KR102191080B1 - Photosensitive resin laminate roll - Google Patents

Abstract

There is provided a photosensitive resin laminate roll capable of easily removing foreign matters from an end face of the photosensitive resin laminate roll when unwinding the roll. This photosensitive resin laminate roll is a photosensitive resin laminate roll in which a photosensitive resin laminate is wound around a core in a roll shape, and a roll end surface protection member is disposed so as to contact an end surface of the wound photosensitive resin laminate, and a roll end protection member Has a pressure-sensitive adhesive composition on the side in contact with the end surface of the roll, and the photosensitive resin laminate includes at least a support layer and a photosensitive resin layer laminated on the support layer.

Description

Photosensitive resin laminated body roll {PHOTOSENSITIVE RESIN LAMINATE ROLL}

The present invention relates to a photosensitive resin laminate roll.

Conventionally, several aspects have been disclosed as packaging of a photosensitive element. For example, in order to protect an end face of a roll, a packing in which an end face protection member is disposed is disclosed (Patent Document 1).

Japanese Patent Application Publication No. 2005-41537

The problem to be solved by the present invention is to provide a photosensitive resin laminate roll capable of easily removing foreign matter from the end face of the photosensitive resin laminate roll when unwinding the roll.

The said subject can be solved by the following structure of this invention. That is, the present invention is as follows:

[One]

The photosensitive resin laminate is wound up in a roll shape around the core,

As a photosensitive resin laminate roll disposed so that the roll end surface protection member is in contact with the end face of the wound photosensitive resin laminate,

The roll end surface protection member has an adhesive composition on the side in contact with the roll end surface,

The photosensitive resin layered product roll includes at least a support layer and a photosensitive resin layer laminated on the support layer.

[2]

The photosensitive resin laminate roll according to [1], which is covered with a light-shielding sheet.

[3]

The photosensitive resin laminate roll according to [2], wherein the light-shielding sheet has a cylindrical shape.

[4]

The length of the winding core is longer than the width of the photosensitive resin laminate,

The roll end surface protection member is a ring-shaped sheet provided on an end surface of the photosensitive resin laminate wound in a roll shape, and the ring-shaped sheet is provided through insertion of the protrusion of the winding core according to any one of [1] to [3]. Photosensitive resin laminate roll.

[5]

The photosensitive resin laminate roll according to [4], wherein the inner diameter of the ring-shaped sheet is 1 to 1.1 times the outer diameter of the winding core.

[6]

On a flat plate protruding horizontally, the ring-shaped sheet is installed so that the half of the ring-shaped sheet is in the air, and the tip of the ring-shaped sheet furthest from the flat plate in the air-existing portion of the ring-shaped sheet, and the ring-shaped sheet of the flat plate H/R is 0.06 to 0.59 when the distance of the surface in contact is the bending distance H (mm) and half the outer diameter of the ring-shaped sheet is R (mm), [4] Or the photosensitive resin laminated body roll as described in [5].

[7]

The photosensitive resin laminate roll according to any one of [1] to [6], wherein the adhesion between the end surface protection member and the low-density polyethylene film is 5 gf/inch to 250 gf/inch.

[8]

The photosensitivity according to any one of [1] to [7], wherein the substrate of the roll end surface protection member is formed by bonding non-dust-free paper, low-dust paper, synthetic paper, or paper and a resin substrate. Resin laminate roll.

[9]

The photosensitive resin according to any one of [1] to [8], wherein the photosensitive resin layer is a layer made of a photosensitive resin composition containing an alkali-soluble polymer containing a carboxyl group, an addition polymerizable monomer, and a photopolymerization initiator. Laminate roll.

[10]

The photosensitive resin laminate roll according to [9], wherein the alkali-soluble polymer containing a carboxyl group is copolymerized with styrene or a derivative thereof.

[11]

The photosensitive resin laminate roll according to [9] or [10], wherein the addition polymerizable monomer contains a bisphenol A-based (meth)acrylate compound.

[12]

The photosensitive resin laminate roll according to any one of [9] to [11], wherein the photopolymerization initiator contains hexaarylbiimidazole or a derivative thereof.

[13]

The photosensitive resin laminate roll according to any one of [1] to [12], wherein the pressure-sensitive adhesive composition contains an acrylic resin.

[14]

The pressure-sensitive adhesive composition contains a pressure-sensitive adhesive and particles, and 50% by mass or more of the particles has a diameter of 80 to 120% of the coating thickness of the pressure-sensitive adhesive composition, and the content of the particles is 100 parts by weight of the pressure-sensitive adhesive. The photosensitive resin layered product roll according to any one of [1] to [13], which is 5 parts by weight to 30 parts by weight relative to each other.

[15]

A method for producing a photosensitive resin laminate roll, comprising winding a photosensitive resin laminate on a core in a roll shape, and providing a roll end surface protection member so as to contact an end face of the wound photosensitive resin laminate,

The length of the winding core is longer than the width of the photosensitive resin laminate,

The photosensitive resin laminate includes at least a support layer and a photosensitive resin layer laminated on the support layer,

The roll end surface protection member,

It has an adhesive composition on the side in contact with the end surface of the roll,

The inner diameter is 1 to 1.1 times the outer diameter of the core after it is provided integrally or divided into a plurality of parts on the end face of the photosensitive resin laminate wound in a roll shape, and is provided on the end face of the photosensitive resin laminate wound in a roll shape. Characterized in that it is a ring-shaped sheet,

A method for producing a photosensitive resin laminate roll.

[16]

The method for producing a photosensitive resin laminate roll according to [15], wherein the ring-shaped sheet has an inner diameter of 1.001 to 1.1 times the outer diameter of the core, and is provided through the protrusion of the core.

[17]

On a flat plate protruding horizontally, the ring-shaped sheet is installed so that the half of the ring-shaped sheet is in the air, and the tip of the ring-shaped sheet farthest from the flat plate in the air-existing portion of the ring-shaped sheet, H/R is 0.06 to 0.59 when the distance of the surface in contact is the bending distance H (mm) and half the outer diameter of the ring-shaped sheet is R (mm), [15] Or the manufacturing method of the photosensitive resin laminated body roll of [16].

[18]

The method for producing a photosensitive resin laminate roll according to any one of [15] to [17], wherein the adhesive force between the ring-shaped sheet and the low-density polyethylene film is 5 gf/inch to 250 gf/inch.

[19]

A method of packaging a photosensitive resin laminate roll, comprising producing a photosensitive resin laminate roll by the method according to any one of [15] to [18], and covering it with a tubular light-shielding sheet.

[20]

As a ring-shaped sheet for a film roll in which a film is wound in a roll shape around a core,

The length of the winding core is longer than the width of the film,

The inner diameter of the ring-shaped sheet is 1 to 1.1 times the outer diameter of the winding core, and

The ring-shaped sheet is in contact with an end surface of the wound film, has a pressure-sensitive adhesive composition on a side in contact with the end surface, and is provided on a film roll through the protrusion of the winding core

Ring-shaped sheet.

[21]

The film is the ring-shaped sheet according to [20], which is a photosensitive resin laminate.

[22]

On a flat plate protruding horizontally, the ring-shaped sheet is installed so that the half of the ring-shaped sheet is in the air, and the tip of the ring-shaped sheet farthest from the flat plate in the air-existing portion of the ring-shaped sheet, H/R is 0.06 to 0.59 when the distance of the surface in contact is the bending distance H (mm) and half the outer diameter of the ring-shaped sheet is R (mm), [20] Or the ring-shaped sheet according to [21].

[23]

The ring-shaped sheet according to any one of [20] to [22], wherein the adhesive force to the low-density polyethylene film is 5 gf/inch to 250 gf/inch.

[24]

A ring-shaped sheet according to any one of [20] to [23], comprising: a non-dusting paper, a low-dusting paper, or a substrate obtained by bonding paper and a resin substrate.

[25]

The ring shape according to any one of items 21 to 24, wherein the photosensitive resin layer is a layer made of a photosensitive resin composition containing an alkali-soluble polymer containing a carboxyl group, an addition polymerizable monomer, and a photopolymerization initiator. Sheet.

[26]

The ring-shaped sheet according to [25], wherein the alkali-soluble polymer containing a carboxyl group is copolymerized with styrene or a derivative thereof.

[27]

The ring-shaped sheet according to [25] or [26], wherein the addition polymerizable monomer contains a bisphenol A (meth)acrylate compound.

[28]

The ring-shaped sheet according to any one of [25] to [27], wherein the photopolymerization initiator contains hexaarylbiimidazole or a derivative thereof.

[29]

The ring-shaped sheet according to any one of [20] to [28], wherein the pressure-sensitive adhesive composition contains an acrylic resin.

[30]

The pressure-sensitive adhesive composition contains a pressure-sensitive adhesive and particles, and 50% by mass or more of the particles has a diameter of 80 to 120% of the coating thickness of the pressure-sensitive adhesive composition, and the content of the particles is 100 parts by weight of the pressure-sensitive adhesive. The ring-shaped sheet according to any one of [20] to [29], wherein it is 5 parts by weight to 30 parts by weight.

[31]

The film roll provided with the ring-shaped sheet of [20]-[30] covered with a light-shielding sheet.

When the photosensitive resin laminate roll of the present invention is used, foreign matter can be easily removed from the end face of the photosensitive resin laminate roll when unwinding the roll.

1 is a schematic diagram of an embodiment of a photosensitive resin laminate roll in which a photosensitive resin laminate is wound around a core in a roll shape, and a roll end surface protection member is disposed so as to contact an end face of a wound photosensitive resin laminate.
2: is a figure which shows the bending distance H and half R of the outer diameter of a ring-shaped sheet.
Fig. 3 shows a schematic view of an aspect of a photosensitive resin laminate roll covered with a tubular light-shielding sheet.

Hereinafter, the best mode for carrying out the present invention (hereinafter, abbreviated as "embodiment") will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.

In the photosensitive resin laminate roll, a long (band-shaped) photosensitive resin laminate is wound around a winding core in its longitudinal direction, and a roll end surface protection member is a cross section of the wound photosensitive resin laminate (the above strip-shaped photosensitive resin laminate It is a photosensitive resin laminated body roll arrange|positioned so that it may contact with the width direction end side of a sieve).

1 shows a schematic diagram of an aspect of such a photosensitive resin laminate roll 10. Herein, the photosensitive resin laminate (1) includes a support layer (4), a photosensitive resin layer (5) laminated on the support layer, and a protective layer (6) of veterinary care, and the laminate (1) Is wound around the core (2). And the roll end surface protection member 3 is arrange|positioned in contact with both end surfaces of this wound photosensitive resin laminated body. Here, the roll end surface protection member 3 is shown as a ring-shaped sheet.

(Photosensitive resin laminate)

The photosensitive resin laminate includes at least a support layer and a photosensitive resin layer laminated on the support layer, and preferably further includes a protective layer laminated on the photosensitive resin layer. A photosensitive film called dry film resist and dry film photoresist is also included in the photosensitive resin laminate.

The supporting layer should just support the photosensitive resin layer. As the supporting layer to be used, a transparent one that transmits light emitted from an exposure light source is preferable. As such a supporting layer, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a 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 can be stretched as needed. From the viewpoint of resolution, a film having a haze value of 5 or less is preferable. A haze value of 3 or less is more preferable, a haze value of 2.5 or less is still more preferable, and a haze value of 1 or less is even more preferable. The thickness of the supporting layer is advantageous in terms of image formation and economy, but a thickness of 10 to 30 µm is preferably used in view of the need to maintain heat shrinkage during coating of the photosensitive resin composition layer. For example, Teijin DuPont Film Co., Ltd. GR19, GR16, Mitsubishi Resin Co., Ltd. R310-16, R340G16, Toray Polyester Film Co., Ltd. FB40 (16 ㎛ film thickness), FB60 (16 ㎛ film Thickness) and the like.

The protective layer can be easily peeled off because the protective layer is sufficiently smaller than the support layer with respect to the adhesion to the photosensitive resin layer. For example, a polyethylene film, a polypropylene film, a stretched polypropylene film, etc. can be preferably used as a protective layer. In addition, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The film thickness of the protective layer is preferably 10 to 100 µm, more preferably 10 to 50 µm. For example, Tama Poly Co., Ltd. GF-18, GF-818, GF-858, etc. are mentioned.

The photosensitive resin layer can be laminated by applying and drying the photosensitive resin composition to the support layer. The thickness of the photosensitive resin layer is preferably 5 to 100 µm, and a more preferable upper limit is 50 µm. As the thickness of the photosensitive resin layer approaches 5 µm, the resolution improves, and as the thickness of the photosensitive resin layer approaches 100 µm, the film strength improves.

As a method of manufacturing a photosensitive resin laminate, a conventionally known method can be employed. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent and prepared as a photosensitive resin composition combination liquid, applied to the support layer using a bar coater or roll coater, dried, and the photosensitive resin composition on the support layer The photosensitive resin layer consisting of is laminated. It is preferable to add and combine a solvent so that the photosensitive resin composition combination liquid may become 500-4000 mPa·s at 25°C. As a solvent, methyl ethyl ketone, acetone, ethanol, methanol, propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, and the like are used in the photosensitive resin composition combination solution viscosity, drying property, residual solvent amount, coating property, foamability. It can be appropriately selected and used from the viewpoint of. Next, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

The photosensitive resin laminate is used in a roll shape by being wound around a core in a long shape. The winding length is not particularly limited, but is preferably 320 m or less from the viewpoint of the weight of the roll and ease of handling. Since efficiency is good when there are many substrates which can be laminated with one photosensitive resin laminated roll, the winding length is preferably 100 m or more from the viewpoint of productivity.

(Kwonssim)

The winding core is sometimes called a core. The shape is not particularly limited, but may be cylindrical or cylindrical. Since the photosensitive resin laminate is used for an electronic material as an etching or plating resist, and furthermore, as a permanent pattern, it is preferable to have been subjected to a treatment that does not oscillate, and a plastic resin agent is preferable. It is preferable that the plastic resin material is light, has excellent strength, and does not dust. Polypropylene (PP) resin, acrylonitrile butadiene styrene (ABS) resin, nylon resin, polyvinyl chloride resin, and the like can be used, and ABS resin is preferable. The diameter of the winding core is not particularly limited, but when the photosensitive resin laminate roll is mounted on the laminator, the diameter is preferably 2 to 5 inches, more preferably 3 inches so as to be mounted on the apparatus. The length of the core (in the case of using a cylindrical or cylindrical core, the length in the axial direction) may be the same as or shorter than the width of the photosensitive resin laminate, but when the photosensitive resin laminate is wound, It is preferable that the length is larger than the width of the photosensitive resin laminate so that an appropriate protrusion can be secured. It is preferable because a ring-shaped sheet is mounted so as to be inserted through the protrusion. Further, a bearing called a core holder can be fitted to this protrusion, and the photosensitive resin laminate roll can be stored in a suspended state so as not to move.

(Roll end face protection member)

The roll end surface protection member is disposed so as to contact the end surface of the wound photosensitive resin laminate. Its shape is not particularly limited, and there is no problem as long as it contacts the end face with a certain area and covers at least a part of the end face of the roll, but among them, the protrusion of the core is inserted so as to contact the end face of the wound photosensitive resin laminate. It is preferably a ring-shaped sheet to be arranged. Further, it is preferable that it is a ring shape having a width of a size that can substantially cover almost the entire cross section of the photosensitive resin laminate roll. The roll end surface protection member may be used only at one end of the wound photosensitive resin laminate, but is preferably used at both ends.

In the case where the roll end surface protection member is a ring-shaped sheet, the inner diameter of the ring is preferably slightly larger than the outer diameter of the core so that it can be used by being inserted into the core. Further, when the center of the ring-shaped sheet and the center of the winding are slightly shifted, the outer periphery of the ring-shaped sheet slightly protrudes from the outer periphery of the photosensitive resin laminate wound in a roll shape. It is preferable that it is slightly larger than the outer diameter of the core from the viewpoint that it becomes easy to remove the ring-shaped sheet by this. Specifically, the inner diameter of the ring is preferably 1.001 times or more than the outer diameter of the core, since there is no sticking to the core during mounting. It is more preferably 1.005 times or more, and still more preferably 1.01 times or more. From the viewpoint of protecting the entire end face of the roll and removing foreign matter, the inner diameter of the ring is preferably 1.1 times or less of the outer diameter of the winding core, more preferably 1.05 times or less, and still more preferably 1.03 times or less.

The outer diameter of the ring is preferably 0.99 times or more of the outer diameter of the photosensitive resin layered product wound up in a roll shape, and more preferably 1 times or more so that the end surface of the photosensitive resin layered product roll can be covered. In addition, from the viewpoint of suppressing adhesion to packaging materials such as a light-shielding cylindrical tube covering the photosensitive resin laminate roll, the outer diameter of the ring is preferably 1.1 times or less of the outer diameter of the photosensitive resin laminate roll, and more preferably It is 1.05 times or less, More preferably, it is 1.03 times or less.

The base material of the roll end surface protection member is polyester, polyethylene terephthalate, polyphenylene sulfide, polypropylene, nylon, each non-stretched, stretched, biaxially stretched, and low-density polyethylene, high-density polyethylene, rigid polyvinyl chloride, Plastic resins such as soft polyvinyl chloride, cellophane, acetate, cellulose triacetate, polystyrene, polycarbonate, polyimide, etc., and paper with anti-dust treatment, high-quality paper with anti-dust treatment, clean paper, and paper and the plastic What laminated resin, synthetic paper, etc. are mentioned. Since the photosensitive resin laminate is used for an electronic material as an etching or plating resist, and furthermore, as a permanent pattern, it is preferable to have been subjected to a treatment that does not oscillate. From the standpoint of less generation of static electricity, good followability to the end face, excellent removal of foreign matter, and excellent mounting, the substrate is made of anti-dust paper, anti-dust paper, clean paper, and paper and the above. What laminated plastic resin and synthetic paper are preferable as a material. It is preferable that the synthetic paper is made mainly of polypropylene.

When the substrate is made of anti-dust paper, anti-dust paper, clean paper, and paper and the plastic resin are bonded together, the thickness of the substrate is preferably 50 to 500 µm. From the viewpoint of attachability, 50 µm or more is preferable, and 500 µm or less is preferable from the viewpoint of followability to a cross section and foreign matter removal. It is more preferably 60 to 200 µm, and still more preferably 60 to 150 µm.

The surface of the roll end surface protection member may be embossed from the viewpoint of releasability and antifouling properties. The roll end surface protection member has a pressure-sensitive adhesive composition on the side in contact with the end surface of the photosensitive resin laminate roll. It is preferable that the roll end surface protection member is a circular ring-shaped sheet in plan view.

The ring-shaped sheet is provided on a flat plate protruding horizontally so that the half of the ring-shaped sheet is in the air, and the tip of the ring-shaped sheet furthest away from the flat plate in the air-existing portion of the ring-shaped sheet, It is preferable that H/R is 0.06 to 0.59 when the distance of the surface on the side in contact with the ring-like sheet of is the bending distance H (mm), and half of the outer diameter of the ring-like sheet is R (mm). . 0.59 or less is preferable from the viewpoint of the roll cross-section attachability of the ring-shaped sheet. More preferably, it is 0.5 or less, and still more preferably, it is 0.45 or less. 0.06 or more is preferable from the viewpoint of followability to the roll cross section and foreign matter removal. It is more preferably 0.1 or more, and still more preferably 0.15 or more.

The method of measuring the bending distance H is as follows. First, as shown in FIG. 2, the ring-shaped sheet 3 is provided on the substantially flat plate 7 protruding substantially in the horizontal direction (direction perpendicular to the vertical direction). At this time, the side with the adhesive is turned upward so that it is not adhered to the flat plate 7. The ring-shaped sheet is fixed so that half of the ring-shaped sheet 3 is in the air, that is, the center of the ring-shaped sheet 3 is on a substantially straight short side existing at the end of the flat plate. When fixing, you may fix with the fixing member 8 as shown in FIG. At this time, the ring-shaped sheet 3 is prevented from being bent or bent due to an influence other than gravity. In the airborne part of the ring-shaped sheet (the part protruding from the end), the distance in the vertical direction of the virtual surface formed by the tip of the ring-shaped sheet farthest from the short side of the flat plate and the surface in contact with the ring-shaped sheet of the flat plate is L-shaped. Measure with a ruler. The measurement location is Fuji City, Shizuoka Prefecture.

(Adhesive composition)

As the pressure-sensitive adhesive composition, a known pressure-sensitive adhesive composition is selected and used so that there is no glue residue on the end face of the photosensitive resin film when the roll end surface protection member is peeled off, and there is no adhesion of the photosensitive resin to the roll end surface protection member when the roll end surface protection member is removed. I can.

Especially, it is preferable to contain an acrylic resin from a viewpoint of a foreign matter removal property and releasability. When the photosensitive resin composition is a photosensitive resin composition containing an alkali-soluble polymer containing a carboxyl group, an addition polymerizable monomer, and a photopolymerization initiator, and the pressure-sensitive adhesive composition contains an acrylic resin, the viewpoint that the foreign matter removal property and the releasability can be highly compatible It is more preferable in

It is preferable that the pressure-sensitive adhesive composition contains particles, and 50% by mass or more of the particles have a diameter of 80 to 120% of the coating thickness of the pressure-sensitive adhesive composition, and the content of the particles is 100 parts by weight of the pressure-sensitive adhesive. It is preferably 5 parts by weight to 30 parts by weight. In addition, the diameter of the particle|grains observed the maximum diameter about arbitrary 100 particles by microscopic observation, and computed it as the average value.

The diameter of the particles is preferably 80% or more from the viewpoint of releasability, and 120% or less is preferable from the viewpoint of adhesiveness. 90-110% is more preferable, and 100% is still more preferable.

Although the particle|grains are usually theoretically possible to have a single particle size, it is often difficult to obtain in practice. It is desirable to have a particle size distribution as narrow as possible, that is, a sharp particle size curve.

It is preferable that 50 mass% or more of the total amount of the adhesive is a diameter of 80 to 120% of the applied thickness of the adhesive. From the viewpoint of balance of releasability and adhesiveness, 70% by mass or more is more preferable, and 80% by mass or more is still more preferable.

The content of the particles is preferably 5 parts by weight to 30 parts by weight based on 100 parts by weight of the pressure-sensitive adhesive. In the case of sticking, 5 parts by weight or more is preferable from the viewpoint of the detachability of air bubbles, and 30 or less is preferable from the viewpoint of adhesiveness. 10 parts by weight to 25 parts by weight are more preferable. When the material of the particle is glass, 15 to 30 parts by weight is preferable, and for plastic, 5 to 25 parts by weight is preferable.

The material of the particle is preferably a plastic or inorganic material. Plastics include polymethacrylate, polyethylene methacrylate, polystyrene, polystyrene acrylic, polyethylene, polypropylene, polystyrene butadiene, polystyrenedivinylbenzene, polyurethane, polybenzoguanamine, and melamine. Can be lifted. As an inorganic material, glass, silica (silicate mineral), and calcium carbonate are mentioned.

The adhesive strength of the pressure-sensitive adhesive can be improved by lowering the softening temperature of the entire composition or raising the polarity of the resin component.

The adhesion between the end surface protection member and the low-density polyethylene film is preferably 5 gf/inch to 250 gf/inch, and more preferably 50 gf/inch to 240 gf/inch from the viewpoint of foreign matter removal and attachability.

In addition, the adhesive force is measured as follows. That is, a low-density polyethylene film (LDPE) sheet is affixed to the surface of the end surface protection member on which the layer of the pressure-sensitive adhesive composition is formed with a hand roller. As the low-density polyethylene film, GF-858 manufactured by Tama Poly Co., Ltd. was used. It is cut into a strip of 1 inch in width and 15 cm in length, and humidity is adjusted at 50% relative humidity and 23 degrees Celsius for 11 hours. Tensilon RTM-500 manufactured by Orien Tech Co., Ltd., a load cell of 1 kg, and a tensile speed of 100 mm/min are subjected to a tensile test. At this time, the end surface protection member of the sample is chucked (fixed) at the lower part of the tensilon, and the low density polyethylene film is chucked (fixed) at the tension part, and a tensile test is performed. During the tensile test, the integral average of the load is taken in the section of 10 mm to 50 mm elongation, the average of two tests is taken, and this is taken as the adhesive value.

(Method of manufacturing photosensitive resin laminate roll)

It is preferable to cover the photosensitive resin laminated roll with a light-shielding sheet from the viewpoint of suppressing adhesion of foreign substances and photosensitivity during transportation. The light-shielding sheet may also be referred to as a light-shielding film. The light-shielding sheet can be covered by winding it around a photosensitive resin laminate roll. As shown in FIG. 3, when the light shielding sheet 9 is cylindrical, since it can cover by inserting the photosensitive resin roll 1 into a cylinder, it is preferable. In addition, when the length of the cylinder is longer than the winding core 2 of the photosensitive resin laminate roll 1, as shown in FIG. 3, by inserting a portion longer than the winding core 2 inside the winding core, adhesion of foreign matters and photosensitivity are prevented. It is preferable because it can be further suppressed.

The light shielding sheet is preferably made of polyethylene from the viewpoint of being able to protect the photosensitive resin laminate roll from contact with a lightweight falling object or slight contact with a packaging container. The film thickness is preferably 10 µm or more from the viewpoint of maintaining moderate strength and suppressing pinholes, and 300 µm or less from the viewpoint of handling properties. More preferably, it is 20 to 200 µm, and still more preferably 30 to 130 µm. Black is preferred in order to increase light-shielding property.

It is preferable that the photosensitive resin laminate roll is suspended and fixed in the air by a pair of members called a core holder in which a convex portion to be fitted with the winding core is formed. By suspending and fixing in the air, it is possible to prevent the photosensitive resin laminate from contacting the bottom surface of the packaging container during transportation. Examples of the core holder include those described in JP-A-2004-42952 and JP-A-2003-89477.

In the case of covering the photosensitive resin laminate roll with a light-shielding sheet, a portion longer than the core of the light-shielding sheet is inserted into the core, and a core holder is additionally mounted with the inserted portion interposed therebetween to suppress adhesion of foreign matter and photosensitivity. It is desirable because it can.

(Photosensitive resin composition)

It is preferable that the photosensitive resin composition contains (a) an alkali-soluble polymer containing a carboxyl group, (b) an addition polymerizable monomer, and (c) a photoinitiator.

When peeling the ring-shaped sheet from the end surface of the roll, the photosensitive resin composition contains the above (a) to (c) from the viewpoint of less glue residue on the end surface of the roll and less adhesion of the photosensitive resin composition to the ring-shaped sheet. desirable.

(a) alkali-soluble polymer containing carboxyl group

(a) It is preferable that the alkali-soluble polymer containing a carboxyl group has an α,β-unsaturated carboxyl group-containing monomer as a polymerization component, and the acid equivalent of the alkali-soluble polymer is 100 to 600, and the weight average molecular weight is 5,000 to 500,000. Do. The carboxyl group in the alkali-soluble polymer containing a carboxyl group is required because the photosensitive resin composition has developability or releasability with respect to a developer or stripper comprising an aqueous alkali solution. The acid equivalent means the mass of an alkali-soluble polymer having 1 equivalent of carboxyl group therein. The more preferable lower limit of the acid equivalent is 250, and the more preferable upper limit is 450. (a) The acid equivalent of the alkali-soluble polymer containing a carboxyl group improves development resistance, improves resolution and adhesion, and also with other components in the solvent or photosensitive resin composition, particularly (b) addition polymerizable monomer described later. 100 or more is preferable from the viewpoint of securing the compatibility of, and 600 or less is preferable from the viewpoint of improving developability and peelability. The measurement of the acid equivalent is carried out by a potentiometric titration method using 0.1 mol/L sodium hydroxide using a Hiranuma Automatic Titrator (COM-555) manufactured by Hiranuma Industrial Co., Ltd.

(a) The weight average molecular weight of the alkali-soluble polymer containing a carboxyl group is preferably 5,000 to 500,000. The weight average molecular weight is preferably 5,000 or more from the viewpoint of obtaining resistance to a developer by maintaining the thickness of the photosensitive resin laminate uniformly, and from the viewpoint of suppressing the edge fuse, and 500,000 or less from the viewpoint of maintaining developability. Is preferred. The edge fuse is a phenomenon in which the photosensitive resin composition seeps out from the end face of the roll when the photosensitive resin laminate is wound in a roll shape. The photosensitive resin composition exuded may adhere to the photosensitive resin composition exuded from the photosensitive resin layer of another neighboring layer through the support layer protective layer in a roll state. The adhered photosensitive resin composition, that is, the edge-fuse photosensitive resin composition, may be peeled off from the end face and scattered as a resist chip when the roll-shaped photosensitive resin laminate is unpacked and laminated. When the resist chip is attached to the laminated substrate, it is then attached to a mask for exposure, exposed to light, and cured. In the case of a negative resist, exposure is blocked, resulting in a pattern defect.

More preferably, (a) the lower limit of the weight average molecular weight of the alkali-soluble polymer containing a carboxyl group is 20,000, and (a) the upper limit of the weight average molecular weight of the alkali-soluble polymer containing a carboxyl group is 250,000. The weight average molecular weight in this specification means the weight average molecular weight measured using the calibration curve of polystyrene (Showa Electric Co., Ltd. product Shodex STANDARD SM-105) by gel permeation chromatography (GPC).

(a) The weight average molecular weight of the alkali-soluble polymer containing a carboxyl group can be measured under the following conditions using gel permeation chromatography manufactured by Nippon Spectroscopy Co., Ltd.:

Parallax Refractometer ： RI-1530

Pump ： PU-1580

Degaeseo ： DG-980-50

Column oven: CO-1560

Column: sequentially KF-8025, KF-806M×2, KF-807

Eluent: THF.

(a) It is preferable that the alkali-soluble polymer containing a carboxyl group is a (co) polymer containing as a component one or more types of monomers selected from the first or second monomers described later.

The first monomer is a carboxylic acid or an acid anhydride having one polymerizable unsaturated group in the molecule. For example, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester are mentioned. Among them, (meth)acrylic acid is particularly preferred.

The second monomer is non-acidic and is a monomer having at least one polymerizable unsaturated group in the molecule. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylic Rate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , Esters of vinyl alcohols such as benzyl (meth)acrylate and vinyl acetate, (meth)acrylonitrile, styrene, and polymerizable styrene derivatives. Among them, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferred, and it is particularly preferred to use styrene from the viewpoint of resolution.

(a) In the alkali-soluble polymer containing a carboxyl group, the above monomers are mixed, and in a solution diluted with a solvent such as acetone, methyl ethyl ketone or isopropanol, a radical polymerization initiator such as benzoyl peroxide, It is preferable that azoisobutyronitrile is added in an appropriate amount and synthesized by heating and stirring. In some cases, synthesis is carried out while dropping a part of the mixture into the reaction solution. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired concentration. As the synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

Particularly preferred (a) alkali-soluble polymer containing a carboxyl group has a copolymerization ratio of the first monomer and the second monomer of 10 to 60 mass% of the first monomer and 40 to 90 mass% of the second monomer, and further Preferably, the first monomer is 15 to 35 mass% and the second monomer is 65 to 85 mass%.

(a) As a more specific example of an alkali-soluble polymer containing a carboxyl group, a polymer containing methyl methacrylate, methacrylic acid and styrene as a copolymerization component, methyl methacrylate, methacrylic acid, and n-butyl acrylate as a copolymerization component And polymers containing benzyl methacrylate, methyl methacrylate, and 2-ethylhexyl acrylate as copolymerization components.

The content of the alkali-soluble polymer containing (a) a carboxyl group in the photosensitive resin composition is in the range of 20 to 90% by mass, preferably 40 to 60% by mass, based on the total solid content of the photosensitive resin composition. (a) The content of the alkali-soluble polymer containing a carboxyl group maintains the alkali developability of the photosensitive resin composition, and the resist pattern formed by exposure and development has properties as a resist, such as tenting, etching, and various plating From the viewpoint of having sufficient resistance in the process, it is preferably 20% by mass or more, and from the viewpoint of having sufficient flexibility of the photosensitive resin composition before curing and the resist pattern after curing, 90% by mass or less is preferable.

(b) addition polymerizable monomer

(b) The addition polymerizable monomer is a compound having at least one polymerizable ethylenically unsaturated bond in the molecule. It is preferable that an ethylenically unsaturated bond is a terminal ethylenic unsaturated group. Further, from the viewpoints of high resolution, edge fuse and tenting properties, it is preferable to use at least one bisphenol A (meth)acrylate compound as (b) addition polymerizable monomer.

In the present specification, the bisphenol A-based (meth)acrylate compound refers to a carbon-carbon unsaturated double bond derived from a (meth)acryloyl group or a (meth)acryloyl group, and -C6H4-C(CH3)2 derived from bisphenol A. It refers to a compound having a -C6H4- group. As a specific example, dimethacrylate of polyethylene glycol to which an average of 2 units of ethylene oxide was added to both ends of bisphenol A (NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.) or an average of 5 units each to both ends of bisphenol A Dimethacrylate of polyethylene glycol to which ethylene oxide was added (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.), and bisphenol A were each added with an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide. The dimethacrylate of one polyalkylene glycol and the dimethacrylate of polyalkylene glycol obtained by adding an average of 15 units of ethylene oxide and an average of 2 units of propylene oxide to both ends of bisphenol A are mentioned.

(b) As the addition polymerizable monomer, a known compound having at least one ethylenically unsaturated group can be used in addition to the above compound. For example, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, half of phthalic anhydride and 2-hydroxypropyl acrylate The reaction product of ester compound and propylene oxide (manufactured by Nippon Catalyst Chemical, trade name OE-A 200),

4-Normaloctylphenoxypentapropylene glycol acrylate, 1,6-hexanediol (meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol Polyoxyalkylene glycol di(meth)acrylate such as di(meth)acrylate, 2-di(p-hydroxyphenyl)propanedi(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol penta (Meth)acrylate, trimethylolpropanetriglycidylethertri(meth)acrylate, 2,2-bis(4-methacryloxypentaethoxyphenyl)propane, hexamethylenediisocyanate and nonapropylene glycol monomethacrylate Polyfunctional group (meth)acrylate containing urethane groups such as urethane products of, and polyfunctional (meth)acrylates of isocyanuric acid ester compounds. These may be used alone, may be used in combination of two or more, and may be used in combination with a bisphenol A-based (meth)acrylate compound.

The content of the (b) addition polymerizable monomer in the photosensitive resin composition is in the range of 5 to 75 mass%, more preferably 15 to 70 mass%, based on the total solid content of the photosensitive resin composition. (b) The content of the addition polymerizable monomer is 5% by mass or more from the viewpoint of resolution, adhesiveness, and copper line formation, and 75% by mass or less from the viewpoint of flexibility of the cured film.

(c) photopolymerization initiator

(c) As the photopolymerization initiator, those commonly used as photopolymerization initiators for photosensitive resins can be appropriately used, but hexaarylbisimidazole (hereinafter, also referred to as triarylimidazolyl dimer) is preferably used. .

As the triarylimidazolyl dimer, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer (hereinafter, "2,2'-bis(2-chlorophenyl)- Also called 4,4',5,5'-tetraphenyl-1,1'-bisimidazole"), 2,2',5-tris(o-chlorophenyl)-4-(3,4-dime Toxyphenyl)-4',5'-diphenylimidazolyl dimer, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylimidazolyl dimer ,

2,4,5-tris(o-chlorophenyl)-diphenylimidazolyl dimer, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-imidazolyl Dimer, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'- Bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2, 4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer,

2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'- Bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2, 3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,3,5 -Trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer,

2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2 '-Bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis -(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer,

2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2 ,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, and 2 ,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer Can be lifted.

In particular, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer is a photopolymerization initiator having a high effect on the strength of a resolution or cured resist film, and is preferably used. These may be used individually or may be used in combination of 2 or more types. Moreover, it can also be used in combination with the following acridine compound, a pyrazoline compound, etc.

In a preferred embodiment, (c) an acridine compound or a pyrazoline compound is used as the photopolymerization initiator. As the acridine compound, acridine, 9-phenylacridine, 9-(4-tolyl)acridine, 9-(4-methoxyphenyl)acridine, 9-(4-hydroxyphenyl) Acridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine,

9-(4-methylphenyl)acridine, 9-(4-ethylphenyl)acridine, 9-(4-n-propylphenyl)acridine, 9-(4-n-butylphenyl)acridine , 9-(4-tert-butylphenyl)acridine, 9-(4-ethoxyphenyl)acridine, 9-(4-acetylphenyl)acridine, 9-(4-dimethylaminophenyl)a Cridine, 9-(4-chlorophenyl)acridine,

9-(4-bromophenyl)acridine, 9-(3-methylphenyl)acridine, 9-(3-tert-butylphenyl)acridine, 9-(3-acetylphenyl)acridine, 9-(3-dimethylaminophenyl)acridine, 9-(3-diethylaminophenyl)acridine, 9-(3-chlorophenyl)acridine, 9-(3-bromophenyl)acridine Dine, 9-(2-pyridyl)acridine, 9-(3-pyridyl)acridine, and 9-(4-pyridyl)acridine. Among them, 9-phenylacridine is preferable.

As a pyrazoline compound, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzooxazol-2-yl) )Phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4- Preferred are tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline.

As photoinitiators other than the above, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di Phenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro Quinones such as -2-methylanthraquinone,

Aromatic ketones such as benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], and 4,4'-bis(diethylamino)benzophenone, benzoin, benzoin ethyl ether, benzoin Benzoin ethers such as phenyl ether, methyl benzoin, and ethyl benzoin,

Benzyldimethylketal, benzyldiethylketal, a combination of thioxanthones and alkylaminobenzoic acid, 1-phenyl-1,2-propanedione-2-O-benzoinoxime, 1-phenyl-1,2-propanedione- Oxime esters, such as 2-(O-ethoxycarbonyl)oxime, are mentioned.

In addition, as a combination of thioxanthones and alkylaminobenzoic acid described above, for example, a combination of ethyl thioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorthioxanthone and ethyl dimethylaminobenzoate, and isopropyl tea The combination of oxanthone and ethyl dimethylaminobenzoate is mentioned. Moreover, you may use an N-arylamino acid. Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among them, N-phenylglycine is particularly preferred.

The content of the photopolymerization initiator (c) in the photosensitive resin composition is in the range of 0.01 to 30% by mass based on the total solid content of the photosensitive resin composition, the more preferable lower limit is 0.05% by mass, the more preferable lower limit is 0.1% by mass, more A preferable upper limit is 15 mass%, and a more preferable upper limit is 10 mass%. (c) The content of the photopolymerization initiator is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity during photopolymerization by exposure, and sufficient light is sufficiently transmitted to the bottom surface of the photosensitive resin composition (ie, a portion far from the light source) during photopolymerization. It is 30 mass% or less from a viewpoint of making it permeate and obtaining good resolution and adhesiveness.

(e) other additives

In addition to the components (a) to (c), various additives can be included in the photosensitive resin composition. Specifically, coloring substances such as dyes and pigments are contained. As such a coloring substance, phthalocyanine green, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, basic blue 20, diamond green, etc. are mentioned, for example.

In the case of containing the colored substance, the amount of the colored substance added is preferably 0.001 to 1% by mass based on the total solid content of the photosensitive resin composition. When the amount of the colored substance added is 0.001% by mass or more, there is an effect of improving the handling properties, and when it is 1% by mass or less, there is an effect of maintaining storage stability.

Moreover, you may contain a coloring agent in the photosensitive resin composition so that a visible image can be provided by exposure. Examples of such a color developing dye include a Leuco dye or a combination of a fluorane dye and a halogen compound.

For example, as a leuco dye, tris(4-dimethylamino-2-methylphenyl)methane [leucocrystal violet], tris(4-dimethylamino-2-methylphenyl)methane [leucomalachite green], and a fluorane dye are mentioned. I can. Among them, when using Royco Crystal Violet, the contrast is good, which is preferable.

Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenylsulfone, carbon 4 bromide, tris(2,3-dibromo) Propyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, hexachloroethane, chlorinated triazine compounds, etc. I can.

When these dyes are contained, the content of the dye in the photosensitive resin composition is preferably 0.1 to 10% by mass, respectively, based on the total solid content of the photosensitive resin composition.

In addition, in order to improve the thermal stability and storage stability of the photosensitive resin composition, it is preferable to contain a radical polymerization inhibitor or at least one or more compounds selected from the group consisting of benzotriazoles and carboxybenzotriazoles in the photosensitive resin composition. Do.

As such a radical polymerization inhibitor, for example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p -Cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum Salt and diphenylnitrosoamine.

As benzotriazoles, for example, 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 Can be lifted.

As carboxybenzotriazoles, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, (N,N-dibutylamino)carboxybenzotria Sol, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N, N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole is mentioned.

The total addition amount of the radical polymerization inhibitor, benzotriazoles, and/or carboxybenzotriazoles is preferably 0.001 to 3% by mass based on the total solid content of the photosensitive resin composition, and a more preferable lower limit is 0.05% by mass, more A preferable upper limit is 1 mass%. This total addition amount is preferably 0.001 mass% or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and 3 mass% or less from the viewpoint of maintaining sensitivity.

The photosensitive resin composition may contain other plasticizers as necessary. As such a plasticizer, a compound obtained by modifying bisphenol A with polyalkylene oxide is mentioned, for example.

In addition, for example, sorbitan derivatives such as polyoxyethylene sorbitan laurate and polyoxyethylene sorbitan oleate, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and phthalic acid esters such as diethylphthalate. , o-toluene sulfonic acid amide, p-toluene sulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, and tri-n-butyl acetyl citrate can be used. In particular, it is preferable to use sorbitan derivatives and polyalkylene glycols.

The content of the plasticizer in the photosensitive resin composition is preferably 1 to 50% by mass based on the total solid content of the photosensitive resin composition, a more preferable lower limit is 3% by mass, and a more preferable upper limit is 30% by mass. 1 mass% or more is preferable from the viewpoint of suppressing the delay of the development time and providing flexibility to the cured film, and 50 mass% or less is preferable from the viewpoint of suppressing insufficient curing or cold flow.

Example

Hereinafter, although it demonstrates more concretely in an Example, it is not limited to this.

First, a method of preparing a sample for evaluation in Examples and Comparative Examples is described, and then, an evaluation method for the obtained sample and the evaluation result thereof are shown. Here, a ring-shaped sheet was used as the roll end surface protection member.

(Examples 1 to 12, Comparative Example 1)

1. Preparation of sample for evaluation

Samples for evaluation in Examples and Comparative Examples were produced as follows.

<Production of photosensitive resin laminate>

Composition 1 shown in Table 1 below (however, the number of each component indicates the blending amount (parts by mass) as a solid content. Abbreviations in Table 1 follow Table 2.) and a solvent are sufficiently stirred and mixed to obtain a photosensitive resin composition combination solution. Then, as a support, a 16 µm thick polyethylene terephthalate film (R310 manufactured by Mitsubishi Resin Co., Ltd.) was prepared, and the photosensitive resin composition mixture was uniformly applied and dried on the surface of the polyethylene terephthalate film using a die coater. , A photosensitive resin layer was formed. The thickness of the photosensitive resin layer was 15 µm. Next, on the surface of the photosensitive resin layer on which the polyethylene terephthalate film has not been laminated, a 33 µm-thick polyethylene film (GF-858 manufactured by Tama Poly Co., Ltd.) was bonded as a protective layer to the photosensitive resin laminate (1). Got it.

Moreover, in the said photosensitive resin laminated body (1), except having made composition 1 into compositions 2-6, it produced similarly to the photosensitive resin laminated body (1), and the photosensitive resin laminated body (2-6) was obtained. . In the photosensitive resin laminate (1), except that the composition 1 is compositions 7 to 10, and the thickness of the photosensitive resin layer is 10 µm, it is prepared in the same manner as the photosensitive resin laminate (1), and a photosensitive resin A laminate (7-10) was obtained.

<Production of photosensitive resin laminate roll>

As the ring-shaped sheet, the sheets shown in Tables 3 to 5 were used. For the pressure-sensitive adhesive composition containing the acrylic resin of the ring-shaped sheet, when there is no description in particular, the pressure-sensitive adhesive composition of Erierutech NS80/SBG85S/removed (manufactured by Erieru Taxel Corporation) was used as it is.

About samples F and G, the adhesive composition was adjusted as follows. That is, B-1 and M-8 described in Table 2 were blended in a solid content ratio of 45:55 and 40:60 to adjust the base material by coating and drying so that the film thickness after drying was 15 µm.

The photosensitive resin laminate (1) was slit to a width of 495 mm, and wound around a core (core) made of ABS resin having an inner diameter of 77 mm, an outer diameter of 88 mm, and a length of 530 mm. The outer diameter of the photosensitive resin laminate wound up in a roll shape was 180 mm.

The photosensitive resin laminate, which was wound around a core and formed into a roll, was held in a rod-shaped stainless steel lock holder designed to be fixed at the other end and held horizontally.

The roll-shaped photosensitive resin laminate was covered with a cylindrical light-shielding polyethylene tube having an outer circumference of 500 mm, a length of 800 mm, and a thickness of 80 µm.

The roll-shaped photosensitive resin laminate covered with the light-shielding polyethylene tube was removed from the lock holder, and the upper portion of the 330 mm wide, 100 mm high curved concave shape was placed on a cushion designed to fix the roll.

One end of the light-shielding polyethylene tube was folded back, the end face of the roll-shaped photosensitive resin laminate was exposed, and a ring-shaped sheet was attached. The other end was also carried out similarly, and the ring-shaped sheet was attached|attached, and the photosensitive resin laminated body roll 1 was manufactured.

The light-shielding polyethylene tube was inserted into the core, and a core holder designed to fit the core in a convex shape was attached, and the photosensitive resin roll 1 was packaged.

2. Evaluation Criteria

The photosensitive resin laminate roll was evaluated and ranked according to the following evaluation items and evaluation criteria. The evaluation results are shown in Tables 3 to 5.

(1) Foreign matter removal

The ring-shaped sheet was peeled off from the photosensitive resin laminate roll, and it was checked whether a foreign substance adhered to the ring-shaped sheet. They were ranked as follows.

○: Foreign matter adhered to the ring-shaped sheet. Another adhesive tape was affixed to the end face of the roll and peeled off, but adhesion of foreign matter could not be confirmed.

?: Foreign matter adhered to the ring-shaped sheet, but as a result of peeling by attaching another adhesive tape to the end face of the roll, adhesion of the foreign matter to this adhesive tape was also confirmed.

X: No foreign matter adhered to the ring-shaped sheet. When another adhesive tape was affixed to the end face of the roll and peeled off, adhesion of foreign matter was confirmed.

(2) Ring-shaped seat attachability

A roll was produced as described in the above <production of a photosensitive resin laminate roll>, and the attachability at the time of attaching the ring-shaped film to the end face of the roll was ranked as follows.

○: The ring-shaped sheet could be easily attached. When affixed to the end face of the roll, it could be adhered without wrinkles.

?: A ring-shaped sheet was affixed to the lock holder or the core, and time was required for mounting. When affixed to the end face of the roll, some wrinkles occurred or air entered.

X: The ring-shaped sheet was affixed to the lock holder or the winding core, and time was required for attachment. When the ring-shaped sheet affixed to an undesired point was peeled off and affixed again, the ring-shaped sheet was stretched and deformed or torn, making it difficult to affix to the end face of the roll.

(3) Adhesion of ring-shaped sheet packaging

After producing a roll as described in the above <Preparation of a photosensitive resin laminate roll>, this was unwound. The glue observed whether the ring-shaped sheet was attached to the end face in the same manner as at the time of attachment, and ranked as follows.

○: It is installed in the same way as when it was installed.

Δ: When unwinding the roll, there is a point where the ring-shaped sheet is affixed to the light-shielding cylindrical polyethylene sheet and peeled off from a partial end surface.

X: When the roll is unwound, the ring-shaped sheet is affixed to the light-shielding cylindrical polyethylene sheet and peeled off together with the light-shielding cylindrical polyethylene sheet.

(4) Removability of ring-shaped sheet

After producing a roll as described in the above <Preparation of a photosensitive resin laminate roll>, this was released and the ring-shaped sheet was peeled off with a hand wearing a resin-made glove. The workability at the time of peeling was ranked as follows.

○: The ring-shaped sheet can be easily peeled off within 5 seconds.

Δ: It takes 5 seconds or more for peeling of the ring-shaped sheet.

(5) Number of foreign substances

As described in the above <production of photosensitive resin laminate roll>, 14 roll-shaped photosensitive resin laminates were produced. Foreign matters were removed from the end faces of all rolls, and a total of four foreign matters were attached to the end faces of the rolls randomly among the 14. After that, the ring-shaped sheet was attached to all the rolls and peeled off, and foreign matter adhering to the end face of the roll was counted.

A photosensitive resin laminate roll was produced in the same manner as the photosensitive resin laminate roll 1, except that the photosensitive resin laminate (1) was used as the photosensitive resin laminate (2 to 6), and sample B was used for the ring-shaped sheet, This was made into the photosensitive resin laminated body roll (2-6). As a result of evaluating (1) to (5) using the photosensitive resin rolls (2 to 6), the same results as in the case of using the photosensitive resin laminate roll (1) were obtained.

Photosensitive resin laminate roll (1), except that the photosensitive resin laminate (1) was used as the photosensitive resin laminate (7 to 10), the sample B was used for the ring-shaped sheet, and the outer diameter was 180 mm and the outer diameter was 176 mm. Likewise, a photosensitive resin laminate roll was produced, and this was made into a photosensitive resin laminate roll (7-10). The outer diameter of the photosensitive resin laminate wound up in a roll shape was 176 mm. As a result of evaluating (1) to (5) using the photosensitive resin rolls (7 to 10), the same results as those in the case of using the photosensitive resin laminate roll (1) were obtained.

Industrial availability

The photosensitive resin laminate roll described above is useful for processing precision equipment and electronic materials because foreign matter is easily removed when unwinding the roll, and is useful also as a permanent pattern inserted into precision equipment and electronic materials.

1: photosensitive resin laminate
2: Kwon Shim
3: Roll end face protection member (ring-shaped sheet)
4: support layer
5: photosensitive resin layer
6: protective layer
7: reputation
8: fixing member
9: shading sheet
10: photosensitive resin laminated body roll

Claims (31)

The photosensitive resin laminate is wound up in a roll shape around the core,
As a photosensitive resin laminate roll disposed so that the roll end surface protection member is in contact with the end face of the wound photosensitive resin laminate,
The roll end surface protection member has an adhesive composition on the side in contact with the roll end surface,
The photosensitive resin laminate includes at least a support layer and a photosensitive resin layer laminated on the support layer,
A photosensitive resin laminate roll, characterized in that the adhesive force between the roll end surface protection member and the low-density polyethylene film is 5 gf/inch to 250 gf/inch. The method of claim 1,
A photosensitive resin laminate roll, which is covered with a light-shielding sheet. The method of claim 2,
The photosensitive resin laminate roll, wherein the light-shielding sheet has a cylindrical shape. The method of claim 1,
The length of the winding core is longer than the width of the photosensitive resin laminate,
The roll end surface protection member is a ring-shaped sheet provided on an end surface of the photosensitive resin laminate wound in a roll shape, and the ring-shaped sheet is provided by inserting a protrusion of the core. The method of claim 4,
The photosensitive resin laminate roll, characterized in that the inner diameter of the ring-shaped sheet is 1 to 1.1 times the outer diameter of the winding core. The method of claim 4,
On a flat plate protruding horizontally, the ring-shaped sheet is installed so that the half of the ring-shaped sheet is in the air, and the tip of the ring-shaped sheet furthest from the flat plate in the air-existing portion of the ring-shaped sheet, and the ring-shaped sheet of the flat plate A photosensitive resin laminate, characterized in that H/R is 0.06 to 0.59 when the distance of the surface in contact is the bending distance H (mm) and half the outer diameter of the ring-shaped sheet is R (mm). role. delete The method of claim 1,
A photosensitive resin laminate roll, characterized in that the base material of the roll end surface protection member is formed of non-dusting paper, low-dusting paper, synthetic paper, or bonding paper and a resin base material. The method according to any one of claims 1 to 6 and 8,
The photosensitive resin layered product roll, wherein the photosensitive resin layer is a layer made of a photosensitive resin composition containing an alkali-soluble polymer containing a carboxyl group, an addition polymerizable monomer, and a photopolymerization initiator. The method of claim 9,
A photosensitive resin laminate roll, wherein the alkali-soluble polymer containing a carboxyl group is copolymerized with styrene or a derivative thereof. The method of claim 9,
The photosensitive resin laminate roll, characterized in that the addition polymerizable monomer contains a bisphenol A (meth)acrylate compound. The method of claim 9,
The photosensitive resin laminate roll, characterized in that the photopolymerization initiator contains hexaarylbiimidazole or a derivative thereof. The method according to any one of claims 1 to 6 and 8,
The photosensitive resin laminate roll, characterized in that the pressure-sensitive adhesive composition contains an acrylic resin. The method according to any one of claims 1 to 6 and 8,
The pressure-sensitive adhesive composition contains a pressure-sensitive adhesive and particles, and 50% by mass or more of the particles has a diameter of 80 to 120% of the coating thickness of the pressure-sensitive adhesive composition, and the content of the particles is 100 parts by weight of the pressure-sensitive adhesive. 5 to 30 parts by weight based on the photosensitive resin laminate roll, characterized in that. A method for producing a photosensitive resin laminate roll, comprising winding a photosensitive resin laminate on a core in a roll shape, and providing a roll end surface protection member so as to contact an end face of the wound photosensitive resin laminate,
The length of the winding core is longer than the width of the photosensitive resin laminate,
The photosensitive resin laminate includes at least a support layer and a photosensitive resin layer laminated on the support layer,
The roll end surface protection member,
It has an adhesive composition on the side in contact with the end surface of the roll,
The inner diameter is 1 to 1.1 times the outer diameter of the core after it is provided integrally or divided into a plurality of parts on the end face of the photosensitive resin laminate wound in a roll shape, and is provided on the end face of the photosensitive resin laminate wound in a roll shape. It is a ring-shaped sheet,
The method of manufacturing a photosensitive resin laminate roll, characterized in that the adhesive force between the ring-shaped sheet and the low density polyethylene film is 5 gf/inch to 250 gf/inch. The method of claim 15,
The method of manufacturing a photosensitive resin laminate roll, wherein the ring-shaped sheet has an inner diameter of 1.001 to 1.1 times the outer diameter of the core, and is provided through the protrusion of the core. The method of claim 15,
On a flat plate protruding horizontally, the ring-shaped sheet is installed so that the half of the ring-shaped sheet is in the air, and the tip of the ring-shaped sheet furthest from the flat plate in the air-existing portion of the ring-shaped sheet, and the ring-shaped sheet of the flat plate A photosensitive resin laminate, characterized in that H/R is 0.06 to 0.59 when the distance of the surface in contact is the bending distance H (mm) and half the outer diameter of the ring-shaped sheet is R (mm). How to make a roll. delete A method for packaging a photosensitive resin laminate roll, comprising producing a photosensitive resin laminate roll by the method according to any one of claims 15 to 17 and covering it with a tubular light-shielding sheet. As a ring-shaped sheet for a film roll in which a film is wound in a roll shape around a core,
The length of the winding core is longer than the width of the film,
The inner diameter of the ring-shaped sheet is 1 to 1.1 times the outer diameter of the winding core, and
The ring-shaped sheet is in contact with the end face of the wound film,
It has a pressure-sensitive adhesive composition on the side in contact with this end face, and is provided on the film roll through the protrusion of the winding core
The ring-shaped sheet, characterized in that the adhesion between the ring-shaped sheet and the low-density polyethylene film is 5 gf/inch to 250 gf/inch. The method of claim 20,
The film is a ring-shaped sheet which is a photosensitive resin laminate. The method of claim 20,
On a flat plate protruding horizontally, the ring-shaped sheet is installed so that the half of the ring-shaped sheet is in the air, and the tip of the ring-shaped sheet furthest from the flat plate in the air-existing portion of the ring-shaped sheet, and the ring-shaped sheet of the flat plate A ring-shaped sheet, wherein H/R is 0.06 to 0.59 when the distance of the contacting side is set as the bending distance H (mm) and half of the outer diameter of the ring-shaped sheet is set as R (mm). delete The method of claim 20,
A ring-shaped sheet comprising: a non-dusting paper, low-dusting paper, synthetic paper, or a substrate obtained by bonding paper and a resin substrate. The method of claim 21,
Ring-shaped, characterized in that the photosensitive resin laminate comprises a support layer and a photosensitive resin layer, and the photosensitive resin layer is a layer made of a photosensitive resin composition containing an alkali-soluble polymer containing a carboxyl group, an addition polymerizable monomer, and a photoinitiator. Sheet. The method of claim 25,
A ring-shaped sheet, wherein the alkali-soluble polymer containing a carboxyl group is copolymerized with styrene or a derivative thereof. The method of claim 25,
The ring-shaped sheet, wherein the addition polymerizable monomer contains a bisphenol A (meth)acrylate compound. The method of claim 25,
The ring-shaped sheet, wherein the photopolymerization initiator contains hexaarylbiimidazole or a derivative thereof. The method according to any one of claims 20 to 22 and 24,
The ring-shaped sheet, wherein the pressure-sensitive adhesive composition contains an acrylic resin. The method according to any one of claims 20 to 22 and 24,
The pressure-sensitive adhesive composition contains a pressure-sensitive adhesive and particles, and 50% by mass or more of the particles has a diameter of 80 to 120% of the coating thickness of the pressure-sensitive adhesive composition, and the content of the particles is 100 parts by weight of the pressure-sensitive adhesive. Ring-shaped sheet, characterized in that 5 to 30 parts by weight relative to. The film roll provided with the ring-shaped sheet in any one of Claims 20-22 and 24 covered with a light-shielding sheet.

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