosensitive layer after that.

<33> The exposure of the head-to-head connection area as described in <32>, wherein the exposure is performed by a plurality of exposure heads, and the use drawing part designation means is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. It is a permanent pattern formation method which designates the said drawing part used in order to implement | achieve N-weight exposure in the said head-to-head connection area | region among the drawing parts which participate in. In the method of forming a permanent pattern according to the above <33>, exposure is performed by a plurality of exposure heads, and the use drawing part designation means is a head-to-head connection which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. Among the drawing parts involved in the exposure of the area, the drawing part used for realizing N-exposure in the head-to-head connection area is designated, whereby the photosensitive layer is caused by the deviation of the installation position and the installation angle of the exposure head. The variation in the resolution and the variation in density of the pattern formed in the head-to-head connection area on the exposed surface are even. As a result, exposure to the said photosensitive layer is performed with high definition. For example, a high-definition pattern is formed by developing the said photosensitive layer after that.

<34> The above-mentioned <33>, wherein the exposure is performed by a plurality of exposure heads, so that the use drawing part designation means is other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. It is a permanent pattern formation method which designates the said drawing part used in order to implement | achieve exposure among N in the area | regions other than the said head-to-head connection area | region among the drawing parts participating in exposure. In the method of forming a permanent pattern according to the above <34>, exposure is performed by a plurality of exposure heads, and the use drawing part designation means is an inter-head connection that is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. The photosensitive layer due to the shift of the installation position and the installation angle of the exposure head is designated by designating the drawing part used for realizing N-exposure in the area other than the head-to-head connection area among the drawing parts involved in exposure other than the area. In addition to the connection area between the heads on the to-be-exposed surface, the variation in the resolution and the variation in density of the pattern formed are even. As a result, exposure to the said photosensitive layer is performed with high definition. For example, a high-definition pattern is formed by developing the said photosensitive layer after that.

<35> In any one of <32> to <34>, the set inclination angle θ inclines the number of exposures N of N, the number s in the column direction of the drawing part, the interval p in the column direction of the drawing part, and the exposure head. In the above state, with respect to the pitch δ in the column direction of the drawing part along the direction orthogonal to the scanning direction of the exposure head, the relationship of θ ≥ θ _ideal is satisfied with respect to θ _ideal satisfying spsinθ _ideal ≥Nδ Permanent pattern forming method is set to.

<36> The method of forming a permanent pattern according to any one of <32> to <35>, wherein N of the N exposures is a natural number of 3 or more. In the permanent pattern formation method as described in said <36>, multiple drawing is performed when N of N exposure is three or more natural numbers. As a result, by the replenishment effect, the deviation of the resolution and the unevenness of the density of the pattern formed on the exposed surface of the photosensitive layer due to the deviation of the installation position and the installation angle of the exposure head are more precisely selected.

<37> The use drawing material designation means in any one of said <32> to <36>,

Light point position detection means, which is generated by a drawing unit and detects a light point position as a drawing unit constituting an exposure area on the to-be-exposed surface on the to-be-exposed surface,

It is a permanent pattern formation method provided with the drawing part selecting means which selects the drawing part used in order to implement N-exposure based on the detection result by the said light spot position detection means.

<38> In any one of said <32> to <37>, the use drawing part designation means is a permanent pattern formation method which designates the use drawing part used in order to implement | achieve N exposure.

<39> The column direction of the light spot on the to-be-exposed surface in the state which inclined the exposure head based on the two or more light spot positions detected by said light spot position detection means in the said <37> or <38>. It is a permanent pattern formation method which specifies the actual inclination angle (theta) 'which the scanning direction of an exposure head makes, and selects the used drawing part so that a drawing part selection means may absorb the error of the said actual inclination angle (theta)' and the set inclination angle (theta).

<40> The above-mentioned <39>, wherein the actual inclination angle θ 'is an average value of a plurality of actual inclination angles formed by the column direction of the light spot on the exposed surface and the scanning direction of the exposure head in a state in which the exposure head is inclined, The permanent pattern forming method is any one of a median, a maximum value, and a minimum value.

<41> The method of any of the above <37> to <40>, wherein the drawing unit selection means is based on the actual inclination angle θ ', where ttan θ' = N (where N represents N of the number of exposures in N). Deriving a natural number T close to t satisfying the relationship of, and selecting the drawing part in the T row from the first row in the drawing part arranged in m rows (where m represents a natural number of 2 or more), It is a permanent pattern formation method.

<42> The method according to any one of <37> to <41>, wherein the drawing part selecting means is configured such that ttan θ '= N (where N represents N of the number of exposures in N) based on the actual inclination angle θ'. A natural number T close to t satisfying the relationship is derived, and the above-mentioned drawing part from the (T + 1) line to the m line arranged in the m rows (where m represents a natural number of 2 or more) is an unused mausoleum. It is a permanent pattern formation method which identifies as a part and selects the said drawing part except the said unused drawing part as a using drawing part.

<43> The region according to any one of <37> to <42>, wherein the drawing unit selecting means includes at least an overlapping exposure area on the exposed surface formed by a plurality of rows of drawing units,

(1) Means for selecting the use drawing part so that the total area of the area | region which becomes overexposure and the area | region which become underexposure with respect to ideal N medium exposure is minimum,

(2) a means for selecting the use drawing section so that the number of drawing units in the overexposure region and the number of drawing units in the underexposure region are equal with respect to the ideal N-exposure exposure;

(3) Means for selecting the use drawing part so that the area of the area which becomes overexposure becomes minimum and the area which becomes underexposure occurs with respect to ideal N medium exposure, and

(4) It is a permanent pattern formation method which is any one of means which selects a use drawing part so that the area of the area which becomes underexposure becomes small and the area which becomes overexposure occurs with respect to ideal N exposure.

<44> In any one of <37> to <43>, in the head-to-head connection area which is the overlapping exposure area on the to-be-exposed surface formed by a plurality of exposure heads,

(1) With respect to the ideal N-exposure, the unused drawing part is specified in the drawing part which is involved in exposure of the said head-connection area | region so that the total area of the area which becomes overexposure and the area which becomes underexposure becomes minimum, and said unused Means for selecting the drawing section except the drawing section as the use drawing section,

(2) With respect to the ideal N-exposure, the unused drawing part is identified in the drawing part involved in the exposure of the head-to-head connection area such that the number of drawing units in the overexposed area and the number of the drawing units in the underexposed area are the same. Means for selecting the drawing part except the unused drawing part as the using drawing part,

(3) With respect to the ideal N-exposure, the unused drawing part in the drawing part involved in the exposure of the head-to-head connection area so that the area of the area that becomes overexposure is minimized and the area that becomes underexposure is not generated. Means for selecting the seedling portion except for the unused seedling portion as a using seedling portion, and

(4) In the drawing part involved in exposure of the said head-connection area | region so that the area of the area which becomes underexposure may become minimum and the area which becomes overexposure with respect to ideal N medium exposure, the unused drawing part may be used. Specifically, it is the said permanent pattern formation method which is any one of means which selects the said drawing part except a unused drawing part as a using drawing part.

<45> The method of forming a permanent pattern according to <44>, wherein the unused drawing part is specified in units of rows.

<46> In any of the above <37> to <45>, in order to designate a drawing material in the use drawing part designation means, with respect to N of exposure among N among the available drawing parts, (N-1 It is a permanent pattern formation method which performs reference exposure using only the said drawing part which comprises a drawing part row for every column. In the permanent pattern formation method as described in said <46>, in order to designate a use drawing part in use drawing part designation means, among the said drawing parts which can be used, A reference exposure is performed using only the drawing portion constituting the sub column, thereby obtaining a simple pattern of about single drawing. As a result, the drawing part in the connection area between the heads is easily designated.

<47> The 1 / N row according to any one of the above <37> to <46>, in order to designate the use drawing part in the use drawing part designation means, with respect to N of the N-exposure exposure among the available drawing parts. It is a permanent pattern formation method which performs reference exposure using only the said drawing part which comprises a drawing row every time. In the method of forming a permanent pattern according to the above <47>, in order to designate a drawing material in use drawing part designation means, a drawing part column is used every 1 / N rows with respect to N of exposure among N among the available drawing parts. Reference exposure is performed using only the drawing part which comprises the above, and the simple pattern of about single drawing can be obtained. As a result, the drawing part in the connection area between the heads is easily designated.

<48> The method of any of the above-mentioned <32> to <47>, wherein the drawing element specifying means has a slit and a photodetector as the light spot position detecting means, and an arithmetic unit connected to the photodetector as the drawing element selecting means. Permanent pattern formation method.

<49> The method of forming a permanent pattern according to any one of <32> to <48>, wherein N of the N exposures is a natural number of 3 or more and 7 or less.

<50> The light according to any one of <32> to <49>, further comprising pattern signal generating means for generating a control signal based on the pattern information formed by the light modulating means, and irradiated from the light irradiation means. Is a permanent pattern forming method for modulating according to the control signal generated by the pattern signal generating means. In the pattern forming apparatus according to the above <50>, the light modulating means includes the pattern signal generating means, so that the light irradiated from the light irradiation means is modulated in accordance with the control signal generated by the pattern signal generating means. .

<51> The method of forming a permanent pattern according to any one of <32> to <50>, wherein the light modulating means is a spatial light modulating element.

<52> The method of forming a permanent pattern according to <51>, wherein the spatial light modulator is a digital micro mirror device (DMD).

<53> The method according to any one of <32> to <52>, wherein the drawing portion is a micromirror.

<54> The pattern information according to any one of the above <32> to <53>, so that the dimension of the predetermined portion of the pattern indicated by the pattern information matches the dimension of the corresponding portion that can be realized by the designated use drawing part. It is a permanent pattern formation method which has a conversion means to convert.

<55> The method of forming a permanent pattern according to any one of <32> to <54>, wherein the light irradiation means is capable of synthesizing two or more lights and irradiating them. In the permanent pattern formation method as described in said <55>, since the said light irradiation means synthesize | combines and irradiates 2 or more lights, exposure is performed by exposure light with a depth of focus. As a result, exposure to the said photosensitive film is performed very highly. For example, when the said photosensitive layer is developed after that, a very high definition pattern will be formed.

<56> The light emitting device according to any one of <32> to <55>, wherein the light irradiation means focuses the laser light irradiated from the plurality of lasers, the multimode optical fiber, and the plurality of lasers, and couples the combined light to the multimode optical fiber. It is a permanent pattern formation method which has a collection optical system to make. In the method for forming a permanent pattern according to the above <56>, the light irradiation means focuses the laser light irradiated from the plurality of lasers on the collective optical system so that the light can be coupled to the multi-mode optical fiber, thereby focusing exposure. Depth is performed with deep exposure light. As a result, exposure to the said photosensitive film is performed very highly. For example, when the said photosensitive layer is developed after that, a very high definition pattern will be formed.

<57> It is a permanent pattern formation method in any one of said <29> to <56> which develops a photosensitive layer after exposure is performed. In the permanent pattern formation method as described in said <57>, after the said exposure is performed, a fine pattern is formed by developing the said photosensitive layer.

<58> The method according to <57>, wherein after the development is performed, a permanent pattern is formed.

<59> The above-mentioned <58> is a permanent pattern forming method of performing a curing treatment on a photosensitive layer after development is performed.

<60> The said <59> description is a permanent pattern formation method which is at least any one of a front surface exposure process and a front surface heat processing performed at 120-200 degreeC.

<61> It is a permanent pattern formed by the pattern formation method in any one of said <29>-<60>. Since the permanent pattern described in the above <61> is formed by the pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and is highly fixed, and has high density to a multilayer wiring board or a buildup wiring board of a semiconductor or a component. Useful for mounting.

<62> The above-mentioned <61> is a permanent pattern which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern. Since the permanent pattern described in the above <62> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the wiring is protected from an impact, warpage, etc. from the outside by the insulation, heat resistance, etc. of the film.

<63> A printed circuit board is formed by the permanent pattern forming method according to any one of <29> to <60>.

Effects of the Invention

ADVANTAGE OF THE INVENTION According to this invention, in order to solve the conventional problem and to be able to respond to laser exposure, the improvement in the sensitivity in the photosensitive composition can be aimed at further, and also the resolution, storage stability, surface hardness, and A photopolymerization initiator capable of maintaining dielectric properties satisfactorily, a photosensitive composition using the same, a photosensitive film, a photosensitive laminate, a method of forming a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) using the photosensitive laminate, And a printed circuit board on which a pattern is formed by the permanent pattern forming method.

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

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

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

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

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

5A is a surface view illustrating an example of a detailed configuration of an exposure head.

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

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

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

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

Fig. 8 is an explanatory diagram showing an example of nonuniformity generated in a pattern on the exposed surface when there is an installation angle error and pattern deformation of the exposure head.

9 is a surface view showing the positional relationship between the exposure area by one DMD and the corresponding slit.

10 is a surface view for explaining a method of measuring the position of a light spot on an exposed surface by using a slit.

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

It is explanatory drawing which showed the example of the nonuniformity which arises in the pattern on a to-be-exposed surface, when there exists a shift of a relative position between adjacent exposure heads.

Fig. 13 is a surface diagram showing the positional relationship between the exposure area by two adjacent exposure heads and the corresponding slit.

14 is a surface view for explaining a method of measuring the position of a light spot on an exposed surface by using a slit.

FIG. 15 is an explanatory diagram showing a state in which only the use pixel selected in the example of FIG. 12 is activated to improve the unevenness occurring in the pattern on the exposed surface.

FIG. 16 is an explanatory diagram showing an example of nonuniformity occurring in a pattern on the exposed surface when there is a shift in relative position and an installation angle error between adjacent exposure heads.

17 is an explanatory diagram showing exposure using only the use drawing part selected in the example of FIG. 16.

18A is an explanatory diagram showing an example of magnification deformation.

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

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

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

20 is an explanatory diagram showing a first example of a reference exposure using a plurality of exposure heads.

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

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

22 is an explanatory diagram showing a second example of the reference exposure using the multiple exposure heads.

(Photopolymerization initiator)

The photoinitiator of this invention is a compound represented by either of following General formula (1)-(5).

However, in said general formula (1)-(5), a dashed double line represents either a single bond or a double bond. R ¹ represents any ^one of a hydrogen atom, an aliphatic group which may have a substituent, and an aryl group which may have a substituent, and R ² represents a hydrogen atom, = O, = NOCOY, an aliphatic group which may have a substituent, and a substituent Any one of the aryl groups which may have is shown. R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁸ , R ¹⁹ , and R ²⁰ have the same meanings as R ¹ , R ⁵ , R ⁸ , R ¹³ , and R ¹⁷ have the same meaning as R ² . At least ^one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ , R ^8, and R ⁹ may be bonded to each other to form a ring, and R ¹² , R ¹³ , R ¹⁶ , R ¹⁷ may be bonded to each other to form a ring. A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , and A ⁸ independently represent any one of a single bond, an oxygen atom, a sulfur atom, NHCO, and CONH. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ independently represent a hydrogen atom and any of the groups shown below, and X ¹ and X ² and X ³ , and X ⁴ and X ⁵ are all hydrogen atoms Except when Y ¹ , Y ² , and Y ³ independently represent any of the groups shown below. G represents either the aliphatic group which may have a substituent, and the aryl group which may have a substituent. J has the same meaning as R ¹ .

In the compounds represented by the general formulas (1) to (5), examples of the aliphatic group which may have a substituent represented by R ¹ , R ² , or G include an alkyl group, an alkenyl group, and an alkynyl group, which may each have a substituent. Can be mentioned.
Examples of the alkyl group which may have the substituent include any one of linear, branched, and cyclic alkyl groups having 1 to 30 carbon atoms.

Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group And a cyclohexyl group, a cyclopentyl group, and 2-norbornyl group. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.

As a substituent of the alkyl group which may have the said substituent, the substituent which consists of monovalent nonmetallic atoms except a hydrogen atom is mentioned.

Preferred examples include halogen atoms (-F, -Br, -Cl, -I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, Amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcar Baroyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkyl sulfoxy group, Aryl sulfoxy group, acylthio group, acylamino group, N-alkyl acylamino group, N-aryl acylamino group, ureido group, N'- alkyl ureido group, N ', N'- dialkyl ureido group, N'- aryl ureido group , N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'- Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group , N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'- Alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl -N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N- Dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo (-SO ₃ H) and its conjugated salts device (sulfo Ney Group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamomo Diary, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (-PO ₃ H ₂ ), its conjugated base group (referred to as phosphonate group), dialkyl phosphono group (-PO ₃ (alkyl) ₂ ) = alkyl group, hereinafter the same ", a diaryl phosphono group (-PO ₃ (aryl) _2)" aryl = an aryl group, hereinafter the same ", an alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl Phosphono group (-PO ₃ (alkyl)) and its conjugated salt group (referred to as alkyl phosphonate group), monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated salt group (arylphosphonate group Phosphonooxy group (-OPO ₃ H ₂ ) and its conjugated base group (phosphone) Yttoxy group), dialkylphosphonooxy group (-OPO ₃ H (alkyl) ₂ ), diarylphosphonooxy group (-OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (-OPO ₃ ( alkyl) (aryl)), monoalkylphosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (referred to as alkylphosphonateoxy group), monoarylphosphonooxy group (-OPO ₃ H (aryl) )) And its conjugated salt group (referred to as arylphosphonateoxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

The alkyl group mentioned above is mentioned as a specific example of the alkyl group in these substituents. Specific examples of the aryl group in the substituent include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group and methoxyphenyl group. , Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group , Phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulfonatephenyl group, phosphonophenyl group, phosphonatephenyl group and the like.

As an example of the alkenyl group in the said substituent, a vinyl group, 1-propenyl group, 1-butenyl group, cinnammyl group, 2-chloro-1-ethenyl group, etc. are mentioned.

Examples of the alkynyl group in the substituent include an ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.

Examples of the aryl group represented by R ¹ , R ² , or G include one in which one to three benzene rings form a condensed ring, and one in which a benzene ring and a five-membered unsaturated ring form a condensed ring.

As a specific example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group are mentioned. In these, a phenyl group and a naphthyl group are more preferable.

In the said aryl group, as an aryl group which has a substituent, what has a group which consists of a monovalent nonmetallic atom group except a hydrogen atom as a substituent on the cyclic carbon atom of the aryl group mentioned above is mentioned.

As an example of a preferable substituent, what was shown as a substituent in the alkyl group mentioned above and a substituted alkyl group first is mentioned.

As a preferable specific example of the aryl group which has the said substituent, a biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxy Phenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N -Cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group , Carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-meth -N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatephenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl -N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatephenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatephenyl group, tolylphosphonophenyl group, tolyl Phosphonatephenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynyl A phenyl group etc. are mentioned.

Among the compounds represented by the above general formulas (1) to (5), the third to fifth atoms are counted from the nitrogen atom constituting the bond of the nitrogen atom and the oxygen atom which are cleaved by light to form a free group, and the nitrogen atom is the nitrogen atom. The compound represented by General formula (1) from a viewpoint which has an unsaturated bond with the atom adjacent to another side and is preferable.

Moreover, as a compound represented by the said General formula (1), it is preferable to form a 5-7 membered ring with the produced | generated free group and the said unsaturated bond, for example, and when a ring structure exists in the position adjacent to this formed ring, From the viewpoint of making it difficult to cause deformation in both, it is more preferable that the raw number of the ring and the formed ring are different.

As said unsaturated bond, except for the unsaturated bond which a carbonyl bond and an aromatic group may have, it is preferable that it is at least any one of an ethylenically unsaturated bond and an acetylene unsaturated bond.

Here, the "third to fifth atoms counted from nitrogen atoms constituting a bond that cleaves with light to form a free group" refers to a nitrogen atom constituting a bond that cleaves with light having a wavelength of 300 to 700 nm to form a free group. In the case of minimum, it means the 3rd-5th atom. It is preferable that the said wavelength is 350-600 nm.

It is generally known that the bond of the nitrogen atom and the oxygen atom is cleaved by light having a wavelength of 300 to 700 nm to generate a free group. Formation of the said ring can irradiate the light of the said wavelength 300-700nm to the photosensitive layer obtained by the photosensitive composition containing the said photoinitiator, for example, and can confirm that a cyclized substance exists in the decomposition | disassembly thing.

Among the compounds represented by the general formula (1), for example, the compound represented by the following general formula (6) is more preferable.

However, in said general formula (6), R <^21> , R <^22> , R <^23> , R <^24> , R <^25> and R <^26> represent the same meaning as R <^1> in General formula (1)-(5), A ⁹ represents the same meaning as a ¹ in the formula (1) to (5), Y ⁴ represents the same meaning as Y ¹ in the formula (1) to (5). R ²¹ and R ²² , R ²³ and R ²⁴ , and R ²⁵ and R ²⁶ may be bonded to each other to form a ring.

Although there is no restriction | limiting in particular as a photoinitiator represented by the said General formula (6), For example, what is shown by following compound examples 1-52 is mentioned preferably.

Synthetic Method

Although there is no restriction | limiting in particular as a synthesis | combining method of the said photoinitiator, For example, the method of synthesize | combining in order of the following (1)-(3), etc. are mentioned.

(1) Into a three-necked flask, sodium hydride of mineral oil removal is added, changed to a nitrogen atmosphere, and a solution containing tetrahydrofuran (THF) is added from the dropping funnel, followed by stirring. At this time, diethyl carbonate may be added.

(2) After the solution of allyl bromide or proparbromide and tetrahydrofuran (THF) was added from the dropping funnel, the mixture was stirred, water was added, ethyl acetate was added for extraction, and the solvent of the organic layer was distilled off under reduced pressure. By producing by silica gel chromatography, the intermediate product of the compound of the present invention is obtained. At this time, sodium hydroxide, ethanol and water may be added to the oily substance obtained by the above-mentioned vacuum distillation, and the external temperature may be set to about 75 degreeC, and after stirring, hydrochloric acid may be added and water may be added.

(3) The intermediate, hydroxyamine hydrochloride, potassium acetate, and ethanol are placed in a eggplant flask and refluxed. After the reaction was completed, water was added, extraction was performed with ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Then, pyridine and acetonitrile were added and the external temperature was set at about 0 ° C., a solution of acetyl chloride and acetonitrile was added with a dropping funnel, followed by stirring, i) water was added, and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and distilled off under reduced pressure to obtain an oily compound of the present invention, or ii) crystals obtained by adding iced water were recrystallized with acetonitrile to obtain white crystals of the compound of the present invention.

In addition, you may react with the following (0) before said (1).

(0) 1-naphthylaldehyde, malonic acid, piperidine, and pyridine are added to a three-necked flask to reflux, and the reaction solution is put into iced water to obtain a white solid by filtration. Then, this white solid is dissolved in methanol and ethyl acetate, palladium carbon is added, and reacted under hydrogen atmosphere. After the reaction is completed, the reaction solution is filtered through Celite, and the solvent is distilled off under reduced pressure. Then, chlorobenzene and aluminum chloride are added to set the external temperature to 0 ° C, and the white solid and chlorobenzene are added dropwise from the dropping funnel, followed by reaction, and ice water is added. The obtained white crystals are recrystallized from methanol to obtain an intermediate product corresponding to the intermediate product.

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The photopolymerization initiator of the present invention can further improve the sensitivity so as to cope with laser exposure, and can also maintain the resolution, storage stability, surface hardness, and dielectric properties satisfactorily. For this reason, the protective film of a printed wiring board (multilayer wiring board, a buildup wiring board, etc.), an interlayer insulation film, and a display member, such as a soldering resist pattern, a color filter, a pillar material, a rib material, a spacer, a partition, a hologram, a micromachine, It can be used widely for permanent pattern formation, such as a proof and an adhesive agent, and can be especially used for the photosensitive composition of this invention, the photosensitive film, the photosensitive laminated body, and the permanent pattern formation method.

(Photosensitive composition)

The photosensitive composition of this invention contains (A) binder, (B) polymeric compound, (C) said photoinitiator of this invention, and (D) thermal crosslinking agent, Preferably it contains (E) thermosetting accelerator, Moreover, if necessary, it contains other components, such as a coloring pigment, an extender pigment, a thermal polymerization inhibitor, and surfactant.

((A) binder (polymer)]

As said binder, the compound which shows swelling property with respect to alkaline aqueous solution is preferable, and the compound which is soluble with respect to alkaline aqueous solution is more preferable.

As a binder which shows swelling property or solubility with respect to alkaline aqueous solution, what has an acidic group is preferable, for example, Specifically, the compound which introduce | transduced an ethylenically unsaturated double bond and an acidic group into an epoxy compound (epoxyacrylate compound) The vinyl copolymer which has a (meth) acryloyl group and an acidic group in a side chain, an epoxy acrylate compound, the mixture of the vinyl copolymer which has a (meth) acryloyl group and an acidic group in a side chain, a maleamic acid type copolymer, etc. are preferable. .

There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned, Among these, a carboxyl group is preferable from a viewpoint of the availability of a raw material, etc. among these. Can be mentioned.

<Epoxyacrylate Compound>

There is no restriction | limiting in particular as a compound (epoxy acrylate compound) which introduce | transduced ethylenically unsaturated double bond and an acidic group into the said epoxy compound, According to the objective, it can select suitably, For example, a polyfunctional epoxy compound and a carboxyl group-containing monomer react. And polybasic acid anhydride can be obtained.

As said polyfunctional epoxy compound, the heterocyclic epoxy resin ("TEPIC") which has a bixylenol type or bisphenol-type epoxy resin ("YX4000; the Japan epoxy resin company", etc.) or a mixture thereof, an isocyanurate skeleton etc. Nissan Chemical Industries, Ltd., "Araldite PT810; Chiba Specialty T Chemicals", etc.), bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, Phenol novolak type epoxy resin, Cresol novolak type epoxy resin, Halogenated phenol novolak type epoxy resin, Glycidyl amine type epoxy resin (for example, tetraglycidyl diamino diphenylmethane, etc.), Hydantoin type epoxy resin , Alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenyrolethane type epoxy resin, glycidylphthalay T resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (`` ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd. '', `` HP-4032, EXA-4750, EXA-4700; Dainippon Ink) Chemical company ", etc.), the epoxy resin which has a dicyclopentadiene skeleton (" HP-7200, HP-7200H; Dainippon Ink Chemical company ", etc.); phenol compounds, such as phenol, o-cresol, naphthol, and phenol A reaction product of epichlorohydrin with a polyphenol compound obtained by condensation of an aromatic aldehyde having a hydroxyl group (for example, p-hydroxybenzaldehyde); Reactant of the polyphenol compound obtained by addition reaction of a phenol compound with diolefin compounds, such as divinylbenzene and dicyclopentadiene, and epichlorohydrin; Epoxidation of the ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracetic acid or the like; Epoxy resins having heterocycles such as triglycidyl isocyanurate; Glycidyl methacrylate copolymer type | system | group epoxy resin ("CP-50S, CP-50M; the product made by Japan Holdings", etc.), the copolymerization epoxy resin of cyclohexyl maleimide, glycidyl methacrylate, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

Examples of the carboxyl group-containing monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, and acrylic acid dimers; In addition, addition reaction product of monomer which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, and cyclic acid anhydrides, such as maleic anhydride, a phthalic anhydride, cyclohexane dicarboxylic anhydride; The reaction product with a halogen containing carboxylic acid compound, (omega)-carboxy polycaprolactone mono (meth) acrylate, etc. are mentioned. Moreover, as a commercial item, NK ester CB-1 and CBX-1 by Aronix M-5300, M-5400, M-5500, and M-5600 by Toagosei Chemical Co., Ltd. and Shin-Nakamura Chemical Co., Ltd. , HOA-MP and HOA-MS manufactured by Kyoeisha Oil Chemical Co., Ltd., biscoat # 2100 manufactured by Osaka Organic Chemical Industry Co., Ltd., etc. can be used. These may be used individually by 1 type and may use 2 or more types together.

Moreover, as said polybasic acid anhydride, for example, succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, dodecenyl succinic anhydride, nonenyl succinic anhydride, maleic anhydride , Methylmaleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cisaconitic anhydride, phthalic anhydride, Tetrahydro phthalic anhydride, tetrachloro phthalic anhydride, tetrabromo phthalic anhydride, hexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydro phthalic anhydride, endomethylenetetrahydro phthalic anhydride, methyl endomethylene tetrahydro phthalic anhydride, chloro anhydride Diacid salts such as lentic acid and 5- (2,5-diiotetetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride Also anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic polybasic acid anhydride such as a tetracarboxylic acid can be used. These may be used individually by 1 type and may use 2 or more types together.

Epoxy acrylate is obtained by sequentially reacting each, but the ratio of reacting them is 0.8 to 1.2 equivalents, preferably 0.9 to 1.1 equivalents, of the carboxyl group of the carboxyl group-containing monomer relative to 1 equivalent of the epoxy group of the polyfunctional epoxy compound. 0.1-1.0 equivalent of anhydride, Preferably it is 0.3-1.0 equivalent.

Moreover, the compound etc. which can be obtained by adding the said polybasic acid anhydride to the epoxy acrylate (compound which does not have a carboxyl group) which have a fluorene skeleton as described in Unexamined-Japanese-Patent No. 5-70528 can also be used as an epoxy acrylate of this invention. have.

Among the compounds in which an ethylenically unsaturated double bond and an acidic group are introduced into the epoxy compound, an epoxy acrylate compound represented by the following structural formulas (1) and (2) is preferable.

In the structural formula (1), X represents any one of a hydrogen atom and a substituent including at least an acidic group, Y represents any one of a methylene group, an isopropylidene group, and a sulfonyl group, and n represents 1 to 1 The integer of 20 is shown.

However, in said structural formula (2), n represents the integer of 1-20.

As the epoxy acrylate compound represented by the structural formula (1), specifically, a bisphenol F type epoxy acrylate compound represented by the following structural formula (3), and a bisphenol A type epoxy acrylate compound represented by the following structural formula (4) More preferred.

As for the mass mean molecular weight of the said epoxy acrylate compound, 1, OOOO-100000 and OOO are preferable, and 2,000-50,000 are more preferable. When the said mass average molecular weight is less than 1,000, the viscosity of the surface of a photosensitive layer may become strong, and after hardening of the photosensitive layer mentioned later, a film may become weak or surface hardness may deteriorate, and when it exceeds 100,000, it is developable. There is this deterioration. Moreover, synthesis | combination of resin also becomes difficult.

<Vinyl copolymer having a (meth) acryloyl group and an acidic group in the side chain>

As a vinyl copolymer which has a (meth) acryloyl group and an acidic group in the said side chain, it is (1) the vinyl monomer which has an acidic group, (2) the vinyl monomer which has a functional group which can be used for the polymer reaction mentioned later as needed, And (3) synthesizing the (co) polymer obtained from the vinyl (co) polymerization of other copolymerizable vinyl monomers as necessary, and (4) in the acidic groups in the (co) polymer or functional groups available for polymer reactions. It can obtain by making polymer-react the compound which has a functional group and (meth) acryloyl group which are reactive with respect to 1 or more types.

There is no restriction | limiting in particular as an acidic group of the vinyl monomer which has the said (1) acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned, Among these, a carboxyl group is preferable. Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimers, monomers having a hydroxyl group (for example, Addition reaction of 2-hydroxyethyl (meth) acrylate) and cyclic anhydride (e.g., maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxypolycaprolactone mono (meth) Acrylates and the like. Among these, (meth) acrylic acid is especially preferable from a viewpoint of copolymerizability, cost, and solubility. In addition, these monomers may be used individually by 1 type, and may use 2 or more types together.

Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, a citraconic anhydride, as a precursor of a carboxyl group.

The functional group usable for the polymer reaction in the vinyl monomer having the functional group usable for the polymer reaction of the above (2) includes a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, and the like. Moreover, the carboxyl group and acid anhydride group of said (1) can be mentioned as a functional group which can be used.

As a vinyl monomer which has the said hydroxyl group, the compound represented by following Structural formula (5)-(13) is mentioned, for example.

However, in the structural formulas (5) to (13), R ₁ represents a hydrogen atom or a methyl group, and n, n1 and n2 represent an integer of 1 or more.

As a vinyl monomer which has the said amino group, vinyl benzylamine, aminoethyl methacrylate, etc. are mentioned, for example.

As a monomer which has the said isocyanate group, the compound represented by following Structural formula (14)-(16) is mentioned, for example.

However, in the structural formulas (14) to (16), R ¹ represents a hydrogen atom or a methyl group.

As a vinyl monomer which has the said epoxy group, the compound etc. which are represented by glycidyl (meth) acrylate and the following structural formula (17) are mentioned, for example.

However, in the structural formula (17), R represents either of H and Me.

As a vinyl monomer which has the said acid halide group, (meth) acrylic acid chloride etc. are mentioned, for example.

As a vinyl monomer which has the said active halide group, chloromethyl styrene etc. are mentioned, for example.

As these commercial items, for example, "Kaneka Resin AXE; Kanegafuchi Chemical Co., Ltd. product", "Cyclomer (CYCLOMER) A-200; Daicel Chemical Industry Co., Ltd. product", "Cyclomer ( CYCLOMER) M-200; "made by Daicel Chemical Industries, Ltd.", "SPCP1X, SPCP2X, SPCP3X; Showa Polymer Co., Ltd.", etc. can be used.

In addition, each said monomer may be used individually by 1 type, and may use 2 or more types together.

There is no restriction | limiting in particular as another copolymerizable monomer which can be used as needed of said (3), Although it can select suitably according to the objective, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester , Maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohols, styrenes (e.g., styrene, styrene derivatives, etc.), (meta ) Acrylonitrile, a heterocyclic group substituted with a vinyl group (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinyl acetamide, N-vinylimidazole, Vinylcaprolactone, 2-acrylamide-2-methylpropanesulfonic acid, monophosphate mono (2-acryloyloxyethyl ester), monophosphate mono (1-methyl-2-acryloyloxyethyl ester), functional group (for example Urethane, urethane Vinyl monomers having a baby, a sulfonamide group, an imide group), and the like.

As said (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth), for example Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2 -Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol mono Methyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth (2) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylic Latex, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (Meth) acrylate, tribromophenyloxyethyl (meth) acrylate, etc. are mentioned.

As said crotonic acid ester, crotonate butyl, crotonate hexyl, etc. are mentioned, for example.

As said vinyl ester, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate, etc. are mentioned, for example.

As said maleic acid diester, dimethyl maleate, diethyl maleate, dibutyl maleate, etc. are mentioned, for example.

As said fumaric acid diester, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, etc. are mentioned, for example.

As said itaconic acid diester, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc. are mentioned, for example.

As said (meth) acrylamide, it is (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl, for example. (Meth) acrylamide, Nn-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N , N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone Acrylamide etc. are mentioned.

As said styrene, the said styrene, the said styrene derivative (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, methoxy styrene, butoxy styrene, acetoxy styrene) , Chlorostyrene, dichlorostyrene, bromostyrene, hydroxystyrene, methylvinylbenzoate, α-methylstyrene, and the like protected from a group deprotectable by an acidic substance (e.g., t-Boc). have.

As said vinyl ether, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy ethyl vinyl ether, etc. are mentioned, for example.

As a synthesis | combining method of the vinyl monomer which has a urethane group or a urea group as said functional group, addition reaction of an isocyanate group, a hydroxyl group, or an amino group is mentioned, for example, The compound which contains one monomer which has an isocyanate group, and one hydroxyl group specifically, is mentioned. Or addition reaction of a compound having one primary or secondary amino group, a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and an addition reaction of monoisocyanate.

As a monomer which has the said isocyanate group, the compound represented by the said structural formula (14)-(16) is mentioned, for example as shown to (2) mentioned above.

As said monoisocyanate, cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, phenyl isocyanate, etc. are mentioned, for example.

As a monomer which has the said hydroxyl group, the compound represented by said structural formulas (5)-(13) is mentioned, for example as shown to (2) mentioned above.

Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2). -Ethylhexanol, n-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc., phenols (e.g., phenol, cresol, naphthol, etc.) And fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, acetoxyphenol and the like.

As a monomer which has the said primary or secondary amino group, vinylbenzylamine etc. are mentioned, for example.

Examples of the compound containing one primary or secondary amino group include alkyl amines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t- Butylamine, hexylamine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkyl amines (cyclopentylamine, cyclohexyl Amines), aralkylamines (benzylamine, phenethylamine, etc.), aryl amines (aniline, toluylamine, xylylamine, naphthylamine, etc.), and combinations thereof (N-methyl-N-benzylamine, etc.) And amines containing a substituent (trifluoroethylamine, hexafluoroisopropylamine, methoxyaniline, methoxypropylamine, etc.) and the like.

In addition, these monomers may be used individually by 1 type, and may use 2 or more types together.

By vinyl (co) polymerizing these, the (co) polymer containing an acidic group, an acid anhydride group, and if necessary, a hydroxyl group, an amino group, an isocyanate group, an epoxy group, an acid halide group, an active halide group, etc. can be obtained. The said vinyl (co) polymer can be prepared by copolymerizing a monomer corresponding to each according to a conventional method by a well-known method. For example, it can prepare by using the method (solution polymerization method) which melt | dissolves the said monomer in a suitable solvent, and adds a radical polymerization initiator to it and superposes | polymerizes in solution. Furthermore, it can prepare by using superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.

Regarding the (co) polymer obtained in this way, as (4), reactivity with at least one of an acidic group in these copolymers and a hydroxyl group, an amino group, an isocyanate group, a glycidyl group, and an acid halide group is required. It can obtain by making the compound which has a functional group which has, and a (meth) acryloyl group react with a polymer.

As a compound which has the functional group and (meth) acryloyl group which are reactive with at least 1 sort (s) among the acidic group in the (co) polymer of said (4), or the functional group which can be used for polymer reaction, the compound shown to above-mentioned (2) Etc. can be used.

As an example of the combination of the functional group at the time of performing these polymer reactions, the combination of the copolymer which has an acidic group (carboxyl group etc.), the vinyl monomer which has an epoxy group, the copolymer which has an amino group, and the combination of the vinyl monomer which has an epoxy group is mentioned, for example. , A combination of a copolymer having an amino group and a vinyl monomer having an isocyanate group, a combination of a copolymer having a hydroxyl group and a vinyl monomer having an isocyanate group, a combination of a copolymer having a hydroxyl group and a vinyl monomer having an acid halide group, a copolymer having an amino group, Combination of a vinyl monomer having an active halide group, a copolymer having an acid anhydride group and a vinyl monomer having a hydroxyl group, a combination of a copolymer having an isocyanate group and a vinyl monomer having an amino group, a copolymer having an isocyanate group and a vinyl monomer having a hydroxyl group Combination, active challah Having a DE may be mentioned combinations of a vinyl monomer having a copolymer with an amino group. Moreover, these combinations are not cared about even if they use 2 or more types together.

<Maleamic Acid Copolymer>

The said maleamic acid type copolymer is a copolymer obtained by making 1 or more types of primary amine compounds react with the anhydride group of a maleic anhydride copolymer. It is preferable that the said copolymer is a maleamic acid type copolymer containing at least the maleamic acid unit B which has a maleic acid half amide structure represented by following formula (17), and the unit A which does not have the said maleic acid half amide structure.

The unit A may be one kind or two or more kinds. For example, when the unit A is one kind, when the unit A is one kind, the maleamic acid copolymer means a binary copolymer. When the unit A is two kinds, the maleamic acid type is used. Copolymer means tertiary copolymer.

As said unit A, the combination with the aryl group which may have a substituent and the vinyl monomer (c) whose glass transition temperature (Tg) of the homopolymer of the said vinyl monomer is less than 80 degreeC is mentioned preferably.

However, in said structural formula (17), R <^3> and R < ⁴ > represents either a hydrogen atom and a lower alkyl group. x and y represent the mole fraction of a repeating unit. For example, when the said unit A is 1 type, x is 85-50 mol% and y is 15-50 mol%.

delete

In the structural formula (17), as R ¹ , for example, (-COOR ¹⁰ ), (-CONR ¹¹ R ¹² ), an aryl group which may have a substituent, (-OCOR ¹³ ), (-OR ¹⁴ ), ( And substituents such as -COR ¹⁵ ). Here, said R <^10> -R <^15> represents either a hydrogen atom (-H), the alkyl group which may have a substituent, an aryl group, and an aralkyl group. The alkyl group, aryl group and aralkyl group may have a cyclic structure or a branched structure.

As said R <^10> -R <^15> , for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, allyl, n-hexyl, cyclohexyl , 2-ethylhexyl, dodecyl, methoxyethyl, phenyl, methylphenyl, methoxyphenyl, benzyl, phenethyl, naphthyl, chlorophenyl and the like.

As a specific example of said R <^1> , For example, benzene derivatives, such as phenyl, (alpha)-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2, 4- dimethylphenyl; n-propyloxycarbonyl, n-butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, n-butyloxycarbonyl, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, methyl Oxycarbonyl etc. are mentioned.

As said R <^2> , the alkyl group which may have a substituent, an aryl group, an aralkyl group, etc. are mentioned. These may have a annular structure or a branched structure. Specific examples of R ² include benzyl, phenethyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, and α- Methylbenzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2- (p-tolyl) ethyl, β-methylphenethyl, 1-methyl-3-phenylpropyl, 2-chlorobenzyl, 3-chloro Benzyl, 4-chlorobenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 4-bromophenethyl, 2- (2-chlorophenyl) ethyl, 2- (3-chlorophenyl) ethyl , 2- (4-chlorophenyl) ethyl, 2- (2-fluorophenyl) ethyl, 2- (3-fluorophenyl) ethyl, 2- (4-fluorophenyl) ethyl, 4-fluoro-α , α-dimethylphenethyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 2-methoxyphenethyl, 3-methoxyphenethyl, 4-methoxyphen Netyl, methyl, ethyl, propyl, i-propyl, butyl, t-butyl, sec-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, lauryl, phenyl, 1-naphthyl, methoxymethyl, 2-meth Methoxyethyl, 2-ethoxyethyl, 3- Methoxypropyl, 2-butoxyethyl, 2-cyclohexyloxyethyl, 3-ethoxypropyl, 3-propoxypropyl, 3-isopropoxypropylamine, and the like.

delete

The binder is, in particular, a copolymer of (a) maleic anhydride, (b) an aromatic vinyl monomer, (c) a vinyl monomer, the vinyl monomer having a glass transition temperature (Tg) of the homopolymer of the vinyl monomer being less than 80 ° C. It is preferable that it is a copolymer obtained by making a primary amine compound react with an anhydride group. Although the high surface hardness of the photosensitive layer mentioned later can be obtained in the copolymer which consists of said (a) component and said (b) component, securing of lamination property may become difficult. In addition, in the copolymer which consists of said (a) component and said (c) component, although lamination property can be ensured, securing of the said surface hardness may become difficult.

-(b) Aromatic Vinyl Monomers-

There is no restriction | limiting in particular as said aromatic vinyl monomer, Although it can select suitably according to the objective, Since the surface hardness of the photosensitive layer formed using the photosensitive composition of this invention can be made high, the glass transition temperature (Tg) of a homopolymer ) Is preferably 80 ° C or higher, and more preferably 100 ° C or higher.

As a specific example of the said aromatic vinyl monomer, For example, styrene (Tg = 100 degreeC of homopolymer), (alpha) -methylstyrene (Tg = 168 degreeC of homopolymer), 2-methylstyrene (Tg = 136 degreeC of homopolymer) Styrene derivatives such as 3-methyl styrene (Tg = 97 ° C. of homopolymer), 4-methyl styrene (Tg = 93 ° C. of homopolymer), and 2,4-dimethylstyrene (Tg = 112 ° C. of homopolymer) It can be heard. These may be used individually by 1 type and may use 2 or more types together.

-(c) vinyl monomers-

As for the said vinyl monomer, it is necessary that the glass transition temperature (Tg) of the homopolymer of the said vinyl monomer is less than 80 degreeC, 40 degrees C or less is preferable, and 0 degrees C or less is more preferable.

As said vinyl monomer, n-propyl acrylate (Tg = -37 degreeC of homopolymer), n-butyl acrylate (Tg = -54 degreeC of homopolymer), pentyl acrylate, or hexyl acrylate ( Tg = -57 degreeC of a homopolymer, n-butyl methacrylate (Tg = -24 degreeC of a homopolymer), n-hexyl methacrylate (Tg = -5 degreeC of a homopolymer), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

-Primary amine compound-

As said primary amine compound, for example, benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, 6-phenyl-1 -Hexylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3 -Phenylpropylamine, 2-chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4-bromophenetyl Amine, 2- (2-chlorophenyl) ethylamine, 2- (3-chlorophenyl) ethylamine, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- ( 3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethylphenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4 -Methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine , Methylamine, ethylamine, propylamine, 1-propylamine, butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, aniline, Octylaniline, anisidine, 4-chloroaniline, 1-naphthylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, etc. are mentioned. Among these, benzylamine and phenethylamine are especially preferable.

The said primary amine compound may be used individually by 1 type, and may use 2 or more types together.

The reaction amount of the said primary amine compound needs to be 0.1-1.2 equivalent with respect to the said anhydride group, and 0.1-1.0 equivalent is preferable. When the said reaction amount exceeds 1.2 equivalent, when one or more types of said primary amine compounds are reacted, solubility may deteriorate remarkably.

15-50 mol% is preferable, as for content in the said binder of said (a) maleic anhydride, 20-45 mol% is more preferable, 20-40 mol% is especially preferable. If the content is less than 15 mol%, alkali developability cannot be imparted. If the content exceeds 50 mol%, alkali resistance deteriorates, and the synthesis of the copolymer becomes difficult, so that a normal permanent pattern may not be formed. . In this case, the content in the binder of the vinyl monomer in which the glass transition temperature (Tg) of the (b) aromatic vinyl monomer and (c) homopolymer is less than 80 ° C is 20 to 60 mol% and 15, respectively. 40 mol% is preferable. When the said content satisfies the said numerical range, both surface hardness and lamination | stackability can be aimed at.

3,000-500,000 are preferable and, as for the molecular weight of the said maleamic acid type copolymer, 8,000-150,000 are more preferable. When the said molecular weight is less than 3,000, after hardening of the photosensitive layer mentioned later, a film quality may fall and surface hardness may deteriorate. When it exceeds 500,000, the fluidity at the time of heat lamination of the said photosensitive composition will become low, and ensuring appropriate lamination property It may become difficult, and developability may deteriorate.

<Other binders>

As said other binder, the polyamide (imide) resin of Unexamined-Japanese-Patent No. 11-288087, the polyimide precursor of Unexamined-Japanese-Patent No. 11-282155, etc. can be used. These may be used singly or in combination of two or more kinds.

As mass average molecular weight of binders, such as the said polyamide (imide) or a polyimide precursor, 3,000-500,000 are preferable and 5,000-100,000 are more preferable. When the said mass average molecular weight is less than 3,000, the viscosity of the surface of a photosensitive layer may become strong, and after hardening of the photosensitive layer mentioned later, a film quality may regress or surface hardness may deteriorate, and when it exceeds 500,000, it will develop. There is a deterioration of sex.

5-70 mass% is preferable, and, as for solid content in the photosensitive composition solid content of the said binder, 10-50 mass% is more preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer described later tends to be weak, and the viscosity of the surface of the photosensitive layer may deteriorate. When the content exceeds 70% by mass, the exposure sensitivity may decrease.

[(B) Polymerizable Compound]

There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, The compound which has at least 1 addition polymerization group in a molecule | numerator, and whose boiling point is 100 degreeC or more at normal pressure is preferable, For example, (meth) acryl 1 or more types chosen from the monomer which has a group are mentioned preferably.

There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl ( Monofunctional acrylates such as meth) acrylate and monofunctional methacrylates; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimetholethane triacrylate, trimetholpropane triacrylate, trimetholpropanediacrylate, neopentyl glycol di (meth) Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimetholol After addition reaction of ethylene oxide and propylene oxide to polyfunctional alcohols, such as propane, glycerin, and bisphenol, (meth) Methacrylate screen would be, Japanese Patent Publication No. 48-41708 cattle, Japanese Patent Publication No. 50-6034 cattle, urethane acrylates described in each publication such as Japanese Unexamined Patent Publication No. 51-37193 cattle and the like; Polyester acrylates described in each publication such as Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates, methacrylates, etc., such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned. Among these, trimetholpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

5-50 mass% is preferable, and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. If the solid content is less than 5% by mass, there may be a problem such as deterioration of developability, a decrease in exposure sensitivity, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may be too strong, which is not preferable.

[(C) Photoinitiator]

As said photoinitiator, the said photoinitiator of this invention is included. Moreover, you may contain other photoinitiators as needed.

-Other photopolymerization initiators-

As said other photoinitiator, there is no restriction | limiting in particular as long as it has the ability to start superposition | polymerization of the said polymeric compound, Although it can select suitably from well-known photoinitiators, For example, it has photosensitivity with respect to visible light in an ultraviolet range. It is preferable that it be an activator which causes some action with a photoexcited sensitizer and produces | generates an active radical, and may be an initiator which starts cationic polymerization according to the kind of monomer.

Moreover, it is preferable that the said photoinitiator contains 1 or more types of components which have a molecular extinction coefficient of at least about 50 in the range of about 300-800 nm of wavelengths. As for the said wavelength, 330-500 nm is more preferable.

As said other photoinitiator, a halogenated hydrocarbon derivative (for example, having triazine skeleton, having an oxadiazole skeleton, etc.), hexaaryl biimidazole, an organic peroxide, a thio compound, a ketone compound And metallocenes. Specifically, the compounds described in [0288] to [0299] and [0305] to [0307] of JP 2005-258431 A etc. are mentioned.

Moreover, as said organic peroxide, 3,3 ', 4,4'- tetra (t-butylperoxycarbonyl) benzophenone etc. are mentioned, for example.

As said thio compound, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy citoxanthone, 2-benzoylmethylene-3-methyl naphthothia, for example Sleepy etc. are mentioned.

Moreover, as a photoinitiator of that excepting the above, polyhalogen compounds, such as N-phenylglycine (for example, carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), amines (for example, 4- Ethyl dimethylaminobenzoic acid, n-butyl 4-dimethylaminobenzoic acid, phenethyl 4-dimethylaminobenzoic acid, 2-phthalimide ethyl 4-dimethylaminobenzoic acid, 2-methacryloyloxyethyl 4-dimethylaminobenzoic acid, pentamethylene Bis (4-dimethylaminobenzoate), phenethyl, pentamethylene ester of 3-dimethylaminobenzoic acid, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4- Dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetine, tribenzylamine, dibenzyl Phenylamine, N-methyl-N-phenylbenzylamine, 4-bromine-N, N-di Tianiline, tridodecylamine, crystal violet lactone, leucocrystal violet, etc.), Japanese Patent Publication No. 53-133428, Japanese Patent Publication No. 57-1819, Japanese Patent Publication No. 57-6096, and US Patent No. 3615455 The compound etc. which were described in an identification document are mentioned.

0.05-30 mass% is preferable, as for content in the said photosensitive layer of all the photoinitiators containing the said oxime ester, 0.1-15 mass% is more preferable, 0.1-10 mass% is especially preferable.

-Sensitizer-

Moreover, in order to adjust the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer mentioned later, it is possible to add to a said photoinitiator and to add a sensitizer.

The said sensitizer can be suitably selected with visible light, ultraviolet light, visible light laser, etc. as light irradiation means mentioned later.

The sensitizer is excited by an active energy ray and interacts with other substances (e.g., radical generator, acid generator, etc.) (e.g., energy transfer, electron transfer, etc.) It is possible to generate useful groups such as acids.

In addition, these compounds not only improve the sensitivity of the photosensitive layer, but also have a function as a photopolymerization initiator for initiating polymerization of the monomer by photo-excitation.

There is no restriction | limiting in particular as said sensitizer, Although it can select suitably from a well-known sensitizer, For example, it selects from a condensed cyclic compound and an amine compound substituted by any of 2 or more aromatic hydrocarbon rings and aromatic heterocycles. 1 or more types are mentioned. Here, the said condensed cyclic compound means the ring compound which the aromatic ring and heterocycle condensed.

Although there is no restriction | limiting in particular as said condensed cyclic compound, For example, a heterocyclic condensed cyclic ketone compound and an acridine type compound are more preferable.

As said heterocyclic condensed cyclic compound, an acridon type compound, a thioxanthone type compound, a coumarin type compound etc. are mentioned, for example.

Examples of the acridon-based compound include acridon, chloroacridone, N-methylacridone, N-butylacridone, and N-butyl-chloroacridone (for example, 2-chloro -10-butyl acridone etc.) etc. are mentioned.

As said thioxanthone type compound, for example, thioxanthone, isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 1-chloro-4-propyloxy thioxanthone, 2-chloro thioxanthone, QuantacureQTX etc. are mentioned.

Examples of the coumarin compound include 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin and 3-benzoyl -7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonyl bis (5,7-di-n-propoxycoumarin), 3,3'-carbonyl bis (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 -Dipropoxy coumarin, Japanese Patent Laid-Open No. 5-19475, Japanese Patent Laid-Open No. 7-271028, Japanese Patent Laid-Open 2002-363206, Japanese Patent Laid-Open 2002-363207, Japanese Patent Laid-Open 2002-363208, Japanese Patent The coumarin compound described in each publication, such as Unexamined-Japanese-Patent No. 2002-363209, etc. are mentioned.

Examples of the acridine-based compound include acridine orange, chloroflavin, acriflavin, 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, and the like. Can be.

Among the heterocyclic condensed cyclic compounds, an acridon-based compound and a thioxanthone compound are particularly preferable.

The amine compound substituted with any one of the two or more aromatic hydrocarbon rings and the aromatic heterocycle is not particularly limited. For example, two or more aromatic rings represented by the following general formulas (I) to (III) may be added to the nitrogen atom. The compound which has a bonded structure is mentioned, Among these, a triarylamine type compound is preferable.

In the above general formulas (I) to (III), rings A to G each independently represent any one of an aromatic hydrocarbon ring and an aromatic heterocycle, and each of ring A, ring B, ring D, and ring E, ring F and ring G may be bonded to each other to form a ring containing N.

In the general formula (II), the linking group L represents a linking group containing at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, the linking groups L and N are bonded to any one of the aromatic hydrocarbon ring and the aromatic heterocycle, n represents an integer of 2 or more.

In said general formula (III), R represents the alkyl group which may have a substituent.

In addition, the ring A-G and the linking group L may have a substituent, These substituents may combine with each other, and may form the ring.

In the general formulas (I) to (III), as the aromatic hydrocarbon ring represented by rings A to G, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an azulene ring, a fluorene ring, an acenaphthylene ring, And an indene ring etc. are mentioned, Among these, a benzene ring, a naphthalene ring, an anthracene ring is preferable, and a benzene ring is more preferable.

Moreover, as an aromatic heterocycle represented by ring A-G, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furanzan ring, a triazole ring, Pyran ring, thiadizole ring, oxadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and the like. Among these, furan ring, thiophene ring, pyrrole ring, pyridine ring, oxazole ring and thiazole A ring is preferable and a furan ring, a thiophene ring, and a pyrrole ring are more preferable.

In addition, the ring included in ring A, ring B, ring D, ring E, ring F, ring G, and linking group L may combine with each other to combine a condensed ring including N, in which case each ring is bonded to N The example which forms the carbazole ring containing an atom is mentioned. When forming a carbazole ring, although any of A-G's ring is not exceptionally ring structure and arbitrary substituents may be sufficient, the alkyl group which may have a substituent as said substituent in that case is preferable.

Rings A to G may each have arbitrary substituents at arbitrary positions, and these substituents may be bonded to each other to form a ring.

In the general formula (II), the linking group L is a linking group containing at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, and N is directly connected to the aromatic hydrocarbon ring or the aromatic heterocycle of the linking group L. Combining

Examples of the aromatic hydrocarbon ring and the aromatic heterocycle contained in the linking group L include the same ones as those exemplified as the aromatic hydrocarbon ring and the aromatic heterocycle of Rings A to G.

As an aromatic hydrocarbon ring contained in the linking group L, a benzene ring, a naphthalene ring, and an anthracene ring are preferable, and a benzene ring is more preferable.

As the aromatic heterocycle contained in the linking group L, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, an oxazole ring, a thiazole ring, a thiadizole ring and an oxadiazole ring are preferable, and a furan ring, a thiophene ring and a pyrrole The ring is more preferable.

When the linking group L contains two or more of at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, these rings may be directly connected, and a divalent or more linking group (also, the linking group is not limited to a divalent or more group). And divalent or more atoms). In this case, a well-known thing can be mentioned as a bivalent or more coupling group, For example, the alkylene group represented by following formula (a), the acetylene group represented by following formula (b), an amine group, O atom, S atom, ketone group , Thioketone group, -C (= O) O-, amide group, Se, Te, P, As, Sb, Bi, Si, B and other metal atoms, aromatic hydrocarbon ring group, aromatic heterocyclic group (unsaturated heterocyclic group), Non-aromatic heterocyclic group (saturated heterocyclic group), arbitrary combinations thereof, etc. are mentioned.

Formula (a) Formula (b)

However, in said formula (a) and (b), m <_3> represents the integer of 1 or more.

Examples of the linking group which may be interposed between at least one of the aromatic hydrocarbon ring and the aromatic heterocycle contained in the linking group L include an alkylene group represented by the following formula (a), an acetylene group represented by the following formula (b), an amine group and O Atom, S atom, ketone group, -C (= O) 0-, amide group, aromatic hydrocarbon ring group, aromatic heterocyclic group, -C = N-, -C = NN =, saturated or unsaturated heterocyclic group are preferable, 1 to 3 carbon atoms in the alkylene _{group, -OCH 2 O-, -OCH 2 CH} 2 O-, -O-, a ketone group, a benzene group, a furan group, thiophene group, more preferably a pyrrole ventilation.

In General Formula (II), n is preferably 2 to 5.

In the linking group L, it is preferable to have an absorption maximum and an appropriate absorption in the wavelength region of 350 to 430 nm by adjusting the combination of the aromatic hydrocarbon ring or the aromatic heterocycle and the unsaturated linking group.

The ring contained in the linking group L and the linking group which connected the rings may have arbitrary substituents in arbitrary places, and these substituents may mutually connect and may form the ring.

As an arbitrary substituent which Ring A-G and the linking group L may have, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; A hydroxyl group; A nitro group; Cyano; Monovalent organic groups and the like, and examples of the monovalent organic groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, amyl group and tert- C1-C18 linear or branched alkyl groups, such as an amyl group, n-hexyl group, n-heptyl group, n-octyl group, and tert-octyl group; Cycloalkyl groups having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and adamantyl group; C2-C18 linear or branched alkenyl groups, such as a vinyl group, a propenyl group, and a hexenyl group; Cycloalkenyl groups having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; Methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, amyloxy group, tert-amyloxy group, n-hexyloxy group, n Linear or branched alkoxy groups having 1 to 18 carbon atoms such as -heptyloxy group, n-octyloxy group, and tert-octyloxy group; Methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, amylthio group, tert-amylthio group, n- Linear or branched alkylthio groups having 1 to 18 carbon atoms such as hexylthio group, n-heptylthio group, n-octylthio group, and tert-octylthio group; C6-C18 aryl groups, such as a phenyl group, a tolyl group, a xylyl group, and a mesityl group; Aralkyl groups having 7 to 18 carbon atoms such as benzyl and phenethyl; Linear or branched alkenyloxy groups having 2 to 18 carbon atoms such as vinyloxy group, propenyloxy group and hexenyloxy group; Linear or branched alkenylthio groups having 2 to 18 carbon atoms such as vinylthio group, propenylthio group and hexenylthio group; Acyl group represented by -COR ¹¹ ; A carboxyl group; Acyloxy group represented by -OCOR ¹² ; Amino group represented by -NR ¹³ R ¹⁴ ; Acylamino group represented by -NHCOR ¹⁵ ; Carbamate groups represented by -NHCOOR ¹⁶ ; Carbamoyl group represented by -CONR ¹⁷ R ¹⁸ ; Carboxylic ester group represented by -COOR ¹⁹ ; Sulfamoyl group represented by -SO ₃ NR ²⁰ R ²¹ ; Sulfonic acid ester group represented by -SO ₃ R ²² ; A group represented by -C = NR ²³ ; A group represented by -C = N-NR ²⁴ R ²⁵ ; Saturation such as 2-thienyl group, 2-pyridyl group, furyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophenedioxide group or the like Unsaturated heterocyclic group etc. are mentioned.

R ¹¹ to R ²⁵ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. In these substituent groups, the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, alkylthio group, aryl group, aralkyl group, alkenyloxy group, and alkenylthio group may be further substituted by a substituent.

There is no restriction | limiting in particular in the substitution position in rings A-G and linking group L of these substituents, Moreover, when it has a some substituent, these may be the same type, and may differ.

Rings A to G and the linking group L are unsubstituted, or as a substituent, a halogen atom, a cyano group, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkenyl group which may be substituted, an alkoxy group which may be substituted, and a substitution An aryl group which may be substituted, an aralkyl group which may be substituted, an alkenyloxy group which may be substituted, an alkenylthio group which may be substituted, an amino group which may be substituted, an acyl group which may be substituted, a carboxyl group, or -C = NR ²³ . by indicating group, -C = group represented by N-NR ²⁴ R ^25, saturated or unsaturated heterocyclic group is preferably substituted. As a substituent in the case of having a substituent, a halogen atom, a cyano group, the alkyl group which may be substituted, the cycloalkyl group which may be substituted, the alkenyl group which may be substituted, the alkoxy group which may be substituted, the aryl group which may be substituted, substituted Aralkyl groups which may be present, amino groups which may be substituted, groups represented by -C = NR ²³ , groups represented by -C = N-NR ²⁴ R ²⁵ , and saturated or unsaturated heterocyclic groups are preferable.

When the arbitrary substituents which the ring A to G and the linking group L may have are further substituted with an arbitrary substituent, examples of the substituent include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, alkoxy groups having 1 to 10 carbon atoms such as n-butoxy group, sec-butoxy group and tert-butoxy group; Alkoxyalkoxy groups having 2 to 12 carbon atoms such as methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, ethoxyethoxy group, propoxyethoxy group and methoxybutoxy group; C3-C15 alkoxyalkoxyalkoxy groups, such as a methoxy methoxy methoxy group, a methoxy methoxy ethoxy group, a methoxy ethoxy methoxy group, an ethoxy methoxy methoxy group, an ethoxy ethoxy methoxy group; C6-C12 aryl groups, such as a phenyl group, a tolyl group, and a xylyl group (They may further substitute by the substituent.); Aryl oxy groups having 6 to 12 carbon atoms such as a phenoxy group, tolyloxy group, xylyloxy group, and naphthyloxy group; Alkenyloxy groups having 2 to 12 carbon atoms such as vinyl oxy group and allyl oxy group; acyl groups such as acetyl group and propionyl group; Cyano; A nitro group; Hydroxyl group; tetrahydrofuryl group; amino group; Alkylamino groups having 1 to 10 carbon atoms such as N, N-dimethylamino group and N, N-diethylamino group; Alkylsulfonylamino groups having 1 to 6 carbon atoms such as methylsulfonylamino group, ethylsulfonylamino group and n-propylsulfonylamino group; Halogen atoms such as fluorine atom, chlorine atom and bromine atom; Alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl group and n-butoxycarbonyl group; Alkylcarbonyloxy groups having 2 to 7 carbon atoms such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group and n-butylcarbonyloxy group; Methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, iso-propoxycarbonyloxy group, n-butoxycarbonyloxy group, tert-butoxycarbonyloxy group, etc. C2-C7 alkoxycarbonyloxy group; C2-C18 linear or branched alkenyl groups, such as a vinyl group, a propenyl group, and a hexenyl group, etc. are preferable.

The sensitizer represented by the general formulas (I) to (III) preferably has an absorption in the wavelength region of 390 to 430 nm, and has an absorption maximum in the wavelength region of 330 to 450 nm, preferably in the wavelength region of 350 to 430 nm. It is more preferable to have an absorption maximum. Therefore, it is preferable to have at least any one of four or more aromatic hydrocarbon rings and aromatic heterocycle in a molecule | numerator, and it is more preferable to have at least any one of five or more aromatic hydrocarbon rings and aromatic heterocycles.

Although the specific example of a compound represented by said general formula (I)-(III) is shown below, it is not limited to these.

However, in said Formula (I-1), R <^31> , R <^32> , R <^33> respectively independently represents either of the following groups.

However, in the formula (II-g), the bonding position is either two terminal phenyl groups or two terminal tolyl groups on the two benzene rings.

In the formula (II-j), R ⁴¹ , R ⁴² and R ⁴³ each independently represent any one of the following groups.

As a combination of the photoinitiator and the sensitizer, for example, the electron transfer initiator described in JP 2001-305734 A (1) electron donating initiator and sensitizing dye, (2) electron accepting initiator and sensitizing Pigment | dye, (3) electron donor type initiator, a sensitizing dye, and an electron accepting type initiator (three-way clock)] etc. are mentioned.

0.05-30 mass% is preferable with respect to the all components in the said photosensitive composition, as for content of the said sensitizer, 0.1-20 mass% is more preferable, 0.2-10 mass% is especially preferable. When the said content is less than 0.05 mass%, the sensitivity of an active energy ray will fall, an exposure process may take time, productivity may fall, and when it exceeds 30 mass%, the sensitizer will precipitate from the said photosensitive layer at the time of storage. There is.

[(D) Thermal Crosslinking Agent]

There is no restriction | limiting in particular as said thermal crosslinking agent, According to the objective, in order to improve the film strength after hardening of the photosensitive layer formed using the said photosensitive composition, in the range which does not adversely affect developability etc., for example, For example, an epoxy compound having two or more oxirane groups in one molecule and an oxetane compound having two or more oxetanyl groups in one molecule can be used.

As an epoxy compound which has two or more oxirane groups in the said molecule, For example, a bixylenol type or a biphenol type epoxy resin ("YX4000; the Japan epoxy resin company", etc.), or a mixture thereof, isocyanurate skeleton Heterocyclic epoxy resin ("TEPIC; Nissan Chemical Co., Ltd.", "Araldite PT810; product made by Chiba Specialty Chemicals", etc.), bisphenol-A epoxy resin, novolak-type epoxy resin, bisphenol F-type epoxy Resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy Resin, tetraphenylol ethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group containing epoxy resin ("ESN-190, ESN-360 Nippon Steel Chemical Co., Ltd. "," HP-4032, EXA-4750, EXA-4700; Dainippon Ink & Chemicals Co., Ltd. ", etc., epoxy resin which has a dicyclopentadiene skeleton (" HP-7200, HP-7200H; Copolymerization of cyclohexyl maleimide and glycidyl methacrylate, such as Dainippon Ink & Chemicals Co., Ltd.), glycidyl methacrylate co-polymeric epoxy resin (CP-50S, CP-50M; Although an epoxy resin etc. are mentioned, it is not limited to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

In addition to the epoxy compound having two or more oxirane groups in one molecule, an epoxy compound containing two epoxy groups having at least one epoxy group having an alkyl group at the β-position may be used, and an epoxy group having a β-position substituted with an alkyl group ( More specifically, the compound containing (beta) -alkyl substituted glycidyl group etc.) is especially preferable.

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

The epoxy compound containing the epoxy group which has an alkyl group in the said (beta) position is a ratio of the (beta) -alkyl substituted glycidyl group in all the epoxy groups in the total amount of the said epoxy compounds contained in the said photosensitive composition from a storage stability at room temperature. It is preferable that it is 70% or more.

There is no restriction | limiting in particular as said (beta) -alkyl substituted glycidyl group, According to the objective, it can select suitably, For example, (beta) -methyl glycidyl group, (beta)-ethyl glycidyl group, (beta) -propyl glycidyl group, (beta)- A butyl glycidyl group etc. are mentioned, Among these, the (beta) -methyl glycidyl group is preferable from a viewpoint of improving the storage stability of the said photosensitive resin composition, and the ease of synthesis.

As an epoxy compound containing the epoxy group which has an alkyl group in the said (beta) position, the epoxy compound derived from a polyhydric phenol compound and (beta) -alkyl epihalohydrin, for example is preferable.

There is no restriction | limiting in particular as said (beta) -alkyl epihalohydrin, According to the objective, it can select suitably, For example, (beta) -methyl epichlorohydrin, (beta) -methyl epibromohydrin, (beta) -methyl epifluoro Β-methyl epihalohydrin such as hydrin; β-ethyl epihalohydrin such as β-ethyl epichlorohydrin, β-ethyl epibromohydrin and β-ethyl epifluorohydrin; β-propyl epihalohydrin such as β-propyl epichlorohydrin, β-propyl epibromohydrin and β-propyl epifluorohydrin; (beta) -butyl epihalohydrin, such as (beta) -butyl epichlorohydrin, (beta) -butyl epibromohydrin, (beta) -butyl epifluorohydrin, etc. are mentioned. Among these, (beta) -methyl epihalohydrin is preferable from a viewpoint of the reactivity with the said polyhydric phenol, and fluidity | liquidity.

As said polyhydric phenol compound, if it is a compound containing two or more aromatic hydroxyl groups in 1 molecule, there will be no restriction | limiting in particular, According to the objective, it can select suitably, For example, Bisphenol compounds, such as bisphenol A, bisphenol F, bisphenol S; Biphenol compounds, such as biphenol and tetramethyl biphenol; Naphthol compounds such as dihydroxynaphthalene and vinaphthol; Phenol novolak resins such as phenol formaldehyde polycondensate; Monoalkyl substituted phenol formaldehyde polycondensates having 1 to 10 carbon atoms such as cresol formaldehyde polycondensate; C1-C10 dialkyl substituted phenol formaldehyde polycondensates, such as a xylenol formaldehyde polycondensate; Bisphenol compound-formaldehyde polycondensates such as bisphenol A-formaldehyde polycondensate; Co-condensates of phenol and monoalkyl substituted phenols having 1 to 10 carbon atoms and formaldehyde; And polyaddition products of phenol compounds and divinylbenzene. Among these, when selecting for the purpose of improving fluidity | liquidity and storage stability, the said bisphenol compound is preferable, for example.

As an epoxy compound containing the epoxy group which has an alkyl group in the said (beta) position, For example, the di- (beta)-alkyl glycidyl ether of bisphenol A, the di- (beta) -alkyl glycidyl ether of bisphenol F, and the di- of bisphenol S are mentioned, for example. di-β-alkylglycidyl ethers of bisphenol compounds such as β-alkylglycidyl ether; di-β-alkylglycidyl ethers of biphenols, di-β-alkylglycidyl ethers of tetramethylbiphenol, and the like. Di-β-alkylglycidyl ether of a non-phenolic compound; β-alkyl of a naphthol compound such as di-β-alkyl glycidyl ether of dihydroxynaphthalene and di-β-alkylglycidyl ether of vinaphthol Glycidyl ethers; Poly-β-alkylglycidyl ethers of phenol formaldehyde polycondensates; Poly-β-alkylglycidyl ethers of monoalkyl substituted phenol formaldehyde polycondensates having 1 to 10 carbon atoms, such as poly-β-alkylglycidyl ethers of cresol formaldehyde polycondensates; Poly-β-alkylglycidyl ethers of dialkyl substituted phenol formaldehyde polycondensates having 1 to 10 carbon atoms such as poly-β-alkylglycidyl ethers of xylenol formaldehyde polycondensates; Poly-β-alkylglycidyl ethers of bisphenol compound-formaldehyde polycondensates such as poly-β-alkylglycidyl ethers of bisphenol A-formaldehyde polycondensates; And poly-β-alkylglycidyl ethers of polyaddition products of phenol compounds and divinylbenzene.

Among these, β-alkylglycidyl ethers derived from bisphenol compounds and polymers obtained from these, epichlorohydrin and the like, and poly-β-alkylglycidyl ethers of phenol compound-formaldehyde polycondensates are preferable. Do.

Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4- Bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl3-oxetanyl) Methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) methylmethacrylate or In addition to polyfunctional oxetanes, such as these oligomers and copolymers, an oxetane group, a novolak resin, poly (p-hydroxy styrene), a cardo type bisphenol, a charix arene, a charix resolcin arene, a silses Ether compounds, such as resin which has hydroxyl groups, such as a quoxane, are mentioned, In addition, the copolymer of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate, etc. are mentioned.

In addition, a melamine derivative may be used as the thermal crosslinking agent. Examples of the melamine derivatives include metyrolmelamine, alkylated metyrolmelamine (compounds obtained by etherification of a methrol group with methyl, ethyl, butyl, etc.) and the like. These may be used individually by 1 type and may use 2 or more types together. Among them, alkylated metyrolmelamine is preferred, and hexamethylated metyrolmelamine is particularly preferable because of its good storage stability, and the effect of improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

1-50 mass% is preferable, and, as for solid content in the photosensitive composition solid content of the said thermal crosslinking agent, 3-30 mass% is more preferable. When the said solid content is less than 1 mass%, the improvement of the film strength of a cured film is not recognized, and when it exceeds 50 mass%, there exists a thing which shows developability fall and exposure sensitivity fall.

[Thermal curing accelerator]

In order to accelerate thermosetting of the epoxy acrylate compound in the said binder, a conventionally well-known thermosetting accelerator can be mix | blended. As said thermosetting accelerator, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl- Amine compounds such as N, N-dimethylbenzylamine; Quaternary ammonium salt compounds such as triethylbenzyl ammonium chloride; Block isocyanate compounds blocked with dimethylamine or the like; Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2- Imidazole derivative bicyclic amidine compounds such as phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and salts thereof; Phosphorus compounds such as triphenylphosphine; Guanamine compounds such as melamine, guanamine, acetoguanamine and benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S- S-triazine derivatives, such as a triazine isocyanuric acid adduct and a 2, 4- diamino-6-methacryloyloxyethyl-S-triazine and an isocyanuric acid adduct, etc. can be used. These may be used individually by 1 type and may use 2 or more types together.

The thermosetting accelerator is not particularly limited as long as it can promote thermosetting of the epoxy acrylate compound, and a compound capable of promoting thermosetting other than the above may be used.

It is preferable that solid content in the said photosensitive composition solid content of the said thermosetting accelerator is 0.01-15 mass%.

[Other components]

As said other components, a thermal polymerization inhibitor, a plasticizer, a coloring agent (color pigment or dye), a extender pigment, etc. are mentioned, for example, Adhesion promoter to a surface of a base material, and other preparations (for example, For example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, and the like may be used in combination. By containing these components suitably, properties, such as stability, a photographic property, and a film | membrane property, of the target photosensitive composition or photosensitive film can be adjusted.

-Thermal polymerization inhibitor-

The thermal polymerization inhibitor may be added in order to prevent thermal polymerization or polymerization with time of the polymerizable compound.

Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, and 4-methoxy-2- Hydroxybenzophenone, cuprous chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis- (4- Methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound And chelates of Al and the like.

0.001-5 mass% is preferable with respect to the said polymeric compound, 0.005-2 mass% is more preferable, and, as for content of the said thermal polymerization inhibitor, 0.01-1 mass% is especially preferable. When the said content is less than 0.001 mass%, stability at the time of storage may fall, and when it exceeds 5 mass%, the sensitivity with respect to an active energy ray may fall.

-Pigment pigment-

There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI42595), Oramine (CI41000), Fat black HB (CI26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146) Hostal Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Pastel Pink B Spura (CI Pigment Red 81) Monastral First Blue (CI Pig) Blue 15), Monolight First Black B (CI Pigment Black 1), Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Lean 7, CI Pigment Green 36, CI Pigment Blue 15: 1, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 22, CI Pigment Blue 60 CI pigment blue 64, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

Solid content content in the said photosensitive composition solid content of the said pigment may be determined in consideration of exposure sensitivity, resolution, etc. of the photosensitive layer at the time of permanent pattern formation, and although it changes with kinds of the said pigment, generally it is 0.01-10 mass % Is preferable and 0.05-5 mass% is more preferable.

-Constitutional Pigments-

In the photosensitive composition, inorganic pigments and organic fine particles are used for the purpose of improving the surface hardness of the permanent pattern, or reducing the coefficient of linear expansion low, or reducing the dielectric constant and dielectric loss tangent of the cured film itself. Can be added.

There is no restriction | limiting in particular as said inorganic pigment, It can select from a well-known thing suitably, For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, fine-phase silicon oxide, vapor phase silica, amorphous silica, crystalline silica, Fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica and the like.

The average particle size of the inorganic pigment is preferably less than 10 µm, more preferably 3 µm or less. When the said average particle diameter is 100 micrometers or more, the resolution may deteriorate by optical confusion.

There is no restriction | limiting in particular as said organic fine particle, According to the objective, it can select suitably, For example, a melamine resin, benzoguanamine resin, crosslinked polystyrene resin, etc. are mentioned. Moreover, the spherical porous fine particles which consist of silica of about 1-5 micrometers of average particle diameters, the oil absorption amount of about 100-200m <^2> / g, crosslinking resin, etc. can be used.

As for the addition amount of the said extender pigment, 5-60 mass% is preferable. If the added amount is less than 5% by mass, the coefficient of linear expansion may not be sufficiently reduced. If the amount is more than 60% by mass, when the cured film is formed on the surface of the photosensitive layer, the film quality of the cured film is subdued to use a permanent pattern. In the case of forming wiring, the function as a protective film of the wiring may be impaired.

-Adhesion Promoter-

In order to improve the adhesiveness between each layer, or the adhesiveness of a photosensitive layer and a base material, a well-known adhesion promoter can be used for each layer.

As said adhesion promoter, the adhesion promoter described in Unexamined-Japanese-Patent No. 5-11439, Unexamined-Japanese-Patent No. 5-341532, Unexamined-Japanese-Patent No. 6-43638, etc. are mentioned preferably, for example. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyltria Sol2-thione, 3-morpholinomethyl-5-phenyloxadiazole-2-thione, 5-amino3-morpholinomethylthiadiazole-2-thione, and 2-mercapto-5-methylthiothiadia Sol, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.

delete

As for content of the said adhesion promoter, 0.001 mass%-20 mass% are preferable with respect to the all components in the said photosensitive composition, 0.01-10 mass% is more preferable, 0.1 mass%-5 mass% are especially preferable.

(Photosensitive film)

The photosensitive film of this invention has a support body and the photosensitive layer which consists of the said photosensitive composition of this invention at least on the said support body, and is laminated | stacked by the other layer suitably selected, such as a thermoplastic resin layer, according to the objective.

<Photosensitive Layer>

The said photosensitive layer is formed using the photosensitive composition of this invention.

In the case of exposing and developing the photosensitive layer, the minimum energy of light used for the exposure which does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is 0.1 to 50,000 mJ / cm. it is preferred that ^two of, and, and O.1 ~ more preferably 1OOmJ / cm ² 1~8OmJ / cm ² is particularly preferred.

When the said minimum energy is less than 0.1 mJ / cm <^2> , fog may generate | occur | produce in a processing process, and when it exceeds 100 mJ / cm < ² >, the time required for exposure may become long and a processing speed may become low. .

Here, "minimum energy of the light employ | adopted for the said exposure which does not change the thickness of the part which exposes the said photosensitive layer after the said exposure and image development" is what is called image development sensitivity, for example, when the said photosensitive layer is exposed, It can obtain | require from the graph (sensitivity curve) which shows the relationship between the energy amount (exposure amount) of the light used for the said exposure, and the thickness of the said hardened layer produced | generated by the said developing process similar to the said exposure.

The thickness of the said hardened layer increases as the said exposure amount increases, and after that, it becomes substantially the same and substantially constant with the thickness of the said photosensitive layer before the said exposure. The said developing sensitivity is the value calculated | required by reading the minimum exposure amount when the thickness of the said hardened layer becomes substantially constant.

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

There is no restriction | limiting in particular as a measuring method of the thickness of the said hardened layer and the said photosensitive layer before the said exposure, Although it can select suitably according to the objective, A film thickness measuring apparatus and a surface roughness measuring instrument (for example, Fucom 1400D (made by Tokyo Precision Co., Ltd.) The method of measuring using)) etc. is mentioned.

Although the thickness of the said photosensitive layer does not have a restriction | limiting in particular, According to the objective, it can select suitably, For example, 1-100 micrometers is preferable, 2-50 micrometers is more preferable, 4-30 micrometers is especially preferable.

<Support and protective film>

There is no restriction | limiting in particular as said support body, Although it can select suitably according to the objective, It is preferable that the said photosensitive layer is peelable and that light transmittance is favorable, and it is more preferable that surface smoothness is more favorable. As said support body and protective film, it specifically describes in [0342]-[0348] of Unexamined-Japanese-Patent No. 2005-258431, for example.

<Other floors>

There is no restriction | limiting in particular as another layer in the said photosensitive film, According to the objective, it can select suitably, For example, a cushion layer, an oxygen barrier layer (PC layer), a peeling layer, an adhesive layer, a light absorption layer, a surface protective layer You may have a layer, such as a back. You may have these layers individually by 1 type, and may have 2 or more types. Moreover, you may have a protective film on the said photosensitive layer.

<Other floors>

There is no restriction | limiting in particular as another layer in the said photosensitive film, According to the objective, it can select suitably, For example, a cushion layer, an oxygen barrier layer (PC layer), a peeling layer, an adhesive layer, a light absorption layer, a surface protective layer You may have a layer, such as a back. You may have these layers individually by 1 type, and may have 2 or more types. Moreover, you may have a protective film on the said photosensitive layer.

-Cushion layer-

There is no restriction | limiting in particular as said cushion layer, According to the objective, it can select suitably, Swelling-soluble may be sufficient with respect to alkaline liquid, and insoluble may be sufficient.

When the cushion layer is swellable or soluble with respect to the alkaline liquid, the thermoplastic resin may be, for example, a saponified product of ethylene and an acrylic ester copolymer, a saponified product of styrene and a (meth) acrylic acid ester copolymer, and vinyltoluene. Saponified products of the (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, saponified products such as (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate, (meth) acrylic acid ester and (meth) acrylic acid And copolymers of styrene, (meth) acrylic acid ester and (meth) acrylic acid, and the like.

The softening point Vicat of the thermoplastic resin in this case is not particularly limited and can be appropriately selected according to the purpose, but, for example, 80 ° C. or less is preferable.

As the thermoplastic resin having the softening point of 80 ° C. or less, in addition to the thermoplastic resin described above, in the "Plastic Performance Manual" (Nihon Plastics Industry Association, All Japan Plastic Molding Industry Association, published by the Industrial Association, issued October 25, 1968) The softening point by which it is soluble in alkaline liquid in the organic polymer of about 80 degreeC or less is mentioned. In addition, even in an organic polymer material having a softening point of 80 ° C. or more, it is also possible to add various plasticizers compatible with the organic polymer material to the organic polymer material to lower the actual softening point to 80 ° C. or less.

In addition, when the cushion layer is swellable or soluble with respect to the alkaline liquid, there is no particular limitation as to the interlayer adhesive force of the photosensitive film, and it can be appropriately selected depending on the purpose. It is preferable that the interlayer adhesive force between and the cushion layer is the smallest. By setting it as such an interlayer adhesive force, after peeling only the said support body from the said photosensitive film and exposing the said photosensitive layer through the said cushion layer, an alkaline developing solution can be used and the said photosensitive layer can be developed. Moreover, after exposing the said photosensitive layer leaving the said support body, only the said support body can be peeled from the said photosensitive film, and the said photosensitive layer can also be developed using alkaline developing solution.

There is no restriction | limiting in particular as a adjustment method of the said interlayer adhesive force, According to the objective, it can select suitably, For example, the method of adding a well-known polymer, a supercooling substance, an adhesion improving agent, surfactant, a mold release agent, etc. to the said thermoplastic resin is mentioned. Can be.

There is no restriction | limiting in particular as said plasticizer, Although it can select suitably according to the objective, For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, Alcohols and esters such as biphenyl diphenyl phosphate; Amides, such as toluene sulfonamide, etc. are mentioned.

In the case where the cushion layer is insoluble in an alkaline liquid, examples of the thermoplastic resin include copolymers in which the main component contains ethylene as an essential copolymer component.

There is no restriction | limiting in particular as a copolymer which makes the said ethylene an essential copolymer component, Although it can select suitably according to the objective, For example, ethylene-vinyl acetate copolymer (EVA), ethylene ethyl acrylate copolymer (EEA), etc. are mentioned. Can be mentioned.

In the case where the cushion layer is insoluble in the alkaline liquid, the interlayer adhesive force of the photosensitive film is not particularly limited and can be appropriately selected according to the purpose. For example, the photosensitive layer and the cushion may be selected from the interlayer adhesive force of each layer. It is preferable that the adhesion of the layer is the smallest. By setting it as such an interlayer adhesive force, after peeling the said support body and a cushion layer from the said photosensitive film, and exposing the said photosensitive layer, the said photosensitive layer can be developed using alkaline developing solution. Moreover, after exposing the said photosensitive layer leaving the said support body, you may peel off the said support body and the said cushion layer from the said photosensitive film, and develop the said photosensitive layer using alkaline developing solution.

There is no restriction | limiting in particular as a adjustment method of the said interlayer adhesive force, According to the objective, it can select suitably, For example, the method of adding various polymers, a supercooling substance, an adhesion improving agent, surfactant, a mold release agent, etc. in the said thermoplastic resin, The method of adjusting the ethylene copolymerization ratio demonstrated, etc. are mentioned.

There is no restriction | limiting in particular in the ethylene copolymerization ratio in the copolymer which makes the said ethylene the essential copolymerization component, Although it can select suitably according to the objective, For example, 60-90 mass% is preferable, and 60-80 mass% is More preferably, 65-80 mass% is especially preferable.

When the copolymerization ratio of the ethylene is less than 60% by mass, the interlayer adhesion between the cushion layer and the photosensitive layer becomes high, and it may be difficult to peel off at the interface between the cushion layer and the photosensitive layer. Since the interlayer adhesive force of the said cushion layer and the said photosensitive layer becomes too small, it is easy to peel very much between the said cushion layer and the said photosensitive layer, and it may become difficult to manufacture the photosensitive film containing the said cushion layer.

Although the thickness of the said cushion layer does not have a restriction | limiting in particular, Although it can select suitably according to the objective, For example, 5-50 micrometers is preferable, 10-50 micrometers is more preferable, 15-40 micrometers is especially preferable.

When the thickness is less than 5 µm, irregularities on the surface of the substrate, irregularities followability to bubbles, etc. may decrease, and a high-precision permanent pattern may not be formed. When the thickness exceeds 50 µm, dry load on manufacturing There may be a defect such as increase.

Oxygen barrier layer (PC layer)

It is preferable that the said oxygen barrier layer is normally formed with polyvinyl alcohol as a main component, and it is preferable that it is a film about 0.5-5 micrometers in thickness.

[Production Method of Photosensitive Film]

The said photosensitive film can be manufactured as follows, for example.

First, the material contained in the said photosensitive composition is melt | dissolved, emulsified, or disperse | distributed in water or a solvent, and the photosensitive resin composition solution for photosensitive films is prepared.

There is no restriction | limiting in particular as said solvent, 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 and diisobutyl ketone; Esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; Aromatic hydrocarbons such as toluene, xylene, benzene and ethylbenzene; Halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride and monochlorobenzene; Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and 1-methoxy-2-propanol; Dimethylformamide, dimethylacetoamide, dimethyl sulfoxide, sulfolane and the like. These may be used individually by 1 type and may use 2 or more types together. Moreover, you may add a well-known surfactant.

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

There is no restriction | limiting in particular as a coating method of the said photosensitive composition solution, Although it can select suitably according to the objective, For example, the spraying method, the roll coating method, the rotary coating method, the slit coating method, the extrusion coating method, the curtain coating method, the die coating Various coating methods, such as the method, the gravure coating method, the wire bar coating method, and the knife coating method, are mentioned.

As said drying conditions, although it changes also with each component, a kind of solvent, a use ratio, etc., it is about 30 to 15 minutes normally at the temperature of 60-110 degreeC.

(Photosensitive laminated body)

The photosensitive laminated body of this invention has at least the said photosensitive layer on a base, and laminates the other layer suitably selected according to the objective.

<Gas>

The substrate is a target substrate on which the photosensitive layer is formed or a transfer member to which at least the photosensitive layer is transferred among the photosensitive films of the present invention. There is no particular limitation, and the base can be appropriately selected according to the purpose. It can select arbitrarily from the thing with high smoothness to the thing with the surface with an unevenness. A plate-shaped base is preferable and a so-called substrate is used. Specifically, a well-known printed wiring board (print board), a glass plate (such as a soda glass plate), a synthetic resin film, paper, a metal plate, etc. are mentioned.

[Manufacturing Method of Photosensitive Laminate]

As a manufacturing method of the said photosensitive laminated body, the method of apply | coating the said photosensitive composition to the surface of the said base material as a 1st embodiment is mentioned, As a 2nd embodiment, at least the photosensitive layer in the photosensitive film of this invention. The method of transferring and laminating | stacking, performing at least any one of heating and pressurization is mentioned.

In the manufacturing method of the photosensitive laminated body of said 1st embodiment, the said photosensitive composition is apply | coated and dried on the said base | substrate, and a photosensitive layer is formed.

There is no restriction | limiting in particular as said coating and drying method, According to the objective, it can select suitably, For example, the photosensitive composition solution is made to melt | dissolve, emulsify, or disperse | distribute the said photosensitive composition in water or a solvent on the surface of the said base | substrate. The method of preparing, laminating | stacking by applying the said solution directly and drying is mentioned.

There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, The same solvent used for the said photosensitive film is mentioned. These may be used individually by 1 type and may use 2 or more types together. Moreover, you may add a well-known surfactant.

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

The manufacturing method of the photosensitive laminated body of the said 2nd Embodiment laminates | stacks on the surface of the said base | substrate, performing at least any one of heating and pressurization of the photosensitive film of this invention. Moreover, when the said photosensitive film has the said protective film, it is preferable to peel off the said protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.

There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.

There is no restriction | limiting in particular in the pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, a laminating machine (for example, VP-II made from Daesung laminated articles, Nippon-Morton Co., Ltd. product) VP130) etc. are mentioned preferably.

Since the photosensitive composition of the present invention, the photosensitive film, and the photosensitive laminate use the photopolymerization initiator of the present invention, the sensitivity can be further improved, and resolution, storage stability, surface hardness, and dielectric properties can be satisfactorily improved. I can keep it. For this reason, the protective film of a printed wiring board (multilayer wiring board, a buildup wiring board, etc.), an interlayer insulation film, and a display member, such as a soldering resist pattern, a color filter, a pillar material, a rib material, a spacer, a partition, a hologram, a micromachine, It can be used widely for permanent pattern formation, such as a proof, and can use especially for permanent pattern formation of a printed circuit board.

(Pattern forming apparatus and permanent pattern forming method)

The pattern formation apparatus of this invention is equipped with the said photosensitive laminated body of this invention, and has at least light irradiation means and light modulation means.

The permanent pattern formation method of this invention includes an exposure process at least, and contains other processes, such as a suitably selected development process.

In addition, the said pattern forming apparatus of this invention becomes clear through description of the said permanent pattern formation method of this invention.

[Exposure step]

The said exposure process is a process of exposing to the photosensitive layer in the photosensitive film of this invention. The material of the photosensitive film and the substrate of the present invention is as described above.

There is no restriction | limiting in particular as long as it is a photosensitive layer in the said photosensitive film as an object for the said exposure, For example, as above-mentioned, At least any of heating and pressurizing a photosensitive film on a base material as mentioned above. It is preferable to carry out with respect to the laminated body formed by laminating | stacking while performing one.

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

There is no restriction | limiting in particular as said analogue exposure, According to the objective, it can select suitably, For example, the method of exposing with a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, etc. through the negative mask which has a predetermined pattern is mentioned. .

There is no restriction | limiting in particular as said digital exposure, According to the objective, it can select suitably, For example, it is preferable to generate | generate a control signal based on the pattern formation information to form, and to use it using the light modulated according to the said control signal. For example, with respect to the photosensitive layer, there are n light emitting means and light drawing means arranged in a two-dimensional shape (n is a natural number of two or more), which receives and emits light from the light irradiation means. An exposure head including light modulation means capable of controlling the drawing part in accordance with pattern information, and using an exposure head arranged such that a column direction of the drawing part reaches a predetermined set inclination angle θ with respect to a scanning direction of the exposure head, The exposure head is used for exposure among N (where N is a natural number of two or more) among the available drawing parts by use drawing part designation means. Designates the drawing part, and controls the drawing part so that only the drawing part specified by the using drawing part designation means is involved in the exposure by the drawing part control means with respect to the exposure head. In contrast, a method of moving the exposure head relatively in the scanning direction is preferable.

In the present invention, "N-exposure" means N light spots on which the straight lines parallel to the scanning direction of the exposure head are irradiated on the exposed surface in almost all regions of the exposure region on the exposed surface of the photosensitive layer. Exposure by the setting which intersects (pixel row) is indicated. Here, the term "light spot row (pixel row)" refers to a row in a direction in which the angle formed by the scanning direction of the exposure head is smaller in the row of light spots (pixels) as the drawing unit generated by the drawing section. . In addition, the arrangement of the drawing portions may not necessarily be a rectangular lattice shape, for example, may be a parallelogram-shaped arrangement or the like.

Here, what is described as "approximately all the area | regions" of an exposure area | region is inclined by the seedling row at the both edge part of each drawing part, and the number of the drawing part rows of the using drawing part which intersects the straight line parallel to the scanning direction of the said exposure head In this case, even if the plurality of exposure heads are connected to each other in this case, the number of the drawing part rows intersecting a straight line parallel to the scanning direction due to an error such as an installation angle or an arrangement of the exposure heads is slightly reduced. In addition, in some very few parts below the resolution range of the connection between the drawing section rows of each using drawing section, according to the direction orthogonal to a scanning direction by an error, such as an installation angle or a drawing section arrangement | positioning, The pitch of the cemetery does not exactly match the pitch of the cemetery of the other part, but intersects with the straight line parallel to the scanning direction. This is because the number of seedling part rows in the used seedling part may be increased or decreased in the range of ± 1. In addition, in the following description, N double exposure which N is a natural number of two or more is named generically, and is called "multiple exposure." Moreover, in the following description, with respect to the embodiment which implemented the exposure apparatus or the exposure method of this invention as a drawing apparatus or the drawing method, as a term corresponding to "N-exposure exposure" and "multiple exposure", "N-imaging drawing" and We shall use term called "multiple drawing".

As N of said N exposure, there is no restriction | limiting in particular if it is two or more natural numbers, Although it can select suitably according to the objective, 3 or more natural numbers are preferable and 3 or more natural numbers are more preferable.

An example of the pattern forming apparatus which concerns on the permanent pattern formation method of this invention is demonstrated, referring drawings.

As the pattern forming apparatus, a so-called flat bed type exposure apparatus is provided, and as shown in FIG. 1, at least the photosensitive layer 12 in which the photosensitive layer in the photosensitive film is laminated (hereinafter, The photosensitive layer 12 ”) is provided with a flat plate-shaped moving stage 14 for absorbing and retaining it on the surface. Two guides 20 extending along the stage moving direction are provided on the surface of the thick plate-shaped mounting table 18 supported by the four leg portions 16. The stage 14 is arrange | positioned so that the longitudinal direction may face a stage movement direction, and is supported by the guide 20 so that reciprocation is possible. In addition, the pattern forming apparatus 10 is provided with a stage driving device (not shown) for driving the stage 14 along the guide 20.

In the center part of the mounting table 18, the gate 22 of the letter “CO” is provided so as to cross the movement path of the stage 14. Each of the ends of the gate letter 22 having the letter 'CO' is fixed to both sides of the mounting table 18. The scanner 24 is provided on one side with this gate 22 inserted, and a plurality (for example, two) sensors 26 for detecting the front and rear ends of the photosensitive material 12 are provided on the other side. It is done. The scanner 24 and the sensor 26 are provided in the gate 22, respectively, and are fixedly arrange | positioned above the movement path of the stage 14. As shown in FIG. In addition, the scanner 24 and the sensor 26 are connected to the controller which is not shown which controls these.

Here, in order to demonstrate, as shown in FIG. 1, in the plane parallel to the surface of the stage 14, the X-axis and Y-axis orthogonal to each other are prescribed | regulated.

Depending on the scanning direction of the stage 14, the slit 28 formed in the letter "u" opened in the direction of the X-axis is located at the short edge of the upstream side (hereinafter, simply referred to as "upstream side"). Ten are formed at intervals. Each slit 28 consists of a slit 28a located upstream and the slit 28b located downstream. The slits 28a and the slits 28b are orthogonal to each other, and the slits 28a have an angle of -45 ° and the slits 28b have an angle of + 45 ° with respect to the X axis.

delete

The position of the slit 28 can be approximately coincided with the center of the exposure head 30. In addition, the size of each slit 28 becomes the size which fully covers the width | variety of the exposure area 32 by the corresponding exposure head 30. As shown in FIG. In addition, as a position of the slit 28, you may make it substantially correspond to the center position of the overlapping part between adjacent exposure completed area | regions 34. As shown in FIG. In this case, the size of each slit 28 is set to the size which fully covers the width | variety of the overlapping part between exposure completed area | regions 34. As shown in FIG.

A single cell type photodetector (not shown) as a light spot position detecting means for detecting a light spot as a drawing unit in the use drawing section designation process, which will be described later, at a position below each slit 28 inside the stage 14, respectively. ) Is provided.

In addition, each photodetector is connected to the arithmetic unit (not shown) as a drawing part selection means which selects the drawing part in the use drawing part designation process mentioned later.

The operation mode of the pattern forming apparatus at the time of exposure may be a form in which exposure is continuously performed while the exposure head is continuously moved, or the exposure operation is performed by stopping the exposure head at the position of each moving destination while moving the exposure head in stages. The form may be performed.

<< exposure head >>

Each of the exposure heads 30 is a scanner 24 such that the drawing part (micromirror) column direction of the internal digital micromirror device (DMD) 36 described later forms a scanning direction and a predetermined set tilt angle θ. ) Is installed. For this reason, the exposure area | region 32 by each exposure head 30 turns into a rectangular area inclined with respect to a scanning direction. In accordance with the movement of the stage 14, a strip-shaped exposed area 34 is formed in each photosensitive layer 12. In the example shown to FIG. 2 and FIG. 3B, the scanner 24 is equipped with ten exposure heads arrange | positioned in substantially matrix form of 2 rows 5 columns.

In addition, below, when each exposure head arranged in the nth column of the m-th row is represented, it is represented by the exposure head 30 _mn , and the exposure area | region by each exposure head arranged in the nth column of the mth row is represented. When it shows, it expresses with exposure area | region _32mn .

3A and 3B, each row of exposure heads 30 arranged in a line shape so that each of the stripe-shaped exposed areas 34 partially overlaps with the adjacent exposed area 34. Are arranged at a predetermined interval (natural arrangement of the long sides of the exposed area, twice in this embodiment) in the arrangement direction. Because of this, the portion not exposed to an exposure area between the first row (32 ₁₁₎ and the exposed area (32 ₁₂₎ can be exposed by an exposure area (32 ₂₁₎ of the second row.

4, 5A, and 5B, each of the exposure heads 30 is a light modulating means (spatial light modulator for modulating for each drawing part) for modulating the incident light for each drawing part in accordance with image data. , DMD (36) (made by Texas Instruments Inc.). The DMD 36 is connected to a controller as a drawing section control means including a data processing section and a mirror drive control section. The data processing unit of this controller generates a control signal for driving control of each micromirror in the use area on the DMD 36 for each of the exposure heads 30 based on the input image data. The mirror drive control unit controls the angle of the reflecting surface of each micromirror of the DMD 36 on the basis of the control signal generated by the image data processing unit.

As shown in Fig. 4, on the light incidence side of the DMD 36, a fiber having laser exits arranged in a line along the direction in which the exit end (light emission point) of the optical fiber coincides with the long side direction of the exposure area 32; A lens system 40 for correcting the laser light emitted from the array light source 38, the fiber array light source 38 and condensing on the DMD, and a mirror for reflecting the laser light transmitted through the lens system 40 toward the DMD 36 ( 42 are arranged in this order. 4, the lens system 40 is schematically shown.

As shown in detail in FIGS. 5A and 5B, the lens system 40 includes a pair of combination lenses 44 for parallelizing the laser light emitted from the fiber array light source 38 and a light amount distribution of the parallel light laser light. And a pair of combined lenses 46 for correcting to be uniform, and a condensing lens 48 for condensing laser light whose light quantity distribution is corrected on the DMD 36.

Further, on the light reflection side of the DMD 36, a lens system 50 for imaging the laser light reflected by the DMD 36 on the exposed surface of the photosensitive layer 12 is disposed. The lens system 50 is composed of two lenses 52 and 54 which are arranged such that the DMD 36 and the exposed surface of the photosensitive layer 12 are in an conjugated relationship.

In the present embodiment, the laser light emitted from the fiber array light source 38 is substantially enlarged five times, and then the light rays from each micromirror on the DMD 36 are tightened to about 5 μm by the lens system 50. It is set to lose.

-Light modulation means-

The light modulating means is not particularly limited as long as it has the drawing parts arranged in a two-dimensional shape of n pieces (where n is a natural number of two or more), and the drawing parts can be controlled in accordance with the pattern information. It is possible to select, for example, a spatial light modulator is preferable.

As said spatial light modulator, for example, a digital micro mirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (S LM; Spatial Light Modulator), an electro-optical effect and transmitted light And optical elements (PLZT elements), liquid crystal light shutters (FLCs), etc. for modulating the above, and among these, DMD is preferable.

In addition, it is preferable that the light modulating means has pattern signal generating means for generating a control signal based on the pattern information to be formed. In this case, the light modulating means modulates light in accordance with the control signal generated by the pattern signal generating means.

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 preferably.

Hereinafter, an example of the said optical modulation means is demonstrated, referring drawings.

As shown in Fig. 6, the DMD 36 is a drawing part that constitutes a drawing (pixel) on the SRAM cell (memory cell) 56, and is formed by arranging a plurality of micromirrors 58 in a lattice shape. Device. In the present embodiment, the DMD 36 formed by combining the 1024 rows x 768 rows of the micro mirrors 58 is used, but among these, the micro mirrors 58 that can be driven by the controller connected to the DMD 36 can be used. ) Should only be 1024 columns x 256 rows. The data processing speed of the DMD 36 is limited, and since the modulation speed per line is determined in proportion to the number of micro mirrors used, the modulation speed per line is increased by using only a part of the micro mirrors. Each micromirror 58 is supported by a support | pillar, and the material with high reflectance, such as aluminum, is deposited on the surface. In addition, in this embodiment, the reflectance of each micromirror 58 is 90% or more, and the arrangement pitch is 13.7 micrometers together with a longitudinal direction and a horizontal direction. The SRAM cell 56 is of CM0S of a silicon gate manufactured by a manufacturing line of a normal semiconductor memory via a support including a hinge and a yoke, and the whole is monolithic (integrated).

When an image signal indicating the density of each point constituting the desired two-dimensional pattern in two values is written into the SRAM cell (memory cell) 56 of the DMD 36, each micromirror 58 supported by the post is Inclined with respect to the board | substrate side in which DMD 36 is arrange | positioned centering on a diagonal line in any one of +/- (alpha) (for example, +/- 10 degrees). FIG. 7A shows a state in which the micromirror 58 is inclined at + α °, and FIG. 7B shows a state in which the micromirror 58 is inclined at -α °. Thus, by controlling the inclination of the micromirror 58 in each pixel of the DMD 36 in accordance with the image signal, as shown in Fig. 6, the laser light B incident on the DMD 36 is each micromirror. It is reflected in the inclination direction of 58.

6 shows an example of a state in which a part of the DMD 36 is enlarged and each micromirror 58 is controlled at + α ° or α °. On-off control of each micromirror 58 is performed by the said controller connected to DMD36. Further, a light absorber (not shown) is arranged in the direction in which the laser light B reflected by the micromirrors 58 in the off state travels.

 -Light irradiation means-

There is no restriction | limiting in particular as said light irradiation means, According to the objective, it can select suitably, For example, (super) high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a fluorescent tube, such as a copier, LED, a semiconductor laser, etc. Known light sources such as a light source, or means capable of synthesizing two or more lights and irradiating the light, and among these, means capable of synthesizing two or more lights and irradiating the light are preferable.

As light irradiated from the said light irradiation means, for example, when performing light irradiation through a support body, the electromagnetic wave which permeate | transmits the said support body, and activates the photoinitiator and sensitizer which can be used, visible light from an ultraviolet, An electron beam, an X-ray, a laser beam, etc. are mentioned, Among these, a laser beam is preferable and the laser which synthesize | combined two or more lights (henceforth a "multiplex laser") is more preferable. Moreover, even when light irradiation is performed after peeling a support body, the same light can be used.

As for the wavelength of visible light from the said ultraviolet-ray, 300-1500 nm is preferable, for example, 320-800 nm is more preferable, 330-650 nm is especially preferable.

As for the wavelength of the said laser light, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330-500 nm is still more preferable, 400-450 nm is especially preferable.

As means capable of irradiating the haptic laser, for example, a means having a plurality of lasers, a multimode optical fiber, and a collective optical system for condensing the laser beams irradiated from the plurality of lasers and coupling them to the multimode optical fiber is preferable. .

As a means (fiber array light source) which can irradiate the said haptic laser, the means as described in Unexamined-Japanese-Patent No. 2005-258431 [0109]-[0146] is mentioned, for example.

<< use cemetery designation means >>

As the use drawing part designating means, a drawing part used for realizing N-exposure based on the light spot position detecting means for detecting the position of the light spot as the drawing unit on the exposed surface, and the detection result by the light spot position detecting means. It is preferable to provide at least the drawing part selection means to select.

Hereinafter, the example of the designation method of the drawing part used for N-exposure by the said use drawing part designation means is demonstrated.

(1) Designation method of use drawing part in single exposure head

In this embodiment (1), when the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, the deviation and density of the resolution due to the installation angle error of each exposure head 30 are reduced. A method of designating a drawing part to be used for reducing unevenness and realizing an ideal double exposure will be described.

As the set inclination angle θ in the column direction of the drawing section (micromirror 58) with respect to the scanning direction of the exposure head 30, if the ideal state without an installation angle error of the exposure head 30, etc., 1024 rows X can be used. It is assumed that a slightly larger angle is adopted than the angle θ _ideal of exactly double exposure using 256 rows of drawing parts.

The angle θ _ideal is the number of exposures N of N, the number s of the column directions of the usable micromirrors 58, the interval p of the column directions of the usable micromirrors 58, and the state where the exposure head 30 is inclined. Regarding the pitch δ of the scan line formed by the micromirrors in Equation 1,

spsinθ _ideal ≥Nδ (Equation 1)

Lt; / RTI &gt; In the DMD 36 according to the present embodiment, as described above, a plurality of micromirrors 58 having the same vertical and horizontal arrangement intervals are arranged in a rectangular lattice shape.

pcosθ _ideal = δ (Equation 2)

Equation 1 is

stanθ _ideal = N (Equation 3)

. In this Embodiment (1), since s = 256 and N = 2 as mentioned above, angle (theta) _ideal is about 0.45 degrees by said Formula (3). Therefore, the set tilt angle θ may be, for example, an angle of about 0.50 degrees. The pattern forming apparatus 10 shall be initially adjusted so that the installation angle of each exposure head 30, ie, each DMD 36 may become an angle close to this set inclination angle (theta) within an adjustable range.

FIG. 8 shows an example of non-uniformity generated in the pattern on the exposed surface due to the influence of the installation angle error and the pattern deformation of one exposure head 30 in the pattern forming apparatus 10 initially adjusted as described above. It is explanatory drawing which shows. In the following figures and descriptions, the light points r (m) of the mth row and the nth column are formed with respect to the light spots which are generated by each drawing unit (micromirror) and constitute the exposure area on the exposed surface. It is assumed that the light spot is denoted by c (n) and the light spot in the m-th nth column as P (m, n).

The upper part of Fig. 8 shows the pattern of light spot groups from usable micromirrors 58 projected onto the exposed surface of the photosensitive material 12 with the stage 14 stationary, the lower part being the upper part. When the continuous exposure is performed by moving the stage 14 in the state where the pattern of the light spot group as shown is shown, the state of the exposure pattern formed on the to-be-exposed surface is shown.

In addition, in FIG. 8, although the exposure pattern by the odd row and the exposure row by the even row is shown in the figure for the convenience of description, the exposure pattern on an actual to-be-exposed surface is these two exposures. The patterns overlap.

In the example of Fig. 8, since the setting inclination angle θ is an angle slightly larger than the angle θ _ideal , and fine adjustment of the installation angle of the exposure head 30 is difficult, the actual installation angle and the setting inclination angle are difficult. As a result of FIG. Θ having an error, concentration unevenness is shown in either region on the exposed surface. Specifically, in the overlapping exposure area on the to-be-exposed surface formed by a plurality of rows of tombs in both the exposure pattern by the odd-numbered micromirrors and the exposure pattern by the even-numbered micromirrors, the ideal double exposure is achieved. It becomes overexposure, the area | region in which drawing becomes verbose arises, and a density | variation nonuniformity arises.

Furthermore, in the example of FIG. 8, as an example of the pattern deformation appearing on the to-be-exposed surface, "angle deformation" in which the inclination angle of each pixel column projected on the to-be-exposed surface becomes uneven occurs. Examples of such angular distortion include various aberrations and misalignments in the optical system between the DMD 36 and the exposed surface, deformation of the DMD 36 itself, and arrangement errors of the micromirrors.

The angular deformation shown in the example of Fig. 8 is a deformation in which the inclination angle with respect to the scanning direction is as small as the left column of the figure and as large as the right column of the figure. As a result of this angular deformation, the area overexposed is as small as on the exposed surface shown on the left side of the drawing, and as large as on the exposed surface shown on the right side of the drawing.

In order to reduce the density nonuniformity in the overlapping exposure area | region on the to-be-exposed surface formed by the several tomb part row as mentioned above, the exposure head is used as the said light spot position detection means using the combination of the slit 28 and the photodetector. The micromirror used for actual exposure using the said arithmetic unit connected to the said photodetector as said drawing part selection means based on the said actual inclination angle (theta) 'for every 30, and specifying the actual inclination angle (theta)'. It is assumed that the process of selecting is performed.

The actual inclination angle θ 'is based on the position of two or more light spots detected by the light spot position detecting means, and is determined by the angle between the column direction of the light spot on the exposed surface and the scanning direction of the exposure head in the inclined state of the exposure head. Is specified by.

9 and 10, the specification of the actual tilt angle θ 'and the pixel selection processing to be used will be described.

-Specifying the actual tilt angle θ '-

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

In the example of this Embodiment (1), the angle formed by the light spot array of the 512th row and the scanning direction of the exposure head 30 located in the substantially center of the exposure area | region 32 is measured as said actual inclination angle (theta) '. Specifically, the micromirrors 58 of the first row 512th column and the micromirrors 58 of the 256th row 512th column on the DMD 36 are turned on, respectively, and the light spots on the corresponding exposed surface, respectively. 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 tilt angle θ '.

10 is a surface diagram illustrating a method of detecting the positions of the light spots P (256, 512).

First, while the micromirrors 58 of the 256th row and the 512th row are turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spots P (256, 512) are located upstream. The slit 28 is positioned at an arbitrary position as coming between the slit 28a and the slit 28b on the downstream side. The coordinate of the intersection of the slit 28a and the slit 28b at this time is set to (X0, Y0). The value of these coordinates (X0, Y0) is determined and recorded from the moving distance of the stage 14 to the position indicated by the drive signal given to the stage 14, and the X-direction position of the known slit 28. .

Next, the stage 14 is moved, and the slit 28 is relatively moved to the right side in FIG. 10 along the Y axis. As shown by the dashed-dotted line in Fig. 10, the stage 14 is stopped where light at the light spots P 256 and 512 passes through the slit 28b on the left side and is detected by the photodetector. The coordinates (X0, Y1) of the intersections of the slit 28a and the slit 28b at this time are recorded as the positions of the light points P (256, 512).

Next, the stage 14 is moved in the opposite direction, and the slit 28 is moved relative to the left side in FIG. 10 along the Y axis. As shown by the dashed-dotted line in FIG. 10, the stage 14 is stopped at the place where the light of the light spots P 256 and 512 passes through the slit 28a on the right side and is detected by the photodetector. The coordinates (X0, Y2) of the intersections of the slit 28a and the slit 28b at this time are recorded as the positions of the light spots P (256, 512).

From the above measurement results, coordinates (X, Y) indicating the position on the exposed surface of the light spot P (256, 512) are calculated for the calculation of X = X0 + (Y1-Y2) / 2 and Y = (Y1 + Y2) / 2. Decide by By such measurement, the coordinates indicating the position of P (1,512) are also determined, and the inclination angle formed by the straight line connecting the respective coordinates and the scanning direction of the exposure head 30 is derived, and this is regarded as the actual inclination angle θ '. It is specified.

-Selection of mausoleum used-

The computing device connected to the photodetector using the actual tilt angle θ 'specified in this way is represented by the following equation (4).

ttanθ '= N (Equation 4)

The natural number T closest to the value t satisfying the relationship of D is derived, and a process of selecting the micromirrors in the T-th row from the first row on the DMD 36 as the micromirrors actually used in the present exposure is performed. Thereby, in the exposure area near the 512th row, the micromirror which actually uses the micromirror such that the area total of the overexposure area and the underexposure area becomes the minimum is ideal for the ideal double exposure. Can be selected as

Here, instead of deriving the natural number closest to the value t, a minimum natural number equal to or greater than the value t may be derived. In that case, in the exposure area near the 512th row, with respect to the ideal double exposure, the micromirror in which the area of the overexposure area becomes the minimum and the area underexposure is not generated is actually used as the micro mirror. You can choose.

It is also acceptable to derive the maximum natural number below the value t. In that case, in the exposure area near the 512th row, with respect to the ideal double exposure, the micromirror in which the area of the area which becomes underexposure becomes minimum and the area which becomes overexposure does not occur is actually used as the micromirror. You can choose.

FIG. 11 is an explanatory diagram showing how the unevenness on the exposed surface shown in FIG. 8 is improved in exposure performed by employing only the light points generated by the micromirror selected as the micromirror actually used as described above.

In this example, it is assumed that T = 253 is derived as the natural number T, and the micromirrors of the first to the 253rd rows are selected. With respect to the micromirrors of the 254th to 256th rows that are not selected, a signal that is always set to an off state angle is sent by the drawing unit control means, and these micromirrors do not substantially participate in exposure. . As shown in FIG. 11, in the exposure area near the 512th column, the overexposure and the underexposure are almost completely eliminated, and uniform exposure very close to the ideal double exposure is realized.

On the other hand, in the area on the left side of FIG. 11 (near c (1) in the drawing), the inclination angle of the light spot on the to-be-exposed surface is in the region near the center (near c (512) in the drawing) by the above-described angle transformation. It becomes smaller than the inclination angle of the light ray. Therefore, in the exposure using only the micromirror selected based on the actual inclination angle θ 'measured on the basis of c (512), for the ideal double exposure in each of the exposure pattern with even rows and the exposure pattern with odd rows, The area which becomes underexposure occurs a little.

However, in the actual exposure pattern formed by overlapping the exposure pattern with odd rows and the exposure pattern with even rows, the areas where the exposure amount is insufficient are compensated for each other, and the exposure unevenness caused by the angle deformation is compensated for by double exposure. I can minimize it with an effect.

In addition, in the area on the right side of FIG. 11 (near c (1024) in the figure), the angle of inclination of the ray of light on the exposed surface is determined by the angular deformation in the region near the center (near c (512) in the figure). It becomes larger than the inclination angle of the light ray in. Therefore, in exposure by the micromirror selected based on the actual inclination angle θ 'measured on the basis of c (512), as shown in the drawing, a region slightly overexposed to the ideal double exposure occurs.

However, in the actual exposure pattern formed by overlapping the exposure pattern by odd rows and the exposure pattern by even rows, the areas that become overexposed are complemented with each other to compensate for the concentration unevenness due to the angle deformation by double exposure. I can minimize it with an effect.

In the present embodiment (1), as described above, the actual inclination angle θ 'of the light beam row of the 512th column is measured, and the actual inclination angle θ' is used, based on T derived by the above formula (4). Although the micromirror 58 used was selected, as a specific method of the said actual inclination angle (theta) ', the several actual inclination angle which the column direction (light spot row) of the several drawing parts and the scanning direction of the said exposure head make, respectively is made, respectively. It is good also as a form which measures and measures any one of those average values, the median value, the maximum value, and the minimum value as actual inclination-angle (theta) ', and selects the micromirror actually used at the time of actual exposure by Formula (4).

When the average value or the median value is set to the actual inclination angle θ ', exposure with good balance between the area overexposed and the area underexposed with respect to the ideal N-level exposure can be realized. For example, the total area of the area | region which becomes overexposure and the area | region which become light exposure amount can be suppressed to the minimum, and also the number of seedling units (light spot number) of the area | region which becomes overexposure, and the area | region which become underexposure It is possible to realize exposure so that the number of seedling units (the number of light points) becomes the same.

In addition, when the maximum value is set to the actual inclination angle θ ', it is possible to realize exposure in which the exclusion of the area that is overexposure is more important than the ideal N-exposure. For example, the area of the area that becomes underexposure is minimized. It is possible to realize the exposure which is suppressed to and further suppresses the area of overexposure.

Further, when the minimum value is set to the actual inclination angle θ ', it is possible to realize exposure in which the exclusion of the area which becomes underexposure is more important than the ideal N-exposure. For example, the area of the area that becomes excessive exposure is minimized. It is possible to realize exposure which suppresses and does not produce the area which becomes short of exposure.

In addition, the specification of the said actual inclination angle (theta) 'is not limited to the method based on the position of two or more light spots among the rows (light spot string) of the same drawing part. For example, the angle obtained from the position of one or a plurality of light spots in the same seedling section column c (n) and the position of one or a plurality of light spots in the column near the c (n) is obtained from the actual tilt angle θ '. You may specify as.

Specifically, one light spot position in c (n) and one or a plurality of light spot positions included in a linear or near light spot line are detected according to the scanning direction of the exposure head, and from these position information, The inclination angle θ 'can be obtained. Further, the angle obtained based on the positions of two or more light spots (for example, two light spots arranged as exceeding c (n)) among the light spots near the c (n) column is expressed as the actual tilt angle θ '. You may specify.

As mentioned above, according to the designation method of the using drawing part of this embodiment (1) using the pattern forming apparatus 10, the dispersion | variation in the resolution and the nonuniformity of density by the influence of the installation angle error of each exposure head or the pattern deformation are reduced. The ideal N-level exposure can be realized.

(2) Designation method of use drawing part between plural exposure heads <1>

In this embodiment (2), when the pattern forming apparatus 10 performs double exposure with respect to the photosensitive material 12, it is an overlapping exposure area on the to-be-exposed surface formed by the some exposure head 30. As shown in FIG. In the head-to-head connection area, the deviation of the resolution and the density unevenness due to the deviation from the ideal state of the relative position of the two exposure heads (for example, the exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction are reduced. The designation method of the drawing material part for realizing an ideal double exposure is demonstrated.

As the setting inclination angle θ of each exposure head 30, that is, each DMD 36, an ideal state in which there is no installation angle error or the like of the exposure head 30, 1024 rows × 256 rows of drawing part micromirrors 58 can be used. ), An angle θ _ideal for precise double exposure is adopted.

This angle θ _ideal is obtained in the same manner as in the first embodiment (1), and is obtained from the above formulas (1) to (3). In this embodiment (2), the pattern forming apparatus 10 shall be initially adjusted so that the installation angle of each exposure head 30, ie, each DMD 36, may become this angle (theta) _ideal .

FIG. 12 shows an ideal state of the relative position with respect to the X-axis direction of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the pattern forming apparatus 10 initially adjusted as described above. It is explanatory drawing which showed the example of the density | variation nonuniformity which arises in the pattern on a to-be-exposed surface under the influence of the misalignment. The shift of the relative position with respect to the X-axis direction of each exposure head may arise because fine adjustment of the relative position between exposure heads is difficult.

The upper portion of FIG. 12 shows usable micromirrors 58 of the DMD 36 with the exposure heads 30 ₁₂ and 30 ₂₁ , projected onto the exposed surface of the photosensitive material 12 with the stage 14 stationary. Fig. Shows the pattern of light spot groups from. 12 shows the state of the exposure pattern formed on the to-be-exposed surface when the stage 14 is moved while the stage 14 is moved in a state where the light spot group pattern as shown in the upper portion is shown. ₁₂ and 32 ₂₁ ).

delete

In FIG. 12, for convenience of explanation, the single-column exposure pattern of the usable micromirrors 58 is divided into the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B, but the actual pino is shown. The exposure pattern on a light surface overlaps these two exposure patterns.

In the example of FIG. 12, the exposure pattern and pixel column group B by pixel column group A as a result of the deviation from the ideal state of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ regarding the X-axis direction mentioned above. the two sides of the exposure pattern by, in the connecting area between the head of the exposure area (32 ₁₂ and 32 _21), faded than the exposure amount blossomed the excessive part of the state of an ideal double exposure.

In order to reduce the density nonuniformity which appears in the said head connection area | region formed on the to-be-exposed surface by a plurality of said exposure heads as mentioned above, in this Embodiment 2, the slit 28 and light as said light spot position detection means are provided. Using a pair of detectors, the position (coordinate) is detected for some of the light spots constituting the head-to-head connection region formed on the exposed surface among the light spot groups from the exposure heads 30 ₁₂ and 30 ₂₁ . Based on the position (coordinate), a processing for selecting a micromirror used for actual exposure is performed by using a computing device connected to the photodetector as the drawing unit selection means.

Detection of position (coordinates)

FIG. 13 is a surface view showing the positional relationship between the exposure areas 32 ₁₂ and 32 ₂₁ and the slits 28 corresponding to those in FIG. 12. The size of the slit 28 is larger than that of the exposure heads 30 ₁₂ and 30 ₂₁ to sufficiently cover the width of the overlapping portion between the exposed areas 34 by the exposure heads 30 ₁₂ and 30 ₂₁ . It becomes size enough to cover the said head connection area | region formed on the optical surface.

14 is a surface view illustrating a detection method when detecting the positions of the light spots P (256, 1024) of the exposure area 32 ₂₁ as an example.

First, while the micromirror of the 256th row 1024th column is turned on, the stage 14 is moved slowly and the slit 28 is moved relative to the Y-axis direction, and the light spots P (256, 1024) are located upstream. The slit 28 is positioned at an arbitrary position as coming between the slit 28a and the downstream slit 28b. The coordinate of the intersection of the slit 28a and the slit 28b at this time is set to (X0, Y0). The values of these coordinates (X0, Y0) are determined and recorded from the moving distance of the stage 14 to the position indicated by the drive signal given to the stage 14, and the X-direction position of the known slit 28.

Next, the stage 14 is moved, and the slit 28 is relatively moved to the right side in FIG. 14 along the Y axis. As shown by the dashed-dotted line in FIG. 14, the stage 14 is stopped at the place where the light of the light spots P (256, 1024) passes through the left slit 28 b and is detected by the photodetector. The coordinates (X0, Y1) of the intersections of the slit 28a and the slit 28b at this time are recorded as the positions of the light points P (256,1024).

Next, the stage 14 is moved in the opposite direction, and the slit 28 is moved relative to the left side in FIG. 14 along the Y axis. As shown by the dashed-dotted line in FIG. 14, the stage 14 is stopped at the place where the light of the light spots P (256, 1024) passes through the slit 28 a on the right side and is detected by the photodetector. The coordinates (X0, Y2) of the intersections of the slit 28a and the slit 28b at this time are recorded as the light points P (256,1024).

From the above measurement results, the coordinates (X, Y) indicating the position on the exposed surface of the light spot P (256, 1024) are defined as X = X 0 + (Y 1-Y 2) / 2, Y = (Y 1 + Y 2) / 2. Determined by calculation

-Specific of unused graveyard-

In the example of Figure 12, first, detected by the position of the light spot P (256,1) of the exposure area (32 _12), Article of the slit 28 and the photodetector as the light spot position detection means. Subsequently, the positions of the respective light spots on the light spot r r 256 in the 256th row of the exposure area 32 ₂₁ are detected in the order of P (256,1024), P (256,1023). The detection operation is terminated where the light spots P (256, n) of the exposure area 32 ₂₁ indicating the X coordinate larger than the light spots P (256,1) of the area 32 ₁₂ are detected. Then, the particular as a micro mirror corresponding to the light spots constituting c (1024) from the radiant heat c (n + 1) of the exposure area (32 _21), a micro mirror (sub unused graves) is not used at the time of the exposure .

For example, in FIG. 12, the light spots P (256, 1020) of the exposure area 32 ₂₁ represent an X coordinate larger than the light spots P (256, ₁ ) of the exposure area 32 ₁₂ , and the exposure area ( Assuming that the detection operation is terminated where the light spots P (256, 1020) of 32 ₂₁ are detected, it is determined from row 1021 of the exposure area 32 ₂₁ corresponding to the portion 70 covered by the oblique line in FIG. The micromirror corresponding to the light spot which comprises 1024 rows is specified as a micromirror which is not used at the time of this exposure.

Next, with respect to the number N of exposures in N, the positions of the light points P 256 and N of the exposure area 32 ₁₂ are detected. In the present embodiment (2), since N = 2, the positions of the light spots P (256, 2) are detected.

Subsequently, among the light spots in the exposure area 32 ₂₁ , the positions of the light spots constituting the rightmost 1020 column are determined except as specified as the light spots corresponding to the micromirrors not used in the above exposure. , P (1,1020), P (2,1020) ... in order from P (1,1020), indicating that the X coordinate is larger than the light spot P (256,2) of the exposure area 32 ₁₂ . The detection operation is terminated where the light spot P (m, 1020) is detected.

Then, in the arithmetic unit connected to the photodetector, the light spot P (m, 1020) of the X coordinate and the exposure area (32 ₂₁₎ of the light spot P (256,2) of the exposure area _(12, 32) and P ( The X coordinate of m-1,1020 is compared, and the X coordinate side of the light spot P (m, 1020) of the exposure area 32 ₂₁ is compared to the X coordinate of the light spot P (256,2) of the exposure area 32 ₁₂ . Nearby case, the exposure area (32 ₂₁₎ is a micro mirror corresponding to P (m-1,1020) from the light spot P (1,1020) is specified as the micro-mirror is not used at the time of the exposure.

Further, when the X-coordinate-side of the light spot P (m-1,1020) of the exposure area (32 ₂₁₎ near to the X-coordinate of the light spot P (256,2) of the exposure area (32 _12), the exposure area _(21, 32 The micromirrors corresponding to P (m-2,1020) are specified as the micromirror which is not used for this exposure from the light point P (1,1020) of ().

Further, the light spots P (256, N-1) of the exposure area 32 ₁₂ , that is, the positions of the light spots P (256, 1) and the respective light spots constituting the 1019th column which is the next row of the exposure area 32 ₂₁ . Also for the position, the same detection process and the specification of the unused micromirror are performed.

As a result, for example, the micromirror corresponding to the light point which comprises the area | region 72 covered with the crossing parallel line in FIG. 15 is added as a micromirror which is not used at the time of an actual exposure. The signals which always set the angle of the micromirror to the angle of an off state are sent to these micromirrors, and those micromirrors are not substantially used for exposure.

Thus, by specifying the micromirrors not used at the time of actual exposure and selecting the thing except the said unused micromirrors as the micromirrors used at the time of actual exposure, the exposure area 32 ₁₂ and 32 ₂₁ of the In the said head-to-head connection area | region, the sum total area of the area which becomes overexposure and the area which becomes underexposure with respect to ideal double exposure can be minimized, and as shown in the lower part of FIG. A very close uniform exposure can be realized.

Further, in the above example, the degree constituting the area 72 covered by the light spot in the parallel lines cross 15 when particular, X-coordinate and the exposure area of the light spot P (256,2) of the exposure area (32 ₁₂₎ (32 ₂₁₎ of the light spot P (m, 1020) and P (m-1,1020) without performing a comparison of the X coordinate, and immediately, the exposure area (32 _21), the light spot P from P (m (1,1020) of You may specify the micromirror corresponding to -2,1020 as a micromirror not used at the time of this exposure. In that case, the micromirror in which the area | region which becomes overexposure becomes minimum and the area | region which becomes underexposure with respect to ideal double exposure in the said head-to-head connection area | region can be selected as a micromirror to actually use. .

In addition, the micromirrors corresponding to P (m-1,1020) from the light spot P (1,1020) of the exposure area (32 _21), the exposure may be specified as micro mirrors not to use. In that case, the micromirror in which the area | region which becomes underexposure becomes small and the area which becomes overexposure with respect to ideal double exposure in the said head-to-head connection area | region can be selected as a micromirror to actually use. .

Further, in the head-to-head connection area, the number of drawing units (light spots) in the area overexposed to the ideal double drawing and the number of drawing units (light spots) in the area underexposing become the same. You may select a micromirror.

As mentioned above, according to the designation method of the use drawing part of this embodiment (2) using the pattern forming apparatus 10, the dispersion | variation in a resolution and density | variation nonuniformity resulting from the shift of the relative position with respect to the X-axis direction of several exposure heads. It is possible to reduce the exposure and realize the ideal N-exposure.

(3) Designation method of use drawing part between plural exposure heads <2>

In this embodiment (3), when the pattern forming apparatus 10 performs double exposure with respect to the photosensitive material 12, it is an overlapping exposure area on the to-be-exposed surface formed by the some exposure head 30. As shown in FIG. In the head-to-head connection area, the deviation from the ideal state of the relative position with respect to the X-axis direction of the two exposure heads (for example, the exposure heads 30 ₁₂ and 30 ₂₁ ), and the installation angle error of each exposure head, and 2 The method of designating the use drawing part for reducing the deviation of the resolution and the density unevenness caused by the relative installation angle error between the two exposure heads and realizing the ideal double exposure will be described.

As the setting inclination angle of each exposure head 30, that is, each DMD 36, if there is no installation angle error or the like of the exposure head 30, a drawing part (micromirror 58 of 1024 rows x 256 rows) can be used. Use)) to adopt an angle slightly larger than the angle θ _ideal for double exposure.

This angle θ _ideal is a value obtained by using the formulas (1) to (3) in the same manner as in the embodiment (1). In the present embodiment, since s = 256 and N = 2 as described above, the angle θ _ideal is about 0.45 °. Therefore, the set tilt angle θ may be, for example, about 0.50 degrees. The pattern forming apparatus 10 shall be initially adjusted so that the installation angle of each exposure head 30, ie, each DMD 36 may become an angle close to this set inclination angle (theta) within the adjustable range.

FIG. 16 shows two exposure heads (for example, exposure heads 30 ₁₂ and 2) in the pattern forming apparatus 10 in which the installation angles of the respective exposure heads 30, that is, each DMD 36 are initially adjusted as described above. 30 ₂₁ )) Explanatory drawing showing an example of the nonuniformity which arises in the pattern on a to-be-exposed surface by the influence of the installation angle error of the exposure head 30 ₁₂ and 30 ₂₁ , and the shift of a relative position. to be.

In the example of FIG. 16, the exposure by the group of light spots grouped together (pixel column groups A and B) as a result of the shift of the relative positions of the exposure heads 30 ₁₂ and 30 ₂₁ with respect to the X-axis direction as in the example of FIG. In both of the patterns, in the exposure area overlapping on the exposed surfaces of the exposure areas 32 ₁₂ and 32 ₂₁ on the coordinate axis orthogonal to the scanning direction of the exposure head, the exposure dose excess area 74 is larger than the ideal double exposure state. Occurs, which causes concentration unevenness.

Moreover, in the example of FIG. 16, since the setting inclination-angle (theta) of each exposure head was made slightly larger than the angle (theta) _ideal which satisfy | _fills said Formula (1), and since fine adjustment of the installation angle of each exposure head is difficult, As a result of the fact that the actual installation angle is shifted from the set inclination angle θ, even in areas other than the exposure area overlapping on the coordinate axis orthogonal to the scanning direction of the exposure head on the exposed surface (pixel column group A) And in the connection area between the drawing part rows, which are overlapping exposure areas on the exposed surface, formed by a plurality of drawing part rows, both of the exposure patterns according to B), which are overexposed than the ideal double exposure state ( 76), which causes even more concentration unevenness.

In the present embodiment (3), first, a use pixel selection process for reducing the density unevenness caused by the influence of the installation angle error and the deviation of the relative installation angle of each of the exposure heads 30 ₁₂ and 30 ₂₁ is performed.

Specifically, using a pair of slits 28 and a photodetector as the light spot position detecting means, the actual tilt angle θ 'is specified for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the actual tilt angle Based on θ ', a process of selecting a micromirror used for actual exposure is performed using a computing device connected to a photodetector as the drawing unit selection means.

-Specifying the actual tilt angle θ '-

The location of the actual inclination angle θ is specified, the exposure head exposed area (32 ₂₁₎ for (30, _12), within the light spot P (1,1) and P (256,1), the exposure head (30, ₁₂₎ For example, the positions of the light spots P (1 1024) and P (256, 1024) in the exposure area 32 ₂₁ are detected by the combination of the slit 28 and the photodetector used in the above-described embodiment (2), respectively. Is measured by measuring the angle of inclination of the straight line connecting the cross section and the angle formed by the scanning direction of the exposure head.

-Specific of unused graveyard-

In this way, the calculation device connected to the photodetector using the specified actual tilt angle θ 'is the same as the calculation device in the above-described Embodiment (1).

ttanθ '= N (Equation 4)

The natural number T closest to the value t satisfying the relation of D is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the micromirror of the 256th row from the (T + 1) th row on the DMD 36 is obtained. Is specified as a micromirror not used for this exposure.

For example, when T = 254 for the exposure head 30 ₁₂ and T = 255 for the exposure head 30 ₂₁ , the light spots forming the diagonally covered portions 78 and 80 in FIG. The micromirror to be specified is specified as a micromirror not used for this exposure. As a result, in each of regions other than the connected region between of the head exposed area (32 ₁₂ and 32 _21), to the sum of the areas of the ideal second area to which the exposure excessive with respect to the exposure of, and underexposure region to a minimum Can be.

Here, instead of deriving the natural number closest to the value t, a minimum natural number equal to or greater than the value t may be derived. In that case, the exposed area (32 ₁₂ and 32 _21), in each area of Pinot other than light surface overlapping exposed areas of connection between the head area of the upper formed by the plurality of exposure heads, the ideal 2 out of which the amount of exposure over against the exposure The area can be minimized and the area where the exposure dose is insufficient can be prevented from occurring.

Alternatively, the maximum natural number below the value t may be derived. In that case, 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 of the exposure areas 32 ₁₂ and 32 ₂₁ , the area that becomes underexposed to the ideal double exposure It is possible to minimize the area of and to prevent the occurrence of an area of excessive exposure.

In each region other than the inter-head connection region, which is an overlapping exposure region on the to-be-exposed surface formed by a plurality of exposure heads, the number of light units in the region that becomes overexposed with respect to the ideal double exposure, and the lack of exposure It is good also as specifying the micromirror which is not used at the time of this exposure so that the drawing unit number (light spot number) of the area | region used may become the same.

Subsequently, a process similar to the present embodiment (3) described with reference to Figs. 12 to 15 is applied to the micromirrors corresponding to the light points other than the light points constituting the diagonal areas 78 and 80 in FIG. In FIG. 17, a micromirror corresponding to a light point constituting an area 82 covered with an oblique line and an area 84 covered with an intersecting parallel line is specified, and is added as a micromirror not used in the present exposure.

With respect to the micromirror specified as not being used at the time of these exposures, the signal set by the said drawing part small control means always sends the signal set to the angle of an off state, and those micromirrors do not substantially participate in exposure. .

As mentioned above, according to the designation method of the use drawing part of this embodiment 3 using the pattern forming apparatus 10, the shift | offset | difference of the relative position with respect to the X-axis direction of several exposure heads, and the installation angle error of each exposure head It is possible to reduce the deviation of the resolution and the density unevenness due to the relative installation angle error between the exposure head and the exposure head, and to realize the ideal N-level exposure.

As mentioned above, although the use drawing part designation method by the pattern forming apparatus 10 was demonstrated in detail, the said embodiment (1)-(3) is only an example, and various changes are made, without deviating from the range of this invention. This is possible.

Further, in the above embodiments (1) to (3), although a slit 28 and a pair of single cell photodetectors are used as means for detecting the position of the light spot on the to-be-exposed surface, the present invention is not limited thereto. May be used, for example, a two-dimensional detector or the like may be used.

Further, in the above embodiments (1) to (3), the actual tilt 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 based on the actual tilt angle θ'. Although the micromirror used was selected, it is good also as a form which selects the usable micromirror, without deriving the actual inclination angle (theta) '. Further, for example, the reference exposure using all available micromirrors is performed, and the micromirrors used by the operator are manually designated by the eye of the reference exposure result, and the confirmation of the nonuniformity of the concentration. It is included in the scope of the invention.

In addition, there are various forms of pattern deformation that may occur on the exposed surface, in addition to the angle deformation described above.

As an example, as shown in FIG. 18A, there is a form of magnification deformation in which the light rays from the micromirrors 58 on the DMD 36 reach the exposure area 32 on the exposure surface at different magnifications.

As another example, as shown in FIG. 18B, the beam diameter deformation in which the light rays from each micromirror 58 on the DMD 36 reaches the exposure area 32 on the other beam diameter path exposed surface. There is also a form. These magnification deformation and beam diameter deformation mainly occur due to various aberrations and alignment misalignments of the optical system between the DMD 36 and the exposed surface.

As another example, there is also a form of light amount deformation in which the light rays from the micromirrors 58 on the DMD 36 reach the exposure area 32 on the exposed surface at different amounts of light. In addition to various aberrations and alignment misalignments, this light quantity deformation is a position dependence of the transmittance of the optical element (for example, the lenses 52 and 54 of FIGS. 5A and 5B, which are single-lens lenses) between the DMD 36 and the exposed surface. Or due to light quantity unevenness caused by the DMD 36 itself. Pattern deformation in these forms also causes variations in resolution and density in the pattern formed on the exposed surface.

According to the above embodiments (1) to (3), after the micromirrors to be actually used for the present exposure are selected, the remaining elements of the pattern deformation of these forms are also supplemented by the multi-exposure as with the remaining elements of the angular deformation. It can make it even, and the nonuniformity of a resolution and a density can be reduced over the whole exposure area of each exposure head.

<< reference exposure >>

As a modification of the above-mentioned embodiments (1) to (3), among the usable micromirrors, the micromirror columns filtered by (N-1) columns or the adjacent rows corresponding to 1 / N rows of all light spots are formed. It is also possible to specify a micromirror not used at the time of actual exposure among the micromirrors used for the above-mentioned reference exposure so as to perform the reference exposure using only the micromirror group and to realize uniform exposure.

The results of the reference exposure by the reference exposure means are sampled, and the analysis of the output reference exposure results is performed such as checking the variation in the resolution and the variation in the density and estimating the actual tilt angle. The analysis of the result of the reference exposure may be analysis by the operator's eyes.

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

In this example, N = 2 is assumed as double exposure at the time of this exposure. First, reference exposure is performed using only the micromirrors corresponding to the light spots of odd rows shown in solid lines in Fig. 19A, and the reference exposure results are sampled. The micromirror used at the time of this exposure can be specified by confirming the dispersion | variation in a resolution, the nonuniformity of density | concentration, or estimating actual tilt angle based on the sample exposure reference exposure result.

For example, micromirrors other than the micromirrors corresponding to the light spots covered with diagonal lines in FIG. 19B are designated as actually used in the present exposure among the micro mirrors constituting the odd light spots. About even-numbered light spots, reference exposure may be performed separately similarly, the micromirror used at the time of this exposure may be designated, and the same pattern as the pattern with respect to the light spots of odd-numbered rows may be applied.

In this way, by specifying the micromirrors used in the present exposure, in the present exposure using the micromirrors in both odd and even columns, an ideal state of near double exposure can be realized.

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

In this example, N = 2 is assumed as double exposure at the time of this exposure. First, reference exposure is performed using only micromirrors corresponding to the light spots of odd rows of two adjacent exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction shown by solid lines in FIG. 20. The sample exposure results in the reference exposure result. Based on the above-described output reference exposure results, the variation of the resolution and the variation of the concentration in the regions other than the inter-head connection region formed on the exposed surface by the two exposure heads are confirmed, or the actual inclination angle is estimated. The micromirror used at the time of exposure can be specified.

For example, among the micromirrors other than the micromirror corresponding to the light spot in the area | region 86 shown by the oblique line in FIG. 20 and the area | region 88 shown by the crossing parallel line, this exposure is the micromirror which comprises the light spot of odd rows. It is specified as actually used in the poem. For even-numbered light spots, the reference exposure may be performed separately, and the micromirrors used in the present exposure may be designated, or the same pattern may be applied in the pattern for the odd-numbered pixel columns.

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In this way, by designating the micromirrors to be used during the actual exposure, in the present exposure using the micromirrors of both odd and even columns, it is possible to use the micromirrors in regions other than the inter-head connection region formed on the exposed surface by the two exposure heads. Thus, a state close to the ideal double exposure can be realized.

21A and 21B are explanatory diagrams showing an example in which a reference exposure is performed using a single exposure head and using only a micromirror group constituting adjacent rows corresponding to 1 / N rows of total light spot rows.

In this example, N = 2 is assumed as double exposure at the time of this exposure. First, reference exposure is performed using only the micromirrors corresponding to the light spots from the first row to the 128 (= 256/2) row shown in solid lines in Fig. 21A, and the reference exposure result is sampled. The micromirror used at the time of this exposure can be specified based on the sample exposure reference exposure result.

For example, micromirrors other than the micromirrors corresponding to the light spot group shown by the oblique line shown in FIG. 21B can be designated as actually used at the time of this exposure among the micromirrors of the 1st to 128th rows. The micromirrors of the 129th to 256th rows may be subjected to the same reference exposure separately, and the micromirrors used during the main exposure may be designated, and the same pattern as that of the micromirrors of the first to 128th rows. You may apply.

In this way, by specifying the micromirrors used in the present exposure, in the present exposure using the entire micromirror, a state close to an ideal double exposure can be realized.

Fig. 22 corresponds to 1 / N rows of total light spot rows for two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction using a plurality of exposure heads. It is explanatory drawing which showed an example of the form which carries out a reference exposure using only the micromirror group which comprises the adjacent row which is mentioned.

In this example, N = 2 is assumed as double exposure at the time of this exposure. First, reference exposure is performed using only the micromirror corresponding to the light spot of the 128th (= 256/2) th row from the 1st line shown by the solid line in FIG. 22, and the reference exposure result is sampled. Based on the result of the sample exposure reference exposure, this exposure can be realized with a minimum suppression of the variation in the resolution and the variation in density in an area other than the connection area between the heads formed on the exposed surface by the two exposure heads. The micromirror used at the time of this exposure can be specified so that it may be used.

For example, among the micromirrors other than the micromirror corresponding to the light spot in the area | region 90 shown by the oblique line in FIG. 22 and the area | region 92 shown by the crossing parallel line, among the micromirrors of the 1st row to the 128th row, It is specified as what is actually used at the time of this exposure. For the micromirrors of the 129th to 256th rows, the same reference exposure may be performed separately, and the micromirrors used for the main exposure may be designated, and the same pattern as the pattern for the micromirrors of the first to 128th rows may be designated. You may apply.

By specifying the micromirrors used in this exposure, the state close to the ideal double exposure can be realized in a region other than the inter-head connection region formed on the exposed surface by the two exposure heads.

In the above embodiments (1) to (3) and the modification examples, the case where all the exposures are referred to as double exposures has been described. However, the present invention is not limited to this, and any multiple exposures above the double exposures may be used. In particular, by setting the exposure level from triple exposure to seven times, high resolution can be ensured, and exposure with reduced resolution variation and density unevenness can be realized.

Further, in the exposure apparatus according to the embodiment and the modification, the image data is further converted so that the dimension of the predetermined portion of the two-dimensional pattern represented by the image data matches the dimension of the corresponding portion that can be realized by the selected use pixel. It is preferable that a mechanism to be provided is provided. By converting the image data in such a manner, a fine pattern like the desired two-dimensional pattern can be formed on the exposed surface.

[Development step]

As the said development, it is performed by removing the unexposed part of the said photosensitive layer.

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

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

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About pH of the said weakly alkaline aqueous solution, about 8-12 are preferable, for example, about 9-11 are more preferable. As said weak alkaline aqueous solution, 0.1-5 mass% sodium carbonate aqueous solution or potassium carbonate aqueous solution etc. are mentioned, for example.

Although the temperature of the said developing solution can be suitably selected according to the developability of the said photosensitive layer, about 25-40 degreeC is preferable, for example.

The developer may be a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanol amine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanol amine, etc.) or development. In order to accelerate | stimulate, you may use together with organic solvents (for example, alcohol, ketones, ester, ether, amide, lactone, etc.). The developing solution may be an aqueous developing solution obtained by mixing water or an alkaline aqueous solution with an organic solvent, or may be an organic solvent alone.

Curing Treatment Step

The said hardening process process is a process of performing hardening process with respect to the photosensitive layer in the formed pattern after the said image development process is performed.

There is no restriction | limiting in particular as said hardening process process, Although it can select suitably according to the objective, For example, a front surface exposure process, a front surface heat treatment, etc. are mentioned preferably.

As a method of the said front surface exposure process, the method of exposing the whole surface on the said laminated body in which the said permanent pattern was formed after the said image development is mentioned, for example. By the said front exposure, hardening of resin in the photosensitive composition which forms the said photosensitive layer is accelerated | stimulated, and the surface of the said permanent pattern is hardened.
There is no restriction | limiting in particular as an apparatus which performs the said front surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, an xenon lamp use exposure machine, a laser exposure machine, etc. are mentioned preferably. The exposure amount is usually 10 to ² , OOmJ / cm ² .

As a method of the said front surface heat processing, the method of heating the whole surface on the said laminated body in which the said permanent pattern was formed after the said image development is mentioned. By the front surface heating, the film strength of the surface of the permanent pattern can be increased.

120-250 degreeC is preferable and, as for the heating temperature in the said front heating, 120-200 degreeC is more preferable. When the said heating temperature is less than 120 degreeC, the improvement of the film strength by heat processing may not be acquired, and when it exceeds 250 degreeC, decomposition | disassembly of resin in the said photosensitive composition may arise, and the film quality may fall weakly.

10-120 minutes are preferable and, as for the heat time in the said front heating, 15-60 minutes are more preferable.

There is no restriction | limiting in particular as an apparatus which performs said whole surface heating, From a well-known apparatus, it can select suitably according to the objective, For example, a dry oven, a hotplate, an IR heater, etc. are mentioned.

 -Protective film, interlayer insulating film, solder resist pattern formation method-

When the pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, a permanent pattern is formed on the printed wiring board by the permanent pattern forming method. Soldering can be performed as follows.

That is, by the said development, the hardened layer which is the said permanent pattern is formed, and a metal layer is exposed on the surface of the said printed wiring board. After plating is performed on the site | part of the metal layer exposed to the surface of the said printed wiring board, soldering is performed. And a semiconductor, a component, etc. are mounted in the soldered part. At this time, the permanent pattern by the hardened layer functions as a protective film, an insulating film (interlayer insulating film), a solder resist, and external shock or conduction of adjacent electrodes is prevented.

In the pattern forming apparatus and the permanent pattern forming method, if the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from external impact or warping. In the case of an interlayer insulating film, for example, it is useful for high-density packaging of semiconductors and components in multilayer wiring boards, build-up wiring boards, and the like.

In order to use the photosensitive laminated body of this invention, the permanent pattern formation method of this invention is for forming various patterns, such as a permanent pattern, such as a protective film, an interlayer insulation film, and a soldering resist pattern, a color filter, a pillar material, a rib material, a spacer It can be used suitably for manufacture of liquid crystal structural members, such as a partition and a hologram, a micromachine, a proof, etc., and especially can be used for formation of a permanent pattern of a printed circuit board.

Example

Hereinafter, although the Example of this invention is described, this invention is not limited to a following example at all.

(Synthesis Example 1)

Synthesis of Compound Example 1

In a 100 ml three-necked flask, 2.2 parts by mass of sodium hydride (mineral oil removed) was added, and after changing to nitrogen atmosphere, 30 parts by mass of tetrahydrofuran (THF) was added. Then, a solution of 12 parts by mass of propiophenone and 30 parts by mass of THF was added over 1 hour from the dropping funnel. Thereafter, the mixture was stirred for 1 hour. 3.2 mass parts of intermediate products were obtained by silica gel column chromatography (hexane / ethyl acetate = 9/1).

Then, 12 mass parts of allyl bromide and 15 mass parts of THF were added over 1 hour from the dropping funnel. Then, it stirred for 1 hour, added 150 mass parts of water, and extracted by adding 50 mass parts of ethyl acetate. The solvent of the organic layer was distilled off under reduced pressure, and produced by silica gel column chromatography (hexane / ethyl acetate = 9/1) to obtain 5.2 parts by mass of the following intermediate product A.

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5.2 parts by mass of this intermediate product, 4 parts by mass of hydroxyamine hydrochloride, 6 parts by mass of potassium acetate, and 30 parts by mass of ethanol were placed in a 100 ml eggplant flask and refluxed for 2 hours. 150 mass parts of water were added after completion | finish of reaction, the extract was extracted with 50 mass parts of ethyl acetate, the organic layer was dried over magnesium sulfate, and it distilled off under reduced pressure. Subsequently, 6 parts by mass of pyridine and 30 parts by mass of acetonitrile were added, the external temperature was set to 0 ° C, and a solution of 4 parts by mass of acetyl chloride and 20 parts by mass of acetonitrile was added over 30 minutes with a dropping funnel. Thereafter, the mixture was stirred for 1 hour, 150 parts by mass of water was added, 50 parts by mass of ethyl acetate was extracted, the organic layer was dried over magnesium sulfate, and distilled off under reduced pressure to obtain 2.8 parts by mass of the oily compound (Compound Example 1) (yield 14%). )

The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). 7.49-7.37 (m, 4H), 7.20-7.16 (m, 1H), 5.88-5.68 (m, 1H), 5.09-5.02 (m, 2H), 3.51-3.42, 3.00-2.92 (m, 1H), 2.52 -2.38 (m, 1H), 2.33-2.08 (m, 2H), 2.26 (s, 3H), 1.23 (dd, 1H)

Compound Example 1

(Synthesis Example 2)

Synthesis of Compound Example 3

Into a 100 ml three-necked flask, 2.6 parts by mass of sodium hydride (mineral oil was removed) was added to a nitrogen atmosphere, and then 50 parts by mass of THF and 20 parts by mass of dimethylacetoamide were added. Next, 8.3 parts by mass of diethyl carbonate was added.

The external temperature was set at 50 ° C., and a solution of 7 parts by mass of 1-indanone and 8 parts by mass of THF was added from the dropping funnel over 1 hour. Thereafter, the mixture was stirred for 1 hour.

Then, the solution of 13 mass parts of allyl bromide and 15 mass parts of THF was added over 1 hour from the dropping funnel. Then, it stirred for 1 hour, added 150 mass parts of water, and extracted by adding 50 mass parts of ethyl acetate. 4.6 parts by mass of a 48% sodium hydroxide solution, 20 parts by mass of ethanol, and 20 parts by mass of water were added to the oily substance obtained by distilling off the solvent of the organic layer under reduced pressure, and the external temperature was set to 75 degreeC, and it stirred for 2 hours. Thereafter, 7 parts by mass of 12N hydrochloric acid was added, followed by 200 parts by mass of water. The mixture was extracted with 50 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Next, 3.2 mass parts of following intermediate products B were obtained by producing by silica gel column chromatography (hexane / ethyl acetate = 9/1).

3.2 parts by mass of this intermediate product, 2 parts by mass of hydroxyamine hydrochloride, 3 parts by mass of potassium acetate and 50 parts by mass of ethanol were placed in a 100 ml flask and refluxed for 2 hours. After the reaction was completed, 150 parts by mass of water were added, extracted with 50 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Next, 2 parts by mass of pyridine and 30 parts by mass of acetonitrile were added, the external temperature was set to 0 ° C, and a solution of 1.5 parts by mass of acetyl chloride and 20 parts by mass of acetonitrile was added over 30 minutes with a dropping funnel. Thereafter, the mixture was stirred for 1 hour, and the crystal obtained by adding 100 parts by mass of ice water was recrystallized and purified by acetonitrile, thereby obtaining 2.8 parts by mass (yield 23%) of white crystals (Compound Example 3).

The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). 8.25,7.87 (dd, 1H), 7.50-7.30 (m, 3H), 5.89-5.68 (m, 1H), 5.14-5.03 (m, 2H), 3.62-3.54,3.27-3.15 (m, 1H), 2.90 -2.81 (m, 1H), 2.75-2.61 (m, 1H), 2.31,2.26 (s, 3H)

Compound Example 3

(Synthesis Example 3)

Synthesis Example of Compound Example 4

30 mass parts of 1-naphthylaldehyde, 30 mass parts of malonic acid, 5 mass parts of piperidine, and 100 mass parts of pyridine were put into a 300 ml three neck flask, and it refluxed for 3 hours. The reaction solution was put in 1000 mass parts of ice water, and was obtained by filtering a white solid. Subsequently, this white solid was dissolved in 50 parts by mass of methanol and 50 parts by mass of ethyl acetate, 5 parts by mass of palladium carbon (Pd content of 10%) was added, and reacted in a hydrogen atmosphere for 5 hours. After the reaction was completed, the reaction solution was filtered through Celite, and the solvent was distilled off under reduced pressure. Subsequently, 150 parts by mass of chlorobenzene and 40 parts by mass of aluminum chloride were added thereto, and the external temperature was set at 0 ° C. The white solid and 50 parts by mass of chlorobenzene obtained above were added dropwise for 30 minutes from the dropping funnel. Then, it was made to react for 2 hours and 1000 mass parts of ice water were added. The obtained white crystals were recrystallized from methanol to obtain 25 parts by mass (yield 68%) of the following intermediate product C.

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0.87 parts by mass of sodium hydride (mineral oil removed) was placed in a 100 ml three-necked flask, and changed to a nitrogen atmosphere, and then 10 parts by mass of THF and 5 parts by mass of dimethylacetoamide were added. Next, 2.4 parts by mass of diethyl carbonate was added.

The external temperature was set at 50 ° C., and a solution of 3 parts by mass of α-tetrarone and 10 parts by mass of THF was added from the dropping funnel over 1 hour. Then stirred for 1 hour.

Then, the solution of 3 mass parts of allyl bromide and 10 mass parts of THF was added over 1 hour from the dropping funnel. Thereafter, the mixture was stirred for 1 hour, 100 parts by mass of water was added, and 30 parts by mass of ethyl acetate was added and extracted. 2.5 mass parts of 48% sodium hydroxide aqueous solution, 15 mass parts of ethanol, and 15 mass parts of water were added to the oily substance obtained by distilling a solvent off under reduced pressure under reduced pressure, the external temperature was set to 75 degreeC, and it stirred for 2 hours. Thereafter, 4 parts by mass of 12N hydrochloric acid was added, followed by 100 parts by mass of water.

The mixture was extracted with 30 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Then, 2.2 mass parts of the following intermediate products D were obtained by producing by silica gel column chromatography (hexane / ethyl acetate = 7/3).

2.2 parts by mass of this intermediate product, 0.7 parts by mass of hydroxyamine hydrochloride, 1.2 parts by mass of potassium acetate and 20 parts by mass of ethanol were placed in a 100 ml eggplant flask and refluxed for 2 hours. After the reaction was completed, 100 parts by mass of water were added, extracted with 80 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Then, 0.5 mass part of pyridine and 20 mass parts of acetonitrile were added, the external temperature was set to 0 degreeC, and the solution of 0.5 mass part of acetyl chloride and 5 mass parts of acetonitrile was added over 10 minutes with the dropping funnel. Thereafter, the mixture was stirred for 1 hour, 100 parts by mass of water was added, extraction was performed with 30 parts by mass of ethyl acetate, and the solvent was distilled off under reduced pressure to obtain 0.84 parts by mass (yield 18%) of an oily compound (Compound Example 4).

The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). 9.05 (t, 1H), 7.92 (q, 2H), 7.71-7.62 (m, 1H), 7.58-7.50 (m, 1H), 7.45 (dd, 1H), 5.84-5.70 (m, 1H), 5.17- 5.01 (m, 1H), 3.78-3.71,3.58-3.49 (m, 1H), 3.32 (dd, 1H), 2.92 (dd, 1H), 2.77-2.66 (m, 1H), 2.36 (s, 3H), 2.34-2.27 (m, 1H)

Compound Example 4

(Synthesis Example 4)

Synthesis of Compound 7

11 parts by mass of sodium hydride (mineral oil removed) was placed in a 300 ml three-necked flask, and the mixture was changed to a nitrogen atmosphere, and then 70 parts by mass of THF and 40 parts by mass of dimethylacetoamide were added. Next, 48.5 mass parts of diethyl carbonates were added.

The external temperature was set at 50 ° C., and a solution of 30 parts by mass of α-tetrarone and 45 parts by mass of THF was added over 1 hour from the dropping funnel. Then stirred for 1 hour.

Then, the solution of 30.2 parts by mass of allyl bromide and 30 parts by mass of THF was added over 1 hour from the dropping funnel. After that, the mixture was stirred for 1 hour, 300 parts by mass of water was added, and 100 parts by mass of ethyl acetate was added and extracted. 33 mass parts of 48% sodium hydroxide aqueous solution, 80 mass parts of ethanol, and 80 mass parts of water were added to the oily substance obtained by distilling a solvent of the organic layer under reduced pressure distillation, the external temperature was set to 75 degreeC, and it stirred for 2 hours. Thereafter, after adding 90 parts by mass of 12N hydrochloric acid, 1000 parts by mass of water was added. The mixture was extracted with 100 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Then, 17.5 parts by mass of the following intermediate product E were obtained by producing by silica gel column chromatography (hexane / ethyl acetate = 9/1).

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17.5 mass parts of this intermediate product, 18 mass parts of hydroxyamine hydrochloride, 27 mass parts of potassium acetate, and 80 mass parts of ethanol were put into a 200 ml eggplant flask, and it refluxed for 2 hours. After the reaction was completed, 300 parts by mass of water were added, extracted with 80 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Subsequently, 8 parts by mass of pyridine and 50 parts by mass of acetonitrile were added, the external temperature was set to 0 ° C, and a solution of 7 parts by mass of acetyl chloride and 30 parts by mass of acetonitrile was added over a dropping funnel over 30 minutes. Then, it stirred for 1 hour, added 500 mass parts of water, extracted with 50 mass parts of ethyl acetate, and distilled off the solvent under reduced pressure, 16 mass parts (yield 48%) of oily compounds (compound example 7) were obtained.

The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). 8.14 (d, 1H), 7.34 (t, 1H), 7.25 (d, 1H), 7.18 (t, 1H), 5.88-5.75 (m, 1H), 5.07 (d, 2H), 3.63-3.55 (m, 1H), 3.01-2.90 (m, 1H), 2.74-2.69 (m, 1H), 2.41-2.20 (m, 2H), 2.27 (s, 3H), 1.98-1.92 (m, 2H)

Compound Example 7

(Synthesis Example 5)

Synthesis of Compound 9

In a 300 ml three-necked flask, 7.2 parts by mass of sodium hydride (mineral oil was removed) was added to a nitrogen atmosphere, and then 40 parts by mass of THF and 30 parts by mass of dimethylacetoamide were added. Next, 26 mass parts of diethyl carbonates were added.

The external temperature was set at 50 ° C., and a solution of 20 parts by mass of α-tetrarone and 30 parts by mass of THF was added over 1 hour from the dropping funnel. Then stirred for 1 hour.

Next, a solution of 21 parts by mass of propargyl bromide and 20 parts by mass of THF was added from the dropping funnel over 1 hour. It stirred for 1 hour after that, 300 mass parts of water was added, 100 mass parts of ethyl acetate were added, and it extracted. 24.1 parts by mass of an aqueous 48% sodium hydroxide solution, 45 parts by mass of ethanol, and 50 parts by mass of water were added to the oily substance obtained by distilling off the solvent of the organic layer under reduced pressure, the external temperature was set to 75 degreeC, and it stirred for 2 hours. Thereafter, after adding 30 parts by mass of 12N hydrochloric acid, 1000 parts by mass of water was added. The mixture was extracted with 100 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Subsequently, 11 mass parts of following intermediate products F were obtained by producing by silica gel column chromatography (hexane / ethyl acetate = 9/1).

11 mass parts of this intermediate product, 7 mass parts of hydroxyamine hydrochloride, 12 mass parts of potassium acetate, and 80 mass parts of ethanol were put into a 200 ml eggplant flask, and it refluxed for 2 hours. After the reaction was completed, 300 parts by mass of water were added, extracted with 50 parts by mass of ethyl acetate, and the organic layer was dried over magnesium sulfate and distilled off under reduced pressure. Next, 5.4 mass parts of pyridine and 50 mass parts of acetonitrile were added, the external temperature was set to 0 degreeC, and the solution of 4.7 mass parts of acetyl chloride and 20 mass parts of acetonitrile was added over 30 minutes with the dropping funnel. Thereafter, the mixture was stirred for 1 hour, and 500 parts by mass of ice water was added to recrystallize and refine the obtained crystals with acetonitrile to obtain 9 parts by mass (yield 27%) of white crystals (Compound Example 9).

The product was identified by ¹ H-NMR (300 MHz: CDCl ₃ ). 8.15 (d, 1H), 7.36 (t, 1H), 7.24-7.17 (m, 2H), 3.75-3.68 (m, 1H), 3.04-2.92 (m, 1H), 2.81-2.71 (m, 1H), 2.60- 2.51 (m, 1H), 2.60-2.51 (m, 1H), 2.44-2.22 (m, 2H), 2.30 (s, 3H), 2.07-1.95 (m, 2H)

Compound Example 9

(Synthesis Example 6)

Synthesis of Acrylic Resin (B)

A mixed solution consisting of 45.1 parts by mass of methyl methacrylate, 47.3 parts by mass of methacrylic acid, 1 part by mass of azoisovaleronitrile, and 215 parts by mass of propylene glycol monomethyl ether in a reaction vessel at 90 ° C. under a nitrogen gas atmosphere for 3 hours. Dropped over. After dropping, the mixture was reacted for 4 hours to obtain an acrylic resin (b).

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Then, 35.9 parts by mass of glycidyl methacrylate, 0.2 parts by mass of hydroquinone monomethyl ether, and 1 part by mass of triphenylphosphine were added to the obtained acrylic resin (b) solution at 80 ° C while blowing air. Reaction for 8 hours, acryl resin (B) solution having an unsaturated group as a binder (solid dispersion value; 104, mass average molecular weight (Mw); 20,000, double bond equivalent 2.0 mmol / g, propylene glycol monomethyl ether 37 mass% solution) Got.

(Example 1)

-Preparation of Photosensitive Composition-

Based on the following composition, the photosensitive composition was prepared. In addition, methyl ethyl ketone was used as a solvent, the solid content concentration was 55 mass%, and it knead | mixed by three rolls and prepared.

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[Composition of Photosensitive Composition Solution]

Barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30)

Binder represented by a following formula (A) ... 40.0 mass parts

2,2-bis (4-glycidylphenyl) propane (thermocrosslinking agent) 15.7 parts by mass

Dipentaerythritol hexaacrylate ... 16.0 parts by mass

Compound Example 1 (photopolymerization initiator) ... 2.0 parts by mass

Hydroquinone monomethyl ether ... 0.056 parts by mass

Dicyandiamide (amine thermosetting agent) ... 0.77 parts by mass

Isocyanuric acid adduct of 2MAOK (2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, manufactured by Shikoku Kogyo Kogyo Co., Ltd. 0.47 parts by mass

However, in said Formula (A), n is about 6-7.

Preparation of Photosensitive Film

The obtained photosensitive composition was apply | coated and dried on 20-micrometer-thick PET (polyethylene terephthalate) film as said support body, and it dried, and formed the photosensitive layer of a film thickness of 30 micrometers. Then, it laminated | stacked by the polypropylene film lamination of 12 micrometers thickness as said protective film on the said photosensitive layer, and produced the photosensitive film.

-Formation of permanent patterns-

Preparation of Photosensitive Laminates

Next, as the base material, a chemical polishing treatment was performed on the surface of the copper-clad laminate (without through hole and copper thickness of 12 µm) of the completed wiring formation as a printed board. On the copper clad laminate, the photosensitive layer of the photosensitive film is brought into contact with the copper clad laminate, and the protective film in the photosensitive film is peeled off, and laminated using a vacuum laminating machine (Nipchi Motor Co., Ltd., VP130). The photosensitive laminated body by which the said copper clad laminated board, the said photosensitive layer, and the said polyethylene terephthalate film (support) were laminated | stacked in this order was prepared.

The crimping conditions were made into a vacuum time of 40 seconds, a crimping temperature of 70 degreeC, a crimping pressure of 0.2 MPa, and a pressurizing time of 10 seconds.

-Exposure Process-

With respect to the photosensitive layer in the prepared photosensitive laminated body, a laser exposure apparatus is used on the polyethylene terephthalate film (support) side to irradiate laser light of 405 nm so as to obtain a pattern in which holes having different diameters are formed. Then, a part of the region of the photosensitive layer was cured.

-Development Process-

After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate, and an aqueous solution of 1% by mass of sodium carbonate was used as an alkali developing solution on the entire surface of the photosensitive layer on the copper clad laminate, and 30 ° C. The shower was developed for 60 seconds at, and the uncured area was dissolved and removed. Thereafter, the mixture was washed with water and dried to form a permanent pattern.

-Hardening Process

The whole surface of the photosensitive laminated body in which the said permanent pattern was formed was heat-processed at 160 degreeC for 60 minutes, the surface of the permanent pattern was hardened, and the film strength was raised. When the permanent pattern was visually observed, no bubble was recognized on the surface of the permanent pattern.

Exposure sensitivity, resolution, and storage stability were evaluated about the produced photosensitive film, and pencil hardness and dielectric properties were evaluated about the formed permanent pattern. The results are shown in Table 1.

<Measurement of the shortest developing time>

In the photosensitive film prepared above, a polyethylene terephthalate film (support) was peeled from the laminate, and a 30 ° C. aqueous 1% by mass aqueous sodium carbonate solution was sprayed at a pressure of 0.15 MPa on the entire surface of the photosensitive layer on the copper clad laminate. The time required until the photosensitive layer on a copper clad laminated board was dissolved and removed from the spray start of the sodium hydrogencarbonate aqueous solution was measured, and this was made into the shortest developing time.

&Lt; Exposure sensitivity >

In a photosensitive film prepared above, and the polyethylene terephthalate film (support) side from the exposure apparatus to the O.1 mJ / cm ^{2 2 1/2} times the interval 1OOmJ / cm ² on page how the amount of the light energy different from the light used Was irradiated and exposed, and a part of area | region of the said photosensitive layer was hardened. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled from the photosensitive film, and an aqueous sodium hydrogen carbonate solution (30 ° C., 1% by mass) was obtained by the above method on the entire photosensitive layer on the copper clad laminate. The spray was carried out for twice the time of the shortest developing time, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Then, the relationship between the irradiation amount of light and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve thus obtained, the amount of light energy when the thickness of the cured area became the same as before exposure was regarded as the amount of light energy required to cure the photosensitive layer.

<Resolution>

The surface of the obtained printed wiring board of the permanent pattern formation completed was observed with an optical microscope, the minimum hole diameter without a residual film was measured and this was made into the resolution. The smaller the numerical value, the better the resolution. As a result, the resolution was 70 µm.

<Storage stability>

After the forced photo lapse of 3 days at 40 ° C. in the manufactured photosensitive film, the shortest developing time of the unexposed film was measured, and storage stability was evaluated based on the following criteria.

〔Evaluation standard〕

(Double-circle): Development time is within 30 second, and storage stability is very excellent.

(Circle): The developing time exceeds 30 second and is within 45 second, and is excellent in storage stability.

(Triangle | delta): Storage stability deteriorates in developing time exceeding 45 second and within 60 second.

X: The developing time exceeds 60 seconds, and storage stability deteriorates very much.

<Pencil hardness>

After plating was performed according to the conventional method about the printed wiring board of the said permanent pattern formation completion, water-soluble flux process was performed. Then, it was immersed three times in the solder bath set to 260 degreeC over 5 second, and the flux was removed by water washing. And about the permanent pattern after the said flux removal, pencil hardness was measured based on JISK-5400.

As a result, the pencil hardness was 5H or more. Moreover, when visual observation was performed, peeling, swelling, and discoloration of the cured film in the said permanent pattern were not recognized.

Measurement of Dielectric Properties

Dielectric properties and dielectric loss tangents at 1 GHz were measured at 25 ° C. using a LCR meter manufactured by Azident Technology Inc. and a 4291A solid electrode.

(Example 2)

In Example 1, except having changed the photoinitiator into the compound example 3 from the compound example 1, the photosensitive composition was prepared like Example 1, and the photosensitive film and the photosensitive laminated body were prepared like Example 1, Formed a permanent pattern.

In the same manner as in Example 1, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 1.

(Example 3)

In Example 1, except having changed the photoinitiator into the compound example 4 from the compound example 1, the photosensitive composition was prepared like Example 1, and the photosensitive film and the photosensitive laminated body were prepared like Example 1, Formed a permanent pattern.

In the same manner as in Example 1, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 1.

(Example 4)

In Example 1, except having changed the photoinitiator into the compound example 7 from the compound example 1, the photosensitive composition was prepared like Example 1, and the photosensitive film and the photosensitive laminated body were prepared like Example 1, Formed a permanent pattern.

In the same manner as in Example 1, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 1.

In addition, the photoinitiator irradiated the obtained photosensitive layer with the light of wavelength 405nm, and confirmed that there was a 5-membered ring in the decomposition | disassembly product.

(Example 5)

In Example 1, except having changed the photoinitiator into the compound example 9 from the compound example 1, the photosensitive composition was prepared like Example 1, and the photosensitive film and the photosensitive laminated body were prepared like Example 1, Formed a permanent pattern.

In the same manner as in Example 1, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 2.

(Example 6)

In Example 1, 20 mass parts of acrylic resin (B) which has 40.0 mass parts of binders represented by the said structural formula (A) in the photosensitive composition, 20.0 mass parts of binders represented by the said structural formula (A), and the unsaturated group obtained by the said synthesis example 6 Except having changed to negative, the photosensitive composition was prepared like Example 1, the photosensitive film and the photosensitive laminated body were prepared like Example 1, and the permanent pattern was formed.

In the same manner as in Example 1, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 2.

(Example 7)

In Example 6, except having changed the photoinitiator into the compound example 3 from the compound example 1, the photosensitive composition was prepared like Example 6, and the photosensitive film and the photosensitive laminated body were prepared like Example 6, and are permanent Formed a pattern.

In the same manner as in Example 6, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 2.

(Example 8)

In Example 6, except having changed the photoinitiator into the compound example 4 from the compound example 1, the photosensitive composition was prepared like Example 6, and the photosensitive film and the photosensitive laminated body were prepared like Example 6, Formed a permanent pattern.

In the same manner as in Example 6, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 2.

(Example 9)

In Example 6, the photosensitive composition was prepared like Example 6 except having changed the photoinitiator from the compound example 1 to the compound example 7, The photosensitive film and the photosensitive laminated body were prepared like Example 6, Formed a permanent pattern.

In the same manner as in Example 6, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 3.

(Example 10)

In Example 6, except having changed the photoinitiator into the compound example 9 from the compound example 1, the photosensitive composition was prepared like Example 6, and the photosensitive film and the photosensitive laminated body were prepared like Example 6, Formed a permanent pattern.

In the same manner as in Example 6, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 3.

(Example 11)

In Example 6, evaluation of exposure sensitivity, resolution, and storage stability was performed about the photosensitive composition and the photosensitive film which were produced similarly to Example 1 except having changed the exposure apparatus into the pattern forming apparatus demonstrated below. Pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 3.

<< pattern forming apparatus >>

As the light irradiation means, the haptic laser light source described in Japanese Patent Application Laid-Open No. 2005-258431 and a micromirror array in which 1024 micromirrors 58 are arranged in the main scanning direction shown in the schematic diagram in FIG. In an arrangement of 768 sets in the direction, having a DMD 36 controlled to drive only 1024 x 256 rows, and an exposure head 30 having an optical system for forming the light shown in FIGS. 5A and 5B onto the photosensitive film. One pattern forming apparatus 10 was used.

As the set angle of inclination of each exposure head 30, that is, each DMD 36, an angle slightly larger than the angle θ _ideal of exactly double exposure using a micromirror 58 of 1024 rows x 256 rows that can be used is adopted. did. This angle θ _ideal is obtained by tilting the number N of exposures in N, the number s in the column direction of the usable micromirrors 58, the spacing p in the column direction of the usable micromirrors 58, and the exposure head 30. Regarding the pitch δ of the scan line formed by the micromirror in the state, Equation 1,

spsinθ _ideal ≥Nδ (Equation 1)

Lt; / RTI &gt; In the DMD 36 according to the present embodiment, as described above, a plurality of micromirrors 58 having the same vertical and horizontal arrangement intervals are arranged in a rectangular lattice shape.

pcosθ _ideal = δ (Equation 2)

Equation 1 is

stanθ _ideal = N (Equation 3)

Since s = 256 and N = 2, the angle θ _ideal is about 0.45 °. Therefore, for example, as the set tilt angle θ, 0.50 ° is adopted.

First, the state of the exposure pattern of the to-be-exposed surface was investigated in order to correct the dispersion | variation and the exposure nonuniformity in the double exposure. The results are shown in FIG. In FIG. 16, from the usable micromirror 58 of the DMD 36 which the exposure heads 30 ₁₂ and 30 ₂₁ projected on the to-be-exposed surface of the photosensitive film 12 with the stage 14 stopped. The pattern of the light spot group of was shown. Further, when the stage 14 is moved while the stage 14 is moved while the pattern of the light spot group as shown in the upper end is shown at the lower end, the exposure area formed on the exposed surface is exposed to the exposure area 32. ₁₂ and 32 ₂₁ ). In addition, in FIG. 16, although the exposure pattern of the one-column of the usable micromirror 58 was divided into the exposure pattern by the pixel column group A, and the exposure pattern by the pixel column group B for the convenience of description, the actual pino is shown. The exposure pattern on a light surface overlaps these two exposure patterns.

As shown in Fig. 16, as a result of the deviation from the ideal state of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ , both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B In an exposure area overlapping on a coordinate axis orthogonal to the scanning direction of the exposure heads of the exposure areas 32 ₁₂ and 32 ₂₁ , it can be seen that an overexposure area is generated rather than an ideal double exposure state.

A pair of slits 28 and a photodetector are used as the light spot position detecting means, and the positions of the light spots P (1,1) and P (256,1) in the exposure area 32 ₁₂ with respect to the exposure head 30 ₁₂ . For the exposure head 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 inclination angle of the straight line connecting them and the scanning direction of the exposure head are connected. This angle was measured.

Equation 4 below using the actual tilt angle θ '

ttanθ '= N (Equation 4)

The natural number T closest to the value t satisfying the relationship of was derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ . T = 254 was obtained for the exposure head 30 ₁₂ and T = 255 was derived for the exposure head 30 ₂₁ , respectively. As a result, in Fig. 17, the micromirrors constituting the portions 78 and 80 covered with diagonal lines were identified as micromirrors not used during the present exposure.

Subsequently, the micromirrors corresponding to light points other than the light points constituting the areas 78 and 80 covered with diagonal lines in Fig. 17 are similarly covered with the area 82 covered with diagonal lines and intersecting parallel lines in Fig. 17. The micromirror corresponding to the light point which comprises the area | region 84 was specified, and was added as a micromirror not used at the time of this exposure.

With respect to the micromirror specified as not being used at the time of these exposures, a signal which is always set to an off state angle is sent by the above-mentioned drawing part small control means so that these micromirrors do not substantially participate in exposure. Controlled.

As a result, of the exposed area (32 ₁₂ and 32 _21), in each area of Pinot other than light surface overlapping the exposure area in the coupling area between the head of the upper formed of a plurality of the exposure heads, the ideal double exposure excessive with respect to the exposure of the The total area of the area | region to become and the area | region to become underexposure can be minimized.

(Example 12)

In Example 3, the photosensitive composition was prepared like Example 3 except having changed the addition amount of the photoinitiator into 0.08 mass part, The photosensitive film and the photosensitive laminated body were prepared like Example 3, and a permanent pattern was prepared. Formed.

In the same manner as in Example 3, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 3.

(Example 13)

As the substrate, a chemical polishing treatment was performed on the surface of the copper clad laminate (without through hole and copper thickness of 12 µm) of the completion of wiring formation as a printed circuit board. On the copper clad laminate, the photosensitive composition of Example 1 was applied by a screen printing method to a thickness of 30 μm after drying using a 120 mesh Tetron screen, and dried at 80 ° C. for 15 minutes using a hot air circulation dryer. The photosensitive layer was formed, and the photosensitive laminated body by which the said copper clad laminated board and the said photosensitive layer were laminated | stacked in this order was prepared.

The photosensitive laminate was subjected to laser exposure in the same manner as in Example 1, to evaluate exposure sensitivity, resolution, and storage stability, and to evaluate the pencil hardness and dielectric properties of the formed permanent pattern. The results are shown in Table 4.

(Example 14)

In Example 1, instead of the said pattern forming apparatus, the glass negative mask which has such a pattern was manufactured separately, this negative mask was made to contact on the photosensitive laminated body, and it exposed with the exposure amount of 26mJ / cm < ² > by ultra-high pressure mercury lamp. After that, development was carried out in the same manner as in Example 1, and the resolution and storage stability were evaluated in the same manner as in Example 1, and the pencil hardness and dielectric properties were evaluated for the formed permanent pattern. Done. The results are shown in Table 4.

(Comparative Example 1)

In Example 1, except having changed the photoinitiator into Irgacure 819 (made by Chiba Specialty Chemicals) from compound example 1, the photosensitive composition was prepared like Example 1, and it carried out similarly to Example 1, and the photosensitive film and the photosensitive laminated body. A sieve was prepared and the permanent pattern was formed.

In the same manner as in Example 1, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 5.

(Comparative Example 2)

In Example 1, the photosensitive composition was prepared like Example 1 except having changed the photoinitiator into CGI325 (made by Chiba Specialty Chemicals) from compound example 1, and it carried out similarly to Example 1, and it carried out similarly to the photosensitive film and the photosensitive laminated body. A sieve was prepared and the permanent pattern was formed.

In the same manner as in Example 1, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 5.

(Comparative Example 3)

In Example 1, the photosensitive composition was prepared like Example 1 except having changed the photoinitiator from the compound example 1 to the reference compound example 1 represented by the following structural formula, and it carried out similarly to Example 1, and the photosensitive film and the photosensitive laminated body. A sieve is prepared and a permanent pattern is formed.

In the same manner as in Example 1, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 5.

Reference Compound Example 1

(Comparative Example 4)

In Example 1, except having changed the photoinitiator into Irgacure OXE-01 (made by Chiba Specialty Chemicals) from compound example 1, the photosensitive composition was prepared like Example 1, and it carried out similarly to Example 1, and the photosensitive film And the photosensitive laminated body was prepared and the permanent pattern was formed.

In the same manner as in Example 1, exposure sensitivity, resolution, and storage stability were evaluated for the photosensitive film prepared above, and pencil hardness and dielectric properties were evaluated for the formed permanent pattern. The results are shown in Table 5.

As a result of Tables 1-5, the photosensitive layer formed using the photosensitive composition of Examples 1-14 using the photoinitiator of this invention is excellent in the resolution and storage stability, and is the surface of the hardened layer in a permanent pattern. The hardness and dielectric properties were also found to be good. In particular, in Examples 1-12 which produced the photosensitive film and performed laser exposure, it turned out that it is excellent also in exposure sensitivity.

On the other hand, the photosensitive composition of Comparative Examples 1-4 which did not use the photoinitiator of this invention, and the photosensitive layer in the photosensitive film manufactured using this photosensitive composition have at least any of exposure sensitivity, a resolution, and storage stability. One is inferior.

Since the photoinitiator of the present invention can further improve the sensitivity so as to cope with laser exposure, and can satisfactorily maintain the resolution, storage stability, surface hardness, and dielectric properties, the printed wiring board (multilayer wiring Protective films of substrates, build-up wiring boards, etc.), interlayer insulating films, solder resist patterns, and display members such as color filters, pillars, ribs, spacers, partitions, holograms, micro machines, proofs, adhesives, thermosetting compositions And photosensitive compositions for permanent pattern formation.

The photosensitive composition of the present invention, the photosensitive film and the photosensitive laminate using the photosensitive composition use the photopolymerization initiator of the present invention, so that the sensitivity can be further improved, and resolution, storage stability, surface hardness, and dielectric The property can be kept good. For this reason, the protective film of a printed wiring board (multilayer wiring board, a buildup wiring board, etc.), an interlayer insulation film, and a soldering resist pattern, and display members, such as a color filter, a pillar material, a rib material, a spacer, a partition, a hologram, a micro It can be used widely for permanent pattern formation of a machine, a proof, etc., and can be used especially for permanent pattern formation of a printed circuit board.

Since the permanent pattern method of this invention uses the photosensitive laminated body of this invention, for various patterns formation, such as a permanent pattern, such as a protective film, an interlayer insulation film, and a soldering resist pattern, a color filter, a pillar material, a rib material, a spacer, It can use suitably for manufacture of liquid crystal structure members, such as a partition, manufacture of a hologram, a micromachine, a proof, etc., and can especially use for formation of the permanent pattern of a printed circuit board.

Claims (10)

It is a compound represented by following General formula (6), The photoinitiator characterized by the above-mentioned.

(However, in the general formula (6), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ^{26 each} independently represent a hydrogen atom, an aliphatic group which may have a substituent, and an aryl which may have a substituent). A ⁹ represents any one of a single bond, an oxygen atom, a sulfur atom, NHCO, and CONH, and Y ⁴ represents any of the groups shown below.

G represents either the aliphatic group which may have a substituent, and the aryl group which may have a substituent. J represents either a hydrogen atom, an aliphatic group which may have a substituent, and an aryl group which may have a substituent. R ²¹ and R ²² , R ²³ and R ²⁴ , and R ²⁵ and R ²⁶ may be bonded to each other to form a ring. However, one of the fourth and fifth atoms counted from the nitrogen atom constituting the bond of the nitrogen atom and oxygen atom cleaved by light to form a free group has an atom adjacent to the other side of the nitrogen atom and an aromatic group And at least one of an ethylenically unsaturated bond and an acetylenically unsaturated bond in Y ⁴ except for an unsaturated bond which may be used.) The compound represented by the formula (6) according to claim 1, wherein the fourth atom is counted from the nitrogen atom constituting the bond of the nitrogen atom and the oxygen atom which are cleaved by light to form a free group, and the nitrogen atom and A photopolymerization initiator having an atom adjacent to the other side and at least one of an ethylenically unsaturated bond and an acetylene unsaturated bond in Y ⁴ except for an unsaturated bond which may have an aromatic group. The photosensitive composition containing (A) binder, (B) polymeric compound, (C) photoinitiator of Claim 1, and (D) thermal crosslinking agent. (C) Content of photoinitiator is 0.1-15 mass%, The photosensitive composition of Claim 3 characterized by the above-mentioned. It has a support body and the photosensitive layer which consists of a photosensitive composition of Claim 3 on the said support body, The photosensitive film characterized by the above-mentioned. It has a photosensitive layer which consists of a photosensitive composition of Claim 3 on a base body, The photosensitive laminated body characterized by the above-mentioned. The photosensitive layer was formed of the photosensitive film of Claim 5, The photosensitive laminated body of Claim 6 characterized by the above-mentioned. Exposure to the photosensitive layer in the photosensitive laminated body of Claim 6 is included, The permanent pattern formation method characterized by the above-mentioned. The permanent pattern forming method according to claim 8, wherein the exposure is performed using laser light having a wavelength of 350 to 415 nm. A permanent pattern is formed by the permanent pattern formation method of Claim 8. The printed circuit board characterized by the above-mentioned.

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