JP2006285178A - Photosensitive permanent resist film and permanent pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive permanent resist film which ensures a good film of a permanent pattern covering angular portions of a conductor circuit formed on a printed wiring board, high flatness of the whole surface of the permanent pattern, high definition and excellent production efficiency, and to provide a permanent pattern forming method using the photosensitive permanent resist film. <P>SOLUTION: The photosensitive permanent resist film has a first photosensitive layer and a second photosensitive layer in this order on a support, and satisfies the formula: η<SB>1</SB>>η<SB>2</SB>wherein η<SB>1</SB>represents a melt viscosity of the first photosensitive layer and η<SB>2</SB>represents a melt viscosity of the second photosensitive layer at a lamination temperature in lamination on a substrate. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention refers to a photosensitive permanent resist film (hereinafter referred to as a “photosensitive solder resist film”) used for forming a permanent pattern on a surface where a convex portion on a substrate is exposed, and forming an interlayer insulating film on a multilayer substrate. ) And a method for forming a permanent pattern, in particular, a photosensitive layer (hereinafter referred to as a “photosensitive solder resist layer”) on a surface of the printed circuit board having a conductor circuit or the like on the surface of the conductor circuit or between layers of the multilayer substrate. The photosensitive solder resist layer is used to laminate the photosensitive solder resist layer, or a photosensitive composition (hereinafter referred to as “photosensitive solder resist composition”) solution is applied and the photosensitive. A method of forming a permanent pattern or an interlayer insulating film by laminating a solder resist layer and curing by exposure, and a permanent pattern formed by the method of forming a permanent pattern. A printed wiring board having over emissions and the interlayer insulating layer film.

Generally, a printed wiring board having a conductor circuit is formed with a permanent pattern such as a solder resist or an interlayer insulating film on the surface of the printed wiring board having the conductor circuit in order to protect the conductor circuit from oxidation and peeling. Has been.
In recent printed wiring boards, as electronic devices have become smaller and lighter and have higher performance, there is an increasing need to increase the density of conductive circuits, etc. A high-definition permanent pattern is required for forming a solder resist or forming an interlayer resin insulation layer of a multilayer printed wiring board. As a method for forming such a permanent pattern, a permanent pattern forming method using a liquid photo solder resist in which a photosensitive solder resist composition solution is applied and the photosensitive solder resist layer is laminated is often used.

As a permanent pattern forming method using this liquid photo solder resist, a liquid photo solder resist is directly applied to the conductor circuit surface side of the printed wiring board to form a laminate having a photosensitive solder resist layer, and through a photomask or the like. There is a method of forming a permanent pattern such as a solder resist by developing the photosensitive solder resist layer after exposure and then curing the photosensitive solder resist layer.
As a method for continuously and productively forming such a permanent pattern, a coating method by curtain coating has been proposed (see Patent Document 1). However, in the case of the curtain coating method, the following problems are pointed out.

That is, the viscosity of the liquid photo solder resist that can be used in this curtain coating is generally 10,000 cps or less, and is usually suitable for use in a very low viscosity range of 10 to 2,000 cps. When a low-viscosity coating solution is used, the liquid photo solder resist can enter the corners of fine conductor circuits, but the liquid photo solder resist is dried and cured at the corners of the conductor circuits. In the meantime, the photosensitive solder resist layer becomes extremely thin or the continuity is impaired, and there is a problem that a permanent pattern having a sufficient thickness cannot be obtained at the corners of the conductor circuit.
As shown in FIG. 7, the corner portion indicated by arrow A in the permanent pattern applied and formed on the surface side of the conductor circuit 4 of the printed wiring board 5 becomes thin, and the thickness cannot be formed uniformly. is there.
The problem of the thickness in the curtain coating is caused by the fact that the viscosity of the liquid photo solder resist is too low, and the same problem occurs in the “printed wiring board manufacturing method” described in Patent Documents 2 and 3. Arise.

  Thus, if the corners of the conductor circuit are extremely thin or exposed, the original function of the permanent pattern is impaired, the electrical insulation of the conductor circuit is low, and the printed wiring board as a product is There arises a problem that reliability is impaired.

  Further, in the case of the curtain coating method, the height of the conductor circuit and the permanent pattern formed between them is different, so that, for example, the density is increased on the printed wiring board, resulting in a very large number of pins. When a minute electronic component is mounted, there is a problem that it is not possible to satisfactorily bond to each conductor circuit. That is, when the height of the permanent pattern is higher than that of the conductor circuit, the chip portion cannot be mounted well, and conversely, when the height of the permanent pattern is low, a soldering failure occurs.

  In order to improve the problem of uniformity and flatness of the thickness of the photosensitive solder resist layer, a coating method is proposed in which a liquid photo solder resist is applied many times by a screen printing method to form a photosensitive solder resist layer. (See Patent Document 4). However, in the case of the coating method in which coating is performed many times, more coating steps are required than in one coating, and the production efficiency is lowered. In addition, there is a problem that accurate positioning is required so that pattern displacement does not occur during each application, and work efficiency is lacking.

On the other hand, as a permanent pattern forming method, as shown in FIG. 1, a photosensitive solder resist layer 2 comprising a first photosensitive solder resist layer 2a and a second photosensitive solder resist layer 2b for forming a permanent pattern is formed. A permanent pattern forming method (see Patent Documents 5 and 6) using a photosensitive solder resist film laminated on a support 1 and further laminated with a protective film 3 is also known.
As shown in FIG. 8, the permanent pattern forming method includes laminating the photosensitive solder resist film on the side of the conductor circuit 4 of the printed wiring board 5 on which the conductor circuit 4 is formed, and irradiating with light. In this method, the photosensitive solder resist layer is cured to form a permanent pattern. In the case of Patent Document 5, the photosensitive solder resist layer is laminated by providing fluidity by the outermost photosensitive solder resist layer abutting on the conductor circuit 4 side, and generating bubbles during the lamination. In the case of Patent Document 6, the two layers have different properties, thereby improving the storage stability from production to use of the photosensitive solder resist film. It is. In the case of these permanent pattern forming methods, the thickness is maintained as indicated by an arrow B, and the problem of the thickness of the corner is improved, but the portion covering the conductor circuit 4 is high, and the portion covering other than the conductor circuit 4 is It becomes low and a large unevenness | corrugation will arise in a permanent pattern compared with the said coating method. In the photosensitive solder resist film having two photosensitive solder resist layers (see Patent Documents 5 and 6), there is no disclosure or suggestion about planarization of the permanent pattern.
Further, in the case of the permanent pattern forming method, as shown in FIG. 9, a via hole opening 6 is provided in the region of the conductor circuit 4 for mounting electronic components, or the conductor circuit 4 as shown in FIG. In the case of a very narrow pattern having a width of about 20 μm, a permanent pattern cannot be formed on the conductor circuit, so that there is a pattern that exposes the pattern itself. The part becomes high. For this reason, there is a problem that, when an electronic component is mounted in the opening, a good bonding between the electronic component and the conductor circuit 4 cannot be obtained. For this reason, it is necessary to flatten the protruding portion, and it must be removed by polishing, washing, finishing, or the like before mounting the electronic component or the like, resulting in a reduction in production efficiency.

JP 54-82073 A JP-A-63-252498 Japanese Unexamined Patent Publication No. 63-200594 JP-A-5-191020 JP 61-80236 A Japanese Patent No. 2691130

  In order to improve the above problems, the present invention has a good permanent pattern film covering the corners of the conductor circuit formed on the printed wiring board, and has a peripheral portion such as a via hole and a portion other than the conductor circuit. Provided is a photosensitive solder resist film and a permanent pattern forming method having high flatness, high definition and excellent production efficiency on the entire surface of the permanent pattern to be covered, and a printed wiring board having a permanent pattern using the permanent pattern forming method The purpose is to provide.

Means for solving the problems are as follows. That is,
<1> A first photosensitive solder resist layer having a first photosensitive solder resist layer and a second photosensitive solder resist layer in this order on a support and laminating temperature when laminating on a substrate. ₁ the melt viscosity of _eta, when the melt viscosity of the second photosensitive solder resist layer was eta _2, the following formula, eta _1> eta _2, a photosensitive solder resist film and satisfies the.
<2> The melt viscosity η ₁ is 400 to 5,000 Pa · s at a laminate temperature of 70 to 100 ° C., and the melt viscosity η ₂ is 50 to 300 Pa · s at a laminate temperature of 70 to 100 ° C. The photosensitive solder resist film according to <1>, wherein the melt viscosity η ₃ at room temperature of the first photosensitive solder resist layer and the second photosensitive solder resist layer is 1 × 10 ⁵ Pa · s or more.
<3> A first photosensitive solder resist layer and a second photosensitive solder resist layer are provided on a support, and the first photosensitive solder resist layer includes at least an alkali-soluble photocrosslinkable polymer. <1> to <2> comprising the first photosensitive solder resist composition, wherein the second photosensitive solder resist layer comprises the second photosensitive solder resist composition containing at least an alkali-soluble photocrosslinkable oligomer. It is the photosensitive soldering resist film in any one of these.
<4> The mass average molecular weight of the alkali-soluble photocrosslinkable polymer is 2 × 10 ⁴ to 1 × 10 ⁵ , and the mass average molecular weight of the alkali-soluble photocrosslinkable oligomer is 1 × 10 ³ to 1 × 10 ⁴ . It is the photosensitive soldering resist film as described in said <3>.
<5> The above <1>, wherein the first photosensitive solder resist composition and the second photosensitive solder resist composition contain a polymerizable compound, a photopolymerization initiator, an epoxy curing agent, a curing accelerator, an inorganic filler, and a colorant. > To the photosensitive solder resist film according to any one of <4>.
<6> The alkali-soluble photocrosslinkable polymers contained in the first photosensitive solder resist composition and the second photosensitive solder resist composition are different types of alkali-soluble photocrosslinkable polymers, and the other components are The photosensitive solder resist film according to any one of <3> to <5>, which is the same as each other.
<7> Any one of <1> to <6>, wherein the first photosensitive solder resist layer has a thickness of 1 to 50 μm, and the second photosensitive solder resist layer has a thickness of 1 to 50 μm. Is a photosensitive solder resist film.
<8> When the thickness of the first photosensitive solder resist layer is S1 and the thickness of the second photosensitive solder resist layer is S2, the following formula, S1 / S2 is 1/9 to 9/1. It is the photosensitive soldering resist film in any one of said <1> to <7>.
<9> on a support, a photosensitive solder resist according have three or more layers of photosensitive solder resist layer having different melt viscosities, the items <1> the melt viscosity of the outermost layer is eta ₂ to <2> It is a film.
<10> The photosensitive solder resist film according to any one of <1> to <9>, which has a protective film on a support.

<11> The first photosensitive solder resist composition and the second photosensitive solder resist composition according to any one of <3> to <6> are applied to a surface of a substrate, dried and photosensitive. After forming a soldering resist layer laminated body, it is exposed and developed, It is a permanent pattern formation method characterized by the above-mentioned.
<12> A photosensitive solder resist layer laminated by laminating the photosensitive solder resist film according to any one of <1> to <10> on a surface of the substrate having a convex portion where the convex portion is exposed. A method for forming a permanent pattern is characterized in that a body is formed, and then exposed and developed.
<13> If the height of the convex portion from the substrate surface is T1 (μm), and the thickness of the first photosensitive solder resist layer and the second photosensitive solder resist layer is T2 (μm), the following formula: It is the permanent pattern formation method in any one of said <11> to <12> which exposes and develops with respect to the photosensitive soldering resist layer laminated body which satisfy | fills T1 <T2.
<14> The permanent pattern forming method according to any one of <11> to <13>, wherein the convex portion is a conductor circuit in the printed wiring board.
<15> The method for forming a permanent pattern according to any one of <11> to <14>, wherein the substrate is a printed wiring board having at least one of a through hole and a via hole.
<16> The method for forming a permanent pattern according to any one of <11> to <15>, wherein the exposure is performed with a laser beam.
<17> After the light is modulated by the light modulating unit having n number of pixel parts for receiving and emitting the light from the light irradiating unit, exposure is performed on the exit surface of the pixel unit. The permanent pattern forming method according to any one of <11> to <16>, wherein the permanent pattern forming method is performed using light that has passed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion are arranged.
<18> The method for forming a permanent pattern according to <17>, wherein the aspherical surface is a toric surface.
<19> The <17> to <18, wherein the light modulation unit is capable of controlling any less than n pixel elements arranged continuously from n pixel elements in accordance with pattern information. > The permanent pattern forming method according to any one of the above.
<20> The method for forming a permanent pattern according to any one of <17> to <19>, wherein the light modulator is a spatial light modulator.
<21> The method for forming a permanent pattern according to <20>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<22> The method for forming a permanent pattern according to any one of <11> to <21>, wherein the exposure is performed through an aperture array.
<23> The method for forming a permanent pattern according to any one of <11> to <22>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive solder resist layer.
<24> The permanent pattern forming method according to any one of <17> to <23>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
<25> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects the laser beams irradiated from the plurality of lasers and couples the laser beams to the multimode optical fiber. The permanent pattern forming method according to any one of <17> to <24>.
<26> The method for forming a permanent pattern according to <25>, wherein the wavelength of the laser beam is 395 to 415 nm.
<27> A printed wiring board, wherein the printed wiring board has a permanent pattern, and the permanent pattern is formed by the permanent pattern forming method according to any one of <11> to <26>. .

  According to the present invention, the solder resist film covering the corners of the conductor circuit formed on the printed wiring board is good, and the flatness of the entire permanent pattern covering the peripheral part such as the via hole and the part other than the conductor circuit is good. It is possible to provide a photosensitive solder resist film and a permanent pattern forming method which are high, high definition and excellent in production efficiency, and can provide a printed wiring board having a permanent pattern using the permanent pattern forming method.

The present invention comprises a photosensitive solder resist film for permanent pattern formation, a permanent pattern forming method, and a printed wiring board having a permanent pattern formed by the permanent pattern forming method.
The said photosensitive soldering resist film is a film which has a 1st photosensitive soldering resist layer, a 2nd photosensitive soldering resist layer, a protective film, and the other layer suitably selected as needed on a support body.
There is no restriction | limiting in particular as a layer structure of the said photosensitive soldering resist film, According to the objective, it can select suitably, For example, a 1st photosensitive soldering resist layer and a 2nd photosensitive solder on a support body. A structure in which a resist layer and a protective film are laminated in this order, such as a first photosensitive solder resist layer, a second photosensitive solder resist layer, a third photosensitive solder resist layer, and a protective film on the support. Thus, there may be mentioned a configuration in which three or more photosensitive solder resist layers are laminated.
In the photosensitive solder resist film of the present invention, when two photosensitive solder resist layers are laminated, the hardness of the first photosensitive solder resist layer is made harder than that of the second photosensitive solder resist layer, and conversely, The photosensitive solder resist layer of No. 2 is made softer than the first photosensitive solder resist layer so as to have fluidity, and the photosensitive solder resist film is laminated on the substrate to form a permanent pattern on the substrate. In this case, the second photosensitive solder resist layer is used to improve the adhesion to the substrate while ensuring the uniformity of the thickness of the permanent pattern, and to form the convex portion of the convex portion formed on the substrate. Can be directly absorbed, and the surface of the laminate when the photosensitive solder resist film is laminated on the substrate can be flattened.
When three or more photosensitive solder resist layers are laminated, the surface of the laminate is similarly flattened by making the hardness of the outermost photosensitive solder resist layer softer than other photosensitive solder resist layers. Can do.
The method for forming a permanent pattern of the present invention comprises: laminating the photosensitive solder resist film on a substrate to form a photosensitive solder resist layer laminate; then exposing and developing; the first photosensitive solder resist layer; Examples include a method in which the second photosensitive solder resist layer is directly applied to the surface of the substrate, dried, exposed and developed.

(Photosensitive solder resist film)
The photosensitive solder resist film of the present invention has a first photosensitive solder resist layer and a second photosensitive solder resist layer in this order on a support, and the first solder solder resist layer at the laminating temperature when laminating on a substrate. 1 is a photosensitive solder resist film satisfying the following formula: η ₁ > η _{2 where} η _{1 is} the melt viscosity of the photosensitive solder resist layer ₁ and η ₂ is the melt viscosity of the second photosensitive solder resist layer. .
On the support, if having three or more layers of photosensitive solder resist layer having different melt viscosities, the outermost layer is preferably melt viscosity of eta _2.

The melt viscosity η ₁ is not particularly limited and may be appropriately selected depending on the purpose. For example, at a laminate temperature of 70 to 100 ° C., the melt viscosity η ₁ is 400 to 5,000 Pa · s, and the melt viscosity η ₂ is The laminating temperature is 70 to 100 ° C., and the melt viscosity η ₃ at room temperature of the first photosensitive solder resist layer and the second photosensitive solder resist layer is 1 × 10 ⁵ Pa · s or more. It is preferable that
If the melt viscosity η ₂ is less than 50 Pa · s, the fluidity is too high at the time of lamination, so that it flows out and a sufficient thickness of the resist layer after lamination may not be ensured. On the other hand, when this value exceeds 300 Pa · s, the followability is insufficient at the time of stacking the substrates, and bubbles are mixed in between the substrates, or the substrate adhesion after curing is inferior.
In the case of a photosensitive material for transfer such as a photosensitive solder resist, the adhesiveness with the substrate after lamination to the substrate is important in relation to the temperature of the hot roll during lamination (70 to 100 ° C.) and the melt viscosity, Generally, the melt viscosity of the photosensitive solder resist layer needs to be reduced to about 1 × 10 ^{2 to} 5 × 10 ³ Pa · s at the photosensitive solder resist layer temperature (70 to 100 ° C.) at the time of lamination. .
On the other hand, in order to ensure flatness, it is preferable that the melt viscosity is high. In order to laminate on an uneven substrate and maintain flatness, the melt viscosity is preferably 1 × 10 ^{2 to} 5 × 10 ³ Pa · s at the lamination temperature.
Furthermore, if the melt viscosity is too low at room temperature (or at the storage temperature), there is a problem in that the film rolls out from the edge of the film roll (edge fusion) and the storage stability is adversely affected. The melt viscosity is 1 × 10 ⁵ Pa · It is preferable that it is s or more. When storing at room temperature, it is necessary to design at 1 × 10 ⁵ Pa · s or more at room temperature.
Accordingly, the melt viscosity η ₁ of the first photosensitive solder resist layer is preferably 4 × 10 ^{2 to} 5 × 10 ³ Pa · s at (70 to 100 ° C.), and 1 × 10 ⁵ Pa · s or more at room temperature. Preferably there is. On the other hand, the melt viscosity η ₂ of the second photosensitive solder resist layer is preferably a melt viscosity smaller than the melt viscosity.
The melt viscosity of the photosensitive solder resist layer can be measured by using a melt viscosity measuring device such as Vibron (DD-III type: manufactured by Toyo Baldwin Co., Ltd.).

  The photosensitive solder resist film of this invention has a 1st photosensitive solder resist layer, a 2nd photosensitive solder resist layer, a protective film, and the other layer suitably selected as needed on a support body.

<First photosensitive solder resist layer>
The first photosensitive solder resist layer is directly laminated on the support and has a function of ensuring the uniformity of the thickness of the permanent pattern formed on the substrate by making it harder than the second photosensitive solder resist layer. There is.
The thickness of the first photosensitive solder resist layer is not particularly limited as long as it has the following relationship with the second photosensitive solder resist layer, and can be appropriately selected according to the purpose. 50 micrometers is preferable, 2-50 micrometers is more preferable, and 4-30 micrometers is especially preferable.

  When the thickness of the first photosensitive solder resist layer is S1 and the thickness of the second photosensitive solder resist layer is S2, S1 / S2 is preferably 1/9 to 9/1, More preferably, it is 6-6 / 1. If it is less than 1/9, the elasticity of the first photosensitive solder resist layer becomes weak, and a uniform uniform pattern may not be obtained as a whole. If it exceeds 9/1, the first photosensitive solder resist layer may not be obtained. The resist layer has high elasticity, fluidity is weakened, and the height of the convex portion may not be absorbed by the second photosensitive solder resist layer, and the flattening of the permanent pattern may not be obtained.

  The first photosensitive solder resist layer includes an alkali-soluble photocrosslinkable polymer, a polymerizable compound, a photopolymerization initiator, an epoxy curing agent, a curing accelerator, an inorganic filler, and a colorant, and is appropriately selected as necessary. It consists of a 1st photosensitive soldering resist composition containing another component.

-Alkali-soluble photocrosslinkable polymer-
The alkali-soluble photocrosslinkable polymer has a function as a binder, and has a function of increasing the hardness of the first photosensitive solder resist layer and adding properties as an elastic body.
The alkali-soluble refers to the property that the photosensitive solder resist composition containing it is dissolved by an alkaline developer, and specifically, if it is soluble to the extent that the desired development processing is performed. Good. The alkaline developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkali metal hydroxides such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, hydroxyethylamine, triethylamine Or an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide or a mixture thereof with a miscible organic solvent. pH is 8-14 and 0.01-10 mass% aqueous solution of these alkali agents is preferable. Among these alkaline developers, in the printed wiring board industry, 0.2 to 2 mass% sodium carbonate aqueous solution is generally used, and 1 mass% sodium carbonate aqueous solution is the most common.
An example of the development method is that the surface is leveled and the photosensitive solder resist layer is pressure-bonded to the surface of the dried copper clad laminate using a laminator while peeling off the protective film of the photosensitive solder resist film. Then, a laminate comprising a copper-clad laminate, a photosensitive solder resist layer, and a support film is prepared. The pressure bonding conditions are a laminate temperature of 70 ° C., a pressure roll temperature of 105 ° C., a pressure roll pressure of 3 kg / cm ^2, and a pressure bonding speed of 1.2 m / min.
The support film is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.1 MPa over the entire surface of the photosensitive solder resist layer on the copper-clad laminate. If the photosensitive solder resist layer on the copper clad laminate is removed after spraying for at least 60 seconds, it will be developed.
Such an alkali-soluble resin can be suitably selected from those showing a solubility of 1% by mass or more in a 1% by mass sodium carbonate aqueous solution at 30 ° C., for example.
The photocrosslinking property refers to the property that a linear polymer molecule is changed into a network having a three-dimensional network structure by photochemical reaction. It refers to a polymer that can be networked by polymerization reaction.

The alkali-soluble photocrosslinkable polymer is a resin that is soluble in a 1% aqueous sodium carbonate solution (pH = 10) containing an alkali-soluble group and a crosslinkable group involved in photopolymerization in the molecule.
There is no restriction | limiting in particular as said alkali-soluble photocrosslinkable polymer, According to the objective, it can select suitably, For example, a vinyl polymer type photocrosslinkable resin etc. are mentioned.

--Vinyl polymer photocrosslinkable resin--
The vinyl polymer photocrosslinkable resin is classified into the following types (A-1), (A-2) and (A-3), and is selected from at least one of the types.
Type (A-1): produced by reaction of (a) a carboxyl group-containing copolymer resin and (b) an epoxy group-containing unsaturated compound.
Type (A-2): (c) An epoxy group-containing copolymer resin and (d) a carboxyl group-containing unsaturated compound are subjected to an addition reaction, and (e) a polybasic acid anhydride is further converted into a hydroxyl group of the resulting product. Produced by addition reaction.
Type (A-3): produced by an addition reaction of (f) an acid anhydride group-containing copolymer resin and (g) a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule. The
In the present specification, the term “(meth) acrylate” is a general term for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.

<Type (A-1)>
The (a) carboxyl group-containing copolymer resin used for the production of the vinyl polymer type photocrosslinkable resin of the type (A-1) is one unsaturated group and at least one carboxyl group in one molecule or It is obtained by copolymerizing a compound having an acid anhydride group and at least one of (meth) acrylic acid ester and styrenes.

  The compound (a) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule having the carboxyl group-containing copolymer resin as a structural unit is (meth) acrylic acid, Include those containing two or more carboxyl groups in the molecule, such as maleic acid and itaconic acid. Also included are maleic acid, itaconic acid monoesters, or monoamides. Moreover, the half ester compound which is a reaction product of a hydroxyl group containing (meth) acrylate and a saturated or unsaturated dibasic acid anhydride is mentioned. These half ester compounds can be obtained by reacting a hydroxyl group-containing (meth) acrylate with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio.

  Examples of the hydroxyl group-containing acrylate used in the synthesis of the half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and trimethylolpropane. Examples include di (meth) acrylate, pendaerythritol tri (meth) acrylate, diventaerythritol penta (meth) acrylate, and the like.

Examples of the saturated or unsaturated dibasic acid anhydride used for the synthesis of the half ester compound include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyl nadrahydrophthalic anhydride, ethyl tetrahydro Examples thereof include phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like. Of these, (meth) acrylic acid is preferred.
These compounds having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule may be used alone or in combination of two or more.

  Examples of the (meth) acrylic acid ester that constitutes the structural unit of the carboxyl group-containing copolymer resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth). Acrylate, n-butyl (meth) 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-hydroxyethyl (meth) Acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meta ) Acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, Polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate , Β-phenoxyethoxyethyl acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meta ) Acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

Examples of the styrenes constituting the structural unit of the carboxyl group-containing copolymer resin (a) include, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, Butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc, etc.), methyl vinylbenzoate, α-methyl Examples include styrene.
The (a) carboxyl group-containing copolymer resin is composed of a compound having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule, a (meth) acrylic acid ester monomer, and styrene. It is obtained by copolymerization by a usual copolymerization method with at least one of the above classes, for example, a solution polymerization method.
In addition, (a) maleic acid monoester / styrene copolymers, maleic acid monoamide / styrene copolymers, itaconic acid monoester / styrene copolymers, and itacon included in the carboxyl group-containing copolymer resin. In the case of acid monoamide / styrene copolymers, obtain by polymer reaction of maleic anhydride / styrene copolymers or itaconic anhydride / styrene copolymers with alcohols or primary or secondary amines, respectively. Can do.

Examples of the alcohols used for the polymer reaction with the maleic anhydride include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, pentanol, hexanol, and cyclohexanol. Preferable examples include methoxyethanol, ethoxyethanol, methoxypropanol, and ethoxypropanol.
Examples of the primary amines include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, and 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-bromophenethylamine, 2- (2-chlorophenyl) ethylamine, 2- (3-Chlorophenyl) ethyl Amine, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethyl Phenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methylamine, ethylamine, isopropylamine, n -Propylamine, n-butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, phenylamine, 1-naphth Tylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-iso Propoxypropylamine and the like are preferred.
Further, examples of the secondary amines preferably include dimethylamine, diethylamine, methylethylamine, methylpropylamine, diethylamine, ethylpropylamine, dipropylamine, dibutylamine, N, N-methylbenzylamine and the like. Can do.

-(B) Epoxy group-containing unsaturated compound-
As the (b) epoxy group-containing unsaturated compound used in the production of the vinyl polymer type photocrosslinkable resin of the type (A-1), one radical polymerizable unsaturated group and epoxy group in one molecule Any of the compounds represented by the following general formulas (IV-1) to (IV-14) may be used.

However, in the general formula (IV-1) ~ (IV -14), R 14 is a hydrogen atom or a methyl _{group, R 15} is an alkylene group having 1 to 10 carbon _{atoms, R 16} is a hydrocarbon group having 1 to 10 carbon atoms , P represents 0 or an integer of 1-10.
These (b) epoxy group-containing unsaturated compounds may be used alone or in admixture of two or more. Among these, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferable.

<Type (A-2)>
The epoxy group-containing copolymer resin (c) used for the production of the vinyl polymer type photocrosslinkable resin of the type (A-2) is a non-reactive (meth) acrylic with an epoxy group-containing monomer and other epoxy groups. It can be obtained by copolymerization with esters and / or styrenes.
As the epoxy group-containing monomer, the compounds described above in the description of the vinyl polymer type photocrosslinkable resin of the type (A-1) are preferably used.
At least one of (meth) acrylic acid ester and styrenes that are non-reactive with an epoxy group is a carboxyl group, an alcoholic hydroxyl group, a phenol among the above-mentioned photocrosslinkable resins of the type (A-1). Those which do not contain a functional hydroxyl group, an amino group or the like are preferably used.
The production method is obtained by copolymerizing an epoxy group-containing monomer, a non-reactive (meth) acrylic acid ester and styrenes with a conventional method such as a solution polymerization method.
Here, the molar ratio of the epoxy group-containing monomer and the (meth) acrylic ester non-reactive with other epoxy groups and at least one of styrenes is preferably 60:40 to 20:80. If the amount of the epoxy group-containing monomer is too small and the molar ratio is larger than 20:80, the amount of addition of the next unsaturated carboxylic acid and polybasic acid anhydride to the copolymer is reduced. If the molar ratio is less than 60:40, the softening point tends to be too low.
In addition, the carboxyl group-containing unsaturated compound (d) includes one unsaturated group and at least one carboxyl group or acid per molecule in the description of the vinyl polymer type photocrosslinkable resin of type (A-1). As the compound having an anhydride group, the aforementioned compounds can be preferably used.
Further, as the polybasic acid anhydride (e), maleic anhydride, succinic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic acid Saturated or unsaturated aliphatic, alicyclic or aromatic compounds having one acid anhydride group in the molecule, such as anhydride, 4-ethyltetrahydrophthalic anhydride and phthalic anhydride are preferred. Among these, tetrahydrophthalic anhydride is particularly preferable.
The reaction of the epoxy group-containing copolymer, the carboxyl group-containing unsaturated compound and the subsequent polybasic acid anhydride is preferably carried out as follows. After addition reaction of 0.8 to 1.2 mol of unsaturated carboxylic acid per one epoxy group equivalent of the copolymer to the copolymer of the epoxy group-containing monomer, the resulting hydroxyl group of the resulting product Polybasic acid anhydride is subjected to addition reaction.

<Type (A-3)>
The acid anhydride group-containing copolymer resin (f) used for the production of the vinyl polymer type photocrosslinkable resin of the type (A-3) is a copolymer of maleic anhydride and styrene or itaconic anhydride and styrene. It can be obtained by copolymerization.
As the styrene as the copolymer component, those already described in the description of the photocrosslinkable resin of the type (A-1) are preferably used. The copolymer composition ratio of maleic anhydride or itaconic anhydride and styrenes is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and particularly preferably 70:30 to 30:70. When it is 90:10 or more, the development resistance of the cured portion is inferior, and when it is 10:90 or less, the developability is inferior.
A copolymer having a mass average molecular weight of about 1,000 to 5,000 obtained by copolymerizing styrene at a ratio of 1 mol to 3 mol with respect to 1 mol of maleic anhydride is preferable. For example, ARCO Chemical Company Examples thereof include SMA ranges 1000, 2000, and 3000.

  Examples of the compound (g) having one hydroxyl group and at least one (meth) acryloyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polycaprolactone mono (meth) acrylate, pendaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl glycol mono (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) ) Acid phosphate, glycerol di (meth) acrylate.

The ring-opening addition reaction between the acid anhydride copolymer resin and a monomer having one hydroxyl group and at least one (meth) acryloyl group in the molecule is performed in an organic solvent containing no active hydrogen. It can manufacture by the method of. As a preferable solvent, ethyl acetate, methoxypropyl acetate, methyl ethyl ketone and the like are preferable. In this case, the molar ratio of hydroxyl group in the monomer / acid anhydride group in the copolymer is preferably 0.8 to 1.2. The ring-opening addition reaction is usually carried out at 50 to 200 ° C. In order to prevent gelation, about 80 to 150 ° C. is preferable. As reaction accelerators, tertiary amines such as triethylamine, triethanolamine, morpholine, and pentamethyldiethylenetriamine, or quaternary ammonium salts can be used. On the other hand, a known polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, t-butylcatechol, benzoquinone, phenothiazine and the like can be added and used to prevent the formation of a polymer during the reaction.

As described above, the vinyl polymer photocrosslinkable resin comprising at least one of the types (A-1), (A-2) and (A-3) obtained has an acid value of 50 to 250 mgKOH. / G is required.
The acid value is more preferably from 70 to 200 mgKOH / g, particularly preferably from 90 to 180 mgKOH / g. When the acid value is less than 50 mgKOH / g, it is difficult to remove the unexposed area with a developing solution that is a weak alkaline aqueous solution. There are harmful effects. The vinyl polymer photocrosslinkable polymer (A) preferably has a mass average molecular weight in the range of 5,000 to 200,000. The mass average molecular weight is more preferably 10,000 to 100,000, and particularly preferably 30,000 to 80,000. When the mass average molecular weight is less than 5,000, the dryness to touch is remarkably inferior and the peelability from the support is inferior. On the other hand, a mass average molecular weight exceeding 200,000 is not preferable because problems such as removability of unexposed portions and storage stability due to an alkaline developer are caused.
The solid content of the alkali-soluble photocrosslinkable polymer in the total solid content of the photosensitive solder resist layer is preferably 15 to 70% by mass. If it is less than 15% by mass, the toughness of the cured film is inferior, and if it exceeds 70% by mass, the balance of performance deteriorates such as a decrease in reliability.
In particular, one mixture from the types (A-1) to (A-3) and one mixture from the epoxy resin ester-type photocrosslinkable oligomer described later are preferable because they can provide balanced performance. In this case, the mixing ratio is 10:90 to 90:10 by mass. 20:80 to 80:20 are more preferable, and 30:70 to 70:30 are particularly preferable.

-Polymerizable compound-
There is no restriction | limiting in particular as said polymeric compound, According to the objective, it can select suitably, For example, the monomer or oligomer which has at least any one of a urethane group and an aryl group is mentioned suitably. Moreover, it is preferable that these have 2 or more types of polymeric groups.

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

--Monomer having urethane group--
The monomer having a urethane group is not particularly limited as long as it has a urethane group, and can be appropriately selected according to the purpose. For example, JP-B-48-41708, JP-A-51-37193, Examples include compounds described in JP-B-5-50737, JP-B-7-7208, JP-A-2001-154346, JP-A-2001-356476, and the like. Examples include adducts of the above polyisocyanate compounds having an isocyanate group and a vinyl monomer having a hydroxyl group in the molecule.

  Examples of the polyisocyanate compound having two or more isocyanate groups in the molecule include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, Diisocyanates such as 3,3′-dimethyl-4,4′-diphenyl diisocyanate; polyaddition products of the diisocyanate with bifunctional alcohols (in this case, both ends are isocyanate groups); burettes and isocyanurates of the diisocyanate, etc. The diisocyanate or diisocyanates and trimethylolpropane, Printers Ellis Le Thor, polyfunctional alcohols such as glycerin, or the like adducts of other functional alcohol obtained of such these ethylene oxide adducts and the like.

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

  In addition, examples of the monomer having a urethane group include compounds having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate, di (meth) acrylated isocyanurate, and tri (meth) acrylate of ethylene oxide-modified isocyanuric acid. Is mentioned. Among these, the compound represented by the following structural formula (13) or the structural formula (14) is preferable, and it is particularly preferable that at least the compound represented by the structural formula (14) is included from the viewpoint of tent properties. Moreover, these compounds may be used individually by 1 type, and may use 2 or more types together.

In the structural formulas (13) and (14), R ^{1 to} R ³ each represent a hydrogen atom or a methyl group. X ₁ to X ₃ represents an alkylene oxide, may be alone or in combination of two or more thereof.

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

  In the structural formulas (13) and (14), m1 to m3 represent an integer of 1 to 60, preferably 2 to 30, and more preferably 4 to 15.

In the structural formulas (13) and (14), Y ₁ and Y ₂ represent a divalent organic group having 2 to 30 carbon atoms, for example, an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group. (—CO—), an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group in which the hydrogen atom of the imino group is substituted with a monovalent hydrocarbon group, Preferred examples include a sulfonyl group (—SO ₂ —) or a combination thereof, and among these, an alkylene group, an arylene group, or a combination thereof is preferable.

  The alkylene group may have a branched structure or a cyclic structure, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentylene group, hexylene group, trimethyl hexene. Examples thereof include a xylene group, a cyclohexylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, a nonylene group, a decylene group, a dodecylene group, an octadecylene group, and any of the groups shown below.

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

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

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

  In the structural formulas (13) and (14), n represents an integer of 3 to 6, and 3, 4 or 6 is preferable from the viewpoint of raw material supply capability for synthesizing a polymerizable compound.

  In the structural formulas (13) and (14), Z represents an n-valent (3 to 6-valent) linking group, and examples thereof include any of the following groups.

However, _{X 4} represents an alkylene oxide. m4 represents an integer of 1 to 20. n represents an integer of 3 to 6. A represents an n-valent (3-6 valent) organic group.

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

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

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

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

  The alkylene group may have a branched structure or a cyclic structure. As a carbon atom number of the said alkylene group, the integer of 1-18 is preferable, for example, and the integer of 1-10 is more preferable.

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

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

  Below, the preferable example of said A is as follows.

  Examples of the compounds represented by the structural formulas (13) and (14) include compounds represented by the following structural formulas (15) to (34).

  However, in said structural formula (15)-(34), n, n1, n2 and m mean 1-60, l means 1-20, R represents a hydrogen atom or a methyl group. .

-Monomers with aryl groups-
The monomer having an aryl group is not particularly limited as long as it has an aryl group, and can be appropriately selected according to the purpose. For example, a polyhydric alcohol compound having a aryl group, a polyvalent amine compound, and a polyvalent amino Examples thereof include esters or amides of at least one of alcohol compounds and an unsaturated carboxylic acid.

  Examples of the polyhydric alcohol compound, polyamine compound or polyhydric amino alcohol compound having an aryl group include polystyrene oxide, xylylene diol, di- (β-hydroxyethoxy) benzene, 1,5-dihydroxy-1, 2,3,4-tetrahydronaphthalene, 2,2-diphenyl-1,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1-phenyl-1,2-ethanediol, 2,3,5,6-tetra Methyl-p-xylene-α, α′-diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1,4- Diol, 1,1′-bi-2-naphthol, dihydroxynaphthalene, 1,1′-methylene-di-2-naphth 1,2,4-benzenetriol, biphenol, 2,2′-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, hydroquinone, hydroxybenzyl alcohol, methylhydroquinone, methylene-2,4,6-trihydroxybenzoate, phloroglicinol, pyrogallol, resorcinol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, α -(1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino-4-hydroxyphenylsulfone and the like can be mentioned. In addition, compounds obtained by adding α, β-unsaturated carboxylic acid to glycidyl compounds such as xylylene bis (meth) acrylamide, novolac epoxy resin and bisphenol A diglycidyl ether, phthalic acid, trimellitic acid, etc. Esterified products obtained from vinyl monomers containing hydroxyl groups in the molecule, diallyl phthalate, triallyl trimellitic acid, diallyl benzenedisulfonate, cationically polymerizable divinyl ethers (for example, bisphenol A divinyl ether), epoxy as a polymerizable compound Compound (for example, novolac type epoxy resin, bisphenol A diglycidyl ether, etc.), vinyl ester (for example, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate), styrene Examples of the compound include divinylbenzene, p-allylstyrene, and p-isopropenestyrene. Among these, the compound represented by the following structural formula (35) is preferable.

In the structural formula (35), R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group.

In the structural formula (35), X ₅ and X ₆ represent an alkylene oxide group, which may be used alone or in combination of two or more. As the alkylene oxide group, for example, an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, a group combining these (which may be combined in any of random and block), Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a group combining these is preferable, and an ethylene oxide group and a propylene oxide group are more preferable.

  In the structural formula (35), m5 and m6 are preferably an integer of 1 to 60, more preferably an integer of 2 to 30, and particularly preferably an integer of 4 to 15.

In the structural formula (35), T represents a divalent linking group, and examples thereof include methylene, ethylene, MeCMe, CF ₃ CCF ₃ , CO, and SO ₂ .

In the structural formula _{(35), Ar 1, Ar} 2 represents an aryl group which may have a substituent group, such as phenylene, naphthylene and the like. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, a halogen group, an alkoxy group, or a combination thereof.

  Specific examples of the monomer having an aryl group include 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 2,2-bis [4-((meth)). (Acryloxyethoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane having 2 to 20 ethoxy groups substituted with one phenolic OH group ( For example, 2,2-bis (4-((meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecaet) C) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecaethoxy) phenyl) propane), 2,2-bis [4-((meth) acryloxypropoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane (e.g. 2,2-bis (2) having 2 to 20 ethoxy groups substituted with one phenolic OH group 4-((meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxy) Pentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecapropoxy) phenyl Propane, 2,2-bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane, or the like, or a polyether moiety of these compounds contains both a polyethylene oxide skeleton and a polypropylene oxide skeleton in the same molecule A compound having a bisphenol skeleton and a urethane group (for example, a compound described in WO01 / 98832 or a commercially available product, manufactured by Shin-Nakamura Chemical Co., Ltd., BPE-200, BPE-500, BPE-1000) Compound. These compounds may be compounds obtained by changing the part derived from the bisphenol A skeleton to bisphenol F or bisphenol S.

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

--Other polymerizable compounds--
In the method for forming a permanent pattern of the present invention, a polymerizable compound other than the monomer containing the urethane group and the monomer having an aryl group may be used in combination as long as the characteristics as the photosensitive solder resist film are not deteriorated.

  Examples of the polymerizable compound other than the monomer containing a urethane group and the monomer containing an aromatic ring include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) And an ester of an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and a polyvalent amine compound.

  Examples of the monomer of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, and polyethylene glycol having 2 to 18 ethylene groups. Di (meth) acrylate (for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate , Tetradecaethylene glycol di (meth) acrylate, etc.), propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 18 propylene groups (for example, , Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) acrylate, etc.), neopentyl glycol di (meth) acrylate, ethylene oxide modified Neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ) Ether, trimethylolethane tri (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,5-bentanediol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate Rate, sorbitol hexa (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate A di (meth) acrylate of an alkylene glycol chain having at least one ethylene glycol chain / propylene glycol chain (for example, a compound described in WO01 / 98832), at least one of ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate, polybutylene glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate Relate and xylenol di (meth) acrylate.

  Among the (meth) acrylic acid esters, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meta) from the viewpoint of easy availability. ) Acrylate, di (meth) acrylate of alkylene glycol chain each having at least one ethylene glycol chain / propylene glycol chain, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol triacrylate, penta Erythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (Meth) acrylate, diglycerin di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1, Preference is given to 5-pentanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate added with ethylene oxide, and the like.

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

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

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

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

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

  In addition to the above, as the polymerizable compound, for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Compound obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound such as hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc. Polyester acrylate and polyester (meth) as described in JP-B-64183, JP-B-49-43191, and JP-B-52-30490 Acrylate oligomers, epoxy compounds (for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether , Pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc.) and (meth) acrylic acid and other polyfunctional acrylates and methacrylates such as epoxy acrylates, Vol. 20, no. 7, 300 to 308 pages (1984), photocurable monomers and oligomers, allyl esters (eg, diallyl phthalate, diallyl adipate, diallyl malonate, diallylamide (eg, diallylacetamide), cationic polymerizable Divinyl ethers such as butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, trimethylolpropane trivinyl ether, penta Erythritol tetravinyl ether, glycerin trivinyl ether, etc.), epoxy compounds (for example, butanediol-1,4-diglycidyl ester) Tellurium, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc. ), Oxetanes (for example, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene), epoxy compounds, oxetanes (for example, compounds described in WO01 / 22165), N-β -Hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis (β-methacryloxyethyl) acrylamide, allyl methacrylate Different ethylenically unsaturated double bond to a compound having two or more of over preparative like, and the like.

  Examples of the vinyl esters include divinyl succinate and divinyl adipate.

  These polyfunctional monomers or oligomers may be used alone or in combination of two or more.

If necessary, the polymerizable compound may be used in combination with a polymerizable compound (monofunctional monomer) containing one polymerizable group in the molecule.
Examples of the monofunctional monomer include the compounds exemplified as the raw material of the binder, and the dibasic mono ((meth) acryloyloxyalkyl ester) mono (halohydroxyalkyl ester) described in JP-A-6-236031. Monofunctional monomers such as γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate, etc., compounds described in Japanese Patent No. 2744443, WO00 / 52529, Japanese Patent No. 2548016, etc. Is mentioned.

As content of the polymeric compound in the said photosensitive soldering resist layer, 5-90 mass% is preferable, for example, 15-60 mass% is more preferable, and 20-50 mass% is especially preferable.
If the content is 5% by mass, the strength of the tent film may be reduced, and if it exceeds 90% by mass, edge fusion during storage (exudation failure from the end of the roll) may be deteriorated. .
Moreover, as content of the polyfunctional monomer which has 2 or more of the said polymeric groups in a polymeric compound, 5-100 mass% is preferable, 20-100 mass% is more preferable, 40-100 mass% is especially preferable. .

-Photopolymerization initiator-
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. It may be an activator that produces some action and generates active radicals, or may be an initiator that initiates cationic polymerization according to the type of monomer. Among these, those having photosensitivity to visible light from the ultraviolet region are preferable, those having high sensitivity to exposure with laser light having a wavelength of 395 to 415 nm are more preferable, halogenated hydrocarbon derivatives, phosphine oxides. , Hexaarylbiimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts and at least one selected from ketoxime ethers are particularly preferred.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

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

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

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

Examples of the compound described in the British Patent 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl)- 4-amino-6-trichloromethyl-1,3,5-triazine and the like can be mentioned.
Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl]- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in the specification of German Patent 3333724 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4 -Methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan-2 Vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine etc. are mentioned.

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

  Examples of the compounds described in JP-A-62-258241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- Naphthyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropylphenyl) Ethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) Le) -1,3,5-triazine.

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

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

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

  Examples of the oxime derivative suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

  Further, as photopolymerization initiators other than the above, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, and the like, polyhalogen compounds (for example, Carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbonylbi (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP2002 -363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, N-butyl 4-dimethylaminobenzoate, 4-dimethyla Phenethyl nobenzoate, 2-dimethylimido 4-dimethylaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentamethylenebis (4-dimethylaminobenzoate), phenethyl 3-dimethylaminobenzoate, pentamethylene Ester, 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-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethyla Nilin, tridodecylamine, aminofluoranes (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc., acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis ( 2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), JP Sho 53-133428, Shoko 7-1819, JP same 57-6096 and JP, US Patent compounds described in the 3,615,455 Patent specification mentioned.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

  As solid content in the said photosensitive soldering resist composition solid component of the said photoinitiator, 0.1-30 mass% is preferable, for example, 0.5-20 mass% is more preferable, 0.5 ˜15% by weight is particularly preferred.

In addition to the photopolymerization initiator, a sensitizer can be added for the purpose of adjusting exposure sensitivity and photosensitive wavelength in exposure to the photosensitive solder resist layer.
The sensitizer can be appropriately selected by visible light, ultraviolet light, visible light laser, or the like as a light irradiation means described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue) , Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, chloroacrid) N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7 -(1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3 ′ -Carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylamino Coumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, -Methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and the like, and in addition, JP-A-5-19475, JP-A-7-271028, JP2002 -363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, and the like.

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

  As content of the said sensitizer, 0.05-30 mass% is preferable with respect to all the components in the said photosensitive soldering resist composition, 0.1-20 mass% is more preferable, 0.2-10 Mass% is particularly preferred. When the content is less than 0.05% by mass, the sensitivity to active energy rays is reduced, the exposure process takes time, and productivity may be reduced. The sensitizer may be precipitated from the photosensitive solder resist layer.

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

  As content in the said photosensitive soldering resist composition of the said photoinitiator, 0.1-30 mass% is preferable, 0.5-20 mass% is more preferable, 0.5-15 mass% is especially preferable. .

-Inorganic filler-
There is no restriction | limiting in particular as said inorganic filler, According to the objective, it can select suitably, For example, the inorganic filler etc. which have a functional group are mentioned.
There is no restriction | limiting in particular as an inorganic filler which has the said functional group, According to the objective, it can select suitably, For example, it can be comprised by the inorganic fine particle and the functional group introduce | transduced into this inorganic fine particle.

As the inorganic fine particles, various fine particles such as simple metals, inorganic oxides, inorganic carbonates, inorganic sulfates, and phosphates can be used depending on the function of the inorganic pattern. Examples of inorganic oxides include silica (colloidal silica, aerosil, etc.), alumina, titania, zirconia, zinc oxide, barium titanate, lithium niobate, tin oxide, indium oxide, In ₂ O—SnO, and carbonates. Examples include calcium carbonate and magnesium carbonate, and examples of the sulfate include barium sulfate and calcium sulfate. Examples of the phosphate include calcium phosphate and magnesium phosphate.

  There is no restriction | limiting in particular as a shape of the said inorganic fine particle, According to the objective, it can select suitably, For example, not only spherical shape but elliptical shape, flat shape, rod shape, or fiber shape may be sufficient. There is no restriction | limiting in particular as an average particle diameter of the said inorganic fine particle, According to the objective, it can select suitably, For example, it can select from 1 nm-10 micrometers, 5 nm-5 micrometers according to the grade of the refinement | miniaturization of an inorganic pattern, etc. . In order to form a fine inorganic pattern, it is preferable to use monodispersed inorganic fine particles (particularly colloidal silica) having an average particle diameter of 2 to 100 nm (5 to 50 nm, preferably 7 to 30 nm) by the BET method. It is advantageous. Monodispersed inorganic fine particles (particularly colloidal silica) are commercially available as organosols (organosilica sols), for example, “Snowtex colloidal silica”, particularly “Methanol silica sol”, available from Nissan Chemical Industries, Ltd.

  The inorganic filler preferably has a reactive group or a photosensitive group (particularly a polymerizable photosensitive group) as the functional group. Examples of the reactive group or photosensitive group include the same hydrolyzable polymerizable group and photosensitive group as described above. The functional group includes the inorganic fine particles and an organometallic compound having at least the hydrolyzable polymerizable group and a photosensitive group (particularly the hydrolyzable polymerizable organometallic compound, particularly a silane coupling agent or a titanium coupling agent). It can introduce | transduce into the said inorganic fine particle using reaction, the surface graft polymerization method, CVD method, etc.

  As the organometallic compound having at least the hydrolyzable polymerizable group and the photosensitive group, the hydrolyzable polymerizable metal compound or a condensate thereof (especially a silicon-containing organic compound) can be used, and has the above exemplified photosensitive group. Hydrolytically polymerizable organometallic compounds (particularly silane compounds having a polymerizable group) are preferred.

  In the inorganic filler, the amount of the functional group introduced into the inorganic fine particles is 0.1 to 100 parts by mass and 0.5 to 50 parts by mass in terms of a compound having a functional group with respect to 100 parts by mass of the inorganic fine particles. Part is preferable, and 1 to 20 parts by mass is more preferable.

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

  The solid content in the solid content of the photosensitive solder resist composition of the color pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive solder resist layer when forming the solder resist, Although it varies depending on the type of the color pigment, it is generally preferably 0.05 to 10% by mass, more preferably 0.075 to 8% by mass, and particularly preferably 0.1 to 5% by mass.

―Other ingredients―
The other component is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a thermal crosslinking agent, a thermal polymerization inhibitor, and an extender pigment. Adhesion promoters and other auxiliaries (eg, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer) Or other agents) may be used in combination. By appropriately containing these components, properties such as stability, photographic properties, and film physical properties of the photosensitive solder resist film can be adjusted.

-Thermal crosslinking agent-
There is no restriction | limiting in particular as said thermal crosslinking agent, According to the objective, it can select suitably, The film strength after hardening of the photosensitive soldering resist layer formed using the said photosensitive soldering resist composition is improved. Therefore, for example, an epoxy resin compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used within a range that does not adversely affect developability and the like. .
Examples of the epoxy resin compound include a bixylenol type or biphenol type epoxy resin (“YX4000; manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton (“TEPIC; Nissan”). Chemical Industries, "Araldite PT810; Ciba Specialty Chemicals, etc.), bisphenol A type epoxy resin, novolac 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, tetraphenylolethane type Poxy resin, glycidyl phthalate resin, tetraglycidyl xylenoylethane resin, naphthalene group-containing epoxy resin (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA-4750, EXA-4700; large Nippon Ink Chemical Co., Ltd. ”), epoxy resins having a dicyclopentadiene skeleton (“ HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals ”etc.), glycidyl methacrylate copolymer epoxy resin (“ CP -50S, CP-50M; manufactured by NOF Corporation, etc.), a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, and the like, but is not limited thereto. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

  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-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, oxetane groups and novolak resins , Poly (p-hydroxystyrene), cardo-type bisphe And ether compounds with hydroxyl groups, such as siloles, calixarenes, calixresorcinarenes, silsesquioxanes, and the like, as well as unsaturated monomers having an oxetane ring and alkyl (meth) acrylates. And a copolymer thereof.

  1-50 mass% is preferable and, as for the solid content in the said photosensitive soldering resist composition solid content of the said epoxy resin compound or an oxetane compound, 3-30 mass% is more preferable. When the solid content is less than 1% by mass, the hygroscopicity of the cured film is increased, resulting in deterioration of insulation, or solder heat resistance, electroless plating resistance, and the like may be reduced. If it exceeds 50% by mass, the developability may deteriorate and the exposure sensitivity may decrease, which is not preferable.

Moreover, in order to accelerate the thermosetting of the epoxy resin compound or the oxetane compound, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethyl Amine compounds such as benzylamine and 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole, 2-methylimidazole and 2-ethylimidazole , 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc. Bicyclic amidine compounds and salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2 -Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid S-triazine derivatives such as adducts can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
Solid content in the said photosensitive soldering resist composition solid content of the said epoxy resin, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally. .

Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound.
Specifically, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene diisocyanate, bis (4 -Isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc .; bifunctional isocyanates, trimethylolpropane, pentalysitol, glycerin, etc. An alkylene oxide adduct of the polyfunctional alcohol and an adduct of the bifunctional isocyanate; hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate Cyclic trimers, such as preparative and derivatives thereof; and the like.

Furthermore, for the purpose of improving the preservability of the photosensitive solder resist film, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include isopropanol, tert. Alcohols such as butanol; lactams such as ε-caprolactam, phenol, cresol, p-tert. -Butylphenol, p-sec. -Butylphenol, p-sec. -Phenols such as amylphenol, p-octylphenol, p-nonylphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; dialkylmalonate, methylethylketoxime, acetylacetone, alkylacetoacetate oxime, acetoxime, Active methylene compounds such as cyclohexanone oxime; and the like. In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, an aldehyde condensation product, a resin precursor, etc. can be used. Specifically, N, N′-dimethylolurea, N, N′-dimethylolmalonamide, N, N′-dimethylolsuccinimide, trimethylolmelamine, tetramethylolmelamine, hexamethylolmelamine, 1,3-N, N'-dimethylol terephthalamide, 2,4,6-trimethylolphenol, 2,6-dimethylol-4-methyliloanisole, 1,3-dimethylol-4,6-diisopropylbenzene and the like can be mentioned. Instead of these methylol compounds, the corresponding ethyl or butyl ether, or acetic acid or propionic acid ester may be used. Moreover, you may use the hexamethoxymethyl melamine which consists of a formaldehyde condensation product of a melamine and urea, the butyl ether of a melamine and a formaldehyde condensation product, etc.

  1-40 mass% is preferable, as for solid content in the said photosensitive soldering resist composition solid content of the said thermal crosslinking agent, 3-20 mass% is more preferable, and 5-25 mass% is especially preferable. When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 40% by mass, the developability and the exposure sensitivity may be lowered.

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

  As content of the said thermal-polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said polymeric compound, 0.005-2 mass% is more preferable, 0.01-1 mass% is especially preferable. When the content is less than 0.001% by mass, stability during storage may be lowered, and when it exceeds 5% by mass, sensitivity to active energy rays may be lowered.

--External pigment--
The extender pigment is not particularly limited and may be appropriately selected depending on the intended purpose. The surface hardness of the formed permanent pattern is improved, the coefficient of thermal expansion is reduced, and the dielectric constant and dielectric loss tangent of the cured film itself are reduced. From this point, inorganic pigments and organic fine particles are preferable.
The inorganic pigment is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, gas phase method silica, amorphous Examples thereof include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.
The average particle diameter of the inorganic pigment is preferably less than 10 μm, and more preferably 3 μm or less. When the average particle size is 10 μm or more, resolution may be deteriorated due to light scattering.
There is no restriction | limiting in particular as said organic fine particle, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. Further, silica having an average particle diameter of 1 to 5 μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  There is no restriction | limiting in particular as content in the said photosensitive soldering resist composition of the said extender, According to the objective, it can select suitably, It is preferable that it is 10-60 mass%. When the addition amount is less than 10% by mass, the surface hardness may not be improved and the thermal expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, a cured film is formed on the surface of the photosensitive solder resist layer. In addition, the film quality of the cured film becomes brittle, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

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

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

As content of the said adhesion promoter, 0.001-20 mass% is preferable with respect to all the components in the said photosensitive soldering resist composition, 0.01-10 mass% is more preferable, 0.1-5 Mass% is particularly preferred.
When the said photosensitive soldering resist composition contains the said adhesion promoter, it becomes possible to improve the adhesiveness between each layer or the adhesiveness of a photosensitive soldering resist layer and a base material.

<Second photosensitive solder resist layer>
The second photosensitive solder resist layer is laminated on the support together with the first photosensitive solder resist layer, and is laminated on the substrate by making the hardness softer than the first photosensitive solder resist layer. In the process of improving the adhesion to the substrate surface, the function of absorbing and flattening the surface of the laminated body by plastic deformation with respect to the height direction of the convex portion of the convex portion on the substrate. is there.
The thickness of the second photosensitive solder resist layer is not particularly limited as long as it has the following relationship with the first photosensitive solder resist layer, and can be appropriately selected according to the purpose. 50 micrometers is preferable, 2-50 micrometers is more preferable, and 4-30 micrometers is especially preferable.

  When the thickness of the first photosensitive solder resist layer is S1 and the thickness of the second photosensitive solder resist layer is S2, S1 / S2 is preferably 1/9 to 9/1, More preferably, it is 6-6 / 1. If it is less than 1/9, the elasticity of the first photosensitive solder resist layer is weak and more fluid, and it may not be possible to obtain a uniform uniform pattern as a whole. The elasticity of the first photosensitive solder resist layer is strong, the fluidity is weakened, and the height of the convex part may not be absorbed by the second photosensitive solder resist layer, and the flattening of the permanent pattern cannot be obtained. There is.

--Melt viscosity of photosensitive solder resist layer--
The melt viscosity η ₂ of the _second photosensitive solder resist layer is not particularly limited as long as it is relatively softer than the first photosensitive solder resist layer, and can be appropriately selected according to the purpose. For example, 50 to 300 Pa · s is preferable at a laminating temperature of 70 to 100 ° C. when laminating on a substrate.
If the melt viscosity η ₂ is less than 50 Pa · s, the fluidity is too high at the time of lamination, so that it flows out and a sufficient thickness of the resist layer after lamination may not be ensured. On the other hand, when this value exceeds 300 Pa · s, the followability is insufficient at the time of stacking the substrates, and bubbles are mixed in between the substrates, or the substrate adhesion after curing is inferior.

  The second photosensitive solder resist layer includes at least an alkali-soluble photocrosslinkable oligomer, a polymerizable compound, a photopolymerization initiator, an epoxy resin, a curing accelerator, an inorganic filler, and a colorant, and is appropriately selected as necessary. It consists of the 2nd photosensitive soldering resist composition containing another component, and components other than an alkali-soluble photocrosslinkable oligomer may use the same component as a said 1st photosensitive soldering resist composition.

-Alkali-soluble photocrosslinkable oligomer-
The alkali-soluble photocrosslinkable oligomer has a function of making the second photosensitive solder resist layer relatively soft and imparting plastic deformation properties. By such plastic deformation, the second photosensitive solder resist layer can be absorbed in the height direction even if there is a convex portion on the substrate, and the surface of the laminate can be flattened.
There is no restriction | limiting in particular as said alkali-soluble photocrosslinkable oligomer, According to the objective, it can select suitably, For example, an epoxy resin ester type photocrosslinkable oligomer etc. are mentioned.

-Epoxy resin ester type photocrosslinkable oligomer-
The epoxy resin ester-type photocrosslinkable oligomer is not particularly limited and may be appropriately selected depending on the purpose. For example, (h) an epoxy resin and (i) one unsaturated group in one molecule It produces | generates by further reacting (j) polybasic acid anhydride with the esterification reaction product with the compound which has at least 1 carboxyl group or acid anhydride group.
Examples of the epoxy resin (h) include YDCN-701, YDCN-704 manufactured by Toto Kasei Co., Ltd .; N-665, N-680, N-695 manufactured by Dainippon Ink & Chemicals, Inc .; Nippon Kayaku Co., Ltd. EOCN-102, EOCN-104 manufactured by Asahi Kasei Kogyo Co., Ltd. ECN-265, ECN-293, ECN-285, ECN-299 and other cresol novolac type epoxy resins, and Toto Kasei Co., Ltd. YDPN-638, YDPN -602; DEN-431, DEN-438, DEN-439 manufactured by Dow Chemical Japan Co., Ltd .; EPN-1138, EPN-1235, EPN-1299 manufactured by Ciba Specialty Chemicals Co., Ltd .; Phenol novolac type epoxy resins such as N-730 and N-770 manufactured by the same company may be mentioned. In addition, a part of the novolac type epoxy resin is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, bixylenol type epoxy resin, trishydroxyphenylmethane type epoxy resin, Epoxy resins such as a tetraphenylethane type epoxy resin, an alicyclic epoxy resin, and a salicylaldehyde type epoxy resin can also be advantageously used.

Next, the compound (i) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule is described for the vinyl polymer type photocrosslinkable resin of the type (A-1). Of these, the aforementioned compounds can be preferably used.
Similarly, the polybasic acid anhydride (j) may use the above-mentioned compounds as the component (e) in the description of the vinyl polymer type photocrosslinkable resin of the type (A-2).

――Method for producing epoxy resin ester type photocrosslinkable oligomer――
There is no restriction | limiting in particular as a manufacturing method of the said epoxy resin ester type photocrosslinkable oligomer, According to the objective, it can select suitably, For example, the epoxy resin (h) in the case of manufacture, and 1 piece in 1 molecule In the reaction of the unsaturated group with the compound (i) having at least one carboxyl group or acid anhydride group, one unsaturated group per molecule for one equivalent of the epoxy group of the epoxy resin (h) And the compound (i) having at least one carboxyl group or acid anhydride group are preferably reacted at a ratio of 0.8 to 1.05 equivalent, more preferably 0.9 to 1.0 equivalent.
The epoxy resin (h) and the compound (i) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule are dissolved and reacted in an organic solvent. For example, ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl Glycol ethers such as ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, fats such as octane and decane Hydrocarbons, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha.

Furthermore, it is preferable to use a catalyst to accelerate the reaction. Examples of the catalyst used include triethylamine, benzylmethylamine, methyltriethylammonium chlorite, benzyltrimethylammonium chlorite, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine, and the like. The amount of the catalyst used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the epoxy resin and the vinyl group-containing monocarboxylic acid (b).
Further, it is preferable to use a polymerization inhibitor because it prevents the polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the amount used is 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). The amount is preferably 0.01 to 1 part by mass. The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.

  The epoxy resin ester-type photocrosslinkable oligomer is obtained by reacting the reaction product thus obtained with a polybasic acid anhydride (j). The reaction temperature between the reaction product and the polybasic acid anhydride (j) is preferably 60 to 120 ° C.

The acid value of the epoxy resin ester photocrosslinkable oligomer is adjusted by reacting 0.1 to 1.0 equivalent of polybasic acid anhydride (j) with respect to 1 equivalent of hydroxyl group in the reaction product. it can. The acid value of the epoxy resin ester photocrosslinkable oligomer is preferably 30 to 150 mgKOH / g, and more preferably 50 to 120 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility of the photocurable resin composition in a dilute alkali solution is lowered, and when it exceeds 150 mgKOH / g, the electric characteristics of the cured film tend to be lowered.
The epoxy resin ester type photocrosslinkable oligomer preferably has a mass average molecular weight of 500 to 5,000, more preferably 1,000 to 4,000, and particularly preferably 1,500 to 3,500. When it is 500 or less, the adhesiveness is too high, and it is difficult to peel off the protective film, and when it exceeds 5,000, it becomes difficult to produce the resin.

--- Support--
The support is not particularly limited as long as it has good light transmittance and good surface smoothness, and can be appropriately selected according to the purpose. Can be mentioned. The synthetic resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylate alkyl Ester, Poly (meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene And various plastic films such as polytrifluoroethylene, cellulosic film, nylon film and the like. Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

  There is no restriction | limiting in particular as thickness of the said support body, According to the objective, it can select suitably, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.

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

--Protective film--
The protective film is affixed to the photosensitive solder resist layer side during transportation and the like to protect and protect the photosensitive solder resist layer from contamination and damage, and to protect the photosensitive solder resist film on the substrate. When they are laminated, they are peeled off.
The protective film is not particularly limited and can be appropriately selected depending on the purpose. For example, the protective film is the same as the support, silicone paper, polyethylene, polypropylene laminated paper, polyolefin or polytetrafluorocarbon. An ethylene sheet etc. are mentioned, Among these, a polyethylene film and a polypropylene film are preferable.
There is no restriction | limiting in particular as thickness of the said protective film, According to the objective, it can select suitably, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
When the protective film is used, the adhesive force X of the photosensitive solder resist layer and the support and the adhesive force Y of the photosensitive solder resist layer and the protective film satisfy the relationship of adhesive force X> adhesive force Y. It is preferable.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive strength with the photosensitive solder resist layer, for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation. Treatment, glow discharge irradiation treatment, active plasma irradiation treatment, laser beam irradiation treatment and the like.

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

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

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

The photosensitive solder resist film has a small surface tack, good laminating and handling properties, excellent storage stability, and exhibits excellent chemical resistance, surface hardness, heat resistance, etc. after development. It has the said photosensitive soldering resist layer by which the resist composition was laminated | stacked. For this reason, it can be widely used for forming permanent patterns such as display members such as pillar materials, rib materials, spacers, and partition walls, holograms, micromachines, and proofs, and can be suitably used in a method for producing a printed wiring board. .
In particular, since the photosensitive solder resist film has a uniform thickness, it is more accurately laminated on the base material when the solder resist is formed.

  A solder resist, a protective film, and an insulating film (interlayer insulating film) formed of the photosensitive solder resist film are preferable. The solder resist can protect the wiring from external impact and bending, and is suitable as an insulating film for a multilayer wiring board, a build-up wiring board, and the like.

-Other layers-
There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, there may be a cushion layer, an oxygen barrier layer (PC layer), etc.

―Permanent pattern formation method―
The permanent pattern forming method of the present invention comprises a laminate forming step, an exposure step, a developing step, a support removing step, and other steps appropriately selected as necessary.

--Laminate formation process--
There is no restriction | limiting in particular as said laminated body formation process, According to the objective, it can select suitably, For example, the 1st photosensitive soldering resist layer and 2nd which consist of a photosensitive soldering resist composition on a support body. Even in the step of laminating the photosensitive solder resist film having the photosensitive solder resist layer by bringing the second photosensitive solder resist layer into contact with the surface of the substrate having the convex portion where the convex portion is exposed. It may be a step of directly applying and laminating the solution comprising the photosensitive solder resist composition on the surface of the substrate having a convex portion where the convex portion is exposed.

In the case of the lamination process using the photosensitive solder resist film, the base, the second photosensitive solder resist layer, the first photosensitive solder resist layer, and the support are laminated in this order by the lamination. In the case of a laminating process using the solution, a laminated body is formed in which the base, the second photosensitive solder resist layer, and the first photosensitive solder resist layer are laminated in this order.
There is no restriction | limiting in particular as a layer structure in the said laminated body, According to the objective, it can select suitably, For example, the said 2nd photosensitive soldering resist layer and 1st photosensitive on the conductor circuit side of a printed wiring board. Layer structure in which a solder resist layer and the support are laminated, layer structure in which only the second photosensitive solder resist layer and the first photosensitive solder resist layer are laminated, on an interlayer resin insulating layer of a multilayer printed wiring board A layer structure in which the second photosensitive solder resist layer, the first photosensitive solder resist layer and the support are laminated, and the second photosensitive solder resist layer on an interlayer resin insulating layer of a multilayer printed wiring board. And a layer structure in which only the first photosensitive solder resist layer is laminated.

--Lamination of photosensitive solder resist layer with photosensitive solder resist film--
The laminating method using the photosensitive solder resist film is not particularly limited and may be appropriately selected depending on the purpose. The first surface of the photosensitive solder resist film on the surface where the convex portion on the substrate is exposed. And a method of laminating the photosensitive solder resist layer while contacting at least one of heating and pressurization.
There is no restriction | limiting in particular as 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 as said pressurization pressure, 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 and pressurization, According to the objective, it can select suitably, For example, a laminator, a vacuum laminator, etc. are mentioned suitably.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, a laminator (For example, Taisei Laminator company make, VP-II) etc. are suitable. Can be mentioned.

--Lamination of photosensitive solder resist layer by coating--
As a method for laminating the second photosensitive solder resist layer and the first photosensitive solder resist layer by the coating, the first photosensitive solder resist composition is dissolved, emulsified or dispersed in water or a solvent. Examples thereof include a method in which a resist composition solution and a second photosensitive solder resist composition solution are prepared, and the solution is directly applied to the surface of the printed wiring board and dried to be laminated.

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

The coating method is not particularly limited and can be appropriately selected depending on the purpose. For example, using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. The method of apply | coating is mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

There is no restriction | limiting in particular as thickness of the said 1st photosensitive soldering resist layer and a 2nd photosensitive soldering resist layer, According to the objective, it can select suitably, For example, 3-100 micrometers is preferable, respectively, 70 μm is more preferable.
When the thickness of the first photosensitive solder resist layer is S1, and the thickness of the second photosensitive solder resist layer is S2, S1 / S2 is preferably 1/9 to 9/1, and 1/6 More preferably, it is ˜6 / 1. If the ratio is less than 1/9, the elasticity of the first photosensitive solder resist layer is weak and more fluid, and a uniform uniform pattern may not be obtained as a whole. The elasticity of the first photosensitive solder resist layer is strong, the fluidity is weakened, and the height of the convex portion may not be absorbed by the second photosensitive solder resist layer, and the flattening of the permanent pattern cannot be obtained. There is.

―Substrate―
The substrate is not particularly limited and can be appropriately selected from known materials having a high surface smoothness to a surface having an uneven surface. A plate-like substrate (substrate) is preferable and specific. For example, known printed wiring board forming substrates (for example, copper-clad laminates), resin plates, resin laminates, glass plates (for example, soda glass plates), synthetic resin films, paper, metal plates, etc. Is mentioned. Among these, a printed wiring board forming substrate having a convex portion on the surface, a resin laminate having a convex portion on an interlayer resin insulating layer of a multilayer printed wiring board, and the like are preferable.

―Convex part―
The convex portion is not particularly limited and can be appropriately selected depending on the purpose.For example, a conductor circuit portion in a printed wiring board forming substrate, a conductor circuit portion in an interlayer resin insulating layer of a multilayer printed wiring board, The partition part etc. in a glass plate are mentioned.

-Other layers-
There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, a peeling layer, a light absorption layer, a surface protective layer, etc. are mentioned.
There is no restriction | limiting in particular in arrangement | positioning, thickness, etc. in the said photosensitive soldering resist film of the said other layer, According to the objective, it can select suitably.

――Method for producing photosensitive solder resist film――
The said photosensitive soldering resist film can be manufactured as follows, for example.
First, the above-mentioned various materials are dissolved, emulsified or dispersed in water or a solvent to prepare a first photosensitive solder resist composition solution and a second photosensitive solder resist composition solution.

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

  The emulsifier is not particularly limited and may be appropriately selected depending on the intended purpose. For example, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium dialkylsulfosuccinate, sodium dodecylsulfate, sodium dialkylsulfosuccinate, naphthalene sulfonate And anionic emulsifiers such as polyoxyethylene alkylphenyl ether sulfate ammonium salt, and nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyethylene glycol monostearate and sorbitan monostearate.

Next, the first photosensitive solder resist composition solution is coated on the support, the first photosensitive solder resist layer is laminated, and the second photosensitive solder resist composition solution is further added to the second photosensitive solder resist composition solution. It can apply | coat on a 1st photosensitive soldering resist layer, a 2nd photosensitive soldering resist layer is formed by making it dry, and a photosensitive soldering resist film can be manufactured.
The method for applying each photosensitive solder resist composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include spraying, roll coating, spin coating, slit coating, and extrusion. Examples of the coating method include a coating method, a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.

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

  The photosensitive solder resist film is preferably coated with the protective film before the lamination to the substrate, for example.

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

The photosensitive solder resist film has a small surface tack, good laminating and handling properties, excellent storage stability, and exhibits excellent chemical resistance, surface hardness, heat resistance, etc. after development. It has the said photosensitive soldering resist layer by which the resist composition was laminated | stacked. For this reason, it can be widely used for forming permanent patterns such as display members such as pillar materials, rib materials, spacers, and partition walls, holograms, micromachines, and proofs, and can be suitably used in a method for producing a printed wiring board. .
In particular, since the photosensitive solder resist film has a uniform thickness, it is more accurately laminated on the base material when the solder resist is formed.

  A solder resist, a protective film, and an insulating film (interlayer insulating film) formed of the photosensitive solder resist film are preferable. The solder resist can protect the wiring from external impact and bending, and is suitable as an insulating film for a multilayer wiring board, a build-up wiring board, and the like.

--Exposure process--
In the exposure step, pattern information of a permanent pattern to be formed on the second photosensitive solder resist layer and the first photosensitive solder resist layer on the substrate laminated in the photosensitive solder resist layer laminating step. The second photosensitive solder resist layer and the first photosensitive solder resist subjected to the exposure are steps of modulating the light irradiated from the light irradiation means based on the above and performing laser exposure through the microlens array. The layer is cured by a photopolymerization reaction and further completely cured by a thermal polymerization reaction by post-bake described later.

  FIG. 5 shows a case where the width of the conductor circuit 4 is 80 μm, and FIG. 6 shows a case where the width of the conductor circuit 4 is 20 μm, both of which have undergone development processing to remove uncured portions after the exposure. In the partial cross section of the laminated body, when the laminated body is completely cured by heating and drying (post-baking) in the development step, the thickness of the corners of the conductor circuit 4 is ensured uniformly, and the surface has no unevenness. A permanent pattern can be obtained.

  If necessary, when forming a via hole on the conductor circuit, a region of the photosensitive solder resist layer located on the conductor circuit is provided with a cured resin region to be exposed and cured, and an opening for the via hole. Forming an uncured resin region that does not expose the photosensitive solder resist layer without being exposed to form, and removing the uncured resin region in a later development step to expose the conductor circuit. 6 has via holes 6 as shown in FIG. 6, the thickness of the corners of the conductor circuit 4 is ensured uniformly, and a flat permanent pattern without irregularities on the surface can be formed.

-Measuring method of flatness-
The method for measuring the flatness is not particularly limited as long as the unevenness on the surface of the permanent pattern can be measured, and can be appropriately selected according to the purpose. Examples thereof include a contact type and a non-contact type. However, a non-contact type that does not damage or load the object to be measured is preferable.
There is no restriction | limiting in particular as said non-contact-type measuring method, According to the objective, it can select suitably, For example, the measurement by a laser interferometer, a laser height gauge, etc. are mentioned.
In the laser interferometer, the laser beam is reflected by the object to be measured, the protrusion portion is recognized from the 3D shape data, the peak value of the recognized protrusion portion is extracted, and each coordinate value, height, and PP value are extracted. It is possible to calculate (the difference between the maximum MAX value and the MIN value) and grasp the difference as the flatness.
In the laser height gauge, the object to be measured is irradiated, and the reflected light is collected by a microscope objective lens and guided to a sensor. Can be obtained.
As the flatness, a printed wiring board to be measured is placed on a flat surface such as a measurement table, and a portion located on a conductor circuit on the surface of the permanent pattern of the printed wiring board, a portion located on a portion other than the conductor circuit For example, a method of measuring the height from the plane at a plurality of locations and measuring the difference between the average of the plurality of low portions and the average of the plurality of high portions as the flatness.

  The flatness is preferably 2 μm or less. When the flatness exceeds 2 μm, for example, when it is attempted to mount a minute electronic component having a high density and a very large number of pins, it is not possible to obtain good bonding to each conductor circuit. That is, if the height of the permanent pattern is too higher than the conductor circuit, the chip portion may not be mounted favorably. If the height of the permanent pattern is too lower than the conductor circuit, good soldering cannot be obtained. Sometimes.

--Exposure--
The exposure (hereinafter also referred to as light irradiation) is performed on the laminate formed on the substrate using the photosensitive solder resist film as described above.
There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned, Among these, digital exposure is preferable.

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose. For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is used. It is preferable to carry out.

  The digital exposure means is not particularly limited and may be appropriately selected depending on the purpose. For example, light irradiation means for irradiating light, light emitted from the light irradiation means based on pattern information to be formed And a light modulation means for modulating the light intensity.

--Light modulation means--
The light modulation means is not particularly limited as long as it can modulate light, and can be appropriately selected according to the purpose. For example, it preferably has n pixel portions.
There is no restriction | limiting in particular as a light modulation means which has the said n image drawing part, According to the objective, it can select suitably, For example, a spatial light modulation element is preferable.

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

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

Hereinafter, an example of the light modulation means will be described with reference to the drawings.
In the DMD 50, as shown in FIG. 22, a large number (for example, 1024 × 768) of micromirrors (micromirrors) 62 constituting pixels (pixels) are arranged in a lattice pattern on an SRAM cell (memory cell) 60. This is a mirror device arranged. In each pixel, a micromirror 62 supported by a support column is provided at the top, and a material having high reflectance such as aluminum is deposited on the surface of the micromirror 62. The reflectance of the micromirror 62 is 90% or more, and the arrangement pitch is 13.7 μm as an example in both the vertical and horizontal directions. A silicon gate CMOS SRAM cell 60 manufactured in a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke, and the entire structure is monolithic. ing.

  When a digital signal is written in the SRAM cell 60 of the DMD 50, the micromirror 62 supported by the support is tilted in a range of ± α degrees (for example, ± 12 degrees) with respect to the substrate side on which the DMD 50 is disposed with the diagonal line as the center. It is done. FIG. 23A shows a state in which the micromirror 62 is tilted to + α degrees in the on state, and FIG. 23B shows a state in which the micromirror 62 is tilted to −α degrees in the off state. Therefore, by controlling the inclination of the micromirror 62 in each pixel of the DMD 50 according to the pattern information as shown in FIG. 22, the laser light B incident on the DMD 50 is reflected in the inclination direction of each micromirror 62. The

  24A and 24B show an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled to + α degrees or −α degrees. The on / off control of each micromirror 62 is performed by the controller 302 (see FIG. 33) connected to the DMD 50. Further, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 62 travels.

  Further, it is preferable that the DMD 50 is arranged with a slight inclination so that the short side forms a predetermined angle θ (for example, 0.1 ° to 5 °) with the sub-scanning direction. FIG. 24A shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not tilted, and FIG. 24B shows the scanning trajectory of the exposure beam 53 when the DMD 50 is tilted. Is shown.

In the DMD 50, a number of micromirror arrays in which a large number (for example, 1024) of micromirrors are arranged in the longitudinal direction are arranged in a short direction (for example, 756 sets). as shown in (B), by tilting the DMD 50, the pitch _{P 2} of the scanning locus of the exposure beams 53 from each micromirror (scan line), it becomes narrower than the pitch _{P 1} of the scanning line when not inclined DMD 50 , The resolution can be greatly improved. On the other hand, the inclination angle of the DMD 50 is small, the scanning width _{W 2} in the case of tilting the DMD 50, which is substantially equal to the scanning width _{W 1} when not inclined DMD 50.

Next, a method for increasing the modulation speed in the optical modulation means (hereinafter referred to as “high-speed modulation”) will be described.
It is preferable that the light modulation unit is capable of controlling any less than n pixel elements arranged continuously from the n pixel elements according to pattern information. There is a limit to the data processing speed of the light modulation means, and the modulation speed per line is determined in proportion to the number of pixels to be used. By using, the modulation speed per line is increased.

Hereinafter, the high-speed modulation will be further described with reference to the drawings.
When the DMD 50 is irradiated with the laser beam B from the fiber array light source 66, the laser beam reflected when the micromirror of the DMD 50 is in the on state is imaged on the photosensitive solder resist film 150 by the lens systems 54 and 58. The In this way, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the photosensitive solder resist film 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of pixels used in the DMD 50. Is done. Further, the photosensitive solder resist film 150 is moved at a constant speed together with the stage 152, so that the photosensitive solder resist film 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip shape is formed for each exposure head 166. The exposed area 170 is formed.

  In this example, as shown in FIGS. 25A and 25B, the DMD 50 has 768 sets of micromirror arrays in which 1024 micromirrors are arranged in the main scanning direction. However, in this example, the controller 302 (see FIG. 33) controls so that only a part of micromirror rows (eg, 1024 × 256 rows) are driven.

  In this case, a micromirror array arranged at the center of the DMD 50 as shown in FIG. 25 (A) may be used, and a micromirror array arranged at the end of the DMD 50 as shown in FIG. 25 (B). May be used. In addition, when a defect occurs in some of the micromirrors, the micromirror array to be used may be appropriately changed depending on the situation, such as using a micromirror array in which no defect has occurred.

  Since the data processing speed of the DMD 50 is limited and the modulation speed per line is determined in proportion to the number of pixels used, the modulation speed per line can be increased by using only a part of the micromirror array. Get faster. On the other hand, in the case of an exposure method in which the exposure head is continuously moved relative to the exposure surface, it is not necessary to use all the pixels in the sub-scanning direction.

  When the sub-scan of the photosensitive solder resist film 150 by the scanner 162 is finished and the rear end of the photosensitive solder resist film 150 is detected by the sensor 164, the stage 152 is gated along the guide 158 by the stage driving device 304. It returns to the origin on the most upstream side of 160 and is moved again along the guide 158 from the upstream side to the downstream side of the gate 160 at a constant speed.

  For example, when only 384 sets of 768 sets of micromirror arrays are used, modulation can be performed twice as fast per line as compared with the case of using all 768 sets. Also, when only 256 pairs are used in the 768 sets of micromirror arrays, modulation can be performed three times faster per line than when all 768 sets are used.

  As described above, according to the solder resist forming method of the present invention, the micromirror array in which 1,024 micromirrors are arranged in the main scanning direction includes the DMD in which 768 sets are arranged in the subscanning direction. By controlling so that only a part of the micromirror rows are driven by the controller, the modulation speed per line becomes faster than when all the micromirror rows are driven.

  In addition, an example in which the DMD micromirror is partially driven has been described, but the length of the direction corresponding to the predetermined direction is reflected on the substrate longer than the length of the direction intersecting the predetermined direction according to the control signal. Even if a long and narrow DMD in which a large number of micromirrors capable of changing the surface angle are arranged in a two-dimensional manner is used, the number of micromirrors for controlling the angle of the reflecting surface is reduced. Can do.

  The exposure method is preferably performed while relatively moving the exposure light and the photosensitive solder resist layer. In this case, it is preferable to use the exposure light in combination with the high-speed modulation. Thereby, high-speed exposure can be performed in a short time.

  In addition, as shown in FIG. 26, the entire surface of the photosensitive solder resist film 150 may be exposed by a single scan in the X direction by the scanner 162. As shown in FIGS. 27 (A) and (B), After scanning the photosensitive solder resist film 150 in the X direction by the scanner 162, the scanner 162 is moved one step in the Y direction and scanned in the X direction. The entire surface of the photosensitive solder resist film 150 may be exposed. In this example, the scanner 162 includes 18 exposure heads 166. Note that the exposure head includes at least the light irradiation unit and the light modulation unit.

  The exposure is performed on a partial area of the photosensitive solder resist layer so that the partial area is cured, and an uncured area other than the cured partial area in a development process described later. Are removed to form a pattern.

Next, an example of a solder resist pattern forming apparatus including the light modulation means will be described with reference to the drawings.
As shown in FIG. 28, the pattern forming apparatus including the light modulator includes a flat plate stage 152 that holds the sheet-like photosensitive solder resist film 150 by adsorbing to the surface.
Two guides 158 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 156 supported by the four legs 154. The stage 152 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by a guide 158 so as to be reciprocally movable. The pattern forming apparatus has a drive device (not shown) for driving the stage 152 along the guide 158.

  A U-shaped gate 160 is provided at the center of the installation table 156 so as to straddle the movement path of the stage 152. Each of the ends of the U-shaped gate 160 is fixed to both side surfaces of the installation table 156. A scanner 162 is provided on one side of the gate 160, and a plurality of (for example, two) detection sensors 164 for detecting the front and rear ends of the photosensitive solder resist film 150 are provided on the other side. ing. The scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152. The scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.

As shown in FIGS. 29 and 30, the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in an approximately matrix of m rows and n columns (for example, 3 rows and 5 columns). In this example, four exposure heads 166 are arranged in the third row in relation to the width of the photosensitive solder resist film 150. In addition, when showing each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure head 166 _mn .

An exposure area 168 by the exposure head 166 has a rectangular shape with a short side in the sub-scanning direction. Accordingly, as the stage 152 moves, a strip-shaped exposed region 170 is formed on the photosensitive solder resist film 150 for each exposure head 166. In addition, when showing the exposure area by each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure area 168 _mn .

In addition, as shown in FIGS. 30A and 30B, each of the exposure heads in each row arranged in a line so that the strip-shaped exposed regions 170 are arranged in the direction orthogonal to the sub-scanning direction without gaps. These are arranged with a predetermined interval (natural number times the long side of the exposure area, twice in this example) in the arrangement direction. Therefore, can not be exposed portion between the exposure area _{168 11} in the first row and the exposure area _{168 12,} it can be exposed by the second row of the exposure area _{168 21} and the exposure area _{168 31} in the third row.

As shown in FIGS. 31 and 32, each of the exposure heads 166 _{11 to} 166 _mn serves as the light modulation means (spatial light modulation element that modulates each pixel) according to the pattern information. A digital micromirror device (DMD) 50 manufactured by Texas Instruments, USA is provided. The DMD 50 is connected to the controller 302 (see FIG. 33) having a data processing unit and a mirror drive control unit. The data processing unit of the controller 302 generates a control signal for driving and controlling each micromirror in the area to be controlled by the DMD 50 for each exposure head 166 based on the input pattern information. The area to be controlled will be described later. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the pattern information processing unit. The control of the angle of the reflecting surface will be described later.

  On the light incident side of the DMD 50, a fiber array light source 66 having a laser emitting portion in which emission ends (light emitting points) of optical fibers are arranged in a line along a direction corresponding to the long side direction of the exposure area 168, A lens system 67 that corrects the laser light emitted from the fiber array light source 66 and collects it on the DMD, and a mirror 69 that reflects the laser light transmitted through the lens system 67 toward the DMD 50 are arranged in this order. In FIG. 31, the lens system 67 is schematically shown.

  As shown in detail in FIG. 32, the lens system 67 is inserted into the optical path of the light passing through the condenser lens 71 and the condenser lens 71 that collects the laser light B as the illumination light emitted from the fiber array light source 66. A rod-shaped optical integrator (hereinafter referred to as a rod integrator) 72 and an imaging lens 74 disposed in front of the rod integrator 72, that is, on the mirror 69 side. The condensing lens 71, the rod integrator 72, and the imaging lens 74 cause the laser light emitted from the fiber array light source 66 to enter the DMD 50 as a light beam that is close to parallel light and has a uniform beam cross-sectional intensity. The shape and action of the rod integrator 72 will be described in detail later.

  The laser beam B emitted from the lens system 67 is reflected by the mirror 69 and irradiated to the DMD 50 via the TIR (total reflection) prism 70. In FIG. 32, the TIR prism 70 is omitted.

  Further, on the light reflection side of the DMD 50, an imaging optical system 51 that images the laser light B reflected by the DMD 50 on the photosensitive solder resist film 150 is disposed. The imaging optical system 51 is schematically shown in FIG. 31, but as shown in detail in FIG. 32, the imaging optical system 51 includes a first imaging optical system including lens systems 52 and 54 and lens systems 57 and 58. A second imaging optical system, a microlens array 55 inserted between these imaging optical systems, and an aperture array 59 are included.

  The microlens array 55 is formed by two-dimensionally arranging a large number of microlenses 55a corresponding to the pixels of the DMD 50. In this example, as described later, only 1024 × 256 rows of the 1024 × 768 rows of micromirrors of the DMD 50 are driven, and accordingly, 1024 × 256 rows of microlenses 55a are arranged. The arrangement pitch of the micro lenses 55a is 41 μm in both the vertical and horizontal directions. As an example, the microlens 55a has a focal length of 0.19 mm, an NA (numerical aperture) of 0.11, and is formed from the optical glass BK7. The shape of the micro lens 55a will be described in detail later. The beam diameter of the laser beam B at the position of each microlens 55a is 41 μm.

  The aperture array 59 is formed by forming a large number of apertures (openings) 59 a corresponding to the respective micro lenses 55 a of the micro lens array 55. The diameter of the aperture 59a is, for example, 10 μm.

  The first imaging optical system enlarges the image by the DMD 50 three times and forms an image on the microlens array 55. The second imaging optical system enlarges the image passing through the microlens array 55 by 1.6 times and forms and projects the image on the photosensitive solder resist film 150. Therefore, as a whole, the image by the DMD 50 is magnified 4.8 times, and is imaged and projected on the photosensitive solder resist film 150.

  A prism pair 73 is disposed between the second imaging optical system and the photosensitive solder resist film 150. By moving the prism pair 73 in the vertical direction in FIG. 32, a photosensitive solder resist film is provided. The focus of the image on 150 can be adjusted. In the figure, the photosensitive solder resist film 150 is sub-scanned in the direction of arrow F.

The pixel part is not particularly limited as long as it can receive and emit light from the light irradiation means, and can be appropriately selected according to the purpose. For example, by the permanent pattern forming method of the present invention When the pattern to be formed is an image pattern, it is a pixel, and when the light modulation means includes a DMD, it is a micromirror.
There is no restriction | limiting in particular as the number (the said n) of picture element parts which the said light modulation element has, It can select suitably according to the objective.
There is no restriction | limiting in particular as an arrangement | sequence of the pixel part in the said light modulation element, According to the objective, it can select suitably, For example, it is preferable to arrange in two dimensions, It arranges in a grid | lattice form. It is more preferable.

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

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

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

  Hereinafter, means (fiber array light source) capable of irradiating the combined laser will be described with reference to the drawings.

  As shown in FIGS. 48A to 48D, the fiber array light source 66 includes a plurality of (for example, 14) laser modules 64, and one end of the multimode optical fiber 30 is provided in each laser module 64. Are combined. An optical fiber 31 having the same core diameter as that of the multimode optical fiber 30 and a smaller cladding diameter than the multimode optical fiber 30 is coupled to the other end of the multimode optical fiber 30. As shown in detail in FIG. 48b, seven end portions of the multimode optical fiber 31 opposite to the optical fiber 30 are arranged along the main scanning direction orthogonal to the sub-scanning direction, and are arranged in two rows to form a laser. An emission unit 68 is configured.

  As shown in FIG. 48b, the laser emitting portion 68 formed by the end portion of the multimode optical fiber 31 is sandwiched and fixed between two support plates 65 having a flat surface. In addition, a transparent protective plate such as glass is preferably disposed on the light emitting end face of the multimode optical fiber 31 for protection. The light exit end face of the multimode optical fiber 31 has high light density and is likely to collect dust and easily deteriorate. However, the protective plate as described above prevents the dust from adhering to the end face and deteriorates. Can be delayed.

  In this example, in order to arrange the emission ends of the optical fibers 31 with a small cladding diameter in a line without any gaps, the multimode optical fiber 30 is placed between two adjacent multimode optical fibers 30 at a portion with a large cladding diameter. Two exit ends of the optical fiber 31 coupled to the two multimode optical fibers 30 adjacent to each other at the portion where the cladding diameter is large are the exit ends of the optical fiber 31 coupled to the stacked and stacked multimode optical fibers 30. Are arranged so as to be sandwiched between them.

  For example, as shown in FIG. 49, such an optical fiber is coaxial with an optical fiber 31 having a length of 1 to 30 cm and a small cladding diameter at the tip of the multimode optical fiber 30 having a large cladding diameter on the laser light emission side. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 31 is fused and joined to the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 31 a of the optical fiber 31 is the same as the diameter of the core 30 a of the multimode optical fiber 30.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused to an optical fiber having a short cladding diameter and a large cladding diameter may be coupled to the output end of the multimode optical fiber 30 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 31 may be referred to as an emission end portion of the multimode optical fiber 30.

  The multimode optical fiber 30 and the optical fiber 31 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used. In the present embodiment, the multimode optical fiber 30 and the optical fiber 31 are step index type optical fibers, and the multimode optical fiber 30 has a cladding diameter = 125 μm, a core diameter = 50 μm, NA = 0.2, an incident end face. The transmittance of the coat is 99.5% or more, and the optical fiber 31 has a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2.

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

  However, the cladding diameter of the optical fiber 31 is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber array light source is 125 μm, but the depth of focus becomes deeper as the clad diameter becomes smaller. Therefore, the clad diameter of the multimode optical fiber is preferably 80 μm or less, preferably 60 μm or less. More preferred is 40 μm or less. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 31 is preferably 10 μm or more.

  The laser module 64 is configured by a combined laser light source (fiber array light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6, arrayed and fixed on the heat block 10. And LD7, collimator lenses 11, 12, 13, 14, 15, 16, and 17 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 20, and one multi-lens. Mode optical fiber 30. The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

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

  As shown in FIGS. 51 and 52, the combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements. The package 40 includes a package lid 41 created so as to close the opening thereof. After the deaeration process, a sealing gas is introduced, and the package 40 and the package lid 41 are closed by closing the opening of the package 40 with the package lid 41. 41. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by 41.

  A base plate 42 is fixed to the bottom surface of the package 40, and the heat block 10, a condensing lens holder 45 that holds the condensing lens 20, and the multimode optical fiber 30 are disposed on the top surface of the base plate 42. A fiber holder 46 that holds the incident end is attached. The exit end of the multimode optical fiber 30 is drawn out of the package from an opening formed in the wall surface of the package 40.

  Further, a collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held. An opening is formed in the lateral wall surface of the package 40, and wiring 47 for supplying a driving current to the GaN-based semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 52, in order to avoid complication of the drawing, only the GaN semiconductor laser LD7 among the plurality of GaN semiconductor lasers is numbered, and only the collimator lens 17 among the plurality of collimator lenses is numbered. is doing.

  FIG. 53 shows the front shape of the attachment part of the collimator lenses 11-17. Each of the collimator lenses 11 to 17 is formed in a shape obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the length direction is orthogonal to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 53).

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

Therefore, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the divergence angle is small with respect to the elongated collimator lenses 11 to 17 as described above. Incident light is incident in a state where the direction coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses 11 to 17 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2. 6 mm. Each of the collimator lenses 11 to 17 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 20 is formed by cutting a region including the optical axis of a circular lens having an aspheric surface into a long and narrow shape in parallel planes, and is long in the arrangement direction of the collimator lenses 11 to 17, that is, in a horizontal direction and short in a direction perpendicular thereto. Is formed. This condenser lens 20 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 20 is also formed by molding resin or optical glass, for example.

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

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

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

  Further, as the light irradiation means having a plurality of light emitting points, for example, as shown in FIG. 55, a laser in which a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 are arranged on the heat block 100. An array can be used. Further, a chip-shaped multicavity laser 110 in which a plurality of (for example, five) light emitting points 110a shown in FIG. 55 are arranged in a predetermined direction is known. Since the multicavity laser 110 can arrange the light emitting points with high positional accuracy as compared with the case where the chip-shaped semiconductor lasers are arranged, it is easy to multiplex the laser beams emitted from the respective light emitting points. However, as the number of light emitting points increases, the multi-cavity laser 110 is likely to be bent at the time of laser manufacture. Therefore, the number of light emitting points 110a is preferably 5 or less.

  As the light irradiation means, as shown in FIG. 55, a plurality of multi-cavity lasers 110 are arranged on the heat block 100 in the same direction as the arrangement direction of the light emitting points 110a of each chip. A multi-cavity laser array can be used as a laser light source.

  The combined laser light source is not limited to one that combines laser beams emitted from a plurality of chip-shaped semiconductor lasers. For example, as shown in FIG. 42, a combined laser light source including a chip-shaped multicavity laser 110 having a plurality of (for example, three) emission points 110a can be used. This combined laser light source is configured to include a multi-cavity laser 110, one multi-mode optical fiber 130, and a condensing lens 120. The multi-cavity laser 110 can be composed of, for example, a GaN-based laser diode having an oscillation wavelength of 405 nm.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110 a of the multicavity laser 110 is collected by the condenser lens 120 and enters the core 130 a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  A plurality of light emitting points 110 a of the multicavity laser 110 are arranged in parallel within a width substantially equal to the core diameter of the multimode optical fiber 130, and a focal point substantially equal to the core diameter of the multimode optical fiber 130 is formed as the condenser lens 120. By using a convex lens of a distance or a rod lens that collimates the outgoing beam from the multi-cavity laser 110 only in a plane perpendicular to the active layer, the coupling efficiency of the laser beam B to the multi-mode optical fiber 130 can be increased. it can.

  As shown in FIG. 56, a multi-cavity laser 110 having a plurality of (for example, three) emission points is used, and a plurality of (for example, nine) multi-cavity lasers 110 are equidistant from each other on the heat block 111. A combined laser light source including the laser array 140 arranged in (1) can be used. The plurality of multi-cavity lasers 110 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 110a of each chip.

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

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110a of the plurality of multi-cavity lasers 110 is collected in a predetermined direction by the rod lens 113, and then each microlens of the lens array 114. It becomes parallel light. The collimated laser beam L is condensed by the condenser lens 120 and enters the core 130a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  Still another example of the combined laser light source will be described. As shown in FIGS. 57 (A) and 57 (B), this combined laser light source has a heat block 182 having an L-shaped cross section in the optical axis direction mounted on a substantially rectangular heat block 180 and two heats. A storage space is formed between the blocks. On the upper surface of the L-shaped heat block 182, a plurality of (for example, two) multi-cavity lasers 110 in which a plurality of light emitting points (for example, five) are arranged in an array form the light emitting points 110a of each chip. It is arranged and fixed at equal intervals in the same direction as the arrangement direction.

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

  On the laser beam emission side of the multi-cavity laser 110, a collimator lens array 184 in which collimator lenses are arranged corresponding to the light emission points 110a of the respective chips is arranged. In the collimating lens array 184, the length direction of each collimating lens coincides with the direction in which the divergence angle of the laser beam is large (fast axis direction), and the width direction of each collimating lens is in the direction in which the divergence angle is small (slow axis direction). They are arranged to match. Thus, by collimating and integrating the collimating lenses, the space utilization efficiency of the laser light can be improved, the output of the combined laser light source can be increased, and the number of parts can be reduced and the cost can be reduced. .

  Further, on the laser beam emitting side of the collimating lens array 184, there is one multimode optical fiber 130 and a condensing lens 120 that condenses and couples the laser beam to the incident end of the multimode optical fiber 130. Is arranged.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110a of the plurality of multi-cavity lasers 110 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and condensed. The light is condensed by the lens 120 and enters the core 130 a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

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

  It should be noted that a laser module in which each of the combined laser light sources is housed in a casing and the emission end of the multimode optical fiber 130 is pulled out from the casing can be configured.

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

  Here, the permanent pattern forming method of the present invention will be further described. In each exposure head 166 of the scanner 162, laser light B1, B2, B3, B4, B5, B6 emitted in a divergent light state from each of the GaN-based semiconductor lasers LD1 to LD7 constituting the combined laser light source of the fiber array light source 66. , And B7 are collimated by corresponding collimator lenses 11-17. The collimated laser beams B <b> 1 to B <b> 7 are collected by the condenser lens 20 and converge on the incident end face of the core 30 a of the multimode optical fiber 30.

  In this example, the collimator lenses 11 to 17 and the condenser lens 20 constitute a condensing optical system, and the condensing optical system and the multimode optical fiber 30 constitute a multiplexing optical system. That is, the laser beams B1 to B7 collected as described above by the condenser lens 20 enter the core 30a of the multimode optical fiber 30 and propagate through the optical fiber to be combined with one laser beam B. The light is emitted from the optical fiber 31 coupled to the output end of the multimode optical fiber 30.

  In each laser module, when the coupling efficiency of the laser beams B1 to B7 to the multimode optical fiber 30 is 0.85 and each output of the GaN-based semiconductor lasers LD1 to LD7 is 30 mW, the light arranged in an array For each of the fibers 31, a combined laser beam B with an output of 180 mW (= 30 mW × 0.85 × 7) can be obtained. Therefore, the output from the laser emitting unit 68 in which the six optical fibers 31 are arranged in an array is about 1 W (= 180 mW × 6).

  In the laser emitting portion 68 of the fiber array light source 66, light emission points with high luminance are arranged in a line along the main scanning direction as described above. A conventional fiber light source that couples laser light from a single semiconductor laser to a single optical fiber has a low output, so that a desired output cannot be obtained unless multiple rows are arranged. Since the laser light source has a high output, a desired output can be obtained even with a small number of columns, for example, one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled on a one-to-one basis, a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser, and the core diameter is 50 μm and the cladding diameter is 125 μm. Since a multimode optical fiber having a numerical aperture (NA) of 0.2 is used, if an output of about 1 W (watt) is to be obtained, 48 multimode optical fibers (8 × 6) must be bundled. Since the area of the light emitting region is 0.62 mm ² (0.675 mm × 0.925 mm), the luminance at the laser emitting portion 68 is 1.6 × 10 ⁶ (W / m ² ) and one optical fiber is used. The luminance per hit is 3.2 × 10 ⁶ (W / m ² ).

On the other hand, when the light irradiating means is a means capable of irradiating a combined laser, an output of about 1 W can be obtained with six multimode optical fibers, and the area of the light emitting region at the laser emitting portion 68 can be obtained. Is 0.0081 mm ² (0.325 mm × 0.025 mm), the luminance at the laser emitting portion 68 is 123 × 10 ⁶ (W / m ² ), which is about 80 times higher than the conventional luminance. be able to. Further, the luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 28 times compared with the conventional one.

  Here, with reference to FIGS. 58A and 58B, the difference in depth of focus between the conventional exposure head and the exposure head of the present embodiment will be described. The diameter of the light emission region of the bundled fiber light source of the conventional exposure head in the sub-scanning direction is 0.675 mm, and the diameter of the light emission region of the fiber array light source of the exposure head in the sub-scanning direction is 0.025 mm. As shown in FIG. 58, in the conventional exposure head, since the light emitting area of the light irradiating means (bundle fiber light source) 1 is large, the angle of the light beam incident on the DMD 3 is increased, and as a result, the light beam incident on the scanning surface 5. The angle becomes larger. For this reason, the beam diameter tends to increase with respect to the light condensing direction (shift in the focus direction).

  On the other hand, as shown in FIG. 58, in the exposure head in the pattern forming apparatus, since the diameter of the light emitting region of the fiber array light source 66 is small in the sub-scanning direction, the angle of the light beam passing through the lens system 67 and entering the DMD 50 is As a result, the angle of the light beam incident on the scanning surface 56 is reduced. That is, the depth of focus becomes deep. In this example, the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus substantially corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot. This effect on the depth of focus is more prominent and effective as the required light quantity of the exposure head is larger. In this example, the size of one pixel projected on the exposure surface is 10 μm × 10 μm. DMD is a reflective spatial light modulation element, but FIG. 58 is a developed view for explaining the optical relationship.

  Pattern information corresponding to the exposure pattern is input to a controller (not shown) connected to the DMD 50 and temporarily stored in a frame memory in the controller. This pattern information is data representing the density of each pixel constituting the image as binary values (whether or not dots are recorded).

  The stage 152 that has adsorbed the photosensitive solder resist film 150 to the surface is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device (not shown). When the leading edge of the photosensitive solder resist film 150 is detected by the detection sensor 164 attached to the gate 160 when the stage 152 passes under the gate 160, the pattern information stored in the frame memory is sequentially stored for a plurality of lines. A control signal is generated for each exposure head 166 based on the pattern information read out and read out by the data processing unit. Then, each of the micromirrors of the DMD 50 is controlled on and off for each exposure head 166 based on the generated control signal by the mirror drive control unit.

  When the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the micromirror of the DMD 50 is in the on state is reflected on the exposed surface 56 of the photosensitive solder resist film 150 by the lens systems 54 and 58. Is imaged. In this way, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the photosensitive solder resist film 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of pixels used in the DMD 50. Is done. Further, the photosensitive solder resist film 150 is moved at a constant speed together with the stage 152, whereby the photosensitive solder resist film 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-like pattern is formed for each exposure head 166. An exposed area 170 is formed.

--Micro lens array--
The exposure is preferably performed using the modulated light through a microlens array, and may be performed through an aperture array, an imaging optical system, or the like.

  The microlens array is not particularly limited and may be appropriately selected depending on the purpose. For example, a microlens array having an aspherical surface capable of correcting aberration due to distortion of the exit surface in the pixel portion Are preferable.

  There is no restriction | limiting in particular as said aspherical surface, According to the objective, it can select suitably, For example, a toric surface is preferable.

  Hereinafter, the microlens array, the aperture array, the imaging optical system, and the like will be described with reference to the drawings.

34 shows DMD 50, light irradiation means 144 for irradiating DMD 50 with laser light, lens systems (imaging optical system) 454, 458, and DMD 50 for enlarging and imaging the laser light reflected by DMD 50. A microlens array 472 in which a large number of microlenses 474 are arranged in correspondence with each other, an aperture array 476 in which a large number of apertures 478 are provided in correspondence with each microlens of the microlens array 472, and laser light that has passed through the apertures is covered. An exposure head composed of lens systems (imaging optical systems) 480 and 482 that form an image on the exposure surface 56 is shown.
Here, FIG. 35 shows the result of measuring the flatness of the reflecting surface of the micromirror 62 constituting the DMD 50. In the figure, the same height positions of the reflecting surfaces are shown connected by contour lines, and the pitch of the contour lines is 5 nm. Note that the x direction and the y direction shown in the figure are two diagonal directions of the micromirror 62, and the micromirror 62 rotates around the rotation axis extending in the y direction as described above. 36A and 36B show the height position displacement of the reflecting surface of the micromirror 62 along the x direction and the y direction, respectively.

  As shown in FIGS. 35 and 36, the reflection surface of the micromirror 62 is distorted, and when attention is paid particularly to the central portion of the mirror, the distortion in one diagonal direction (y direction) is different from the other diagonal line. It is larger than the distortion in the direction (x direction). For this reason, the problem that the shape in the condensing position of the laser beam B condensed with the micro lens 55a of the micro lens array 55 may be distorted may occur.

  In the permanent pattern forming method of the present invention, in order to prevent the above problem, the microlens 55a of the microlens array 55 has a special shape different from the conventional one. Hereinafter, this point will be described in detail.

  FIGS. 37A and 37B respectively show the front and side shapes of the entire microlens array 55 in detail. These drawings also show the dimensions of each part of the microlens array 55, and the unit thereof is mm. In the permanent pattern forming method of the present invention, as described above with reference to FIG. 25, the 1024 × 256 rows of micromirrors 62 of the DMD 50 are driven. A row of 1024 microlenses 55a arranged in the horizontal direction is arranged in parallel in the vertical direction. In the drawing, the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and k in the vertical direction.

  38A and 38B show the front shape and the side shape of one microlens 55a in the microlens array 55, respectively. In the figure, the contour lines of the microlens 55a are also shown. The end surface of each microlens 55a on the light emitting side has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62. More specifically, the micro lens 55a is a toric lens, and has a radius of curvature Rx = −0.125 mm in a direction optically corresponding to the x direction and a radius of curvature Ry = − in a direction corresponding to the y direction. 0.1 mm.

  Therefore, the condensing state of the laser beam B in the cross section parallel to the x direction and the y direction is roughly as shown in FIG. That is, when the cross section parallel to the x direction is compared with the cross section parallel to the y direction, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. .

  40A, 40B, and 40D show the results of simulating the beam diameter in the vicinity of the condensing position (focal position) of the microlens 55a when the microlens 55a has the above-described shape by a computer. For comparison, FIGS. 41a, 41b, 41c, and 41d show the same simulation results for the case where the microlens 55a has a spherical shape with a radius of curvature Rx = Ry = −0.1 mm. In addition, the value of z in each figure has shown the evaluation position of the focus direction of the micro lens 55a with the distance from the beam emission surface of the micro lens 55a.

The surface shape of the microlens 55a used for the simulation is calculated by the following calculation formula.

  In the above formula, Cx means the curvature in the x direction (= 1 / Rx), Cy means the curvature in the y direction (= 1 / Ry), and X is the lens optical axis in the x direction. The distance from O means Y, and Y means the distance from the lens optical axis O in the y direction.

  As is apparent from a comparison between FIGS. 40a to 41d and FIGS. 41a to 41d, in the permanent pattern forming method of the present invention, the microlens 55a has a focal length in a cross section parallel to the y direction. By using a toric lens that is smaller than the focal length, distortion of the beam shape in the vicinity of the condensing position is suppressed. If so, it becomes possible to expose a higher-definition image without distortion on the photosensitive solder resist film 150. It can also be seen that the present embodiment shown in FIGS. 40a to 40d has a wider region with a smaller beam diameter, that is, a greater depth of focus.

  In addition, when the magnitude relation of the distortion of the center part in the x direction and the y direction of the micromirror 62 is opposite to the above, the focal length in the cross section parallel to the x direction is in the cross section parallel to the y direction. If the microlens is composed of a toric lens smaller than the focal length, similarly, a higher-definition image without distortion can be exposed to the photosensitive solder resist film 150.

  In addition, the aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is disposed such that only light having passed through the corresponding microlens 55a is incident on each aperture 59a. That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to increase the extinction ratio.

  Originally, if the diameter of the aperture 59a of the aperture array 59 installed for the above purpose is reduced to some extent, an effect of suppressing the distortion of the beam shape at the condensing position of the microlens 55a can be obtained. However, in such a case, the amount of light blocked by the aperture array 59 is increased, and the light use efficiency is reduced. On the other hand, when the microlens 55a has an aspherical shape, the light utilization efficiency is kept high because the light is not blocked.

  In the permanent pattern forming method of the present invention, the microlens 55a may have a secondary aspherical shape or a higher order (4th, 6th,...) Aspherical shape. . By adopting the higher order aspherical shape, the beam shape can be further refined.

  In the embodiment described above, the end surface on the light emission side of the micro lens 55a is an aspherical surface (toric surface). However, one of the two light passing end surfaces is a spherical surface and the other is a cylindrical surface. Thus, the microlens array can be configured to obtain the same effect as the above embodiment.

  Furthermore, in the embodiment described above, the microlens 55a of the microlens array 55 has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62. Such an aspherical shape is adopted. Instead, the same effect can be obtained even if each microlens constituting the microlens array has a refractive index distribution that corrects aberration due to distortion of the reflection surface of the micromirror 62.

  An example of such a microlens 155a is shown in FIG. (A) and (B) of the same figure respectively show the front shape and side shape of the micro lens 155a, and the external shape of the micro lens 155a is a parallel plate shape as shown in the figure. The x and y directions in the figure are as described above.

  44A and 44B schematically show the condensing state of the laser beam B in the cross section parallel to the x direction and the y direction by the microlens 155a. The microlens 155a has a refractive index distribution that gradually increases outward from the optical axis O. In the drawing, the broken line shown in the microlens 155a indicates that the refractive index is predetermined from the optical axis O. The position changed with the pitch is shown. As shown in the figure, when the cross section parallel to the x direction and the cross section parallel to the y direction are compared, the ratio of the refractive index change of the microlens 155a is larger in the latter cross section, and the focal length is larger. It is shorter. Even when a microlens array composed of such a gradient index lens is used, the same effect as when the microlens array 55 is used can be obtained.

  Incidentally, in the microlens whose surface shape is aspherical like the microlens 55a previously shown in FIGS. 38A and 38B, the refractive index distribution as described above is also given, and the surface shape and refraction are given. You may make it correct | amend the aberration by the distortion of the reflective surface of the micromirror 62 by both of rate distribution.

  In the above embodiment, the aberration due to the distortion of the reflection surface of the micromirror 62 constituting the DMD 50 is corrected. However, in the permanent pattern forming method of the present invention using a spatial light modulation element other than the DMD, the spatial When there is distortion on the surface of the picture element portion of the light modulation element, the present invention can be applied to correct the aberration due to the distortion and prevent the beam shape from being distorted.

Next, the imaging optical system will be further described.
In the exposure head, when the laser beam is irradiated from the light irradiation unit 144, the cross-sectional area of the light beam reflected in the ON direction by the DMD 50 is enlarged several times (for example, two times) by the lens systems 454 and 458. The The expanded laser light is condensed by each microlens of the microlens array 472 so as to correspond to each pixel part of the DMD 50, and passes through the corresponding aperture of the aperture array 476. The laser light that has passed through the aperture is imaged on the exposed surface 56 by the lens systems 480 and 482.

  In this imaging optical system, the laser light reflected by the DMD 50 is magnified several times by the magnifying lenses 454 and 458 and projected onto the exposed surface 56, so that the entire image area is widened. At this time, if the microlens array 472 and the aperture array 476 are not arranged, one pixel size (spot size) of each beam spot BS projected onto the exposed surface 56 is the exposure area 468 as shown in FIG. MTF (Modulation Transfer Function) characteristics representing the sharpness of the exposure area 468 are deteriorated.

  On the other hand, when the microlens array 472 and the aperture array 476 are arranged, the laser light reflected by the DMD 50 is condensed corresponding to each pixel part of the DMD 50 by each microlens of the microlens array 472. As a result, as shown in FIG. 34, even when the exposure area is enlarged, the spot size of each beam spot BS can be reduced to a desired size (for example, 10 μm × 10 μm), and the MTF characteristics are reduced. Therefore, high-definition exposure can be performed. The exposure area 468 is tilted because the DMD 50 is tilted and arranged in order to eliminate the gap between the pixels.

  In addition, the aperture array can shape the beam so that the spot size on the surface to be exposed 56 is constant even if the beam is thick due to the aberration of the micro lens. Thus, crosstalk between adjacent picture elements can be prevented by passing through the aperture array.

  Further, by using a high-intensity light source, which will be described later, as the light irradiating means 144, the angle of the light beam incident on each microlens of the microlens array 472 from the lens 458 becomes small. The incident can be prevented. That is, a high extinction ratio can be realized.

-Other optical systems-
In the permanent pattern forming method of the present invention, it may be used in combination with other optical systems appropriately selected from known optical systems, for example, a light quantity distribution correcting optical system composed of a pair of combination lenses.
The light amount distribution correcting optical system changes the light flux width at each exit position so that the ratio of the light flux width at the peripheral portion to the light flux width at the central portion close to the optical axis is smaller on the exit side than on the incident side. When the DMD is irradiated with the parallel light flux from the light irradiation means, the light amount distribution on the irradiated surface is corrected so as to be substantially uniform. Hereinafter, the light quantity distribution correcting optical system will be described with reference to the drawings.

  First, as shown in FIG. 45, a description will be given of a case where the entire luminous flux width (total luminous flux width) H0 and H1 is the same between the incident luminous flux and the outgoing luminous flux. In FIG. 45, the portions denoted by reference numerals 51 and 52 virtually indicate the entrance surface and the exit surface in the light quantity distribution correction optical system.

  In the light quantity distribution correcting optical system, it is assumed that the light flux widths h0 and h1 of the light beam incident on the central portion near the optical axis Z1 and the light flux incident on the peripheral portion are the same (h0 = hl). The light quantity distribution correcting optical system expands the light flux width h0 of the incident light flux at the central portion with respect to the light having the same light flux width h0, h1 on the incident side, and conversely changes the incident light flux at the peripheral portion. On the other hand, the light beam width h1 is reduced. That is, the width h10 of the outgoing light beam at the center and the width h11 of the outgoing light beam at the periphery are set to satisfy h11 <h10. In terms of the ratio of the luminous flux width, the ratio “h11 / h10” of the luminous flux width in the peripheral portion to the luminous flux width in the central portion on the emission side is smaller than the ratio (h1 / h0 = 1) on the incident side ( (H11 / h10) <1).

  By changing the light flux width in this way, the light flux in the central part, which normally has a large light quantity distribution, can be utilized in the peripheral part where the light quantity is insufficient, and the overall light utilization efficiency is not reduced. In addition, the light quantity distribution on the irradiated surface is made substantially uniform. The degree of uniformity is, for example, such that the unevenness in the amount of light in the effective area is within 30%, preferably within 20%.

  The actions and effects of the light quantity distribution correcting optical system are the same when the entire light flux width is changed between the incident side and the exit side (FIG. 45).

  FIG. 45 shows a case where the entire light flux width H0 on the incident side is “reduced” to the width H2 before being emitted (H0> H2). Even in such a case, the light quantity distribution correcting optical system has the same light beam width h0, h1 on the incident side, and the light beam width h10 in the central part is larger than that in the peripheral part on the emission side. Conversely, the luminous flux width h11 at the peripheral part is made smaller than that at the central part. Considering the reduction rate of the light beam, the reduction rate with respect to the incident light beam in the central part is made smaller than that in the peripheral part, and the reduction rate with respect to the incident light beam in the peripheral part is made larger than that in the central part. Also in this case, the ratio “H11 / H10” of the light flux width in the peripheral portion to the light flux width in the central portion is smaller than the ratio (h1 / h0 = 1) on the incident side ((h11 / h10) <1). .

  FIG. 45 shows a case where the entire light flux width H0 on the incident side is “enlarged” by a width Η3 and emitted (H0 <H3). Even in such a case, the light quantity distribution correcting optical system has the same light beam width h0, h1 on the incident side, and the light beam width h10 in the central part is larger than that in the peripheral part on the emission side. Conversely, the luminous flux width h11 at the peripheral part is made smaller than that at the central part. Considering the expansion rate of the light beam, the expansion rate for the incident light beam in the central portion is made larger than that in the peripheral portion, and the expansion rate for the incident light beam in the peripheral portion is made smaller than that in the central portion. Also in this case, the ratio “h11 / h10” of the light flux width in the peripheral portion to the light flux width in the central portion is smaller than the ratio (h1 / h0 = 1) on the incident side ((h11 / h10) <1). .

  As described above, the light quantity distribution correcting optical system changes the light flux width at each emission position, and the ratio of the light flux width in the peripheral portion to the light flux width in the central portion close to the optical axis Z1 is larger on the outgoing side than on the incident side. Since the light having the same luminous flux width on the incident side is larger on the outgoing side, the luminous flux width in the central portion is larger than that in the peripheral portion, and the luminous flux width in the peripheral portion is smaller than that in the central portion. Become smaller. As a result, it is possible to make use of the light beam at the center part to the peripheral part, and it is possible to form a light beam cross-section with a substantially uniform light amount distribution without reducing the light use efficiency of the entire optical system.

Next, an example of specific lens data of a pair of combination lenses used as the light quantity distribution correcting optical system will be shown. In this example, lens data is shown in the case where the light amount distribution in the cross section of the emitted light beam is a Gaussian distribution, as in the case where the light irradiation means is a laser array light source. When one semiconductor laser is connected to the incident end of the single mode optical fiber, the light quantity distribution of the emitted light beam from the optical fiber becomes a Gaussian distribution. The permanent pattern forming method of the present invention can be applied to such a case. Further, the present invention can be applied to a case where the light amount in the central portion near the optical axis is larger than the light amount in the peripheral portion, for example, by reducing the core diameter of the multi-mode optical fiber and approaching the configuration of the single mode optical fiber.
Table 1 below shows basic lens data.

  As can be seen from Table 1. As described above, the pair of combination lenses is composed of two rotationally symmetric aspherical lenses. If the light incident side surface of the first lens disposed on the light incident side is the first surface and the light exit side surface is the second surface, the first surface is aspherical. In addition, when the surface on the light incident side of the second lens disposed on the light emitting side is the third surface and the surface on the light emitting side is the fourth surface, the fourth surface is aspherical.

  In Table 1, the surface number Si indicates the number of the i-th surface (i = 1 to 4), the curvature radius ri indicates the curvature radius of the i-th surface, and the surface interval di indicates the i-th surface and the i + 1-th surface. The distance between surfaces on the optical axis is shown. The unit of the surface interval di value is millimeter (mm). The refractive index Ni indicates the value of the refractive index with respect to the wavelength of 405 nm of the optical element having the i-th surface. Table 2 below shows the aspheric data of the first surface and the fourth surface.

  The above-mentioned aspheric data is represented by a coefficient in the following equation representing the aspheric shape.

In the above formula, each coefficient is defined as follows.
Z: Length of a perpendicular line (mm) drawn from a point on the aspheric surface at a height ρ from the optical axis to the tangent plane (plane perpendicular to the optical axis) of the apex of the aspheric surface
ρ: Distance from optical axis (mm)
K: Conic coefficient C: Paraxial curvature (1 / r, r: Paraxial radius of curvature)
ai: i-th order (i = 3 to 10) aspheric coefficient In the numerical values shown in Table 2, the symbol “E” indicates that the subsequent numerical value is a “power index” with 10 as the base. The numerical value represented by the exponential function with the base of 10 is multiplied by the numerical value before “E”. For example, “1.0E-02” indicates “1.0 × 10 ⁻² ”.

  FIG. 47 shows the light quantity distribution of illumination light obtained by the pair of combination lenses shown in Tables 1 and 2. The horizontal axis indicates coordinates from the optical axis, and the vertical axis indicates the light amount ratio (%). For comparison, FIG. 46 shows a light amount distribution (Gaussian distribution) of illumination light when correction is not performed. It can be seen from FIG. 46 and FIG. As described above, the light amount distribution correction optical system corrects the light amount distribution which is substantially uniform as compared with the case where the correction is not performed. Thereby, it is possible to perform exposure with uniform laser light without reducing the use efficiency of light, without causing any unevenness.

-Support removal process-
The said support body removal process is a process of removing the said support body from the said laminated body, when the said photosensitive soldering resist film is laminated | stacked on a base | substrate. Since the support may be removed before the uncured portion of the photosensitive solder resist layer is dissolved and removed by development, it may be removed between the laminate forming step and the exposure step. You may remove between a process and the said image development process.

--Development process--
The developing step exposes the photosensitive solder resist layer in the laminate by the exposure step, cures the exposed region of the photosensitive solder resist layer, and then removes the uncured resin portion of the laminate. In this step, the conductive circuit in the uncured resin region on the substrate surface is exposed and then dried.

  The developing step can be preferably performed by, for example, developing means. The developing means is not particularly limited as long as it can be developed using a developer, and can be appropriately selected according to the purpose. For example, the means for spraying the developer, and applying the developer And means for immersing in the developer. These may be used alone or in combination of two or more. In addition, the developing unit may include a developer replacing unit that replaces the developer, a developer supplying unit that supplies the developer, and the like.

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

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

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

-Post bake-
The post-bake is a process for further completely curing the cured resin portion formed on the substrate by development. In general, the post-baking is a process of heating and drying the laminated body at 140 to 150 ° C. for about 60 minutes after development. By this post-baking, the thickness of the cured resin portion that becomes a permanent pattern shrinks, and the flattened surface of the permanent pattern is entirely cured.

―Other processes―
There is no restriction | limiting in particular as said other process, Selecting suitably from the process in well-known pattern formation is mentioned, For example, an etching process, a plating process, etc. are mentioned. These may be used alone or in combination of two or more.

-Etching process-
The etching process is a process of dissolving and removing the exposed metal layer with an etching solution.
The etching step can be performed by a method appropriately selected from known etching methods.
There is no restriction | limiting in particular as an etching liquid used for the said etching process, According to the objective, it can select suitably, For example, when the said metal layer is formed with copper, a cupric chloride solution, chloride. A ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, and the like can be given. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor.

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

  Since the permanent pattern forming method and the pattern forming apparatus of the present invention use a photosensitive solder resist film that can suppress a decrease in sensitivity of the photosensitive solder resist layer and can form a high-definition pattern, a smaller amount of energy is used. It is advantageous in that the processing speed increases because the exposure speed increases.

  Since the method for forming a permanent pattern of the present invention uses the photosensitive solder resist film of the present invention, the formation of various patterns, the formation of permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers, partition walls, etc. It can be suitably used for the production of liquid crystal structural members, holograms, micromachines, proofs, and the like, and can be particularly suitably used for the formation of high-definition wiring patterns. Since the pattern forming apparatus includes the photosensitive solder resist film of the present invention, various patterns are formed, permanent patterns such as wiring patterns are formed, liquid crystals such as color filters, pillar materials, rib materials, spacers, and partition walls. It can be suitably used for the production of structural members, holograms, micromachines, proofs, etc., and can be particularly suitably used for the formation of high-definition wiring patterns.

―Method of manufacturing printed wiring board―
The permanent pattern forming method of the present invention can be suitably used for the production of a printed wiring board, particularly for the production of a printed wiring board having a hole portion such as a through hole or a via hole. Hereinafter, the manufacturing method of the printed wiring board using the permanent pattern formation method of this invention is demonstrated. The photosensitive solder resist film is optimal as a material for forming a permanent pattern such as a solder resist or a wiring pattern on the printed wiring board having a wiring pattern.

In particular, as a method of manufacturing a printed wiring board having a hole portion such as a through hole or a via hole,
(1) On the printed wiring board forming substrate having the hole portion, the photosensitive solder resist film is laminated in such a positional relationship that the outermost photosensitive solder resist layer is on the substrate side to form a laminate. Forming,
(2) From the opposite side of the laminate to the printed wiring board, the photosensitive solder resist layer is cured by irradiating light to the wiring pattern forming region and the hole forming region,
(3) Remove the support in the photosensitive solder resist film from the laminate,
(4) The photosensitive solder resist layer in the laminate is developed, and a wiring pattern is formed by removing an uncured portion in the laminate,
(5) A laminated body is formed by laminating the photosensitive solder resist film on the printed wiring board having the wiring pattern in such a positional relationship that the outermost photosensitive solder resist layer is on the substrate side,
(6) The resist formation region is exposed from the side opposite to the printed wiring board of the laminate. Furthermore, a cured region where the photosensitive solder resist layer is cured by light irradiation and an uncured region where no light is irradiated are formed in the opening region,
(7) The photosensitive solder resist layer in the laminate is developed, and a solder resist is formed by removing an uncured portion in the laminate,
(8) In addition, a method of manufacturing a printed wiring board by performing a plasma treatment or the like for printing letters or the like on the solder resist surface or modifying the solder resist layer as necessary may be mentioned.

  The removal of the support in (3) may be performed between (1) and (2) instead of between (2) and (4).

In order to obtain a multilayer printed wiring board, after the step (7), the surface on which the solder resist is formed is subjected to electroless copper plating to form a metal layer, and a photosensitive solder is formed on the metal layer. Examples include a method of laminating a resist film, exposing and developing to form a wiring pattern, and sequentially laminating the formed pattern by etching or plating.
There is no restriction | limiting in particular as the method of laminating | stacking sequentially, According to the objective, it can select suitably, For example, a well-known subtractive method, a semi-additive method, a full additive method etc. are mentioned. Among these, in order to form a printed wiring board with industrially advantageous tenting, the semi-additive method is preferable to the subtractive method. Since the subtractive method forms a pattern by etching the copper over the etching resist after panel plating on the entire surface, the etching proceeds not only in the vertical direction but also in the horizontal direction with respect to the resist, It is difficult to form a pattern faithful to the resist. In the case of the subtractive method, since such an undercut occurs, there is a limit to fine pattern formation. In the semi-additive method, after laminating a photosensitive solder resist film, plating is performed to form a pattern, so that the thickness of the plating becomes the thickness of the copper foil as it is, so the circuit of the fine pattern is controlled by controlling the plating thickness. It can correspond to.

Next, the manufacturing method of the printed wiring board which has a through hole and a via hole using the said photosensitive soldering resist film is demonstrated concretely using FIGS.
The interlayer insulating film is a layer that can be an insulating film when forming a build-up layer on the core substrate in manufacturing a build-up multilayer substrate. A method using a photosensitive interlayer insulating film (photo via method) is used. Are known. A method for manufacturing a build-up substrate that involves formation of a photosensitive interlayer insulating film is shown in FIGS.

― (1) Printed wiring board forming substrate―
As shown in FIG. 11, a printed wiring board forming substrate in which a metal layer 5a is formed on an insulating substrate 5 is prepared. The material of the printed wiring board forming substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a glass epoxy plate, a polyimide substrate, a bismaleimide-triazine resin substrate, a fluororesin substrate, a ceramic substrate And a copper clad laminated substrate.

-(2) Formation of the first circuit pattern-
As shown in FIG. 12, first, a dry film resist is attached to this printed wiring board forming substrate, and a first circuit pattern 4 is formed on the substrate by pattern exposure, development, etching or plating.

― (3) Formation of photosensitive interlayer insulation layer―
As shown in FIG. 13, in order to cover and insulate each first circuit pattern 4, a photosensitive interlayer insulating layer 9b is applied on both sides of the substrate 5 if it is a liquid photo solder resist, and is dried if it is a photosensitive film. To do.

― (4) Photo via formation―
As shown in FIG. 14, a photo via pattern is exposed and developed to form a photo via 9c and a photosensitive interlayer insulating layer 9b.

― (5) Drilling through holes―
As shown in FIG. 15, drilling for the through hole 6 is performed with a drill. Surface roughening treatment is performed on the via hole, the through hole, and the photosensitive interlayer insulating layer. Usually, roughening is performed by removing heat-resistant resin particles present on the surface of the interlayer insulating layer with an acid or an oxidizing agent. The height of the roughened surface formed by acid treatment or the like is preferably Rmax = 0.01 to 20 μm. This is to ensure adhesion with the conductor circuit 4.

― (6) Formation and patterning of plating resist―
As shown in FIG. 16, a plating resist 8a is formed and patterned so as to cover a portion not to be plated.

― (7) Electroless copper plating―
As shown in FIG. 17, electroless copper plating is performed, and a portion not covered with the plating resist 8a is plated 8b. The thickness is preferably 1 to 5 μm, and more preferably 2 to 3 μm.

― (8) Repeat―
If necessary, the steps (3) to (7) are repeated, and the uppermost conductor circuit is subjected to electroless plating under the same conditions as in the above (7), and the roughened layer or the rougher layer is formed on the uppermost conductor circuit. Form a chemical surface.

― (9) Lamination of photosensitive solder resist film―
As shown in FIG. 18, a photosensitive solder resist film is laminated to form a solder resist layer 8c in order to cover a portion where soldering is not desired.

-(10) Formation of solder resist pattern-
As shown in FIG. 19, a solder resist pattern 8d is formed by baking and developing a solder resist pattern.

― (11) Nickel plating / gold plating―
As shown in FIG. 20, the copper portion not covered with the solder resist is nickel-plated, and gold plating 8e is applied thereon.

― (12) Solder paste application―
As shown in FIG. 21, a solder paste 8f is applied and formed, and reflow treatment is performed to solidify and form a solder layer.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
The following synthesis examples 1 to 6 were prepared for the polymer and oligomer compositions used in the examples and comparative examples.

<Synthesis Example 1: Polymer P1>
145 parts by mass of methoxypropyl acetate was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, stirred while replacing with nitrogen, and heated to 120 ° C. Next, t-butyl hydroperoxide (Nippon Yushi Co., Ltd.) was added to a monomer mixture consisting of 10.4 parts by mass of styrene, 71 parts by mass of glycidyl methacrylate and 82 parts by mass of dicyclopentenyl acrylate (FA-511A manufactured by Hitachi Chemical Co., Ltd.). 3.0 parts by weight of perbutyl O). This mixed solution was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 120 ° C. for 2 hours. Next, the inside of the flask was replaced with air, 0.9 parts by mass of trisdimethylaminomethylphenol and 0.145 parts by mass of hydroquinone were added to 34.2 parts by mass of acrylic acid, and the flask was heated at 120 ° C. for 6 hours. The reaction was continued and the reaction was terminated when the solid content acid value was 0.8. Further, 60.8 parts by mass of tetrahydrophthalic anhydride (84.2 mol% of the generated hydroxyl group), 0.8 parts by mass of triethylamine Was added and reacted at 120 ° C. for 3.5 hours, and diluted with methoxypropyl acetate to a solid content concentration of 62% by mass to obtain an alkali-soluble photocrosslinkable polymer (polymer P1). The solid part acid value of the polymer P1 was 84, and the mass average molecular weight was 32,000.

<Synthesis Example 2: Oligomer L1>
EOCN-102S (manufactured by Nippon Kayaku Co., Ltd., cresol novolac type epoxy resin (epoxy equivalent = 210), 210 parts by mass, 72 parts by mass of acrylic acid, 1.0 part by mass of hydroquinone, 180 parts by mass of methoxypropyl acetate, The reaction mixture was dissolved by heating and stirring to 90 ° C. Next, the mixture was cooled to 60 ° C., 1 part by mass of benzyltrimethylammonium chloride was added, and the mixture was heated to 100 ° C., so that the solid content acid value was 1 mg KOH / g. Next, 152 parts by mass of tetrahydrophthalic anhydride and 100 parts by mass of methoxypropyl acetate were charged, heated to 80 ° C., reacted for about 6 hours and cooled, so that the solid content concentration became 60% by mass. Was diluted with methoxypropyl acetate to obtain an alkali-soluble photocrosslinkable oligomer (oligomer L1). 1 of the acid value of the solid at 138 mg KOH / g, weight average molecular weight was 1620.

<Synthesis Example 3: Oligomer L2>
EOCN-102S (manufactured by Nippon Kayaku Co., Ltd., cresol novolak type epoxy resin (epoxy equivalent = 215), 215 parts by mass, 72 parts by mass of acrylic acid, 1.0 part by mass of hydroquinone, 180 parts by mass of methoxypropyl acetate, The reaction mixture was dissolved by heating and stirring to 90 ° C. Next, the mixture was cooled to 60 ° C., 1 part by mass of benzyltrimethylammonium chloride was added, and the mixture was heated to 100 ° C., so that the solid content acid value was 1 mg KOH / g. Next, 152 parts by mass of tetrahydrophthalic anhydride and 100 parts by mass of methoxypropyl acetate were charged, heated to 80 ° C., reacted for about 6 hours and cooled to a solid content concentration of 62% by mass. Was diluted with methoxypropyl acetate to obtain an alkali-soluble photocrosslinkable oligomer (oligomer L2). 2 of the acid value of the solid at 138 mg KOH / g, weight average molecular weight was 2850.

<Synthesis Example 4: Oligomer L3>
EOCN-102S (manufactured by Nippon Kayaku Co., Ltd., cresol novolac type epoxy resin (epoxy equivalent = 220), 220 parts by mass, 72 parts by mass of acrylic acid, 1.0 part by mass of hydroquinone, 180 parts by mass of methoxypropyl acetate, The reaction mixture was dissolved by heating and stirring to 90 ° C. Next, the mixture was cooled to 60 ° C., 1 part by mass of benzyltrimethylammonium chloride was added, and the mixture was heated to 100 ° C., so that the solid content acid value was 1 mg KOH / g. Next, 152 parts by mass of tetrahydrophthalic anhydride and 100 parts by mass of methoxypropyl acetate were charged, heated to 80 ° C., reacted for about 6 hours and cooled, so that the solid content concentration became 60% by mass. Was diluted with methoxypropyl acetate to obtain an alkali-soluble photocrosslinkable oligomer (oligomer L3). 3 of the acid value of the solid in 139mgKOH / g, weight average molecular weight was 4,020.

<Synthesis Example 5: Polymer P2> (for Comparative Example)
Propylene glycol monomethyl obtained by maintaining a mixture of 50 parts by mass of n-butyl methacrylate, 9 parts by mass of hydroxyethyl methacrylate, 32.5 parts by mass of methacrylic acid and 2 parts by mass of azobisisobutylnitrile at 80 ° C. in a nitrogen gas atmosphere. It was dripped in 120 mass parts of ether over 5 hours. Thereafter, after aging for 1 hour, 0.5 parts by mass of azobisisobutylnitrile was further added, followed by aging for 2 hours to synthesize a carboxyl group-containing methacrylic resin. Next, while blowing air, 15 parts by mass of glycidyl methacrylate, 1.5 parts by mass of tetrabutylammonium bromide and 0.15 parts by mass of hydroquinone as a polymerization inhibitor were added and reacted at a temperature of 80 ° C. for 8 hours. Thus, an alkali-soluble photocrosslinkable polymer (polymer P2) having a carboxyl group having a molecular weight of 50,000 to 70,000, an acid value of 1.2 meq / g, and an unsaturated equivalent of 1.14 mol / kg was synthesized.

<Synthesis Example 6: Polymer P3> (for Comparative Example)
Propylene glycol monomethyl obtained by maintaining a mixture of 50 parts by mass of n-butyl methacrylate, 9 parts by mass of hydroxyethyl methacrylate, 32.5 parts by mass of methacrylic acid and 2 parts by mass of azobisisobutylnitrile at 80 ° C. in a nitrogen gas atmosphere. It was dripped in 120 mass parts of ether over 5 hours. Thereafter, after aging for 1 hour, 1 part by mass of azobisisobutylnitrile was further added and aging was performed for 2 hours to synthesize a carboxyl group-containing methacrylic resin. Next, while blowing air, 15 parts by mass of glycidyl methacrylate, 1.5 parts by mass of tetrabutylammonium bromide and 0.15 parts by mass of hydroquinone as a polymerization inhibitor were added and reacted at a temperature of 80 ° C. for 8 hours. Thus, an alkali-soluble photocrosslinkable polymer (polymer P3) having a carboxyl group having a molecular weight of 20,000 to 25,000, an acid value of 2 meq / g, and an unsaturated equivalent of 1.14 mol / kg was synthesized.

Example 1
-Preparation of first photosensitive solder resist composition solution used for first photosensitive solder resist layer-
A first photosensitive solder resist composition solution having the following composition was prepared: ―――――――――――――――――――――――――――――――― ―――――――
Polymer P1 (Synthesis Example 1) ... 46.7 parts by mass Polymerizable compound (DPHA76 (76% by mass)) ... 21.1 parts by mass Photopolymerization initiator (Irgacure 819) ... 6.0 parts by mass Thermal crosslinking agent ... ... 12.1 parts by weight Inorganic filler (B30) / colorant co-dispersion (35% by weight) ... 81.4 parts by weight Colorant (phthalocyanine green)
Thermosetting accelerator (dicyandiamide) ... 0.6 parts by mass Elastomer (SEBS) ... 9.5 parts by mass Adhesion promoter (2MZ-AZINE) ··········· 0.45 parts by mass Application aid (30% by mass of fluorosurfactant)・ ・ ・ ・ 0.2 parts by mass Solvent (MEK / MFGAc) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 10 parts by mass ―――――――――――― ――――――――――――――――――――――――――――
Thermal crosslinking agent: epoxy equivalent 214 g / eq. The following structural formula having a viscosity of 62,000 mPa · s.

-Preparation of second photosensitive solder resist composition solution used for second photosensitive solder resist layer-
A second photosensitive solder resist composition solution having the following composition was prepared: ―――――――――――――――――――――――――――――――― ―――――――
Oligomer L1 (Synthesis Example 2) ... 46.7 parts by mass Polymerizable compound (DPHA76 (76% by mass)) ... 21 1 part by weight Photopolymerization initiator (Irgacure 819) ... 6.0 parts by weight Thermal cross-linking agent ... .... 12.1 parts by weight Inorganic filler (B30) / colorant co-dispersion (35% by weight) 81.4 parts by weight Colorant (phthalocyanine green)
Thermosetting accelerator (dicyandiamide) ... 0.6 parts by mass Elastomer (SEBS) ... 9.5 parts by mass Adhesion promoter (2MZ-AZINE) ··········· 0.45 parts by mass Application aid (30% by mass of fluorosurfactant)・ ・ ・ ・ 0.2 parts by mass Solvent (MEK / MFGAc) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 10 parts by mass ―――――――――――― ――――――――――――――――――――――――――――
Thermal crosslinking agent: epoxy equivalent 214 g / eq. The following structural formula having a viscosity of 62,000 mPa · s.

-Preparation of pigment and inorganic filler dispersion-
Pigment Blue 15: 3, 0.80 parts by weight, Pigment Yellow 180, 0.7 parts by weight, 60 parts by weight of each alkali-soluble photocrosslinkable polymer, and 15 parts by weight of methoxypropyl acetate solution were weighed. Was dispersed using a mill type disperser filled with a green pigment dispersion (solid content: 64% by mass).
Subsequently, 18 parts by mass of barium sulfate as an inorganic filler was mixed and stirred in the green pigment dispersion together with 46.9 parts by mass of an additional solvent methoxypropylene glycol acetate, and 81.4 parts by mass of a co-dispersion with a green pigment ( A solid concentration of 35% by mass was obtained.

-Production of photosensitive solder resist film-
As shown in FIG. 1, the support 1 uses a polyethylene terephthalate film having a thickness of 20 μm, the first photosensitive solder resist composition solution is applied onto the support 1 and dried, and then the first 30 μm thick is formed. A photosensitive solder resist layer 2a is formed, and the second photosensitive solder resist composition is applied onto the first photosensitive solder resist layer 2a and dried to form a second photosensitive solder resist layer having a thickness of 10 μm. Then, a protective film 3 was laminated on the second photosensitive solder resist layer 2a using a polyethylene film having a thickness of 20 μm to produce the photosensitive solder resist film.

-Fabrication of laminates-
While peeling the protective film 3 of the photosensitive solder resist film on the surface of a printed wiring board (no through-hole, copper thickness 12 μm) on which a conductor circuit 4 is formed on the substrate 5 shown in FIG. The second photosensitive solder resist layer 2b of the film is brought into contact with the conductor circuit 4 and is bonded using a laminator (MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.), and the printed wiring board, A laminate shown in FIG. 3 was prepared in which the photosensitive solder resist layer 2b, the first photosensitive solder resist layer 2a, and the polyethylene terephthalate film (support 1) were laminated in this order.
The pressure bonding conditions were a laminated plate temperature (lamination temperature) of 70 ° C., a pressure roll temperature of 105 ° C., a pressure roll pressure of 0.3 MPa, and a lamination speed of 1.2 m / min.

-exposure-
As shown in FIG. 4, laser exposure was performed except for a region having a diameter of 40 μm serving as an opening provided in the central portion of the conductor circuit 4 from the support 1 side of the laminate.

-developing-
Thereafter, the uncured resin portion without light irradiation in the laminate is removed by spraying using an alkaline solution as a developer, and an opening 6 for a via hole is formed on the conductor circuit 4 as shown in FIG. Formed.

-Post bake-
After the development, the laminate was heated for 60 minutes at a temperature of 140 ° C., and the laminate was dried and completely cured. After the drying, as shown in FIG. 5, the surface of each photosensitive solder resist layer located above the corners of the conductor circuit 4 and the conductor circuit and each photosensitive solder resist layer located above the conductor circuit is flat. A printed wiring board having a permanent pattern was obtained.

―Evaluation―
About the photosensitive soldering resist film and laminated body of Example 1, sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive soldering resist layer and the second photosensitive soldering resist layer, and the permanent pattern of the following conditions The flatness of the surface and the uniformity of the thickness of the permanent pattern at the corners of the conductor circuit were evaluated by the following methods. The results are shown in Table 3.

<Resolution>
(1) Measuring method of shortest development time The polyethylene terephthalate film (support) is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is applied to the entire surface of each photosensitive solder resist layer on the copper clad laminate. Spraying was performed at a pressure of 0.15 MPa, and the time required from the start of spraying of the aqueous sodium carbonate solution until each photosensitive solder resist layer on the copper-clad laminate was dissolved and removed was measured. .
As a result, the shortest development time was 10 seconds.

(2) Measurement of sensitivity For each photosensitive solder resist layer of the photosensitive solder resist film in the prepared laminate, from the polyethylene terephthalate film (support) side, using an exposure apparatus, from 0.1 mJ / cm ² The exposure was performed by irradiating with light having different exposure amounts of up to 100 mJ / cm ^{2 at} intervals of 2 ^1/2 times, and a part of the area of each photosensitive solder resist layer was cured. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the laminate, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was formed on the entire surface of each photosensitive solder resist layer on the copper clad laminate. Was sprayed at a spray pressure of 0.15 MPa for twice the shortest development time determined in (1) above, the uncured area was dissolved and removed, and the thickness of the remaining cured area was measured. Next, a sensitivity curve is obtained by plotting the relationship between the light irradiation amount and the thickness of the cured layer. From the sensitivity curve thus obtained, the exposure amount when the thickness of the cured region was 15 μm was determined as the exposure amount necessary to cure each photosensitive solder resist layer.
As a result, the exposure amount required to cure each of the photosensitive solder resist layers was 30 mJ / cm ² .

(3) Measurement of resolution The laminate was prepared by the same method and conditions as the evaluation method for the shortest development time in (1) and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate film (support) of the laminate, exposure is performed for each line width in increments of 5 μm from line / space = 1/1 to a line width of 10 to 50 μm using the pattern forming apparatus. The exposure amount at this time is an exposure amount necessary for curing each photosensitive solder resist layer of the photosensitive solder resist film measured in (2). After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate. Spray the entire surface of each photosensitive solder resist layer on the copper-clad laminate with a 1% by weight aqueous sodium carbonate solution at 30 ° C. at a spray pressure of 0.15 MPa for a time twice as short as the shortest development time determined in (1) above. Dissolve and remove uncured areas. The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twisting was measured on the cured resin pattern line. did. The smaller the numerical value, the better the resolution.

<Exposure speed>
Using the exposure apparatus, the speed at which the exposure light and each photosensitive solder resist layer were moved relative to each other was changed, and the speed at which a general wiring pattern was formed was determined. Exposure was performed from the polyethylene terephthalate film (support) side with respect to each photosensitive soldering resist layer of the photosensitive soldering resist film in the prepared laminated body. Note that efficient pattern formation is possible when the set speed is high.

<Measurement of melt viscosity>
The melt viscosity is determined by vibron (DD-III type: Toyo Baldwin Co., Ltd.) when the temperature of each photosensitive solder resist layer when laminating the first photosensitive solder resist layer and the second photosensitive solder resist layer is 80 ° C. (Manufactured by company).

<Evaluation of lamination>
Regarding the lamination, whether the second photosensitive solder resist layer and the substrate are in close contact with each other is obtained by laminating the second photosensitive solder resist layer on the circuit board and then using a microscope to examine the second photosensitive solder resist layer. And whether or not there are minute bubbles between the substrate and the substrate.
○ ... Air bubbles are not recognized.
X: Air bubbles are observed.

<Evaluation of flatness>
The flatness is measured by using a stylus-type film thickness meter Surfcom (manufactured by Tokyo Seimitsu Co., Ltd.), placing the permanent pattern surface of the printed wiring board upward, and placing it on a measurement table (reference surface). On the surface of the pattern, the height of the three portions of the permanent pattern covering the conductor circuit is measured, the average value thereof is obtained, the height of the three portions of the permanent pattern covering the portion other than the conductor circuit is measured, The average value was calculated | required and the difference of each average value was measured as flatness. The flatness was 1.4 μm.

<Evaluation of Uniformity of Permanent Pattern Thickness at Corner of Conductor Circuit>
Regarding the thickness uniformity at the corners of the permanent pattern, the conductor circuit portion of the obtained printed wiring board is cut perpendicularly to the upper surface of the conductor circuit, and the thickness of the permanent pattern at the corner of the conductor circuit is visually observed. And evaluated whether it was good as a protective film and an insulating film as follows. The thickness of the corner portion was 21.6 μm.
--Evaluation criteria--
○ ... The thickness of the permanent pattern is uniform.
X: The thickness of the permanent pattern is not uniform, and there are thin portions at the corners.

(Example 2)
Example 1 is the same as Example 1 except that the polymer of the first photosensitive solder resist composition solution is 40 parts by mass and the photosensitive oligomer of the second photosensitive solder resist composition solution is 40 parts by mass. Thus, a printed wiring board was produced.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 2, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 3)
Example 1 is the same as Example 1 except that the polymer of the first photosensitive solder resist composition solution is 20 parts by mass and the photosensitive oligomer of the second photosensitive solder resist composition solution is 20 parts by mass. Thus, a printed wiring board was produced.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 3, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

Example 4
A printed wiring board was produced in the same manner as in Example 1 except that the weight average molecular weight of the photosensitive oligomer in the second photosensitive solder resist composition solution was changed to 6,000.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 4, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 5)
A printed wiring board was produced in the same manner as in Example 2 except that the weight average molecular weight of the photosensitive oligomer in the second photosensitive solder resist composition solution was changed to 6,000.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 5, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 6)
A printed wiring board was produced in the same manner as in Example 2 except that the weight average molecular weight of the photosensitive oligomer in the second photosensitive solder resist composition solution was changed to 6,000.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 6, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 7)
A printed wiring board was produced in the same manner as in Example 1 except that the weight average molecular weight of the photosensitive oligomer in the second photosensitive solder resist composition solution was 10,000.

―Evaluation―
For the photosensitive solder resist film and laminate of Example 7, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 8)
A printed wiring board was produced in the same manner as in Example 2 except that the weight average molecular weight of the photosensitive oligomer in the second photosensitive solder resist composition solution was changed to 10,000.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 8, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

Example 9
In Example 3, a printed wiring board was produced in the same manner as in Example 3 except that the weight average molecular weight of the photosensitive oligomer in the second photosensitive solder resist composition solution was 10,000.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 9, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 10)
A printed wiring board was produced in the same manner as in Example 1, except that the thickness of the first photosensitive solder resist layer was 10 μm and the thickness of the second photosensitive solder resist layer was 30 μm.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 10, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 11)
A printed wiring board was produced in the same manner as in Example 2 except that the thickness of the first photosensitive solder resist layer was 10 μm and the thickness of the second photosensitive solder resist layer was 30 μm.

―Evaluation―
For the photosensitive solder resist film and laminate of Example 11, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 12)
A printed wiring board was produced in the same manner as in Example 3, except that the thickness of the first photosensitive solder resist layer was 10 μm and the thickness of the second photosensitive solder resist layer was 30 μm.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 12, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 13)
In Example 4, a printed wiring board was produced in the same manner as in Example 4 except that the thickness of the first photosensitive solder resist layer was 10 μm and the thickness of the second photosensitive solder resist layer was 30 μm.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 13, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 14)
A printed wiring board was produced in the same manner as in Example 5 except that the thickness of the first photosensitive solder resist layer was 10 μm and the thickness of the second photosensitive solder resist layer was 30 μm.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 14, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 15)
A printed wiring board was produced in the same manner as in Example 6 except that the thickness of the first photosensitive solder resist layer was 10 μm and the thickness of the second photosensitive solder resist layer was 30 μm.

―Evaluation―
For the photosensitive solder resist film and laminate of Example 15, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 16)
In Example 7, a printed wiring board was produced in the same manner as in Example 7 except that the thickness of the first photosensitive solder resist layer was 10 μm and the thickness of the second photosensitive solder resist layer was 30 μm.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 16, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 17)
In Example 8, a printed wiring board was produced in the same manner as in Example 8 except that the thickness of the first photosensitive solder resist layer was 10 μm and the thickness of the second photosensitive solder resist layer was 30 μm.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 17, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 18)
A printed wiring board was produced in the same manner as in Example 9, except that the thickness of the first photosensitive solder resist layer was 10 μm and the thickness of the second photosensitive solder resist layer was 30 μm.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 18, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Example 19)
In Example 1, a printed wiring board having a permanent pattern was produced in the same manner as in Example 1 except that the above-described pattern forming apparatus was used as the exposure apparatus.

―Evaluation―
About the photosensitive solder resist film and laminate of Example 19, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Comparative Example 1)
In Example 1, a printed wiring board was produced in the same manner as in Example 1 except that the thickness of the first photosensitive solder resist layer was 40 μm and the second photosensitive solder resist layer was not formed.

―Evaluation―
With respect to the photosensitive solder resist film and laminate of Comparative Example 1, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, permanent under the following conditions: Evaluation of the flatness of the surface of the pattern and the uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was performed in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure each photosensitive solder resist layer was 30 mJ / cm ² .

(Comparative Example 2)
In Example 1, a printed wiring board was produced in the same manner as in Example 1 except that the first photosensitive solder resist layer was not formed and the second photosensitive solder resist layer was applied to a thickness of 40 μm.

―Evaluation―
With respect to the photosensitive solder resist film and laminate of Comparative Example 2, the sensitivity, resolution, exposure speed, melt viscosity of the photosensitive solder resist layer, lamination, surface flatness of the permanent pattern, and corners of the conductor circuit are as follows. Evaluation of the uniformity of the thickness of the permanent pattern was performed in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure the photosensitive solder resist layer was 30 mJ / cm ² .

(Comparative Example 3)
In Example 1, a printed wiring board was produced in the same manner as in Example 1 except that the first photosensitive solder resist layer was not formed and the second photosensitive solder resist layer was applied to a thickness of 40 μm.

―Evaluation―
With respect to the photosensitive solder resist film and laminate of Comparative Example 2, the sensitivity, resolution, exposure speed, melt viscosity of the photosensitive solder resist layer, lamination, surface flatness of the permanent pattern, and corners of the conductor circuit are as follows. Evaluation of the uniformity of the thickness of the permanent pattern was performed in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 10 seconds, and the exposure amount required to cure the photosensitive solder resist layer was 30 mJ / cm ² .

(Comparative Example 4)
In Example 1, the first photosensitive solder resist composition solution is the following composition, the thickness of the first photosensitive solder resist layer is 2 μm, and the second photosensitive solder resist composition solution is A printed wiring board was produced in the same manner as in Example 1 except that the composition was used and the thickness of the second photosensitive solder resist layer was changed to 73 μm.

--Preparation of first photosensitive solder resist composition solution--
1st photosensitive solder resist composition solution which consists of the following photosensitive solder resist composition, melt | dissolves the 1st photosensitive solder resist composition shown in Table 3 in an 8% methanol / 92% methylene chloride solvent system solution. Was prepared.

-Preparation of second photosensitive solder resist composition solution-
A second photosensitive solder resist composition solution comprising the following photosensitive solder resist composition, wherein the second photosensitive solder resist composition shown in Table 3 is dissolved in an 8% methanol / 92% methylene chloride solvent-based solution. Was prepared.

--Photosensitive solder resist composition--
(Binder and co-binder)
"Hycar ^R 1472x26" Methacrylic acid / butadiene / acrylonitrile (5/70/25) from Zeon-Nippon, Cleveland, OH
"Carboset Resin ^R I" B. F. Ethyl acrylate / ethyl methacrylate / methacrylic acid (60/29/11) with M _w = 150,000, acid number = 80 and Tg = 35 ° from Goodrich, Cleveland, OH
“Carboset Resin ^R II” F. Ethyl acrylate / ethyl methacrylate / methacrylic acid (25 / 67.5 / 7.5) from Goodrich with M _w = 217,000, acid number = 59, Tg = 59 ° C.

(monomer)
"TMPTA" Trimethylolpropane triacrylate "PETA" Pentaerythritol triacrylate

(Initiator)
“EMK” Ethyl Michler Ketone

(Thermal crosslinking agent)
"Cymel ^R 303" Hexamethoxymethyl-melamine from American Cyanamide, Wayne, NJ

(Filler)
"Cycrubond ^R " 1% aminosilane treated silicate from Cyprus Minerals, England, CO

(Adhesion promoter)
“3-MT” 3-mercapto-1H-1,2,4-triazole

(Other ingredients)
“DEHA” N, N-diethylhydroxylamine “Dayglo ^R 122-9655” Dayglo Corp. , Cleveland, green and yellow dye in a carrier from OH "Amphomer ^R" National Starch, Bridgewater, methyl methacrylate / t-octylacrylamide / acrylic acid / hydroxypropyl methacrylate / t-butylamino methacrylate from NJ (35/40 / 16/5/4)
“PVP-K-90” GAF Chemicals Corp. , Texas City, TX Polyvinylpyrrolidone solution: 8% methanol / 92% methylene chloride solvent system

―Evaluation―
About the photosensitive solder resist film and laminate of Comparative Example 4, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 60 seconds and the sensitivity was 200 mJ / cm ² .

(Comparative Example 5)
In Example 1, a composition comprising the following first photosensitive solder resist composition solution was used, the thickness of the first photosensitive solder resist layer was 10 μm, and the following second photosensitive solder resist composition solution was used. A printed wiring board was produced in the same manner as in Example 1 except that the thickness of the second photosensitive solder resist layer was 40 μm.

-1st photosensitive soldering resist composition solution-
60 parts by mass of the polymer P2 synthesized earlier, 20 parts by mass of pentaerythritol triacrylate (Aronix M-305 manufactured by Toagosei Co., Ltd.) and urethane acrylate (Aronix M-1600 manufactured by Toagosei Co., Ltd.) 20 as a crosslinking agent 1 part by weight of active energy ray curing reaction initiator, 5 parts by weight of benzophenone, 2 parts by weight of active energy ray curing sensitizer, ethyl michler ketone, and 1 part by weight of methylene blue as a pigment. A solution was prepared.

-Second photosensitive solder resist composition solution-
60 parts by mass of the previously synthesized polymer 3, 20 parts by mass of Aronix M-305 and 20 parts by mass of Aronix M-1600 as a crosslinking agent, 5 parts by mass of an active energy ray curing reaction initiator benzophenone, active energy ray curing sensitization A second photosensitive solder resist composition solution was prepared by thoroughly mixing 2 parts by weight of the agent ethyl Michler ketone and 1 part by weight of methylene blue as a pigment.

--Evaluation--
For the photosensitive solder resist film and laminate of Comparative Example 5, the sensitivity, resolution, exposure speed, melt viscosity of the first photosensitive solder resist layer and the second photosensitive solder resist layer, lamination, flatness of the surface of the permanent pattern The uniformity of the thickness of the permanent pattern at the corners of the conductor circuit was evaluated in the same manner as in Example 1. The results are shown in Table 4.
The shortest development time was 25 seconds, and the necessary exposure amount was 60 mJ / cm ² .

From the result of Table 4, it was recognized that the flatness of the permanent pattern surface of Examples 1-18 was very favorable compared with Comparative Examples 1-5, and the outstanding permanent pattern could be formed. It was recognized that the photosensitive solder resist film used in the present invention is excellent in high sensitivity and high resolution and can form a permanent pattern efficiently.
In Example 19, the pattern forming apparatus was used as an exposure apparatus, and it was confirmed that the exposure speed was faster and the resolution was extremely superior compared to the other examples.

In the permanent pattern forming method of the present invention, the thickness of the permanent pattern at the corners of the conductor circuit formed on the printed wiring board is uniform, the flatness of the entire permanent pattern is high, the definition is high, and the production efficiency is high. Because it is an excellent permanent pattern formation method, it is possible to form solder resists with bump openings in the wiring board field, interlayer insulation layers in multilayer substrates, etc. with high definition and efficiency, so high-definition exposure Can be suitably used for the formation of various patterns that require.
In particular, it can be suitably used for forming a permanent pattern having high definition and excellent flatness. In addition, the printed wiring board manufacturing method using the permanent pattern forming method of the present invention can form a permanent pattern and a solder resist with high definition and efficiency, and thus various types of exposure that require high-definition exposure. It can be suitably used for forming a pattern.

FIG. 1 is a partial cross-sectional view of a photosensitive solder resist film. FIG. 2 is a partial cross-sectional view of the printed wiring board. FIG. 3 is a partial cross-sectional view in which a photosensitive solder resist film is laminated on a printed wiring board. FIG. 4 is a partial cross-sectional view of laser exposure on a laminate of printed wiring boards. FIG. 5 is a partial cross-sectional view of a printed wiring board on which a solder resist is formed. FIG. 6 is a partial cross-sectional view of a printed wiring board on which a solder resist is formed. FIG. 7 is a partial cross-sectional view of a printed wiring board on which a conventional solder resist is formed. FIG. 8 is a partial cross-sectional view of a printed wiring board on which a conventional solder resist is formed. FIG. 9 is a partial cross-sectional view of a printed wiring board on which a conventional solder resist is formed. FIG. 10 is a partial cross-sectional view of a printed wiring board on which a conventional solder resist is formed. FIG. 11 is a partial cross-sectional view of a double-sided copper-clad laminate. FIG. 12 is a partial cross-sectional view of the copper-clad laminate after the formation of the first circuit pattern. FIG. 13 is a partial cross-sectional view of the copper-clad laminate after the formation of the photosensitive interlayer insulating layer. FIG. 14 is a partial cross-sectional view of the copper-clad laminate after the formation of the photovia. FIG. 15 is a partial cross-sectional view of the copper-clad laminate after through-hole drilling. FIG. 16 is a partial cross-sectional view of the copper-clad laminate after forming the plating resist pattern. FIG. 17 is a partial cross-sectional view of the copper-clad laminate after the second circuit pattern measurement by electroless plating. FIG. 18 is a partial cross-sectional view of the copper-clad laminate after lamination of the photosensitive solder resist film. FIG. 19 is a partial cross-sectional view of the copper-clad laminate after forming the solder resist pattern. FIG. 20 is a partial cross-sectional view of a copper-clad laminate after nickel plating and gold plating. FIG. 21 is a partial cross-sectional view of the copper-clad laminate after solder paste application. FIG. 22 is an example of a partially enlarged view showing the configuration of a digital micromirror device (DMD). FIGS. 23A and 23B are examples of explanatory diagrams for explaining the operation of the DMD. FIGS. 24A and 24B are examples of plan views showing the arrangement of the exposure beam and the scanning line in the case where the DMD is not inclined and the case where the DMD is inclined. 25A and 25B are examples of diagrams illustrating examples of DMD usage areas. FIG. 26 is an example of a plan view for explaining an exposure method in which a photosensitive solder resist film is exposed by one scanning by a scanner. FIGS. 27A and 27B are examples of plan views for explaining an exposure method for exposing a photosensitive solder resist film by a plurality of scans by a scanner. FIG. 28 is an example of a schematic perspective view illustrating an appearance of an example of a pattern forming apparatus. FIG. 29 is an example of a schematic perspective view illustrating the configuration of the scanner of the pattern forming apparatus. FIG. 30A is an example of a plan view showing an exposed region formed on the photosensitive solder resist film, and FIG. 30B is an example of a diagram showing an array of exposure areas by each exposure head. . FIG. 31 is an example of a perspective view showing a schematic configuration of an exposure head including a light modulation unit. FIG. 32 is an example of a sectional view in the sub-scanning direction along the optical axis showing the configuration of the exposure head shown in FIG. FIG. 33 is an example of a controller that controls DMD based on pattern information. FIG. 34A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system, and FIG. 34B shows an object to be exposed when a microlens array or the like is not used. FIG. 34C is an example of a plan view showing an optical image projected on an exposed surface when a microlens array or the like is used. FIG. 35 is an example of a diagram showing the distortion of the reflection surface of the micromirror constituting the DMD with contour lines. FIGS. 36A and 36B are examples of graphs showing the distortion of the reflection surface of the micromirror in the two diagonal directions of the mirror. FIG. 37 is an example of a front view and a side view of a microlens array used in the pattern forming apparatus. FIG. 38 is an example of a front view and a side view of the microlens constituting the microlens array. FIG. 39 is an example of a schematic diagram illustrating a condensing state by a microlens in one cross section and another cross section. FIG. 40a is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens of the present invention. FIG. 40b is an example of a diagram showing the same simulation result as in FIG. 40a at another position. FIG. 40c is an example of a diagram illustrating simulation results similar to those in FIG. 40a at different positions. FIG. 40d is an example of a diagram showing the same simulation result as in FIG. 40a at another position. FIG. 41a is an example of a diagram showing a result of simulating the beam diameter in the vicinity of the condensing position of the microlens in the conventional permanent pattern forming method. FIG. 41b is an example of a diagram showing the same simulation result as in FIG. 41a at another position. FIG. 41c is an example of a diagram showing the same simulation result as in FIG. 41a for another position. FIG. 41d is an example of a diagram showing the same simulation result as in FIG. 41a for another position. FIG. 42 is an example of a plan view showing another configuration of the combined laser light source. FIG. 43 is an example of a front view and an example of a side view of a microlens constituting the microlens array. FIG. 44 is an example of a schematic diagram illustrating a condensing state by the microlens of FIG. 42 in an example in one cross section and another cross section. FIG. 45 is an example of an explanatory diagram about the concept of correction by the light quantity distribution correction optical system. FIG. 46 is an example of a graph showing the light amount distribution when the light irradiation means has a Gaussian distribution and the light amount distribution is not corrected. FIG. 47 is an example of a graph showing the light amount distribution after correction by the light amount distribution correcting optical system. 48A (A) is a perspective view showing the configuration of the fiber array light source, FIG. 48A (B) is an example of a partially enlarged view of FIG. 48A (A), and FIGS. 48A (C) and (D) are FIGS. It is an example of the top view which shows the arrangement | sequence of the light emission point in a laser emission part. FIG. 48 b is an example of a front view showing the arrangement of the light emitting points in the laser emission part of the fiber array light source. FIG. 49 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 50 is an example of a plan view showing the configuration of the combined laser light source. FIG. 51 is an example of a plan view showing the configuration of the laser module. FIG. 52 is an example of a side view showing the configuration of the laser module shown in FIG. 53 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 54 is an example of a perspective view showing a configuration of a laser array. FIG. 55 is an example of a perspective view showing the configuration of a multi-cavity laser, and FIG. 55 is an example of a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. 55 are arranged in an array. FIG. 56 is an example of a plan view showing another configuration of the combined laser light source. FIG. 57 is an example of a plan view showing another configuration of the combined laser light source, and FIG. 57 is an example of a cross-sectional view along the optical axis. FIG. 58 is an example of a cross-sectional view along the optical axis showing the difference between the depth of focus in a conventional exposure apparatus and the depth of focus by the permanent pattern forming method (pattern forming apparatus) of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support body 2 Photosensitive soldering resist layer 2a 1st photosensitive soldering resist layer 2b 2nd photosensitive soldering resist layer 2c Permanent pattern 3 Protective film 4 Conductor circuit 5 Board | substrate 5a Metal layer 6 Opening part 7 Through hole 8 Photo via 8a Plating resist 8b Plating 8c Solder resist layer 8d Solder resist 8e Gold plating 8f Solder paste 9 Permanent pattern 9a Weak laser exposure 9b Photosensitive film LD1-LD7 GaN-based semiconductor laser 10 Heat block 11-17 Collimator lens 20 Condensing lens 30-31 Multi Mode optical fiber 44 Collimator lens holder 45 Condenser lens holder 46 Fiber holder 50 Digital micromirror device (DMD)
52 Lens system 53 Reflected light image (exposure beam)
54 Lens of second imaging optical system 55 Micro lens array 55a Micro lens 56 Surface to be exposed (scanning surface)
57 Lens of second imaging optical system 58 Lens of second imaging optical system 59 Aperture array 64 Laser module 66 Fiber array light source 67 Lens system 68 Laser emitting unit 69 Mirror 70 Prism 71 Condensing lens 72 Rod integrator 73 Combination lens 74 Imaging lens 100 Heat block 110 Multi-cavity laser 111 Heat block 113 Rod lens 120 Condensing lens 130 Multimode optical fiber 130a Core 140 Laser array 144 Light irradiation means 150 Photosensitive solder resist film 152 Stage 155a Micro lens 156 Installation base 158 Guide 160 Gate 162 Scanner 164 Sensor 166 Exposure head 168 Exposure area 170 Exposed area 180 Heat block 184 Formate lens array 302 controller 304 stage driver 454 lens system 468 exposure area 472 microlens array 474 microlens 476 aperture array 478 aperture 480 lens system

Claims (20)

The support has at least a first photosensitive layer and a second photosensitive layer in this order, and the melt viscosity of the first photosensitive layer at the laminating temperature when laminating on the substrate is η ₁ , A photosensitive permanent resist film satisfying the following formula: η ₁ > η ₂ when the melt viscosity of the photosensitive layer ₂ is η ₂ . The melt viscosity η ₁ is 400 to 5,000 Pa · s at a laminate temperature of 70 to 100 ° C., and the melt viscosity η ₂ is 50 to 300 Pa · s at a laminate temperature of 70 to 100 ° C. The photosensitive permanent resist film according to claim 1, wherein the melt viscosity η ₃ at room temperature of the photosensitive layer and the second photosensitive layer is 1 × 10 ⁵ Pa · s or more.   A first photosensitive layer and a second photosensitive layer are provided on a support, and the first photosensitive layer comprises a first photosensitive composition containing at least an alkali-soluble photocrosslinkable polymer. The photosensitive permanent resist film according to claim 1, wherein the second photosensitive layer comprises a second photosensitive composition containing at least an alkali-soluble photocrosslinkable oligomer. The mass average molecular weight of the alkali-soluble photocrosslinkable polymer is 2 × 10 ⁴ to 1 × 10 ⁵ , and the mass average molecular weight of the alkali-soluble photocrosslinkable oligomer is 1 × 10 ³ to 1 × 10 ^4. The photosensitive permanent resist film described in 1.   The first photosensitive composition and the second photosensitive composition contain a polymerizable compound, a photopolymerization initiator, an epoxy curing agent, a curing accelerator, an inorganic filler, and a colorant, respectively. Photosensitive permanent resist film.   The alkali-soluble photocrosslinkable polymer contained in the first photosensitive composition and the second photosensitive composition is a different type of alkali-soluble photocrosslinkable polymer, and the other components are the same as each other. To 5. The photosensitive permanent resist film according to any one of 5 to 5.   The photosensitive permanent resist film according to any one of claims 1 to 6, wherein the first photosensitive layer has a thickness of 1 to 50 µm, and the second photosensitive layer has a thickness of 1 to 50 µm.   The following formula, S1 / S2 is 1/9 to 9/1, where S1 is the thickness of the first photosensitive layer and S2 is the thickness of the second photosensitive layer: A photosensitive permanent resist film according to claim 1. On a support, having three or more layers of light-sensitive layers having different melt viscosities, photosensitive permanent resist film according to any one of claims 1 to 2 the melt viscosity of the outermost layer is eta _2.   The photosensitive permanent resist film in any one of Claim 1 to 9 which has a protective film on a support body.   The first photosensitive composition and the second photosensitive composition according to any one of claims 3 to 6 are applied to the surface of a substrate, dried to form a photosensitive layer laminate, and then exposed. And developing the permanent pattern.   The photosensitive permanent resist film according to any one of claims 1 to 10 is laminated on a surface of a substrate having a convex portion where the convex portion is exposed to form a photosensitive layer laminate, and then exposed. And developing the permanent pattern.   When the height of the convex portion from the substrate surface is T1 (μm) and the thicknesses of the first photosensitive layer and the second photosensitive layer are T2 (μm), the photosensitivity satisfying the following formula, T1 <T2. The method for forming a permanent pattern according to claim 11, wherein the conductive layer laminate is exposed and developed.   The method for forming a permanent pattern according to claim 11, wherein the convex portion is a conductor circuit in a printed wiring board.   The permanent pattern forming method according to claim 11, wherein the substrate is a printed wiring board having at least one of a through hole and a via hole.   The permanent pattern forming method according to claim 11, wherein the exposure is performed with a laser beam.   Aberration due to distortion of the exit surface in the pixel part after the light is modulated by the light modulating means having n picture elements for receiving and emitting the light from the light irradiating means. The permanent pattern forming method according to claim 11, wherein the permanent pattern forming method is performed by light that has passed through a microlens array in which microlenses having an aspheric surface capable of correcting the above are arranged.   The permanent pattern forming method according to claim 17, wherein the aspherical surface is a toric surface.   19. The light modulation means can control any less than n number of pixel parts arranged continuously from n number of pixel parts according to pattern information. A permanent pattern forming method. A printed wiring board comprising a permanent pattern, and the permanent pattern is formed by the permanent pattern forming method according to claim 11.