JP2019101405A - Photosensitive resin laminate roll - Google Patents

Abstract

To provide a photosensitive resin laminate roll having good roll winding property while avoiding decrease in resolution caused by foreign substances in a support film.SOLUTION: The photosensitive resin laminate roll comprises a photosensitive resin laminate prepared in a roll form, which includes a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film. The support film has such an area that, when a small piece in a size of 0.75 mm×11 mm is cut out at any 10 positions different from one another in the support film, the number of fine particles having a diameter of 2 μm or more included in each small piece is 200 or less as a number average at the 10 positions; and the back surface of the support film has a region where an arithmetic average roughness is 0.01 μm or more.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin laminate roll.

  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 the thickness of the layer comprising the photosensitive resin composition being 3 to 30 μm Sex elements are described.

WO 2008/093643

  Patent Document 1 relates to a technique for limiting the amount of particles having a diameter of 5 μm or more and aggregates contained in a support film in order to avoid a reduction in resolution caused by foreign matter in the support film. However, in the photosensitive element described in Patent Document 1, after a photosensitive resin composition is applied on a support film and dried to form a photosensitive resin composition layer, the photosensitive resin composition layer is When a cover film is stuck on top and taken up by a roll, there is a problem that winding can not be performed well and the air bites. This invention solves said subject and aims at provision of the photosensitive resin laminated body roll which has favorable roll-winding property, avoiding the fall of the resolution resulting from the foreign material of a support film. In addition, one aspect of the present invention is that in a conventional roll, particularly after storage under a low temperature (for example, 10 ° C. or less) environment, winding deviation due to thermal contraction of the photosensitive resin composition layer (ie, photosensitive resin lamination) The object of the present invention is to provide a photosensitive resin laminate roll which solves the problem that the body is dislocated in the middle of the winding) and has the advantage of reducing the winding deviation at the time of roll storage. .

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

That is, the present invention is as follows.
[1] A photosensitive resin laminate roll obtained by rolling a photosensitive resin laminate including a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film. There,
In the support film, when the small pieces of 0.75 mm × 11 mm are cut out at arbitrary ten different places of the support film, the number of fine particles having a diameter of 2 μm or more included in each small piece is the ten places. Have an area of 200 or less in number average,
The photosensitive resin laminated body roll in which the back surface of the said support film contains the area | region whose arithmetic mean roughness is 0.01 micrometer or more.
[2] The photosensitive resin laminate roll according to the above aspect 1, wherein the back surface of the support film includes a region having an arithmetic average roughness of 0.02 μm or more.
[3] The photosensitive resin laminate roll according to the above aspect 1, wherein the back surface of the support film includes a region having an arithmetic average roughness of 0.03 μm or more.
[4] The photosensitive resin laminate roll according to the above aspect 1, wherein the back surface of the support film includes a region having an arithmetic average roughness of 0.04 μm or more.
[5] The photosensitive resin laminate roll according to the above aspect 1, wherein the back surface of the support film includes a region having an arithmetic average roughness of 0.05 μm or more.
[6] The photosensitive resin laminate roll according to the above aspect 1, wherein the back surface of the support film includes a region having an arithmetic average roughness of 0.06 μm or more.
[7] The photosensitive resin laminate roll according to the above aspect 1, wherein the back surface of the support film includes a region having an arithmetic average roughness of 0.1 μm or more.
[8] The photosensitive resin laminate roll according to any one of the above aspects 1 to 7, wherein the back surface of the support film includes a region having an arithmetic average roughness of 0.3 μm or less.
[9] The photosensitive resin laminate according to any one of the above aspects 1 to 8, further comprising a cover film provided on the side opposite to the side on which the support film of the photosensitive resin composition layer is provided. roll.
[10] The member in contact with the back surface of the support film is the cover film,
The photosensitive resin laminate roll according to the above aspect 9, wherein the cover film includes a region in which the arithmetic mean roughness of the surface on the side in contact with the back surface of the support film is less than 0.1 μm.
[11] The photosensitive resin laminate roll according to the above aspect 10, wherein the cover film includes a region having an arithmetic mean roughness of 0.09 μm or less on the side in contact with the back surface of the support film.
[12] The photosensitive resin laminate roll according to the above aspect 10, wherein the cover film includes a region in which the arithmetic mean roughness of the surface on the side in contact with the back surface of the support film is 0.01 μm or more.
[13] The photosensitive resin laminate roll according to the above aspect 10, wherein the cover film includes a region in which the arithmetic mean roughness of the surface on the side in contact with the back surface of the support film is 0.07 μm or more.
[14] The photosensitive resin laminate roll according to the above aspect 10, wherein the cover film includes a region in which the arithmetic mean roughness of the surface on the side in contact with the back surface of the support film is 0.08 μm or more.
[15] The photosensitive resin laminate roll according to the above-mentioned aspect 10, wherein the cover film includes a region in which the arithmetic mean roughness of the surface on the side in contact with the back surface of the support film is 0.09 μm or more.
[16] In the support film, the number of fine particles having a diameter of 2 μm or more included in each small piece when cutting small pieces of 0.75 mm × 11 mm at arbitrary ten different places of the support film is the above-mentioned The photosensitive resin laminated body roll in any one of the said aspect 1-15 which has an area | region which becomes 50 or less by number average of ten places.
[17] In the support film, the number of fine particles having a diameter of 2 μm or more contained in each small piece when cutting small pieces of 0.75 mm × 11 mm at arbitrary ten different places of the support film is the above-mentioned The photosensitive resin laminated body roll of the said 16 which has an area | region which becomes ten or less by number average of ten places.
[18] In the support film, when the small pieces of 0.75 mm × 11 mm are cut out at arbitrary ten different places of the support film, the number of fine particles having a diameter of 2 μm or more included in each small piece is the above The photosensitive resin laminated body roll of the said 16 which has an area | region which becomes 5 or less by number average of ten places.
[19] When a small piece of 0.75 mm × 11 mm is cut out at arbitrary ten different places of the support film, the difference in the refractive index with the diameter of 1.5 μm or more and the support film is included in each piece The photosensitive resin laminated body roll as described in any one of the said aspect 1-18 which has an area | region where the number of microparticles | fine-particles of 0.3 or less will be 1 or more in a number average of said ten places.
[20] When a small piece of 0.75 mm × 11 mm is cut out at arbitrary ten different places of the support film, the difference in the refractive index with the diameter of 1.5 μm or more and the support film is included in each piece The photosensitive resin laminated body roll as described in the said aspect 19 which has an area | region where the number of microparticles | fine-particles of 0.2 or less will be 1 or more in a number average of said ten places.
[21] When small pieces of 0.75 mm × 11 mm are cut out at arbitrary ten different places of the support film, the difference in the refractive index with the diameter of 1.5 μm or more and the support film is included in each piece The photosensitive resin laminated body roll in any one of the said aspect 1-20 which has an area | region where the number of microparticles | fine-particles of 0.1 or less will be 1 or more in a number average of said ten places.
[22] When a small piece of 0.75 mm × 11 mm is cut out at arbitrary ten different places of the support film, the difference in the refractive index with the diameter of 1.5 μm or more and the support film, contained in each small piece 22. The photosensitive resin laminate roll according to the above aspect 21, having a region in which the number of fine particles of 0.05 or less becomes one or more in a number average of the 10 locations.
[23] The photosensitive resin laminate roll according to any one of the above aspects 1 to 22, wherein the surface resistivity of the back surface of the support film is 1.0 × 10 ¹³ Ω or less.
[24] The photosensitive resin laminate roll according to the above aspect 23, wherein the surface resistivity of the back surface of the support film is 1.0 × 10 ¹¹ Ω or less.
[25] The photosensitive resin laminate roll according to the above-mentioned aspect 23 or 24, wherein the surface resistivity of the back surface of the support film is 1.0 × 10 ⁷ Ω or more.
[26] The photosensitive resin laminate roll according to the above-mentioned aspect 25, wherein the surface resistivity of the back surface of the support film is 1.0 × 10 ⁸ Ω or more.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin laminated body roll which has favorable roll-winding property can be provided, avoiding the fall of the resolution resulting from the foreign material of a support film. Moreover, according to one aspect of the present invention, it is possible to provide a photosensitive resin laminate roll having an advantage of reducing winding deviation during roll storage in addition to the above-mentioned properties.

  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. In addition, with respect to various measured values in the present specification, unless otherwise specified, the methods described in the [Example] section of the present disclosure or methods equivalent to these are equivalent to methods understood by those skilled in the art. Measured.

[Photosensitive resin laminate]
In this embodiment, a photosensitive resin laminate formed by rolling a photosensitive resin laminate including a support film and a photosensitive resin composition layer containing the photosensitive resin composition formed on the support film. Provide body roll.

  In the present embodiment, the support film has 10 fine particles having a diameter of 2 μm or more and contained in each small piece of 0.75 mm × 11 mm at arbitrary ten different points of the support film. It has an area of 200 or less in number average of points.

  In the photosensitive resin laminate of the present embodiment, the surface of the support film on which the photosensitive resin composition layer is provided is the surface of the support film, and the side of the support film on which the photosensitive resin composition layer is provided When the surface on the opposite side is the back surface of the support film, the back surface of the support film has an arithmetic average roughness (Ra) of 0.01 μm or more, preferably 0.02 μm or more, more preferably 0.03 μm or more, more preferably And the region which is 0.04 μm or more, more preferably 0.05 μm or more, still more preferably 0.06 μm or more, particularly preferably 0.1 μm or more. Such arithmetic mean roughness is advantageous in terms of reducing the coefficient of static friction with respect to a member in contact with the back surface of the support film and thus improving the rollability.

  The back surface of the support film includes a region where the arithmetic mean roughness (Ra) is preferably 0.3 μm or less, more preferably 0.2 μm or less, and still more preferably 0.15 μm or less.

  As a method of controlling the arithmetic mean roughness of the back surface of the support film, there can be exemplified a method of roughening the back surface of the support film by sand blasting or the like to a desired degree.

  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 case of a multilayer structure, the number of microparticles of the present disclosure is the sum of the number of microparticles measured in each layer.

  The present inventor is advantageous in that the reduction of the resolution caused by the foreign matter in the support film can be avoided by the small number of fine particles in the support film, while the unevenness of the surface in the support film is reduced, and thus the photosensitivity. It has been found that it is sometimes difficult to wind the resin laminate into rolls. That is, it was found that the fine particles in the support film also functioned as a lubricant, and the reduction of the fine particles resulted in the excessive reduction in friction of the support film. The present inventor further indicates that, in the support film in which such fine particles are reduced, by making the arithmetic mean roughness of the back surface of the support film equal to or greater than a specific value, it is possible to secure the winding property on the roll. I found it. Furthermore, in the case of a support film in which such fine particles have been reduced, the present inventor further provides a photosensitive resin lamination in the case where the static friction coefficient of the back surface of the support film with respect to the member in contact with the back surface of the support film It has been found that the rollability to a roll is improved while maintaining good resolution of the body.

  In the present embodiment, in the support film, the number of fine particles having a diameter of 2 μm or more included in each small piece when cutting out a small piece of 0.75 mm × 11 mm at arbitrary ten different places of the support film is It has an area of 200 or less in number average of 10 places. The fine particles having a diameter of 2 μm or more include primary particles having a diameter of 2 μm or more, and primary particle aggregates having a diameter of an aggregate of primary particles of 2 μm or more. 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.

  The inventor also noted that among the fine particles in the support film, the fine particles that function as a lubricant have a certain size. In the photosensitive resin laminate roll of the present embodiment, fine particles of a certain size (specifically, a diameter of 2 μm or more) because the back surface of the support film and the member in contact with the support film are easily slipped with each other. Even if the number of particles is as small as 200 or less, the photosensitive resin laminate can be rolled while suppressing air entrainment. In addition, since the number of particles having a diameter of 2 μm or more is as small as 200 or less, it is possible to avoid a reduction in resolution due to the particles of the support film.

  In addition, when the number of fine particles is measured at any 10 places in the support film, the photosensitive resin laminate is obtained if there are 10 or more places having the number of fine particles specified in the specific aspect of the present embodiment. It is included in the photosensitive resin laminated body which concerns on the said specific aspect. That is, even if it does not satisfy the specified number of fine particles when it is measured at a certain 10 locations, when it satisfies the specified number of fine particles when it is measured at another 10 locations, the photosensitive resin laminate is Such photosensitive resin laminates are included.

  In a preferred embodiment, the total area of the support film is preferably 10% or more, more preferably 20% or more, more preferably 30% or more, more preferably 40% or more, more preferably 50% or more, more preferably 60 % Or more, more preferably 70% or more, more preferably 80% or more, more preferably 90% or more, particularly preferably about 100% (that is, substantially the entire area) is defined in the specific aspect of the present embodiment. Regions with specific particles (diameter and number of particles).

The number of fine particles in a region where the number of fine particles having a diameter of 2 μm or more is 200 or less in a small piece of 0.75 mm × 11 mm is preferably as small as possible from the viewpoint of obtaining good resolution, preferably 150 or less, preferably 120 or less, preferably 100 or less, preferably 80 or less, preferably 60 or less, preferably 50 or less, preferably 40 or less, preferably 30 or less, more preferably 20 or less, more preferably The number is 10 or less, more preferably 5 or less, more preferably 4 or less, more preferably 3 or less, more preferably 2 or less, further preferably 1 or less, more preferably 0. On the other hand, from the viewpoint of improving the adhesion between the support film and the photosensitive resin composition layer and the winding property of the roll, it is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. More preferably, it may be 4 or more, more preferably 5 or more.
The upper limit of the size of the fine particles having a diameter of 2 μm or more in a small piece of 0.75 mm × 11 mm is not particularly limited, but it may be 10 μm or less, 5 μm or less, or 4.5 μm or less It may be 4.0 μm or less, or 3.5 μm or less.

  As a method of making the support film have a region in which the number of fine particles having a diameter of 2 μm or more becomes 200 or less in a small piece of 0.75 mm × 11 mm, a film material passing through a filter for removing fine particles having a diameter of 2 μm or more is used And the like can be exemplified. In addition, after the use of such a filter, the number of particles may be increased by increasing the number of particles within a desired range by adjusting the number of particles by post-addition of the particles.

  A diameter of 1.5 μm or more and a difference in refractive index with the support film, which are included in each small piece when cutting a small piece of 0.75 mm × 11 mm at arbitrary 10 different places of the support film, have a specific value or less The number of fine particles is preferably 1 or more, 10 or more, or 10 or more in a number average of 10 spots. The refractive index difference described above is preferably 0.3 or less, more preferably 0.25 or less, more preferably 0.2 or less, more preferably 0.25 or less, still more preferably 0.1 or less, still more preferably 0. Or less, particularly preferably 0.05 or less, particularly preferably 0.03 or less, particularly preferably 0.01 or less. Inclusion of fine particles in the support film improves the slipperiness of the support film, but when fine particles are included in order to prevent deterioration of the imageability due to the fine particles, the diameter is 1.5 μm or more (that is, to some extent It is preferable that the difference in refractive index between the fine particles (having a size) and the support film be small. If the difference in refractive index is small, light is unlikely to be scattered. Since the refractive index of the support film for the photosensitive resin laminate is generally 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 refractive index as fine particles is used. The thing of about 1.4-1.7 is mentioned. The refractive index in the present specification means the refractive index at a wavelength of 589 nm. The size of the fine particles having a diameter of 1.5 μm or more is not particularly limited, but may be 10 μm or less, 5 μm or less, or 4.5 μm or less, or 4.0 μm or less And may be 3.5 μm or less.

  The fine particles contained in the support film (in particular, fine particles having a diameter of 2 μm or more) are, for example, inorganic fine particles or organic fine particles, and include lubricants, aggregates of additives, foreign matter mixed in raw materials, foreign matter mixed in manufacturing process, . 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 the support film in which the number of microparticles | fine-particles of diameter 2 micrometers or more was reduced, the method of filtering resin with the filter of 2 micrometers or less etc. is mentioned, for example. In addition, the number of fine particles can be adjusted by the number of times the material constituting the support film is passed through the filter.

  In the present embodiment, the static friction coefficient of the back surface of the support film to the member in contact with the back surface of the support film is preferably 2.0 or less, more preferably 1.8 or less, preferably from the viewpoint of roll winding property. 1.5 or less, more preferably 1.2 or less, more preferably 1.0 or less, more preferably 0.9 or less, more preferably 0.8 or less, more preferably 0.7 or less, more preferably 0. It is 6 or less, more preferably 0.5 or less, particularly preferably 0.4 or less, particularly preferably 0.3 or less, particularly preferably 0.2 or less, particularly preferably 0.1 or less. The smaller the coefficient of static friction, the better the slip of the photosensitive resin laminate and the better the roll winding property, but from the viewpoint of prevention of winding deviation, the coefficient of static friction is preferably 0.05 or more, preferably 0. It can be 1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more. In addition, a coefficient of static friction means the value measured by the method prescribed | regulated to JISK7125.

  As a method of controlling the static friction coefficient of the back surface of the support film to a member in contact with the back surface of the support film, a method of reducing friction by roughening the back surface of the support film, support of a member in contact with the back surface of the support film The method of reducing friction by surface roughening etc. and the surface etc. of these can be illustrated for the surface of a film contact side. Surface roughening can be realized by sand blasting or the like.

The surface resistivity of the back surface of the support film is preferably 1.0 × 10 ¹³ Ω or less, more preferably 1.0 × 10 ¹¹ Ω or less, from the viewpoint of preventing charging of the photosensitive resin laminate roll. When taking out the photosensitive resin laminate by taking it out from the photosensitive resin laminate roll, static electricity may be generated between the member in contact with the back surface of the support film and the back surface of the support film. Etc. may cause adhesion to the back surface of the support film, etc., and deterioration in handling properties. Setting the surface resistivity of the back surface of the support film in the above range is advantageous in terms of the antistatic effect due to the low surface resistivity. On the other hand, the surface resistivity of the back surface of the support film may be preferably 1.0 × 10 ⁷ Ω or more, more preferably 1.0 × 10 ⁸ Ω or more.

  The support film is preferably one having a haze of 5% or less from the viewpoint of suppressing light scattering at the time of exposure. The haze is more preferably 2% or less, further preferably 1.5% or less, and particularly preferably 1.0% or less. From the same viewpoint, the arithmetic average roughness (Ra) of the surface of the support film (that is, the surface in contact with the photosensitive resin composition 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.

  The thickness of the photosensitive resin composition layer in the photosensitive resin laminate varies depending on the use, 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.

  In a preferred embodiment, the photosensitive resin laminate roll further comprises a cover film provided on the side of the photosensitive resin composition layer opposite to the side on which the support film is provided. In addition to being able to implement | achieve favorable roll winding property, when this inventor makes the arithmetic mean roughness of the surface which contacts the back surface of the support film of a cover film in this invention a specific range, for example, It has been found that it is possible to favorably reduce the winding deviation due to the thermal contraction and the like of the photosensitive resin composition layer that is likely to occur after storage in a low temperature (for example, 10 ° C. or less) environment. In a preferred embodiment, the member in contact with the back surface of the support film by the roll is a cover film, and in the cover film of this embodiment, the arithmetic average roughness of the surface in contact with the back surface of the support film is From the viewpoint of prevention of winding deviation, preferably 0.01 μm or more, more preferably 0.03 μm or more, more preferably 0.05 μm or more, more preferably 0.07 μm or more, more preferably 0.08 μm or more, more preferably 0 It can contain a region that is not less than .09 μm, and can also contain a region that is preferably less than 0.10 μm, more preferably not more than 0.09 μm, more preferably not more than 0.08 μm from the viewpoint of preventing winding displacement .

  As a method of controlling the arithmetic mean roughness of the surface of the cover film on the side in contact with the back surface of the support film, a method of roughening the surface of the cover film by sand blasting or the like to a desired degree can be exemplified.

  An important characteristic of the cover film used for the photosensitive resin laminate roll is that the adhesion to the photosensitive resin composition layer is sufficiently smaller than that of the carrier layer, and the film can be easily peeled off. For example, polyethylene film or polypropylene film can be preferably used as a cover film. Moreover, the film excellent in peelability shown by Unexamined-Japanese-Patent No. 59-202457 can also be used. 10 micrometers-100 micrometers are preferable, and, as for the film thickness of a cover film, 10 micrometers-50 micrometers are more preferable.

  The photosensitive resin laminate roll may further include a low friction member provided on the side opposite to the side on which the photosensitive resin composition layer of the cover film is provided. In a preferred embodiment, the member in contact with the back surface of the support film by the roll is a low friction body. Examples of low friction force members include paper with rough surfaces, metal films, and the like. The low friction member may be configured such that at least the surface contacting the back surface of the support film is a surface that satisfies the coefficient of static friction 2.0 or less of the back surface of the support film with respect to the low friction member.

  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 cover film. 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. Next, if necessary, a photosensitive resin laminate can be produced by laminating a cover film on the photosensitive resin composition layer.

[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) alkali-soluble polymer: 10% by mass to 90% by mass; and (B) a compound having an ethylenically unsaturated double bond, based on the total solid mass of the photosensitive resin composition. It is preferable to contain: 5 mass% to 70 mass%; and (C) photo polymerization initiator: 0.01 mass% to 20 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 quantity of the carboxyl group contained in (A) alkali-soluble polymer is 100-600 by an acid equivalent, Preferably it is 250-450. 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 (A) alkali-soluble polymer 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 disclosure, molecular weight is a value measured using gel permeation chromatography. The degree of dispersion is the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight).

  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, and maleic acid half ester. 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, etc .; 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.

｛式中、Ｗ_iは、各々のアルカリ可溶性高分子の固形重量であり、Ｔｇ_iは、各々のアルカリ可溶性高分子のＦｏｘ式で求められるガラス転移温度であり、Ｗ_totalは、各々のアルカリ可溶性高分子の合計固形重量であり、かつｎは、感光性樹脂組成物に含まれるアルカリ可溶性高分子の種類の数である｝
に従って求められる。ここで、ガラス転移温度Ｔｇｉを求める際には、対応するアルカリ可溶性高分子を形成するコモノマーから成るホモポリマーのガラス転移温度として、Ｂｒａｎｄｒｕｐ，Ｊ． Ｉｍｍｅｒｇｕｔ， Ｅ． Ｈ．編集「Ｐｏｌｙｍｅｒ ｈａｎｄｂｏｏｋ， Ｔｈｉｒｄ ｅｄｉｔｉｏｎ， Ｊｏｈｎ ｗｉｌｅｙ ＆ ｓｏｎｓ， １９８９， ｐ．２０９ Ｃｈａｐｔｅｒ ＶＩ 『Ｇｌａｓｓ ｔｒａｎｓｉｔｉｏｎ ｔｅｍｐｅｒａｔｕｒｅｓ ｏｆ ｐｏｌｙｍｅｒｓ』」に示される値を使用できる。 The weight average value Tg ^total of the glass transition temperature Tg of the (A) alkali-soluble polymer is preferably 30 ° C. or more and 135 ° C. or less. Tg ^total has the following formula:

{Wherein, W _i is the solid weight of each alkali-soluble polymer, Tg _i is the glass transition temperature determined by the Fox equation of each alkali-soluble polymer, and W _total is each alkali-soluble polymer Total solid weight of polymer, and n is the number of types of alkali-soluble polymer contained in the photosensitive resin composition}
It is sought according to Here, when determining the glass transition temperature Tgi, as a glass transition temperature of a homopolymer composed of a comonomer that forms a corresponding alkali-soluble polymer, see Brandrup, J. Am. Immergut, E. H. The values given in the editor, "Polymer handbook, Third edition, John wiley & sons, 1989, p. 209 Chapter VI" Glass transition temperatures of polymers "can be used.

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 It is more preferable that the temperature be 100.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. From the viewpoint of controlling the development time, it is preferable to set the ratio of the (A) alkali-soluble polymer to 90% by mass or less with respect to the photosensitive resin composition. 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-normal nonyl phenoxy octa ethylene glycol (meth) acrylate (for example, Toagosei Co., Ltd. product M-114) which is an acrylate of the compound which added the polyethyleneglycol which added 8 mol of ethylene oxides on average to nonyl phenol is mentioned. .

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

  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 meta) acrylates, nonaethylene glycol di (meth) acrylates, decaethylene glycol di (meth) acrylates, and compounds having a (meth) acryloyl group at both ends of an ethylene oxide chain of 12 moles 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 an average of 15 moles of ethylene oxide is further added to both ends of each of polypropylene glycol to which an average of 18 moles of propylene oxide is added, FA-023M, FA-024M, FA-027M (product name) And Hitachi Chemical Co., Ltd.). These are preferable in terms of flexibility, resolution, adhesion and the like.

｛式中、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子又はメチル基を表し、ＡはＣ₂Ｈ₄であり、ＢはＣ₃Ｈ₆であり、ｎ１及びｎ３は各々独立に１〜３９の整数であり、かつｎ１＋ｎ３は２〜４０の整数であり、ｎ２及びｎ４は各々独立に０〜２９の整数であり、かつｎ２＋ｎ４は０〜３０の整数であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよい。そして、ブロックの場合、−（Ａ−Ｏ）−と−（Ｂ−Ｏ）−とのいずれがビスフェニル基側でもよい。｝
で表される化合物を使用することができる。 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 6 -(A-O)-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-(B-O)-may be random or block. And, in the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenyl group side. }
The compounds represented by can be used.

  For example, polyethylene glycol having an average of 5 moles of ethylene oxide added to each end of bisphenol A and polyethylene glycol having an average of 2 moles of ethylene oxide added to each end of bisphenol A A polyethylene glycol dimethacrylate in which 1 mol of ethylene oxide is added to both ends of each of dimethacrylate and bisphenol A is preferable from the viewpoint 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, carbonyl group, mercapto group, alkyl mercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group C1-C20 hydroxyalkyl group, carboxyl group, alkyl group C1-C10 carboxyalkyl group, alkyl group C1-C10 acyl group, C1-C20 alkoxy group, C1-C20 alkoxycarbonyl group, C2-C10 alkylcarbonyl group, C2-C10 alkenyl group, C2-C10 group - 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 hexa (meth) acrylate, hexa (meth) acrylate in which a total of 1 to 40 moles of ethylene oxide is added to six ends of dipentaerythritol, and one to 20 moles of ε total of 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. As other compounds, (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 having an ethylenically unsaturated double bond to the total solid content mass of the photosensitive resin composition is preferably 5 mass% to 70 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 (C) photopolymerization initiator 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 view of sensitivity, resolution and adhesion) Further, hexaarylbiimidazole, pyrazoline compounds, anthracene compounds (eg, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene are preferred in terms of sensitivity, resolution and adhesion), coumarin compounds (eg, 7-diethylamino-4-methyl Marine is 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, 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 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 ', 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-triyl Fluorophenyl) -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) -biimidazole And 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole and the like. These can be used singly or in combination of two or more. From the viewpoint of high sensitivity, resolution and adhesion, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable.

  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 the 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-dimethoxy) Phenyl) -pyrazoline, 1-phenyl-3- (2,3-dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,4-dimethoxystyryl) -5- Preferred are (2,4-dimethoxyphenyl) -pyrazoline and the like from the above-mentioned viewpoints and the like. 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. It is in the range of mass%, more preferably 0.1 mass% to 3 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, 2,2'-methylene bis (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) -Tert-Butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl -4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxyben) 4) Benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-butylidenebis (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 (for example, Kawaguchi Chemical Industry Co., Ltd. product, 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.

  It is preferable that the ratio with respect to the total solid content mass of the photosensitive resin composition of (D) phenol derivative is 0.001 mass%-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 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, the benzotriazoles and the carboxybenzotriazoles is preferably 0.01% by mass to 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 NOF Corp., manufactured by Nippon Oil and Fats Co., Ltd.), BA-P4U glycol, BA-P8 glycol (manufactured by Nippon Emulsifier, Inc.).

  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 photosensitive in an amount such that the viscosity at 25 ° C. of the photosensitive resin composition preparation liquid applied onto the support film at the time of production of the photosensitive resin laminate is 500 mPa · s to 4,000 mPa · s. 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. 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 cover film, the cover film is peeled off, and then the photosensitive resin composition layer is heat-pressed and laminated 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 at the time of lamination is generally 40 ° C to 160 ° C. 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 a support film, 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 film 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, but an aqueous Na ₂ CO ₃ solution having a concentration of about 0.2 mass% to about 2 mass% and a temperature of about 20 ° C. to about 40 ° C. 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 this embodiment is a conductor pattern such as a printed wiring board, a flexible substrate, a lead frame substrate, a COF substrate, a substrate for a semiconductor package, a transparent electrode for liquid crystal, a wiring for TFT for liquid crystal, and an electrode for PDP. Photosensitive resin laminate suitable for the production of

  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 measurement of the physical property value of the polymer, the calculation of the glass transition temperature of the polymer, and the method for producing the evaluation sample of the example and the comparative example will be described. Moreover, the evaluation method about the obtained sample and its evaluation result are shown.

(1) Measurement method <Method of measuring the number of microparticles>
The number of microparticles in the support film was measured using an optical microscope. The light microscope was measured by incident light using MEASURING MICROSCOPE MM-800 manufactured by Nikon Corporation. The support film was placed on a plate having a 0.75 mm × 11 mm hole, and the number of particles in the area of the hole was measured. The magnification was measured at 80% of the maximum light amount using a 20 × objective lens and a 10 × eyepiece. By observing while changing the focal point, all the fine particles in the thickness direction of the support film were measured. In addition, a monitor was installed on the optical microscope to measure the diameter of the particles. The monitor used DIGITAL SIGHT DS-L2 made by Nikon Corporation. The measurement of the particle diameter was performed using a 50 × objective lens and a 10 × eyepiece. When the particles are not perfect spheres, the longest width of the particles is taken as the diameter of the particles. This measurement was repeated 10 times at arbitrary different places, and then the number average value was calculated.

Arithmetic mean roughness
Arithmetic mean roughness was calculated by the following method using a laser microscope.
Measurement item: Ra (arithmetic mean roughness)
Test conditions: Measurement length 259 μm (measured linearly)
Objective lens: 50 times Measurement number: n = 2
Test environment: 23 ° C ± 2 ° C · 50% RH ± 5% RH
Testing machine: OLS 4100 (made by OLYMPUS)

<Surface resistivity>
The surface resistivity was calculated by the following method.
Device: Toa DDK super insulation resistance measuring device SM8220
Measurement temperature: Room temperature Measurement voltage: 250 V
Measurement time: 1 minute

(2) Preparation Method of Evaluation Sample The evaluation sample was prepared as follows.

<Preparation of photosensitive resin laminate roll>
[Examples 1 to 6, Comparative Examples 1 and 2]
The components shown in Table 1 were sufficiently stirred and mixed to obtain a photosensitive resin composition preparation liquid.
As a support film used in Examples 1 to 6, a polyethylene terephthalate film with a thickness of 12 μm and a length of 5000 m was produced. The number of particulates in the support film was adjusted by the filter fineness and the number of passes through the filter. Then, the back surface of the support film used in Examples 2 to 6 was sand blasted under different conditions for each film.
A support film used in Comparative Example 1 was prepared by adding fine particles having a diameter of 2 μm or more to the support film used in Example 1. Using the same material as the material of the support film used in Example 2, prepare a support film as the material of the support film using in Comparative Example 2 a material that passes through more than the number of times of passing through the filter in Example 2 did. The back surface of the produced support film was roughened by sand blasting under the same conditions as in Example 2 to produce a support film used in Comparative Example 2.
The number of fine particles in each support film and the surface roughness of the back surface of each support film are as described in Table 2.
As a cover film, a low density polyethylene film with a thickness of 20 μm and a length of 5000 m was produced.
The surfaces in contact with the support film of the cover films of Examples 1 to 6 and Comparative Examples 1 and 2 were roughened by sand blasting. The surface roughness of the surface of the cover film in contact with the support film is as described in Table 2.

  The above prepared liquid was uniformly coated on the surface of the polyethylene terephthalate film obtained above using a bar coater, and dried in a drier at 95 ° C. for 2.5 minutes to form a photosensitive resin composition layer. Subsequently, after sticking the cover film obtained above on the surface in which the polyethylene terephthalate film of the photosensitive resin composition layer was not laminated | stacked, it wound up with the roll.

<Board surface cleaning>
In Examples 1 to 6 and Comparative Examples 1 and 2, a copper-clad laminate of 0.4 mm in thickness, in which 35 μm-rolled copper foil was laminated, was used as a substrate for evaluation of image quality as a soft etching agent And treated with 10% by mass H ₂ SO ₄ .

<Lamination>
Photosensitive resin laminate using a hot roll laminator (AL-700 manufactured by Asahi Kasei Co., Ltd.) on a copper-clad laminate preheated to 60 ° C while peeling off the low density polyethylene film (cover film) of the photosensitive resin laminate Were laminated at a roll temperature of 105.degree. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Evaluation of rollability>
About the air entrained part between the support film and the cover film when winding up,
0 0% case
In the case of more than 0% and less than 25% ○ In the case of 25% or more ×
And The results are shown in Table 2.

<Evaluation of resist defect>
By using a hot roll laminator (AL-700, manufactured by Asahi Kasei Co., Ltd.) on a copper-clad laminate which has been surfaced and preheated to 60 ° C. while peeling off the cover film of each example and comparative example. The laminate for various evaluations was obtained by laminating so that the photosensitive resin composition layer and the copper clad laminated board might contact at roll temperature 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

Next, using a mask with a line width / space width of 10/30 (unit: μm) and an exposure unit with a main wavelength of 405 ± 5 nm, exposure was performed from the support film side under the conditions of illuminance 80 mW / cm ² .

The support film is peeled off, and an aqueous solution of 1% by mass sodium carbonate at 30 ° C. is developed for the minimum developing time (ie, a photosensitive resin composition layer in the unexposed area) using an alkali developing machine (Droid machine developing machine for dry film). Was sprayed for twice the least time required for complete dissolution, and the unexposed area was removed. Next, the number of resist defects was counted using an optical microscope. When the line length was 1 mm and the number of lines was 10 as an observation unit, the average value when the number of n was 5 was taken as the number of occurrences of resist defects. Regarding the number of resist defects,
6 or more cases x
2 or more and 5 or less cases 〇 1 or less cases
And The results are shown in Table 2.

<Evaluation of winding deviation>
A roll having a width of 141 mm × 180 m and a weight of about 2.5 kg was produced by the method described in <Preparation of photosensitive resin laminate roll> described above. The rolls were stored in an environment of 8 ° C. and about 90% relative humidity for about one day, and then moved to an environment of 23 ° C. and 50% relative humidity. Winding deviation when 30 minutes from the roll is dropped 5 times onto the iron plate from a height of 10 cm (that is, the roll start and end portions of the roll in the width direction of the photosensitive resin laminate) Position deviation) was evaluated according to the following criteria.
:: no winding deviation ○: no more than 2 mm winding deviation △: Table 2 shows the results having more than 2 mm winding deviation.

  As can be seen from the results shown in Table 2, in Examples 1 to 6, good winding performance, reduction in resist defects, and reduction in winding deviation were both well achieved. Above all, in Examples 1 to 4 in which the arithmetic mean roughness of the surface of the cover film on the side in contact with the back surface of the support film is less than 0.1 μm, the winding deviation is further reduced as compared with Examples 5 and 6. . On the other hand, Comparative Example 1 having many fine particles having a diameter of 2 μm or more in the support film had many defects of the resist, and Comparative Example 2 in which the back surface of the support film showed low arithmetic mean roughness was poor in winding property.

  The photosensitive resin laminate roll of the present invention has a good roll winding property while avoiding a reduction in resolution caused by foreign matter on the support film, and a printed wiring board, a flexible substrate, a lead frame substrate, a COF (chip) It can be suitably used for the production of conductor patterns such as substrates for on film), substrates for semiconductor packages, transparent electrodes for liquid crystal, wirings for TFT for liquid crystal, electrodes for PDP (plasma display panel) and the like.

Claims (26)

A photosensitive resin laminate roll obtained by rolling a photosensitive resin laminate comprising a support film and a photosensitive resin composition / material layer containing a photosensitive resin composition formed on the support film, ,
In the support film, when the small pieces of 0.75 mm × 11 mm are cut out at arbitrary ten different places of the support film, the number of fine particles having a diameter of 2 μm or more included in each small piece is the ten places. Have an area of 200 or less in number average,
The photosensitive resin laminated body roll in which the back surface of the said support film contains the area | region whose arithmetic mean roughness is 0.01 micrometer or more.   The photosensitive resin laminate roll according to claim 1, wherein the back surface of the support film includes a region having an arithmetic average roughness of 0.02 μm or more.   The photosensitive resin laminate roll according to claim 1, wherein the back surface of the support film includes a region having an arithmetic mean roughness of 0.03 μm or more.   The photosensitive resin laminate roll according to claim 1, wherein the back surface of the support film includes a region having an arithmetic average roughness of 0.04 μm or more.   The photosensitive resin laminate roll according to claim 1, wherein the back surface of the support film includes a region having an arithmetic average roughness of 0.05 μm or more.   The photosensitive resin laminate roll according to claim 1, wherein the back surface of the support film includes a region having an arithmetic mean roughness of 0.06 μm or more.   The photosensitive resin laminate roll according to claim 1, wherein the back surface of the support film includes a region having an arithmetic average roughness of 0.1 μm or more.   The photosensitive resin laminate roll according to any one of claims 1 to 7, wherein the back surface of the support film includes a region having an arithmetic average roughness of 0.3 μm or less.   The photosensitive resin laminated body roll in any one of Claims 1-8 further equipped with the cover film provided in the opposite side to the side in which the said support film of the said photosensitive resin composition layer was provided. The member in contact with the back surface of the support film is the cover film,
The photosensitive resin laminate roll according to claim 9, wherein the cover film includes a region in which the arithmetic mean roughness of the surface on the side in contact with the back surface of the support film is less than 0.1 μm.   The photosensitive resin laminate roll according to claim 10, wherein the cover film includes a region having an arithmetic average roughness of 0.09 μm or less on the side in contact with the back surface of the support film.   The photosensitive resin laminate roll according to claim 10, wherein the cover film includes a region having an arithmetic average roughness of 0.01 μm or more on the side in contact with the back surface of the support film.   The photosensitive resin laminate roll according to claim 10, wherein the cover film includes a region having an arithmetic average roughness of 0.03 μm or more on the side in contact with the back surface of the support film.   The photosensitive resin laminate roll according to claim 10, wherein the cover film includes a region having an arithmetic average roughness of 0.04 μm or more on the side in contact with the back surface of the support film.   The photosensitive resin laminate roll according to claim 10, wherein the cover film includes a region having an arithmetic average roughness of 0.05 μm or more on the side in contact with the back surface of the support film.   In the support film, when the small pieces of 0.75 mm × 11 mm are cut out at arbitrary ten different places of the support film, the number of fine particles having a diameter of 2 μm or more included in each small piece is the ten places. The photosensitive resin laminate roll according to any one of claims 1 to 15, having an area of 50 or less in number average.   In the support film, when the small pieces of 0.75 mm × 11 mm are cut out at arbitrary ten different places of the support film, the number of fine particles having a diameter of 2 μm or more included in each small piece is the ten places. The photosensitive resin laminated body roll of Claim 16 which has an area | region which becomes ten or less by a number average.   In the support film, when the small pieces of 0.75 mm × 11 mm are cut out at arbitrary ten different places of the support film, the number of fine particles having a diameter of 2 μm or more included in each small piece is the ten places. The photosensitive resin laminated body roll of Claim 16 which has an area | region which becomes 5 or less in a number average.   When a small piece of 0.75 mm × 11 mm is cut out at arbitrary ten different places of the support film, the diameter is 1.5 μm or more and the refractive index difference with the support film is 0.3, which is contained in each small piece The photosensitive resin laminated body roll in any one of Claims 1-18 which has an area | region where the number of the following microparticles | fine-particles will be 1 or more in a number average of said ten places.   When small pieces of 0.75 mm × 11 mm are cut out at arbitrary ten different places of the support film, the difference in the refractive index with the diameter of 1.5 μm or more and the support film included in each small piece is 0.2 The photosensitive resin laminated body roll of Claim 19 which has an area | region where the number of the following microparticles | fine-particles will be 1 or more in a number average of said ten places.   When a small piece of 0.75 mm × 11 mm is cut out at arbitrary 10 different places of the support film, the diameter is 1.5 μm or more and the refractive index difference with the support film is 0.1, which is contained in each small piece The photosensitive resin laminate roll according to any one of claims 1 to 20, wherein the photosensitive resin laminate roll has a region in which the number of the following fine particles is one or more in the number average of the ten locations.   When small pieces of 0.75 mm × 11 mm are cut out at arbitrary ten different places of the support film, the difference in refractive index difference with the support film is 1.5 μm or more and contained in each small piece. 22. The photosensitive resin laminate roll according to claim 21, having a region in which the number of fine particles of 05 or less is one or more in a number average of the ten locations. The photosensitive resin laminate roll according to any one of claims 1 to 22, wherein the surface resistivity of the back surface of the support film is 1.0 × 10 ¹³ Ω or less. The photosensitive resin laminate roll according to claim 23, wherein the surface resistivity of the back surface of the support film is 1.0 × 10 ¹¹ Ω or less. The photosensitive resin laminate roll according to claim 23 or 24, wherein the surface resistivity of the back surface of the support film is 1.0 × 10 ⁷ Ω or more. The photosensitive resin laminate roll according to claim 25, wherein the surface resistivity of the back surface of the support film is 1.0 x 10 ⁸ Ω or more.