WO2019124452A1

WO2019124452A1 - Photosensitive resin laminate

Info

Publication number: WO2019124452A1
Application number: PCT/JP2018/046833
Authority: WO
Inventors: 純宮崎
Original assignee: 旭化成株式会社
Priority date: 2017-12-20
Filing date: 2018-12-19
Publication date: 2019-06-27
Also published as: TW201932307A; JPWO2019124452A1; CN111492309B; CN111492309A; KR102471794B1; MY192613A; JP7068340B2; TWI700183B; KR20200062363A

Abstract

Provided is a photosensitive resin laminate which prevents generation of resist projection, which provides a preferable resist pattern shape, and with which good productivity can be obtained. A photosensitive resin laminate according to one embodiment of the present invention is provided with a support film and a photosensitive resin composition layer formed on the support film, wherein the support film contains fine particles, and includes a region where the total area ratio of optical anomaly regions is not more than 300 ppm when observation is made in an area of 13.5 mm² of the support film using an epi-illumination-type laser microscope.

Description

Photosensitive resin laminate

The present invention relates to a photosensitive resin laminate.

A printed wiring board or the like is used in electronic devices such as personal computers and mobile phones in order to mount components, semiconductors and the like. Conventionally, a photosensitive resin composition layer is laminated on a support film, and a protective film is laminated on the photosensitive resin composition layer as required, as a resist for manufacturing printed wiring boards and the like. Resin laminates, so-called dry film photoresists (hereinafter sometimes referred to as DF) are used. As the photosensitive resin composition layer, at the present time, an alkali developing type using a weak alkaline aqueous solution as a developer is generally used. In order to manufacture a printed wiring board etc. using DF, it goes through the following processes, for example. If the DF has a protective film, the protective film is first peeled off. Thereafter, DF is laminated on a substrate for producing a permanent circuit such as a copper-clad laminate or a flexible substrate using a laminator or the like, and exposure is performed through a wiring pattern mask film or the like. Next, the support film is peeled if necessary, and the photosensitive resin composition layer of the uncured portion (for example, the unexposed portion in the case of a negative type) is dissolved or dispersed and removed by a developer, and a cured resist pattern (described below) , Sometimes referred to as a resist pattern).

After forming a resist pattern, the process of forming a circuit can be roughly divided into two methods. The first method is a method of etching away the substrate surface not covered by the resist pattern (for example, the copper surface of a copper clad laminate) and then removing the resist pattern portion with an alkaline aqueous solution stronger than the developer (etching method) It is. In the second method, the substrate surface is plated with copper, solder, nickel, tin or the like, and then the resist pattern portion is removed in the same manner as in the first method, and the substrate surface (for example, It is a method (plating method) of etching the copper surface of a copper clad laminate. Cupric chloride, ferric chloride, a copper ammonia complex solution or the like is used for the etching. In recent years, with the miniaturization and weight reduction of electronic devices, miniaturization and densification of printed wiring boards have progressed, and high resolution, good line width reproducibility, etc. are given in the above manufacturing steps. High performance DF is required.

Patent Document 1 discloses a photosensitive element including a support film and a layer made of a photosensitive resin composition formed on the support film, wherein the haze of the support film is 0.01 to 2.0. % And the total number of particles having a diameter of 5 μm or more and aggregates having a diameter of 5 μm or more contained in the support film is 5 pieces / mm ² or less, and the layer comprising the photosensitive resin composition is (A) Photosensitivity comprising a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, and having a layer thickness of 3 to 30 μm consisting of the photosensitive resin composition. Sex elements have been described and are aimed at reducing defects in the resist.

WO 2008/093643

The Patent Document 1 focuses on the number of fine particles having a diameter of 5 μm or more in order to reduce defects in the resist. However, as a result of intensive investigations by the inventor of the present application, it has been found that in addition to the fine particles themselves, optically abnormal regions (for example, abnormal refractive index regions) other than the fine particles in the support film can be considered. Patent Document 1 focuses on the number of fine particles having a diameter of 5 μm or more, but does not focus on optically abnormal regions other than the fine particles in the support film. If there is a large number of optically abnormal areas in the support film, light scattering, diffraction, etc. will occur, and light will strike the part where light is not originally desired, or foreign matter will block the exposure light, and it is desirable to apply the exposure light Exposure control defects such as the fact that exposure light does not reach the place occur. Such exposure control defects may cause resist protrusions, making it impossible to obtain a desired resist pattern shape. Patent Document 1 does not pay attention to the occurrence of such resist protrusions, and at present, no photosensitive resin laminate capable of avoiding the resist protrusions has been obtained.

One aspect of the present invention aims to solve the above-mentioned problems, to provide a photosensitive resin laminate that avoids resist protrusions and gives a good resist pattern shape.

The present inventors diligently studied and experimented in order to solve the above problems. As a result, in one aspect, it has been found that such problems can be solved by the following technical means.

That is, the present invention includes the following aspects.
[1] A photosensitive resin laminate comprising: a support film; and a photosensitive resin composition layer formed on the support film,
The support film contains fine particles, and the photosensitive resin laminate includes a region in which the total area ratio of the optically abnormal region is 300 ppm or less when the support film is observed at an area of 13.5 mm ² with an epi-illumination laser microscope .
[2] The support film according to the above mode 1, wherein the support film includes a region in which the total area ratio of the optically abnormal region is 200 ppm or less when the support film is observed at an area of 13.5 mm ² with an incident laser microscope. Photosensitive resin laminate.
[3] The support film described in the above mode 1, wherein the support film includes a region in which the total area ratio of the optically abnormal region is 100 ppm or less when the support film is observed at an area of 13.5 mm ² with an incident laser microscope. Photosensitive resin laminate.
[4] The support film described in the above mode 1, wherein the support film includes a region having a total area ratio of 50 ppm or less of an optically abnormal region when the support film is observed at an area of 13.5 mm ² by an epi-illumination laser microscope Photosensitive resin laminate.
[5] The photosensitive resin laminate according to any one of the above aspects 1 to 4, wherein the support film contains 10 ppm or more of fine particles on a mass basis.
[6] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film,
The support film contains fine particles,
In the support film, among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm ² of the support film, the number of fine particles in contact with the area other than the fine particles in the optically abnormal area is 1,200 in number average The photosensitive resin laminated body which has the area | region which becomes the following.
[7] The number of fine particles in contact with the area other than the fine particles of the optically abnormal area among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm ² of the support film is a number average The photosensitive resin laminate according to the above-mentioned aspect 6, having a region of 1000 or less.
[8] The number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm ² of the support film is 900 The photosensitive resin laminated body of the said aspect 6 which has the area | region which becomes the following.
[9] The number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm ² of the support film is 500 The photosensitive resin laminated body of the said aspect 6 which has the area | region which becomes the following.
[10] The number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm ² of the support film is 200 The photosensitive resin laminated body of the said aspect 6 which has the area | region which becomes the following.
[11] The number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 1.0 μm or more included in the area of 13.5 mm ² of the support film is 500 The photosensitive resin laminate according to any one of the above Embodiments 6 to 10, having a region to be the following.
[12] The number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 1.0 μm or more included in the area of 13.5 mm ² of the support film is 300 The photosensitive resin laminated body of the said aspect 11 which has the area | region which becomes the following.
[13] The number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 1.0 μm or more included in the area of 13.5 mm ² of the support film is 100 The photosensitive resin laminated body of the said aspect 11 which has the area | region which becomes the following.
[14] The number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 1.0 μm or more included in the area of 13.5 mm ² of the support film is 50 The photosensitive resin laminated body of the said aspect 11 which has the area | region which becomes the following.
[15] The number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 2.0 μm or more included in the area of 13.5 mm ² of the support film is 200 The photosensitive resin laminate according to any one of the above aspects 6 to 14, which has a region to be the following.
[16] The number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 2.0 μm or more included in the area of 13.5 mm ² of the support film is 100 The photosensitive resin laminated body of the said aspect 15 which has the area | region which becomes the following.
[17] The number of fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 2.0 μm or more included in the area of 13.5 mm ² of the support film is 50 The photosensitive resin laminated body of the said aspect 15 which has the area | region which becomes the following.
[18] The number of the fine particles in contact with the area other than the fine particles in the optically abnormal area among the fine particles having a diameter of 2.0 μm or more included in the area of 13.5 mm ² of the support film is 10 The photosensitive resin laminated body of the said aspect 15 which has the area | region which becomes the following.
[19] The photosensitive resin laminate according to any one of the above embodiments, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.2 or less.
[20] The photosensitive resin laminate according to the above-mentioned aspect 19, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.1 or less.
[21] The photosensitive resin laminate according to the above-mentioned aspect 19, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.05 or less.
[22] The photosensitive resin laminate according to the above-mentioned aspect 19, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.02 or less.
[23] The photosensitive resin laminate according to any one of the above aspects 1 to 22, wherein the optically abnormal region includes a cavity.
[24] The photosensitive resin laminate according to any one of the above-mentioned aspects 1 to 23, wherein the optically abnormal area includes an area different in orientation from the main area of the support film.
[25] The photosensitive resin laminate according to any one of the above aspects 1 to 24, wherein the optically abnormal region includes a region different in crystallinity from the main region of the support film.
[26] The photosensitive resin laminate according to any one of the above aspects 1 to 25, which is for forming a wiring having a line width / space width of 20/20 (μm) or less.
[27] The photosensitive resin laminate according to the above-mentioned aspect 26, which is for forming a wiring having a line width / space width of less than 10/10 (μm).
[28] A method for producing a resist pattern in a printed wiring board, which uses the photosensitive resin laminate according to any one of the above-mentioned aspects 1 to 27.
[29] The method according to the above aspect 28, by a semi-additive method.
[30] The method according to Aspect 28 or 29, wherein the line width / space width of the resist pattern is less than 10/10 (μm).
[31] A photosensitive resin laminate comprising: a support film; and a photosensitive resin composition layer formed on the support film,
When a resist pattern with a line width / space width of 8/8 (μm) is formed on a substrate using a direct writing exposure machine, the surface on the photosensitive resin composition layer side of the support film is focused The photosensitive resin laminated body whose difference of the line width and the line width at the time of shifting to the board | substrate inner side 400 micrometers in the thickness direction from the said surface is 1.8 micrometers or less.

According to one aspect of the present invention, a photosensitive resin laminate can be provided which avoids resist protrusions and gives a good resist pattern shape.

FIG. 1 is a diagram for explaining a method of measuring the total area of the optical abnormality area. FIG. 2 is a diagram for explaining measurement of the number of microparticles in the laser microscope mode. FIG. 3 is a view for explaining measurement of the number of microparticles in the optical microscope mode.

Hereinafter, exemplary embodiments for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

[Photosensitive resin laminate]
The present embodiment provides a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film. In the present embodiment, the total area ratio of the optically abnormal area is 300 ppm or less when the support film is observed with an area of 13.5 mm ² with an incident-type laser microscope.

As a support film, the transparent support film which permeate | transmits the light radiated | emitted from an exposure light source is preferable. As such a support film, for example, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, A polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film etc. are mentioned. These films may be stretched if necessary.

In addition, the support film may have a single layer structure, or may have a multilayer structure in which resin layers formed of a plurality of compositions are laminated. In the case of a multilayer structure, an antistatic layer may be present. In the case of a multilayer structure such as a two-layer structure or a three-layer structure, for example, a resin layer containing fine particles is formed on one side A, and on the other side B And (2) contains a smaller amount of particles than surface A, (3) contains particles smaller than surface A, and (4) does not contain particles. In the case of the structures of (2), (3) and (4), it is preferable to form a photosensitive resin composition layer on the surface B side. At this time, if there is a resin layer containing fine particles on the surface A side, it is preferable from the viewpoint of slipperiness of the film and the like.

In the support film, the total area ratio of the optically abnormal area when observed in an area of 13.5 mm ² with an incident type laser microscope is 300 ppm or less, more preferably 250 ppm or less, more preferably 200 ppm or less, more preferably Is 150 ppm or less, more preferably 100 ppm or less, more preferably 80 ppm or less, more preferably 70 ppm or less, more preferably 60 ppm or less, more preferably 50 ppm or less, more preferably 40 ppm or less, more preferably 20 ppm or less, more preferably 10 ppm It is below. As the total area ratio is smaller, light shielding, abnormal refraction, diffraction, and the like are reduced, which is advantageous in avoiding the resist protrusions. The resist projection causes a chipping of the wiring (especially in the semi-additive method (SAP)), and causes a deviation from the specified resistance value of the wiring and thus a reduction in the reliability of the circuit (that is, a disturbance of the signal (sinusoidal wave)). Avoiding resist protrusions is advantageous in obtaining good circuit reliability. 1 ppm or more may be sufficient as the total area ratio of an optical abnormal area at the time of observing a support film by the incident type laser microscope in the area of 13.5 mm ² , 5 ppm or more, 10 ppm or more, 20 ppm or more may be sufficient. .

The area of the optically abnormal area and the number of fine particles of the present disclosure mean the area of the optically abnormal area and the number of fine particles observed in the center 2 μm area of the thickness of the support film. It means the area of the optical anomaly area and the number of particles measured in the center 2 μm area of the thickness of the entire structure.

Hereinafter, the reason for measuring the area of the optically abnormal region and the number of fine particles in the region of 2 μm in the thickness center of the support film will be described.
As a result of intensive investigations by the inventor of the present invention, it has been found that the main factor such as light scattering, diffraction, light shielding and the like is an optical abnormality region. In the present disclosure, the optically abnormal region is a region having a different optical property from the main region of the support film (the resin constituting the support film) (specifically, the reflectance or the refractive index is different from the main region, or An area where optical phenomena such as scattering and diffraction occur more strongly than the main area. The optically abnormal area may include both a light shielding portion by the fine particles and an optically abnormal area other than the fine particles (for example, an abnormal refractive index area having a refractive index different from that of the fine area and the main area of the support film). Examples of the optically abnormal area are an area different in orientation and / or crystallinity from the main area of the support film, an area of air, an area of gas other than air, a hollow area where gas is substantially absent, and the like. For example, when stretching is performed in the manufacturing process of the support film, regions having stretching conditions different from other regions may occur in the vicinity of the particles because of the presence of the particles in the support film. Since this region is different in orientation and / or crystallinity from other regions, it has a different refractive index from the other regions. Further, in the process of producing the support film, there may be a region of air, a region of a gas other than air, or a cavity region due to the presence of fine particles in the support film. This region is different in refractive index from the other regions. An optically abnormal region such as an abnormal refractive index region is often present in the vicinity of the fine particle, but is not necessarily present in the vicinity of the fine particle. The optically abnormal area is different from the main area, for example, it looks bright because light is scattered and refracted between the optically abnormal area and the main area when viewed with an optical microscope etc. Show it. In the present disclosure, the thickness center of the support film is 2 μm because in the present disclosure, the optical abnormality region is hard to be generated on the surface of the support film and is easily generated inside the support film due to the generation of the optical abnormality region (in particular, abnormal refractive index region). Measure the area of the optically abnormal area and the number of fine particles in the area.

As a method of reducing the optically abnormal area, a method of improving the affinity of the surface of the fine particle for the support film constituting material (for example, when the support film is a PET film, a method of coating the fine particle surface with an aromatic polymer), support After biaxial stretching of the film, a method of subjecting the film to thermocompression bonding at a temperature higher than the glass transition temperature of the support film again to eliminate the optically abnormal area (particularly, the abnormal refractive index area) is useful. When the support film is a PET film, the temperature of the thermocompression bonding process may be, for example, about 180 to 250.degree.

The measurement method of the total area of the optically abnormal area is as follows. A polarizing filter (OLS4000-QWP) is inserted above the objective lens of the incident type laser microscope (OLS-4100 manufactured by Olympus). Next, a support film sample cut to 30 mm × 30 mm is suctioned and fixed horizontally on a stage of a laser microscope using a porous adsorption plate (65F-HG manufactured by Universal Giken) and a vacuum pump. The suction-fixed support film is observed with a laser light amount 60 (laser wavelength is 405 nm) of 50 times the objective lens. At this time, an area of 2 μm at the center in the thickness direction of the support film is defined as a measurement area, and measurement is performed at 200 measurement points at 259 μm × 260 μm (therefore, the measurement area is a total of 2.259 mm × 0.26 mm × It becomes 200 = 13.5 mm ² ).

The light amount difference between the pixel of the maximum light amount and the pixel of the minimum light amount in the measured image is divided into 4096 gradations (the maximum light amount is 4095 and the minimum light amount is 0). A histogram (horizontal axis: gradation of light quantity (minimum value 0, maximum value 4095), vertical axis: number of pixels) graphing the light quantity distribution of pixels in the image is created. The measured image is binarized using the gradation obtained by adding 400 gradations from the value of the larger one of the two base values in the created histogram as the threshold value, and the areas of the pixels whose light amounts are larger than the threshold are summed. , And the total area thereof is the total area of the optical anomaly region. The ratio of the total area of the optical abnormality area to the measurement area is calculated.

FIG. 1 is a diagram for explaining a method of measuring the total area of the optical abnormality area. An exemplary histogram is shown in FIG. The points of α and β of the histogram are β pixels of the light amount α (normalized with 4096 gradations so that the value of the maximum light amount is 4095 and the value of the minimum light amount is 0) in the measurement screen Indicates that it exists. A gray scale obtained by adding 400 gradations from the large bottom of the histogram (since one of the two bottoms is at the light quantity 0 because the light quantity 0 is also counted as the foot) is used as a threshold. Binarize pixels with light intensity above the threshold (typically, as few as several pixels) with the threshold (that is, pixels with light intensity below the threshold are black and pixels with light intensity above the threshold are white) And, a few pixels white point exists in the black measurement screen. This white point corresponds to the light shielding portion, that is, the portion where the laser of the incident type laser microscope is reflected by the fine particles in the support film and other optically abnormal regions (for example, abnormal refractive index regions). The above measurement is taken as a measurement by OLS-4100 made by Olympus in a laser microscope mode.

Next, the method of measuring the number of microparticles is as follows.
After measuring the total area of the optically abnormal area, the incident type laser microscope (OLS-4100 manufactured by Olympus) is switched to the optical microscope mode. Thereafter, the number of particles in contact with an optically abnormal area (for example, an abnormal refractive index area) other than the microparticles corresponding to the position of the light shielding portion (that is, the position of the microparticles) visually confirmed in the laser microscope mode in the measurement area 259 μm × 260 μm Measure the diameter. That is, a portion counted as a white point (light shielding portion) in the laser microscope mode is visually observed in the optical microscope mode, and it is determined whether the white point is a particle in contact with an optical abnormality area (for example, an abnormal refractive index area) other than the microparticles. Check and also measure the diameter visually.
The same measurement is carried out at 200 measurement points (that is, carried out with an area of 0.259 mm × 0.26 mm × 200 = 13.5 mm ² ), and the total number is calculated for each particle diameter. If the particle is not a perfect sphere, the longest width of the particle is taken as the particle diameter.
FIG. 2 is a diagram for explaining measurement of the number of particles in the laser microscope mode, and a white point corresponds to a light shielding portion. Moreover, FIG. 3 is a figure explaining the measurement by the optical microscope mode of the number of microparticles | fine-particles.
Suppose that the location of the white dotted area in FIG. 2 corresponds to the location of the white dotted area in FIG. In this case, in the area corresponding to the white dotted area in FIG. 2, fine particles in contact with an optical abnormal area (for example, an abnormal refractive index area) other than one fine particle are present. This is observed in the light microscope mode at all white points (light shielding area) observed in the laser microscope mode, and the number and diameter of the microparticles in contact with the optical abnormality area (for example, the abnormal refractive index area) other than the microparticles are measured. . In some cases, the white point (light-shielded area) observed in the laser microscope mode is not a fine particle in contact with an optical abnormal area (for example, an abnormal refractive index area) other than the fine particles.

If the support film does not contain any particulates, it is difficult to obtain sufficient windability when the photosensitive resin laminate is wound on a roll, and in the present embodiment, the support film contains particulates. The content of the fine particles is not particularly limited, but is preferably 5 to 1,000 ppm, more preferably 10 to 800 ppm, particularly preferably 20 to 500 ppm by mass ratio to the support film.

The fine particles contained in the support film include, for example, inorganic fine particles or organic fine particles, such as lubricants, aggregates of additives, foreign matter mixed in the raw material, foreign matter mixed in the manufacturing process, and the like. Specific examples of fine particles include inorganic particles such as calcium carbonate, calcium phosphate, silica (silicon dioxide), kaolin, talc, titanium dioxide, alumina (aluminum oxide), barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide and the like And cross-linked polymer particles, organic particles such as calcium oxalate, and the like. These may be alone or in combination of two or more.

The fine particles are blended into the support film according to a conventional method. In order to manufacture a support film in which the total area of the light shielding portion is in the specific range, for example, a method of filtering the material resin with a filter (for example, an eye filter of 2.0 μm or less) may be mentioned. The finer the filter eyes, and the greater the number of passes of the material resin through the filter, the smaller the number of fine particles in the material resin, the smaller the fine particles, and the smaller the total area of the light shielding portion.

The refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is preferably 0.2 or less, more preferably 0.18 or less, and more preferably 0 from the viewpoint of suppressing the generation of resist protrusions. .15 or less, more preferably 0.12 or less, more preferably 0.1 or less, more preferably 0.08 or less, more preferably 0.05 or less, more preferably 0.04 or less, more preferably 0. It is at most 03, more preferably at most 0.02, particularly preferably at most 0.01. When the difference in refractive index between the fine particles and the support film is small, light scattering tends to be reduced. In the present disclosure, “main region of support film” means a region that occupies most of the support film in the region other than the optical abnormality region of the support film. Since the refractive index of the support film for the photosensitive resin laminate is typically about 1.4 to 1.7, as a means for reducing the difference in refractive index between the fine particles and the support film, the fine particles may be used as fine particles. And using the same refractive index. The refractive index of the support film is preferably 1.4 to 1.7, more preferably 1.5 to 1.7.
The refractive index in the present specification means the refractive index at a wavelength of 589 nm.

As a method of reducing the number of fine particles in the support film, a method of producing a support film using a film material passing through a filter for removing fine particles can be exemplified. For example, when it is desired to reduce the number of particles having a diameter of 0.5 μm or more, a filter that removes particles having a diameter of 0.5 μm or more may be used. The number of particles may be adjusted by increasing the number of particles to a desired range by post-adding the particles after using such a filter.

Since the optically abnormal region is a region that particularly scatters or diffracts light, if the fine particles and the optically abnormal region other than the fine particles are close to each other, the light scattering becomes remarkable, which is not preferable. Therefore, it is preferable that the number of fine particles present in the vicinity of an optically abnormal area (for example, an abnormal refractive index area) other than the fine particles be reduced.

From the viewpoint of reducing the influence of light shielding by the fine particles in the support film, among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm ² of the support film, optical properties different from the main region of the support film (for example, The number of fine particles in contact with an optically abnormal area (for example, an abnormal refractive index area) other than the fine particles having a refractive index) is preferably 1500 or less, preferably 1200 or less, preferably 1000 or less, preferably 900 or less, preferably There are 800 or less, preferably 700 or less, preferably 600 or less, preferably 500 or less, preferably 400 or less, preferably 300 or less, more preferably 200 or less, more preferably 100 or less, more preferably Preferably not more than 80, more preferably not more than 50, still more preferably not more than 30, particularly preferably It is preferable to have a region of 10 or less. There is no upper limit to the diameter of the fine particles having a diameter of 0.5 μm or more, but it may be 10 μm or less, 8 μm or less, 5 μm or less, or 4.5 μm or less It may be 4 μm or less, 3.5 μm or less, or 3 μm or less.

A preferred embodiment is a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film,
The support film contains fine particles, and includes a region in which the total area ratio of the optically abnormal region is 300 ppm or less when the support film is observed at an area of 13.5 mm ² with an incident-type laser microscope,
Among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm ² of the support film, the number of fine particles in contact with the area other than the fine particles in the optically abnormal area is 1200 or less in the support film. Provided is a photosensitive resin laminate having a region.
Moreover, in the photosensitive resin laminated body which concerns on the combination of the alternative of the said aspect, or the said aspect, the line width / space width formed the resist pattern of 8/8 (micrometer) on the board | substrate using direct drawing exposure machine. In this case, the difference between the line width when focusing on the surface of the support film on the photosensitive resin composition layer side and the line width when shifted from the surface toward the inner side of the 400 μm substrate in the thickness direction is 1.8 μm or less is there.

In the present disclosure, fine particles having a specific value of diameter mean that primary particles having a specific value of the diameter and primary particle aggregates having a specific value of the aggregate of primary particles are included. When the primary particles are not perfect spheres, the longest width of the primary particles is taken as the diameter of the primary particles. Also, when the primary particle aggregate is not a complete sphere, the longest width of the primary particle aggregate is taken as the diameter of the primary particle aggregate. For example, the fine particles having a diameter of 0.5 μm or more include primary particles having a diameter of 0.5 μm or more, and aggregates of primary particles having a diameter of 0.5 μm or less and include primary particle aggregates having a diameter of 0.5 μm or more.

When the optically abnormal area is observed in the optical microscope mode, the appearance (transmission and reflection) of the main area around it is different from that of the surrounding area. As shown in FIG. It can be observed visually with an optical microscope whether it is in contact with the region.

In addition, when the number of fine particles in the support film is measured, if there is a place having the number of fine particles defined in the specific aspect of the present embodiment, the photosensitive resin laminate is photosensitive according to the specific aspect. It is included in a resin laminate. That is, even if the specified number of fine particles is not satisfied when measured at a certain place, when the specified number of fine particles is satisfied when measured at another place, the photosensitive resin laminate is exposed to the light according to the specific aspect. Is included in the conductive resin laminate.

In a preferred embodiment, the total area of the support film is preferably 5% or more, preferably 10% or more, preferably 20% or more, preferably 30% or more, preferably 50% or more, more preferably 60% or more. Preferably, 70% or more, more preferably 80% or more, more preferably 90% or more, particularly preferably about 100% (ie substantially all the area) of the particular optical defined in the specific aspect of the present embodiment. It is an abnormal area or an area having a specific particle (light blocking area, diameter and number of particles).

From the viewpoint of obtaining the rollability of the photosensitive resin laminate well, the support film contains fine particles. In addition, among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm ² , the support film is an optically abnormal area other than the fine particles having optical properties (for example, refractive index) different from the main area of the support film The number of fine particles in contact with the extraordinary refractive index region) may be preferably 1 or more, more preferably 3 or more, and still more preferably 5 or more. There is no upper limit to the diameter of the fine particles having a diameter of 0.5 μm or more, but it may be 10 μm or less, 8 μm or less, 5 μm or less, or 4.5 μm or less It may be 4 μm or less, 3.5 μm or less, or 3 μm or less.

In the present embodiment, among the fine particles having a diameter of 1.0 μm or more included in the area of 13.5 mm ² , the support film is an optical component other than the fine particles having optical properties (for example, refractive index) different from the main region of the support film. The number of fine particles in contact with the abnormal area (for example, the abnormal refractive index area) is preferably 500 or less, more preferably 400 or less, more preferably 300 or less, more preferably 200 or less, still more preferably 100 or less. It is possible to have a region which is more preferably 80 or less, more preferably 50 or less, still more preferably 30 or less, particularly preferably 10 or less. There is no particular upper limit to the diameter of the fine particles having a diameter of 1.0 μm or more, but may be 10 μm or less, 8 μm or less, 5 μm or less, or 4.5 μm or less It may be 4 μm or less, 3.5 μm or less, or 3 μm or less.

From the viewpoint of obtaining the rollability of the photosensitive resin laminate well, the support film contains fine particles. Further, among the fine particles having a diameter of 1.0 μm or more included in the area of 13.5 mm ² , the support film is an optical abnormal area (for example, a fine particle other than the fine particles having optical properties (for example, refractive index) different from the main area of the support film) The number of fine particles in contact with the extraordinary refractive index region) may be preferably 1 or more, more preferably 3 or more, and still more preferably 5 or more. There is no particular upper limit to the diameter of the fine particles having a diameter of 1.0 μm or more, but may be 10 μm or less, 8 μm or less, 5 μm or less, or 4.5 μm or less It may be 4 μm or less, 3.5 μm or less, or 3 μm or less.

In the present embodiment, among the fine particles having a diameter of 2.0 μm or more included in the area of 13.5 mm ² , the support film is an optical component other than fine particles having optical properties (for example, refractive index) different from the main region of the support film. The number of fine particles in contact with the abnormal region (for example, the abnormal refractive index region) is preferably 200 or less, more preferably 180 or less, more preferably 150 or less, more preferably 120 or less, at a number average of 10 locations. It is possible to have a region of 100 or less, more preferably 80 or less, still more preferably 50 or less, still more preferably 30 or less, particularly preferably 10 or less. There is no particular upper limit to the diameter of the particles having a diameter of 2.0 μm or more, but it may be 10 μm or less, 8 μm or less, 5 μm or less, or 4.5 μm or less It may be 4 μm or less, 3.5 μm or less, or 3 μm or less.

From the viewpoint of obtaining the rollability of the photosensitive resin laminate well, the support film contains fine particles. Further, among the fine particles having a diameter of 2.0 μm or more included in the area of 13.5 mm ² , the support film is an optically abnormal area other than the fine particles having optical properties (for example, refractive index) different from the main area of the support film The number of fine particles in contact with the extraordinary refractive index region) may be preferably 1 or more, more preferably 3 or more, and still more preferably 5 or more. There is no particular upper limit to the diameter of the particles having a diameter of 2.0 μm or more, but it may be 10 μm or less, 8 μm or less, 5 μm or less, or 4.5 μm or less It may be 4 μm or less, 3.5 μm or less, or 3 μm or less.

The present embodiment is also a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film,
The support film contains fine particles,
Among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm ² , the support film is an optical abnormal area (for example, anomalous refraction) other than the fine particles having optical properties (for example, refractive index) different from the main area of the support film. A photosensitive resin laminate is provided which has an area in which the number of fine particles in contact with the ratio area is 1,500 or less on a number average of ten. The number of fine particles in contact with the optically abnormal area may be 1200 or less, 1000 or less, 800 or less, 500 or less, 300 or less, or 100 or less in number average at 10 locations. May be.
In this photosensitive resin laminate, it is in contact with the abnormal refractive index area as an optical abnormal area other than the fine particles, which is included in the area of 13.5 mm ² , and the difference in refractive index with the main area of the support film is preferable. Is 0.2 or less, preferably 0.15 or less, preferably 0.10 or less, more preferably 0.05 or less, more preferably 0.03 or less, more preferably 0.02 or less, more preferably 0.01 The number of fine particles having a diameter of 0.5 μm or more, which is the following, may be one or more, ten or more, or fifty or more.
The smaller the number of fine particles in contact with the abnormal refractive index region, the better. However, if the fine particles have a small difference in refractive index from the main region of the support film, the problem of light scattering is small. Further, the presence of the fine particles provides the advantage of improving the slipperiness of the photosensitive resin laminate, and can contribute to the excellent winding property when the photosensitive resin laminate is wound on a roll.
There is no upper limit to the diameter of the fine particles having a diameter of 0.5 μm or more, but it may be 10 μm or less, 8 μm or less, 5 μm or less, or 4.5 μm or less It may be 4 μm or less, 3.5 μm or less, or 3 μm or less.

The present embodiment is also a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film,
The support film contains fine particles,
Among the fine particles having a diameter of 1.0 μm or more included in the area of 13.5 mm ² , the support film is an optical abnormal area (for example, anomalous refraction) other than the fine particles having optical properties (for example, refractive index) different from the main area of the support film. The photosensitive resin laminate has a region in which the number of fine particles in contact with the ratio region is 500 or less. The number of particles in contact with the optically abnormal area may be 400 or less, 300 or less, 250 or less, 200 or less, 150 or less, 100 or less, or 80 or less. It may be 50 or less, 30 or less, 10 or less, or 5 or less.

In this photosensitive resin laminate, it is in contact with the abnormal refractive index area as an optical abnormal area other than the fine particles, which is included in the area of 13.5 mm ² , and the difference in refractive index with the main area of the support film is preferable. Is 0.2 or less, preferably 0.15 or less, preferably 0.10 or less, more preferably 0.05 or less, more preferably 0.03 or less, more preferably 0.02 or less, more preferably 0.01 The number of fine particles having a diameter of 1.0 μm or more, which is the following, may be one or more, five or more, or ten or more in a number average of ten places.
There is no particular upper limit to the diameter of the fine particles having a diameter of 1.0 μm or more, but may be 10 μm or less, 8 μm or less, 5 μm or less, or 4.5 μm or less It may be 4 μm or less, 3.5 μm or less, or 3 μm or less.

The present embodiment is also a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film,
The support film contains fine particles,
Among the fine particles having a diameter of 2.0 μm or more included in the area of 13.5 mm ² , the support film is an optical abnormal area (for example, anomalous refraction) other than the fine particles having optical properties (for example, refractive index) different from the main area of the support film. The photosensitive resin laminate has a region in which the number of fine particles in contact with the ratio region is 200 or less. The number of fine particles in contact with the optically abnormal region is more preferably 180 or less, more preferably 150 or less, more preferably 120 or less, still more preferably 100 or less, still more preferably 80 or less, still more preferably 50 Or less, more preferably 30 or less, particularly preferably 10 or less.

In this photosensitive resin laminate, it is in contact with the abnormal refractive index area as an optical abnormal area other than the fine particles, which is included in the area of 13.5 mm ² , and the difference in refractive index with the main area of the support film is preferable. Is 0.2 or less, preferably 0.15 or less, preferably 0.10 or less, more preferably 0.05 or less, more preferably 0.03 or less, more preferably 0.02 or less, more preferably 0.01 The number of fine particles having a diameter of 2.0 μm or more, which is the following, may be one or more, five or more, or ten or more in a number average of ten places.
There is no particular upper limit to the diameter of the particles having a diameter of 2.0 μm or more, but it may be 10 μm or less, 8 μm or less, 5 μm or less, or 4.5 μm or less It may be 4 μm or less, 3.5 μm or less, or 3 μm or less.

The support film preferably has a haze of 5% or less, more preferably 2% or less, still more preferably 1.5% or less, and particularly preferably 1.0% or less, from the viewpoint of suppressing light scattering during exposure. . From the same viewpoint, the surface roughness Ra of the surface in contact with the photosensitive layer is preferably 30 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less.

The smaller the thickness of the support film is, the more advantageous it is to improve the image forming property and the economic efficiency, but in order to maintain the strength of the photosensitive resin laminate, one having a thickness of 10 μm to 30 μm is preferably used.

An important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesion to the photosensitive resin composition layer is sufficiently smaller than that of the carrier layer, and the layer can be easily peeled off. For example, polyethylene film or polypropylene film can be preferably used as a protective layer. Further, it is also possible to use a film with excellent releasability disclosed in JP-A-59-202457. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

On the polyethylene film surface, a gel called a fish eye may be present. When a polyethylene film having a fish eye is used as a protective layer, the fish eye may be transferred to the photosensitive resin composition layer. When the fish eye is transferred to the photosensitive resin composition layer, air may be taken in during lamination to form a void, which leads to a defect in the resist pattern. From the viewpoint of preventing fish eyes, as a material of the protective layer, stretched polypropylene is preferable. As a specific example, Alphan E-200A manufactured by Oji Paper Co., Ltd. can be mentioned.

The thickness of the photosensitive resin composition layer in the photosensitive resin laminate varies depending on the application, but is preferably 1 μm to 300 μm, more preferably 3 μm to 100 μm, particularly preferably 5 μm to 60 μm, and most preferably 10 μm to 30 μm. The thinner the thickness of the photosensitive resin composition layer, the higher the resolution, and the thicker the layer, the higher the film strength.

Next, a method of manufacturing the photosensitive resin laminate will be described.

A known method can be adopted as a method of producing a photosensitive resin laminate by sequentially laminating a support film and a photosensitive resin composition layer, and, if necessary, a protective layer. For example, the photosensitive resin composition used for the photosensitive resin composition layer is mixed with a solvent that dissolves the photosensitive resin composition layer to form a uniform solution, first coated on a support film using a bar coater or a roll coater, and then dried By removing the solvent, a photosensitive resin composition layer composed of the photosensitive resin composition can be laminated on the support film. Subsequently, the photosensitive resin laminated body can be produced by laminating a protective layer on the photosensitive resin composition layer as needed.

[Photosensitive resin composition]
In the present embodiment, the photosensitive resin composition preferably contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator. The photosensitive resin composition comprises (A) an alkali-soluble polymer: 10% by mass to 90% by mass, based on the total solid content mass of the photosensitive resin composition; and (B) a compound having an ethylenically unsaturated double bond. And (C) a photopolymerization initiator: 0.01% by mass to 20% by mass. Hereinafter, each component will be described in order.

<(A) Alkali-soluble polymer>
In the present disclosure, the (A) alkali-soluble polymer includes a polymer that is easily soluble in an alkaline substance. More specifically, the amount of carboxyl groups contained in the (A) alkali-soluble polymer is 100 to 600, preferably 250 to 450 in acid equivalent. The acid equivalent refers to the mass (unit: gram) of a polymer having one equivalent of carboxyl group in the molecule. The carboxyl group in the (A) alkali-soluble polymer is required to give the photosensitive resin composition layer developability and releasability to an aqueous alkali solution. Increasing the acid equivalent to 100 or more is preferable from the viewpoint of improving the development resistance, the resolution and the adhesion. And it is more preferable to make an acid equivalent 250 or more. On the other hand, setting the acid equivalent to 600 or less is preferable from the viewpoint of improving the developability and the releasability. And it is more preferable to make an acid equivalent 450 or less. In the present disclosure, the acid equivalent is a value measured by potentiometric titration with a 0.1 mol / L aqueous solution of NaOH using a potentiometric titrator.

The weight average molecular weight of the (A) alkali-soluble polymer is preferably 5,000 to 500,000. It is preferable from the viewpoint of improving resolution and developability to make the weight average molecular weight 500,000 or less. The weight average molecular weight is more preferably 100,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, setting the weight average molecular weight to 5,000 or more is a viewpoint of controlling the properties of development aggregate and the properties of unexposed film such as edge fuse property and cut tip property in the case of forming a photosensitive resin laminate. It is preferable from The weight average molecular weight is more preferably 10,000 or more, and still more preferably 20,000 or more. With edge fuse property, when it winds up in roll shape as a photosensitive resin laminated body, it is a grade of the ease of protrusion of the photosensitive resin composition layer (namely, layer which consists of photosensitive resin compositions) from the end face of a roll. Say The cut tip property refers to the degree of the chip's flyability when the unexposed film is cut by a cutter. When this chip adheres to the upper surface or the like of the photosensitive resin laminate, it is transferred to a mask in a later exposure process or the like to cause defective products. The dispersion degree of the alkali soluble polymer (A) is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and 1.0 to 4.0. More preferably, it is more preferably 1.0 to 3.0.

In the present embodiment, from the viewpoint of suppressing the line width thickening and the deterioration in resolution when the focal position at the time of exposure shifts, the photosensitive resin composition contains an aromatic hydrocarbon group as the (A) alkali-soluble polymer. It is preferable to contain the monomer component which it has. In addition, as such an aromatic hydrocarbon group, a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group are mentioned, for example. The content ratio of the monomer component having an aromatic hydrocarbon group in the (A) alkali-soluble polymer is preferably 20% by mass or more based on the total mass of all the monomer components, and 40% by mass The content is more preferably 50% by mass or more, particularly preferably 55% by mass or more, and most preferably 60% by mass or more. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 80% by mass or less. In addition, the content rate of the monomer component which has an aromatic hydrocarbon group in, when containing multiple types of (A) alkali-soluble polymer was calculated | required as a weight average value.

As the monomer having an aromatic hydrocarbon group, for example, a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl Benzoic acid, styrene dimer, styrene trimer etc. may be mentioned. Among them, monomers having an aralkyl group or styrene are preferable.

As an aralkyl group, a substituted or unsubstituted phenylalkyl group (except for a benzyl group), a substituted or unsubstituted benzyl group and the like can be mentioned, and a substituted or unsubstituted benzyl group is preferable.

Examples of the comonomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.

As a comonomer having a benzyl group, (meth) acrylates having a benzyl group, such as benzyl (meth) acrylate, chlorobenzyl (meth) acrylate etc .; vinyl monomers having a benzyl group such as vinyl benzyl chloride, vinyl benzyl alcohol etc Can be mentioned. Among them, benzyl (meth) acrylate is preferred.

The (A) alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group is a monomer having an aromatic hydrocarbon group and / or at least one of a first monomer described later and / or It is preferably obtained by polymerizing with at least one of the second monomers described later.

The (A) alkali-soluble polymer which does not contain a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and It is more preferable to be obtained by copolymerizing at least one of the monomers and at least one of the second monomers described later.

The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid half ester and the like. Among these, (meth) acrylic acid is preferable.

In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, “(meth) acryloyl group” means acryloyl group or methacryloyl group, and “(meth) acrylate” "" Means "acrylate" or "methacrylate".

The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all the monomer components. Making the copolymerization ratio 10% by mass or more is preferable from the viewpoint of expressing good developability, controlling edge fuse property, etc., preferably 15% by mass or more, and more preferably 20% by mass or more. . Setting the copolymerization ratio to 50% by mass or less is preferable from the viewpoints of high resolution and shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, and in these aspects, 35% by mass The following is more preferable, 30 mass% or less is further preferable, and 27 mass% or less is particularly preferable.

The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. As the second monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate , (Meth) acrylates such as tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; vinyl acetate And esters of vinyl alcohol, and (meth) acrylonitrile and the like. Among them, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate are preferable.

It is preferable to contain a monomer having an aralkyl group and / or styrene as a monomer from the viewpoint of suppressing the line width thickening and resolution deterioration when the focal position at the time of exposure shifts. For example, a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, and the like are preferable.

The (A) alkali-soluble polymer can be used singly or in combination of two or more. In the case where two or more kinds are mixed and used, two kinds of alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group may be mixedly used, or a monomer component having an aromatic hydrocarbon group It is preferable to use a mixture of an alkali-soluble polymer containing at least one alkali-soluble polymer and an alkali-soluble polymer not containing a monomer component having an aromatic hydrocarbon group. In the latter case, the proportion of the alkali-soluble polymer containing the monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more based on the total of (A) the alkali-soluble polymer, and 70 It is more preferable that it is mass% or more, It is preferable that it is 80 mass% or more, It is more preferable that it is 90 mass% or more.

(A) The synthesis of the alkali-soluble polymer can be carried out by using benzoyl peroxide, azoisobutyronitrile or the like in a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone or isopropanol. It is preferable to be carried out by adding a suitable amount of a radical polymerization initiator and heating and stirring. In some cases, synthesis is performed while a portion of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As a synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used other than solution polymerization.

Weight average Tg ^total glass transition temperature Tg of the (A) alkali-soluble polymer is preferably at 30 ° C. or higher 135 ° C. or less. Tg ^total is calculated by the method described in the examples described later. In the photosensitive resin composition, by using the (A) alkali-soluble polymer having a Tg ^{total of} 135 ° C. or less, it is possible to suppress the line width thickening and the deterioration of resolution when the focal position at the time of exposure shifts. it can. From this viewpoint, the Tg ^total of the (A) alkali-soluble polymer is more preferably 120 ° C. or less, still more preferably 115 ° C. or less, still more preferably 110 ° C. or less, and 105 ° C. or less C., more preferably 110.degree. C. or less. Moreover, it is preferable to use (A) an alkali-soluble polymer having a Tg ^{total of} 30 ° C. or more from the viewpoint of improving the edge fuse resistance. From this viewpoint, the Tg ^total of the (A) alkali-soluble polymer is more preferably 40 ° C. or more, still more preferably 50 ° C. or more, and particularly preferably 60 ° C. or more.

The ratio of the (A) alkali-soluble polymer to the total solid content mass of the photosensitive resin composition is preferably in the range of 10% by mass to 90% by mass, and more preferably 30% by mass to 70% by mass. More preferably, it is 40% by mass to 60% by mass. It is preferable from the viewpoint of controlling the development time that the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition is 90% by mass or less. On the other hand, it is preferable from the viewpoint of improving the edge fuse resistance that the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition is 10% by mass or more.

<(B) Compound Having Ethylenically Unsaturated Double Bond>
It is preferable that the compound which has (B) an ethylenically unsaturated double bond contains the compound which has a (meth) acryloyl group in a molecule | numerator from a curable viewpoint and compatibility with (A) alkali-soluble polymer. The number of (meth) acryloyl groups in the compound (B) may be one or more.

As the (B) compound having one (meth) acryloyl group, for example, a compound obtained by adding (meth) acrylic acid to one end of a polyalkylene oxide, or (meth) acrylic at one end of a polyalkylene oxide Examples thereof include compounds obtained by adding an acid and alkyl etherifying or allyl etherifying the other end, phthalic acid compounds and the like, which are preferable from the viewpoint of peelability and flexibility of a cured film.

As such a compound, for example,
Phenoxyhexaethylene glycol mono (meth) acrylate which is a (meth) acrylate of a compound in which polyethylene glycol is added to a phenyl group
4-normalnonylphenoxyheptaethylene glycol dipropylene glycol which is a (meth) acrylate of a compound obtained by adding polypropylene glycol to which 2 mol of propylene oxide is added and polyethylene glycol to which 7 mol of ethylene oxide is added to nonylphenol on average (Meth) acrylate,
4-normalnonylphenoxypentaethylene glycol monopropylene glycol which is a (meth) acrylate of a compound obtained by adding polypropylene glycol to which 1 mol of propylene oxide is added and polyethylene glycol to which 5 mol of ethylene oxide is added to nonylphenol on average (Meth) acrylate,
4-normalnonylphenoxyoctaethylene glycol (meth) acrylate (eg, Toagosei Co., Ltd. M-114), which is an acrylate of a compound obtained by adding polyethylene glycol added with ethylene oxide on average to 8 moles to nonylphenol .

In addition to the above viewpoints, it is preferable to include γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-о-phthalate from the viewpoints of sensitivity, resolution and adhesion.

As a compound having two (meth) acryloyl groups in the molecule, for example, a compound having a (meth) acryloyl group at both ends of the alkylene oxide chain, or an alkylene in which an ethylene oxide chain and a propylene oxide chain are bound by random or block The compound etc. which have a (meth) acryloyl group in the both ends of an oxide chain can be mentioned.

As such compounds, for example, tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, octaethylene glycol di ( Polyethylene glycol (meth) acrylates such as (meth) acrylates, nonaethylene glycol di (meth) acrylates, decaethylene glycol di (meth) acrylates, and compounds having (meth) acryloyl groups at both ends of a 12 mol ethylene oxide chain In addition to
Polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate and the like can be mentioned. As a polyalkylene oxide di (meth) acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound, for example, an average of 3 moles of ethylene oxide is further added to both ends of polypropylene glycol to which an average of 12 moles of propylene oxide is added. Of diethylene glycol, and dimethacrylate of glycol in which 15 mol of ethylene oxide is further added on average to both ends of polypropylene glycol added with 18 mol of propylene oxide on average, FA-023 M, FA-024 M, FA-027 M (product name) And Hitachi Chemical Co., Ltd.). These are preferable in terms of flexibility, resolution, adhesion and the like.

As another example of a compound having two (meth) acryloyl groups in the molecule, a compound having (meth) acryloyl groups at both ends by alkylene oxide modification of bisphenol A has resolution and adhesion. From the point of view of
Specifically, the following general formula (I):

Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , and n 1 and n 3 are each independently 1 to -(AO)-is an integer of 39, n1 + n3 is an integer of 2 to 40, n2 and n4 are each independently an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30, The arrangement of repeating units of and-(BO)-may be random or block. And in the case of a block, either-(A-O)-or-(B-O)-may be on the side of the bisphenyl group. }
The compounds represented by can be used.

For example, polyethylene glycol dimethacrylate of polyethylene glycol in which ethylene oxide is added in an average of 5 moles at each end of bisphenol A, polyethylene glycol in which ethylene oxide is added at an average of 2 moles in each end of bisphenol A Polyethylene glycol dimethacrylate in which ethylene oxide is added on average at 1 mole each to both ends of dimethacrylate and bisphenol A is preferable in view of resolution and adhesion.

Moreover, you may use the compound in which the aromatic ring in the said General formula (I) has a hetero atom and / or a substituent.

Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group Amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, cyano group, carbonyl group, mercapto group, alkyl mercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group A hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms for the alkyl group, an alkoxy group having 1 to 20 carbon atoms, Alkoxycarbonyl group having 1 to 20 carbon atoms, alkyl carbonyl group having 2 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, 2 to 10 carbon atoms N- alkylcarbamoyl group or a group containing a heterocyclic ring, or an aryl group substituted by these substituents. These substituents may form a condensed ring, or hydrogen atoms in these substituents may be substituted with a heteroatom such as a halogen atom. When the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

The compound having three or more (meth) acryloyl groups in the molecule has, as a central skeleton, three or more moles of a group to which an alkylene oxide group can be added in the molecule, and ethyleneoxy group, propyleneoxy group, etc. It can be obtained by converting an alcohol obtained by adding an alkyleneoxy group such as a butyleneoxy group to (meth) acrylate. In this case, examples of the compound capable of becoming a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, isocyanurate ring and the like. As these compounds, tri (meth) acrylates, such as ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate (for example, Trimethacrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane, and trimethacrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane are preferable from the viewpoint of flexibility, adhesion and suppression of bleed out), etc .; (Meth) acrylates, such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate ; Penta (meth) acrylate, for example, dipentaerythritol penta (meth) acrylate; hexa (meth) acrylate, for example, dipentaerythritol hexa (meth) acrylate. Compounds having three or more (meth) acryloyl groups are preferable from the viewpoint of resolution, adhesion, and resist shape, and compounds having three or more methacryl groups are more preferable.

As tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate is preferable. The pentaerythritol tetra (meth) acrylate may be tetra (meth) acrylate or the like in which a total of 1 to 40 moles of alkylene oxide is added to the four terminals of pentaerythritol.

As the hexa (meth) acrylate, hexa (meth) acrylate in which a total of 1 to 40 moles of ethylene oxide is added to the six ends of dipentaerythritol, and a total of 1 to 20 moles of ε at the six ends of dipentaerythritol Hexa (meth) acrylates to which caprolactone is added are preferred.

The (meth) acrylate compounds described above can be used independently or in combination. The photosensitive resin composition may also contain other compounds as a compound having (B) an ethylenically unsaturated bond. Other compounds include (meth) acrylate having a urethane bond, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, and a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid And compounds obtained by reaction, 1,6-hexanediol di (meth) acrylate and the like.

The ratio of the compound (B) having an ethylenically unsaturated double bond to the total solid content mass of the photosensitive resin composition is preferably 5% by mass to 70% by mass. It is preferable to make this proportion 5% by mass or more from the viewpoint of sensitivity, resolution and adhesion. The proportion is more preferably 20% by mass or more, and still more preferably 30% by mass or more. On the other hand, it is preferable to make this ratio 70% by mass or less from the viewpoint of suppressing the peeling delay of the edge fuse and the cured resist. It is more preferable to make this ratio 50 mass% or less.

<(C) Photopolymerization initiator>
(C) A photoinitiator is a compound which polymerizes a monomer by light. The photosensitive resin composition contains a compound generally known in the art as a (C) photopolymerization initiator.

The total content of the photopolymerization initiator (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05% to 10% by mass, and still more preferably 0.1% by mass. % To 7% by mass, particularly preferably 0.1% to 6% by mass. The total content of the photopolymerization initiator (C) is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and light is sufficiently transmitted to the bottom of the resist to obtain good high resolution. It is preferable that it is 20 mass% or less from a viewpoint of obtaining.

(C) As a photopolymerization initiator, quinones, aromatic ketones, acetophenones, acyl phosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkyl aminobenzoic acid esters, oxime esters And acridines (eg, 9-phenylacridine, bisacridinylheptane, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine are preferred in terms of sensitivity, resolution and adhesion) Further, hexaarylbiimidazole, pyrazoline compounds, anthracene compounds (eg, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene are preferable in terms of sensitivity, resolution and adhesion), coumarin compounds (eg, 7-diethylamino-4-methyl Coumarins are preferred in terms of sensitivity, resolution and adhesion), N-aryl amino acids or ester compounds thereof (eg, N-phenylglycine is preferred in terms of sensitivity, resolution and adhesion), and halogen compounds (eg, such as Tribromomethyl phenyl sulfone) and the like. These can be used singly or in combination of two or more. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4,6-trimethylbenzo It is also possible to use yl-diphenyl-phosphine oxide and triphenyl phosphine oxide.

Examples of aromatic ketones include benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone Can. These can be used singly or in combination of two or more. Among these, from the viewpoint of adhesion, 4,4'-bis (diethylamino) benzophenone is preferable. Furthermore, from the viewpoint of transmittance, the content of the aromatic ketone in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, and more preferably 0.02% by mass to 0.3%. It is in the range of mass%.

Examples of hexaarylbiimidazole include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole and 2,2 ', 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-Diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl) ) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2'-bis- (2-fluorophenyl) -4,4 ' 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4 ', , 5'-Tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -Biimidazole, 2,2'-bis- (2,5-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- ( 2,6-Difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4-trifluorophenyl) -4 4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4', 5,5'- Tetrakis- (3-methoxyphenyl -Biimidazole, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'- Bis- (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4,6- Trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4, 4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4', 5,5 ' -Tetrakis- (3-methoxyphenyl) -biimidazo And 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole etc. These can be used alone or in combination of two or more. From the viewpoint of high sensitivity, resolution and adhesion, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferred.

In the present embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass or more from the viewpoint of improving the peeling characteristics and / or the sensitivity of the photosensitive resin composition layer. It is in the range of 7% by mass, more preferably 0.1% by mass to 6% by mass, and still more preferably 1% by mass to 5% by mass.

It is preferable that the photosensitive resin composition also contains a pyrazoline compound as a photosensitizer from the viewpoints of peeling characteristics or sensitivity, resolution, and adhesiveness of the photosensitive resin composition layer.

As a pyrazoline compound, for example, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropyl) Phenyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3 (3,5-Dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,6-dimethoxystyryl) -5- (2,6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,5-dimethoxystyryl) -5- (2,5-) Dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,3-dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,4-dimethoxystyryl) -5 -(2,4-dimethoxyphenyl) -pyrazoline and the like are preferable from the above-mentioned viewpoint, and can be mentioned. Among these, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is more preferable.

In the present embodiment, the content of the photosensitizer in the photosensitive resin composition is preferably 0.05% by mass to 5% from the viewpoint of improving the peeling characteristics and / or the sensitivity of the photosensitive resin composition layer. The content is preferably in the range of 0.1% by mass to 3% by mass.

<(D) phenol derivative>
In the present embodiment, the photosensitive resin composition preferably further includes (D) a phenol derivative. Examples of (D) phenol derivatives include p-methoxyphenol, hydroquinone, pyrogallol, tert-butyl catechol, 2,6-di-tert-butyl-p-cresol, and 2,2'-methylenebis (4-methyl-6-) tert-Butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2 , 5-Di-tert-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis (2-hydroxy-3-t-butyl-5-ethylphenyl) methane, triethylene glycol -Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) pro Onate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl tetrakis [3- (3,5-di-t-) Butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di) -T-Butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl -4-hydroxybenzyl phosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxyben) B) Benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-butylidene bis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, styrenated phenol (eg, manufactured by Kawaguchi Chemical Industry Co., Ltd.) Antage SP), tribenzylphenol (eg, Kawaguchi Chemical Industry Co., Ltd., TBP, phenol having 1 to 3 benzyl groups), biphenol and the like can be mentioned. The inclusion of the (D) phenol derivative is preferable from the viewpoint of suppressing the line width thickening and the deterioration of resolution when the focal position at the time of exposure shifts, and from the same viewpoint, a hindered phenol or biphenol is preferable. Further, from the same viewpoint, it is preferable that the (D) phenol derivative has two or more phenol nuclei.

The ratio of the (D) phenol derivative to the total solid content mass of the photosensitive resin composition is preferably 0.001 mass% to 10 mass%. This ratio is preferably 0.001% by mass or more, and 0.005% by mass or more from the viewpoint of suppressing the line width thickening and the deterioration of resolution when the focal position at the time of exposure shifts. Is more preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. On the other hand, this ratio is preferably 10% by mass or less, more preferably 5% by mass or less, and 3% by mass or less, from the viewpoint of little decrease in sensitivity and improvement in resolution. Is more preferable, 2% by mass or less is particularly preferable, and 1.5% by mass or less is most preferable.

<Additives>
The photosensitive resin composition may optionally contain additives such as a dye, a plasticizer, an antioxidant, and a stabilizer. For example, additives listed in Japanese Patent Application Laid-Open No. 2013-156369 may be used.

(Dye and colored substance)
In the present embodiment, the photosensitive resin composition may further optionally contain at least one selected from the group consisting of dyes (for example, leuco dyes, fluoran dyes and the like) and coloring substances.

Examples of coloring substances include fuchsin, phthalocyanine green, auramine base, paramagienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (for example, Hoedagaya Chemical Co., Ltd. Eisen (registered trademark) MALACITE GREEN), Basic Blue 20, diamond green (for example, Eiden (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.) can be mentioned. The content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. Setting the content to 0.001% by mass or more is preferable from the viewpoint of improving the handleability of the photosensitive resin composition. On the other hand, making the content 1% by mass or less is preferable from the viewpoint of maintaining the storage stability of the photosensitive resin composition.

The photosensitive resin composition is preferable from the viewpoint of visibility because the exposed portion is colored by containing the dye, and when the inspection machine or the like reads the alignment marker for exposure, the exposed portion and the unexposed portion The larger the contrast of the image, the easier it is to recognize. Preferred dyes in this regard include leuco dyes and fluoran dyes.

Examples of leuco dyes include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green] and the like. In particular, leuco crystal violet is preferably used as the leuco dye, from the viewpoint of achieving good contrast. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass with respect to the total solid content mass of the photosensitive resin composition. Making this content 0.1% by mass or more is preferable from the viewpoint of improving the contrast between the exposed part and the unexposed part. The content is more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more. On the other hand, it is preferable to make this content 10% by mass or less from the viewpoint of maintaining storage stability. The content is more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

Moreover, it is preferable from a viewpoint of optimizing adhesiveness and contrast to use combining a leuco dye and the halogen compound mentioned above in (C) photoinitiator in photosensitive resin composition. When a leuco dye is used in combination with the halogen compound, the content of the halogen compound in the photosensitive resin composition is 0.01 mass based on 100% by mass of the total solid content of the photosensitive resin composition. % To 3% by mass is preferable from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer.

(Other additives)
The photosensitive resin composition further contains at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles in order to improve thermal stability and storage stability. It is also good.

Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. In order not to impair the sensitivity of the photosensitive resin composition, nitrosophenylhydroxyamine aluminum salt is preferred.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like can be mentioned.

As carboxybenzotriazoles, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole and the like.

The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% by mass or less, based on 100% by mass of the total solid content of the photosensitive resin composition. It is 3% by mass, more preferably 0.05% by mass to 1% by mass. The content of 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, setting the content to 3% by mass or less is preferable from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.

In the present embodiment, the photosensitive resin composition may further contain epoxy compounds of bisphenol A. Examples of epoxy compounds of bisphenol A include, for example, compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the end.

In the present embodiment, the photosensitive resin composition may further contain a plasticizer. As a plasticizer, for example, phthalic acid esters (eg, diethylflate etc.), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, triethyl acetyl citrate And n-propyl, acetyl tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether and the like. In addition, adecanol SDX-1569, adecanol SDX-1570, adecanol SDX-1571, adecanol SDX-479 (manufactured by Asahi Denka Co., Ltd.), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, New Paul BPE-20T, New Paul BPE-60, New Paul BPE-100, New Paul BPE-180 (manufactured by Sanyo Chemical Industries, Ltd.), Uniol DB-400, Uniol DAB-800, Uniol DA-350F, Uniol DA- And compounds having a bisphenol skeleton, such as 400, Uniol DA-700 (manufactured by Nippon Oil and Fats Co., Ltd.), BA-P4U glycol, BA-P8 glycol (manufactured by Nippon Emulsifier Co., Ltd.), and the like.

The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, with respect to the total solid content mass of the photosensitive resin composition. It is. It is preferable to make the content 1% by mass or more from the viewpoint of suppressing the delay of development time and imparting flexibility to the cured film. On the other hand, making the content 50% by mass or less is preferable from the viewpoint of suppressing insufficient curing and cold flow.

[solvent]
The photosensitive resin composition can be dissolved in a solvent and used in the form of a photosensitive resin composition preparation liquid for producing a photosensitive resin laminate. Examples of the solvent include ketones and alcohols. The ketones are represented by methyl ethyl ketone (MEK) and acetone. The alcohols are represented by methanol, ethanol and isopropanol. The solvent is used in an amount such that the viscosity at 25 ° C. of the photosensitive resin composition preparation liquid applied onto the support layer is 500 mPa · s to 4,000 mPa · s during the production of the photosensitive resin laminate. Preferably, it is added to the resin composition.

<Method of forming resist pattern>
Next, an example of a method of manufacturing a resist pattern using the photosensitive resin laminate of the present embodiment will be described. The method comprises a laminating step of laminating a photosensitive resin laminate on a substrate, an exposing step of exposing a photosensitive resin composition layer of the photosensitive resin laminate, and developing an unexposed portion of the photosensitive resin composition layer. It can include a developing step to be removed. As the resist pattern, for example, printed wiring board, semiconductor element, printing plate, liquid crystal display panel, flexible substrate, lead frame substrate, substrate for COF (chip on film), substrate for semiconductor package, transparent electrode for liquid crystal, TFT for liquid crystal And wiring patterns, electrodes for PDP (plasma display panel) and the like. The photosensitive resin laminate of the present embodiment has an advantage of avoiding the resist protrusions well, and for example, the line width / space width is 20/20 (μm or less) or the line width / space width is 10 /. It is particularly useful for the formation of fine wiring of less than 10 (μm). The line width / space width (μm) to which the photosensitive resin laminate of the present embodiment can be applied is not particularly limited, and for example, 15/15 (μm) or less, preferably 10/10 (μm) or less, and further Preferably it is 9.5 / 9.5 (μm) or less, particularly preferably 9.0 / 9.0 (μm) or less. The lower limit value of the line width / space width (μm) is not particularly limited, but may be 3/3 (μm) or more, 4/4 (μm) or more, or 5/5 (μm) or more. Further, the photosensitive resin laminate of the present embodiment is particularly useful for wiring formation by the semi-additive method (SAP) from the above advantages. The SAP method can be carried out by a conventional method, and for example, wiring can be formed by a known plating method using a laminate of an insulating resin layer and a copper layer (for example, an electroless copper plating layer containing palladium as a catalyst). As an example, a method of manufacturing a printed wiring board will be described as follows.

The printed wiring board is manufactured through the following steps.
(1) Laminating Step First, in the laminating step, a photosensitive resin composition layer is formed on a substrate using a laminator. Specifically, in the case where the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin composition layer is laminated by heating under pressure on the substrate surface with a laminator. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO) and the like.

In the present embodiment, the photosensitive resin composition layer may be laminated only on one side of the substrate surface, or may be laminated on both sides as needed. The heating temperature during lamination is generally 40.degree. C. to 160.degree. In addition, the adhesion of the obtained resist pattern to the substrate can be improved by performing the thermocompression bonding twice or more at the time of lamination. At the time of thermocompression bonding, a two-stage laminator provided with dual rolls may be used, or the laminate of the substrate and the photosensitive resin composition layer may be crimped by being repeatedly passed through the roll several times.

(2) Exposure step In this step, a mask film having a desired wiring pattern is brought into close contact with the support layer and an exposure method is performed using an active light source, an exposure method by direct drawing of a drawing pattern which is a desired wiring pattern, The photosensitive resin composition layer is exposed by an exposure method by projecting an image of a photomask through a lens. The advantage of the photosensitive resin composition according to the present embodiment is more remarkable in an exposure method by direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens, and exposure by direct drawing of a drawing pattern It is particularly remarkable in the method.

(3) Development Step In this step, after exposure, the support layer on the photosensitive resin composition layer is peeled off, and then the unexposed area is developed and removed using a developing solution of an alkaline aqueous solution to obtain a resist pattern as a substrate. Form on.

An aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used as the alkaline aqueous solution. The alkaline aqueous solution is appropriately selected in accordance with the characteristics of the photosensitive resin composition layer, and an aqueous Na ₂ CO ₃ solution having a concentration of about 0.2% by mass to about 2% by mass and a temperature of about 20 ° C to about 40 ° C is used. preferable.

A resist pattern can be obtained through the above steps (1) to (3). After these steps, optionally, a heating step of about 100 ° C. to about 300 ° C. can also be performed. By performing this heating step, it is possible to further improve the chemical resistance. For heating, a heating furnace of a hot air, infrared or far infrared type can be used. Also, this heating process may be performed after the exposure process.

(4) Etching Step or Plating Step A substrate surface (for example, a copper surface of a copper clad laminate) exposed by development is etched or plated to manufacture a conductor pattern.

(5) Peeling Step Thereafter, the resist pattern is peeled from the substrate by an aqueous solution having a stronger alkalinity than the developer. The aqueous alkaline solution for peeling is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of about 2% by mass to about 5% by mass and a temperature of about 40 to about 70 ° C. is preferable. A small amount of water-soluble solvent can also be added to the stripping solution.

The photosensitive resin laminate of the present embodiment is a resist pattern of a printed wiring board, a flexible substrate, a lead frame substrate, a substrate for COF, a substrate for semiconductor package, a transparent electrode for liquid crystal, a wiring for TFT for liquid crystal, an electrode for PDP, etc. Or it is a photosensitive resin laminated body suitable for manufacture of a conductor pattern.

In addition, about the various parameters mentioned above, unless otherwise indicated, it is measured according to the measuring method in the below-mentioned Example, or the method understood by those skilled in the art to be equivalent to this.

Next, the present embodiment will be more specifically described by way of examples and comparative examples. However, the present embodiment is not limited to the following embodiments unless it deviates from the gist of the present embodiment. Physical properties in the examples were measured by the following methods.

The preparation method of the sample for evaluation of an Example and a comparative example, the evaluation method about the obtained sample, and its evaluation result are shown.

Examples 1 to 3 and Comparative Example 1
1. Preparation of photosensitive resin composition (A) 47 parts by mass of methacrylic acid / benzyl methacrylate copolymer (polymerization ratio 20/80 (mass ratio), acid equivalent 430, weight average molecular weight 50,000) as an alkali soluble polymer,
(B) 0.1 parts by mass of 4,4′-bis (diethylamino) benzophenone and 3 parts by mass of 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer as a photopolymerization initiator,
(C) 14 parts by mass of tetraacrylate in which an average of 15 moles of ethylene oxide is added to four ends of pentaerythritol as a compound having an ethylenic double bond, and 0.05 parts by mass of diamond green and leuco as a dye A photosensitive resin composition was prepared by dissolving 0.3 parts by mass of crystal violet in a solvent.

2. Preparation of Support Film As a support film of each of Examples 1 to 3 and Comparative Example 1, polyethylene terephthalate (PET) was prepared. The total area ratio of the optically abnormal area in each support film is as described in Table 1. The number of particulates in the support film was adjusted by the fineness of the filter and the number of times the material constituting the support film was passed through the filter and the number of particulates added. The adjustment of the area of the optically abnormal area (the part where reflection, scattering, etc. occur) is carried out by thermocompression bonding of the film under the conditions of 180 to 250 ° C. as appropriate after biaxial stretching of the PET film. It was carried out by eliminating the region (that is, the cavity or the region having different orientation or crystallinity).

3. Production of Photosensitive Resin Laminate The photosensitive resin composition prepared above is coated on one surface of a polyethylene terephthalate (PET) support film (12 μm in thickness) with a bar coater, and it is 2.5 in a dryer at 95 ° C. A photosensitive resin laminate was obtained by drying for a minute to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 20 μm. Next, on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film is not laminated, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) is laminated as a protective layer to form a photosensitive resin laminate. I got a body.

<Board surface cleaning>
As a substrate for evaluation of imageability, a 0.4 mm thick copper-clad laminate obtained by laminating 18 μm rolled copper foil is treated with a soft etching agent (CPE-900, manufactured by Hishie Kagaku Co., Ltd.), and 10 mass% H ₂ SO _The substrate surface was washed with ₄ .

<Lamination>
While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate is rolled with a hot roll laminator (AL-700 manufactured by Asahi Kasei Co., Ltd.) on a copper-clad laminate preheated to 60 ° C. It laminated at the temperature of 105 degreeC. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Exposure>
Exposure was carried out with a direct drawing exposure apparatus (FDi-3 manufactured by Oak Manufacturing Co., Ltd., main wavelength 405 ± 5 nm) using a stofer 41-step tablet or a mask pattern for predetermined direct imaging (DI) exposure. The exposure was performed with an exposure amount such that the maximum number of remaining film steps was 14 when exposed and developed using the Stoffer 41-step tablet as a mask.

<Development>
After peeling off the polyethylene terephthalate film (support film), a 1% by mass aqueous solution of Na ₂ CO _{3 at} 30 ° C. is sprayed for a predetermined time using an alkali developing machine (developing machine for dry films made by Fuji Kiko) The unexposed part of the photosensitive resin composition layer was dissolved and removed in a time twice as much as the minimum development time. At this time, the minimum time required for complete dissolution of the photosensitive resin composition layer in the unexposed area was taken as the minimum development time.

<Measurement of Total Area of Optical Anomaly Region>
A polarizing filter (OLS4000-QWP) was inserted above the objective lens of the incident-type laser microscope (OLS-4100 manufactured by Olympus). Next, a support film sample cut to 30 mm × 30 mm was suctioned and fixed horizontally on a stage of a laser microscope using a porous adsorption plate (65F-HG manufactured by Universal Giken) and a vacuum pump. The suction-fixed support film was observed with a 50 × laser light amount 60 (laser wavelength is 405 nm) of an objective lens. At this time, an area of 2 μm at the center in the thickness direction of the support film was defined as a measurement area, and measurement was performed at 200 measurement points at 259 μm × 260 μm (therefore, the measurement area is a total of 2.259 mm × 0.26 mm) X 200 = 13.5 mm ² ).

The difference in light amount between the pixel of the maximum light amount and the pixel of the minimum light amount in the measured image was divided into 4096 gradations (the maximum light amount is 4095 and the minimum light amount is 0). A histogram (horizontal axis: gradation of light quantity (minimum value 0, maximum value 4095), vertical axis: number of pixels) graphing the light quantity distribution of the pixels in the image was created. The measured image is binarized using the gradation obtained by adding 400 gradations from the value of the larger one of the two base values in the created histogram as the threshold value, and the areas of the pixels whose light amounts are larger than the threshold are summed. , And the total area thereof is the total area of the optical anomaly region. The ratio of the total area of the optically abnormal area portion to the measurement area is calculated.

<Number of fine particles having a diameter of 0.5 μm or more, fine particles having a diameter of 1.0 μm or more, and fine particles having a diameter of 2.0 μm or more in contact with the optically abnormal region>
After measuring the total area of the optically abnormal area portion, the incident type laser microscope (OLS-4100 manufactured by Olympus) was switched to the optical microscope mode. Thereafter, the number and the diameter of the fine particles in contact with the optically abnormal area corresponding to the position of the fine particles in the optically abnormal area which was visually confirmed in the laser microscope mode in the measurement area of 259 μm × 260 μm were measured.
The same measurement was carried out at 200 measurement points (that is, carried out with an area of 0.259 mm × 0.26 mm × 200 = 13.5 mm ² ), and the total number was calculated for each diameter of the fine particles.

<Evaluation of resist protrusions>
The entire surface of the 300 mm square evaluation substrate was exposed so that L (line) / S (space) = 8 μm / 8 μm. At this time, the position of the focal point at the time of exposure was aligned with the surface of the polyethylene terephthalate film. Next, the polyethylene terephthalate film (support film) was peeled off, and then development was carried out for a development time twice the minimum development time. Then, the resist pattern was observed by focusing on the surface of the resist with an optical microscope, and protrusions having a size of 2 um or more were counted. The observation area was 3 mm square (9 mm ² ).
The results are shown in Table 1.

<Evaluation of line width fatness>
The entire surface of the 300 mm square evaluation substrate was exposed so that L (line) / S (space) = 8 μm / 8 μm. At this time, the position of the focal point at the time of exposure was aligned with the surface of the polyethylene terephthalate film on the photosensitive layer resin side. Next, the polyethylene terephthalate film (support film) was peeled off, and then development was carried out for a development time twice the minimum development time. The line width was measured, and the line width (without defocus) of the thickest portion was measured. The measurement was performed on 30 lines for each 3 mm range, and the line width of the thickest portion in each line was measured and used as the average value. Next, measurement was carried out under the same conditions as above except that the position of the focal point at the time of exposure was shifted to the inner side of the 400 μm substrate from the surface of the photosensitive layer resin side of the polyethylene terephthalate film. The line width was measured and the average value was obtained.

Examples 4 to 6 and Comparative Example 2
Polyethylene terephthalate (PET) was produced as a support film of each of Examples 4 to 6 and Comparative Example 2. The number of microparticles in each support film is as described in Table 2. The number of particulates in the support film was adjusted by the fineness of the filter and the number of times the material constituting the support film was passed through the filter and the number of particulates added.
At this time, the film is subjected to thermocompression bonding treatment again under the conditions of 180 to 250 ° C. after biaxial stretching of the PET film, so that an optically abnormal area around the fine particles (that is, a cavity or an area having different orientation or crystallinity) Disappeared. Moreover, the refractive index difference of the main area | region of a support film and microparticles | fine-particles was adjusted by changing the refractive index of microparticles | fine-particles.
Preparation of a photosensitive resin laminate and measurement of resist protrusions were performed in the same manner as in Example 1 except that the support film was manufactured by the above method.

As can be seen from the results shown in Tables 1 and 2, in Examples 1 to 3 in which the total area of the optically abnormal area is reduced, the resist protrusion is reduced compared to Comparative Example 1 in which the total area of the optically abnormal area is large. In Examples 4 to 6 in which the number of fine particles in contact with the abnormal refractive index area which is an optical abnormal area other than the fine particles is reduced, the resist protrusion is compared with Comparative Example 2 in which the fine particles are in contact with the abnormal refractive index area. Was reduced.

The photosensitive resin laminate of the present invention avoids resist pattern defects (protrusions) caused by foreign matter on the support film, and gives a good resist pattern shape. Therefore, a printed wiring board, a flexible substrate, a lead frame substrate, COF (COF It can be suitably used for manufacturing conductor patterns such as a substrate for chip on film, a substrate for semiconductor package, a transparent electrode for liquid crystal, a wiring for TFT for liquid crystal, and an electrode for PDP (plasma display panel).

Claims

A photosensitive resin laminate comprising: a support film; and a photosensitive resin composition layer formed on the support film,
The support film contains fine particles, and the photosensitive resin laminate includes a region in which the total area ratio of the optically abnormal region is 300 ppm or less when the support film is observed at an area of 13.5 mm 2 with an epi-illumination laser microscope .
The photosensitivity according to claim 1, wherein the support film includes a region in which the total area ratio of the optically abnormal region is 200 ppm or less when the support film is observed at an area of 13.5 mm 2 with an incident-type laser microscope. Resin laminate.
The photosensitivity according to claim 1, wherein the support film includes a region in which the total area ratio of the optically abnormal region is 100 ppm or less when the support film is observed at an area of 13.5 mm 2 with an epi-illumination laser microscope. Resin laminate.
The photosensitivity according to claim 1, wherein the support film includes a region in which the total area ratio of the optically abnormal region is 50 ppm or less when the support film is observed at an area of 13.5 mm 2 with an incident-type laser microscope. Resin laminate.
The photosensitive resin laminate according to any one of claims 1 to 4, wherein the support film contains fine particles of 10 ppm or more on a mass basis.
A photosensitive resin laminate comprising: a support film; and a photosensitive resin composition layer formed on the support film,
The support film contains fine particles,
In the support film, among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm 2 of the support film, the number of fine particles in contact with the area other than the fine particles in the optically abnormal area is 1,200 in number average The photosensitive resin laminated body which has the area | region which becomes the following.
In the support film, among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm 2 of the support film, the number of fine particles in contact with the area other than the fine particles in the optically abnormal area is 1000 in number average The photosensitive resin laminated body of Claim 6 which has the area | region which becomes the following.
Among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm 2 of the support film, the support film has 900 or less fine particles in contact with the area other than the fine particles in the optically abnormal area. The photosensitive resin laminated body of Claim 6 which has an area | region.
Among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm 2 of the support film, the support film has 500 or less fine particles in contact with the area other than the fine particles in the optically abnormal area. The photosensitive resin laminated body of Claim 6 which has an area | region.
In the support film, among the fine particles having a diameter of 0.5 μm or more included in the area of 13.5 mm 2 of the support film, the number of fine particles in contact with the area other than the fine particles in the optically abnormal area is 200 or less. The photosensitive resin laminated body of Claim 6 which has an area | region.
In the support film, among the fine particles having a diameter of 1.0 μm or more included in the area of 13.5 mm 2 of the support film, the number of fine particles contacting the area other than the fine particles in the optically abnormal area is 500 or less. The photosensitive resin laminate according to any one of claims 6 to 10, having a region.
In the support film, among the fine particles having a diameter of 1.0 μm or more included in the area of 13.5 mm 2 of the support film, the number of fine particles in contact with the area other than the fine particles in the optically abnormal area is 300 or less. The photosensitive resin laminated body of Claim 11 which has an area | region.
In the support film, among the fine particles having a diameter of 1.0 μm or more included in the area of 13.5 mm 2 of the support film, the number of fine particles contacting the area other than the fine particles in the optically abnormal area is 100 or less. The photosensitive resin laminated body of Claim 11 which has an area | region.
Among the fine particles having a diameter of 1.0 μm or more included in the area of 13.5 mm 2 of the support film, the support film has 50 or less fine particles in contact with the area other than the fine particles in the optically abnormal area. The photosensitive resin laminated body of Claim 11 which has an area | region.
In the support film, among the fine particles having a diameter of 2.0 μm or more included in the area of 13.5 mm 2 of the support film, the number of fine particles contacting the area other than the fine particles in the optically abnormal area is 200 or less. The photosensitive resin laminate according to any one of claims 6 to 14, having a region.
Among the fine particles having a diameter of 2.0 μm or more included in the area of 13.5 mm 2 of the support film, the number of fine particles in contact with the area other than the fine particles in the optically abnormal area is 100 or less. The photosensitive resin laminated body of Claim 15 which has an area | region.
Among the fine particles having a diameter of 2.0 μm or more included in the area of 13.5 mm 2 of the support film, the support film has 50 or less fine particles in contact with the area other than the fine particles in the optically abnormal area. The photosensitive resin laminated body of Claim 15 which has an area | region.
Among the fine particles having a diameter of 2.0 μm or more included in the area of 13.5 mm 2 of the support film, the support film has 10 or less fine particles in contact with the area other than the fine particles in the optically abnormal area. The photosensitive resin laminated body of Claim 15 which has an area | region.
The photosensitive resin laminate according to any one of claims 1 to 18, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.2 or less.
The photosensitive resin laminated body of Claim 19 whose refractive index difference of the refractive index of the said microparticles | fine-particles and the refractive index of the main area | region of the said support film is 0.1 or less.
The photosensitive resin laminated body of Claim 19 whose refractive index difference of the refractive index of the said microparticles | fine-particles and the refractive index of the main area | region of the said support film is 0.05 or less.
The photosensitive resin laminated body of Claim 19 whose refractive index difference of the refractive index of the said microparticles | fine-particles and the refractive index of the main area | region of the said support film is 0.02 or less.
The photosensitive resin laminate according to any one of claims 1 to 22, wherein the optically abnormal region includes a cavity.
The photosensitive resin laminate according to any one of claims 1 to 23, wherein the optically abnormal area includes an area different in orientation from the main area of the support film.
The photosensitive resin laminate according to any one of claims 1 to 24, wherein the optically abnormal region includes a region different in crystallinity from the main region of the support film.
The photosensitive resin laminate according to any one of claims 1 to 25, which is for forming a wiring having a line width / space width of 20/20 (μm) or less.
The photosensitive resin laminate according to claim 26, which is for forming a wiring having a line width / space width of less than 10/10 (μm).
A method for producing a resist pattern in a printed wiring board, using the photosensitive resin laminate according to any one of claims 1 to 27.
29. The method of claim 28, wherein the method is semi-additive.
The method according to claim 28 or 29, wherein the line width / space width of the resist pattern is less than 10/10 (μm).
A photosensitive resin laminate comprising: a support film; and a photosensitive resin composition layer formed on the support film,
When a resist pattern with a line width / space width of 8/8 (μm) is formed on a substrate using a direct writing exposure machine, the surface on the photosensitive resin composition layer side of the support film is focused The photosensitive resin laminated body whose difference of the line width and the line width at the time of shifting to the board | substrate inner side 400 micrometers in the thickness direction from the said surface is 1.8 micrometers or less.