TWI522303B - Photosensitive resin laminate roll - Google Patents

Description

Photosensitive resin laminate roll

The present invention relates to a photosensitive resin laminate roll.

Previously, as a bundle of photosensitive elements, a number of aspects have been revealed. For example, a package in which an end face protection member is disposed to protect the end surface of the roll is disclosed (Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-41537

The problem to be solved by the present invention is to provide a photosensitive resin laminate roll which can easily remove foreign matter from the end surface of the photosensitive resin laminate roll at the time of unbundling.

The above problems can be solved by the following constitution of the present invention. That is, the present invention is as follows:

[1]

A photosensitive resin laminated body roll in which a photosensitive resin laminated body is wound on a winding core and formed into a roll shape, and a roll end face protecting member is disposed in contact with an end surface of the wound photosensitive resin laminated body. And the roller end face protection member has an adhesive composition on a side in contact with the end surface of the roller, The photosensitive resin laminate includes at least a support layer and a photosensitive resin layer laminated on the support layer.

[2]

The photosensitive resin laminate roller according to [1], which is characterized in that it is coated with a light-shielding sheet.

[3]

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

[4]

The photosensitive resin laminate roll according to any one of [1] to [3] wherein the length of the winding core is longer than the width of the photosensitive resin laminate, and the roll end face protection member is provided in a roll shape. The annular sheet of the end surface of the photosensitive resin laminate is inserted into the projecting portion of the winding core to provide the annular sheet.

[5]

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

[6]

The photosensitive resin laminated body roll according to [4] or [5], wherein the annular sheet is placed on a horizontally extending flat plate so that half of the annular sheet is present in the air, and the annular sheet is placed. The distance between the front end of the annular sheet which is farthest from the flat plate and the side of the flat plate which is in contact with the annular sheet is the bending distance H (mm), and the ring is present in the air. When one half of the outer diameter of the sheet is set to R (mm), the H/R is 0.06 to 0.59.

[7]

The photosensitive resin laminated body roll of any one of [1] to [6], wherein the end face protection member and the low-density polyethylene film have an adhesion of 5 gf/inch to 250 gf/inch.

[8]

The photosensitive resin laminate roll according to any one of [1] to [7] wherein the substrate of the roll end face protection member is a dust-free paper, a low-dust paper, a synthetic paper, or a paper and a resin base. The material is laminated.

[9]

The photosensitive resin layered roll according to any one of the above aspects, wherein the photosensitive resin layer is a layer containing a photosensitive resin composition containing a carboxyl group. An alkali-soluble polymer, an addition polymerizable monomer, and a photopolymerization initiator.

[10]

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

[11]

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

[12]

The photosensitive resin laminate roller according to any one of the above aspects, wherein the photopolymerization initiator comprises hexaarylbiimidazole or a derivative thereof.

[13]

The photosensitive resin laminated body roll of any one of [1] to [12], wherein the adhesive composition contains an acrylic resin.

[14]

The photosensitive resin laminated body roll according to any one of the above aspects, wherein the adhesive composition contains an adhesive and particles, and 50% by mass or more of the particles are provided with the adhesive composition. The thickness of the coating is 80 to 120% of the thickness, and the content of the particles is 5 parts by weight to 30 parts by weight based on 100 parts by weight of the adhesive.

[15]

A method for producing a photosensitive resin laminated body roll, which is obtained by winding a photosensitive resin laminated body on a winding core to form a roll and contacting an end surface of the wound photosensitive resin laminated body. A method of manufacturing a photosensitive resin laminate roll having a roll end face protection member, wherein the length of the core is longer than a width of the photosensitive resin laminate, the photosensitive resin laminate comprising at least a support layer and laminated on the support layer In the photosensitive resin layer, the roller end face protection member is provided with an adhesive composition on the side in contact with the end surface of the roll, and is provided in a roll-formed photosensitive resin laminate in a state of being integrated or divided into a plurality of portions. The end surface is provided with an annular sheet having an inner diameter of 1 to 1.1 times the outer diameter of the core after the end surface of the photosensitive resin laminate which is wound into a roll.

[16]

The method for producing a photosensitive resin laminated body roll according to [15], wherein the inner diameter of the annular sheet is 1.001 to 1.1 times the outer diameter of the winding core, and the protruding portion of the winding core is inserted. And equipped.

[17]

The method for producing a photosensitive resin laminated body roll according to [15] or [16], wherein the annular sheet is placed on a horizontally extending flat plate so that half of the annular sheet is present in the air, The distance between the front end of the annular sheet which is the farthest from the flat plate and the side of the flat plate which is in contact with the annular sheet in the portion of the annular sheet which is present in the air is set as the bending distance H (mm), When one half of the outer diameter of the annular sheet is R (mm), H/R is 0.06 to 0.59.

[18]

The method for producing a photosensitive resin laminate roll according to any one of [15] to [17] wherein the annular sheet and the low-density polyethylene film have an adhesion of 5 gf/inch to 250 Gf/inch.

[19]

A method for packaging a photosensitive resin laminated body roll, which is characterized in that a photosensitive resin laminated body roll is produced by the method according to any one of [15] to [18], and further packaged by a cylindrical light-shielding sheet cover.

[20]

Ring sheet Rolling the film onto the core to form a roll-shaped film roll, and The length of the core is longer than the width of the film, The inner diameter of the annular sheet is 1 to 1.1 times the outer diameter of the core, and The annular sheet is in contact with an end surface of the wound film, and is in contact with the end surface The side has an adhesive composition, and is inserted into the film roll by inserting the extension of the above-mentioned core.

[twenty one]

The annular sheet according to [20], wherein the film is a photosensitive resin laminate.

[twenty two]

The annular sheet according to [20] or [21], wherein the annular sheet is placed on a horizontally extending flat plate such that half of the annular sheet is present in the air, and the annular sheet is The distance between the front end of the annular sheet which is farthest from the flat plate and the side of the flat plate which is in contact with the annular sheet is the bending distance H (mm), and the annular sheet is present in the portion of the air. When one half of the outer diameter of the material is set to R (mm), the H/R is 0.06 to 0.59.

[twenty three]

The annular sheet according to any one of [20] to [22] wherein the adhesion to the low-density polyethylene film is from 5 gf/inch to 250 gf/inch.

[twenty four]

The annular sheet according to any one of [20] to [23], which is characterized in that it has a substrate that is free from dusting paper, low dusting paper, or a paper and a resin substrate.

[25]

The annular sheet according to any one of the aspects of the present invention, characterized in that the photosensitive resin layer is a layer containing a photosensitive resin composition containing an alkali solubility of a carboxyl group. A polymer, an addition polymerizable monomer, and a photopolymerization initiator.

[26]

The cyclic sheet according to [25], wherein the alkali-soluble polymer having a carboxyl group is obtained by copolymerizing styrene or a derivative thereof.

[27]

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

[28]

The cyclic sheet according to any one of [25] to [27] wherein the photopolymerization initiator comprises hexaarylbiimidazole or a derivative thereof.

[29]

The annular sheet according to any one of [20] to [28] wherein the adhesive composition comprises an acrylic resin.

[30]

The annular sheet according to any one of [20], wherein the adhesive composition contains an adhesive and particles, and 50% by mass or more of the particles are coated with the adhesive composition. The thickness is 80 to 120% of the diameter, and the content of the particles is 5 parts by weight to 30 parts by weight based on 100 parts by weight of the adhesive.

[31]

A film roll which is coated with a light-shielding sheet and which is provided with the annular sheet of any one of [20] to [30].

When the photosensitive resin laminate roll of the present invention is used, it is self-photosensitive at the time of unbundling The resin laminate roll end face simply removes foreign matter.

1‧‧‧Photosensitive resin laminate

2‧‧‧Volume core

3‧‧‧Roll end face protection member (annular sheet)

4‧‧‧Support layer

5‧‧‧Photosensitive resin layer

6‧‧‧Protective layer

7‧‧‧ tablet

8‧‧‧Fixed components

9‧‧‧Light-shielding sheet

10‧‧‧Photosensitive resin laminated roller

H‧‧‧Bending distance

One and a half of the outer diameter of the R‧‧‧ annular sheet

1 is a photosensitive resin laminate roll in which a roll end face protection member is placed in a roll shape and is brought into contact with the end surface of the wound photosensitive resin laminate. A schematic diagram of one aspect.

Fig. 2 is a view showing a bending distance H and one half and half R of the outer diameter of the annular sheet.

Fig. 3 is a schematic view showing one aspect of a photosensitive resin laminated body roll coated with a tubular light-shielding sheet.

The best mode for carrying out the invention (hereinafter simply referred to as "embodiment") will be described in detail below. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

The photosensitive resin laminated body roll is obtained by winding a long (belt-shaped) photosensitive resin laminated body on the winding core along the longitudinal direction thereof and the end surface of the laminated photosensitive resin laminated body (the above-mentioned strip shape) A photosensitive resin laminate roll of the roll end face protection member is disposed so as to be in contact with the end portion of the photosensitive resin laminate in the width direction.

FIG. 1 is a schematic view showing one aspect of the photosensitive resin laminate roll 10. Here, the photosensitive resin laminate 1 includes a support layer 4, a photosensitive resin layer 5 laminated on the support layer, and an optional protective layer 6, which is wound up on the winding core 2. Further, the roll end face protection member 3 is disposed in contact with both end faces of the wound photosensitive resin laminate. Here, the roller end face protection member 3 is in the form of an annular 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 further preferably includes a protective layer laminated on the photosensitive resin layer. The photosensitive resin laminate also includes a photosensitive film called a dry film resist and a dry film photoresist.

The support layer may be any one that supports the photosensitive resin layer. As support for use The layer is preferably a transparent one that transmits light emitted from the exposure source. Examples of the support layer include 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, and A polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, or the like. These films may also be used as needed. From the viewpoint of the resolution, a film having a haze value of 5 or less is preferred. More preferably, the haze value is 3 or less, and further preferably, the haze value is 2.5 or less, and more preferably the haze value is 1 or less. The thickness of the support layer is advantageous in terms of image formation property and economy. However, it is preferable to use 10 to 30 μm in order to maintain heat shrinkage during application of the photosensitive resin composition layer. By. For example, GR19, GR16 manufactured by Teijin Dupont Films, R310-16, R340G16 manufactured by Mitsubishi Plastics Co., Ltd., and TORAY Polyester Film (share) can be cited. FB40 (film thickness: 16 μm), FB60 (film thickness: 16 μm), and the like.

Since the protective layer is sufficiently less in adhesion to the photosensitive resin layer than the support layer, it can be easily peeled off. For example, a polyethylene film, a polypropylene film, an extended polypropylene film or the like can be preferably used as the protective layer. Further, a film excellent in peelability disclosed in Japanese Laid-Open Patent Publication No. SHO 59-202457 can be used. The film thickness of the protective layer is preferably from 10 to 100 μm, more preferably from 10 to 50 μm. For example, GF-18, GF-818, GF-858, etc. manufactured by TAMAPOLY Co., Ltd. are mentioned.

In the photosensitive resin layer, the photosensitive resin composition can be applied onto a support layer and dried to laminate. The thickness of the photosensitive resin layer is preferably from 5 to 100 μm, and more preferably, the upper limit is 50 μm. The closer the thickness of the photosensitive resin layer is to 5 μm, the higher the resolution is, and the closer to 100 μm, the higher the film strength, and therefore it can be appropriately selected depending on the application.

As a method of producing a photosensitive resin laminate, a previously known method can be employed. For example, a photosensitive resin composition for a photosensitive resin layer is mixed with a solvent to prepare a photosensitive resin composition preparation liquid, and the above-mentioned preparation liquid is applied onto a support layer using a bar coater or a roll coater. And drying it, and stacking the photosensitive resin on the support layer A photosensitive resin layer of the composition. The photosensitive resin composition conditioning liquid is preferably blended by adding a solvent at 25 ° C to 500 to 4000 mPa ‧ seconds. The solvent may be appropriately selected from the group consisting of methyl ethyl ketone, acetone, ethanol, methanol, propanol, and propylene glycol from the viewpoints of the viscosity of the photosensitive resin composition, the drying property, the amount of residual solvent, the coatability, and the foamability. Methyl ether, propylene glycol monomethyl ether acetate, toluene, and the like. Then, a protective layer is laminated on the photosensitive resin layer, whereby a photosensitive resin laminate can be produced.

The photosensitive resin layering system is wound up in a long shape on a winding core and used as a roll. The winding length is not particularly limited, and is preferably 320 m or less from the viewpoint of the weight of the roll and the ease of handling. When the number of base materials to be laminated by one photosensitive resin laminate roll is high, the coil length is preferably 100 m or more from the viewpoint of productivity.

(core)

The core is sometimes referred to as the core. The shape thereof is not particularly limited, and may be cylindrical or cylindrical. Since the photosensitive resin laminated system is used as an electronic material as an etching or plating resist and a permanent pattern, it is preferable to carry out a process which does not raise dust, and it is preferable to make it as a plastic resin. The material of the plastic resin is preferably lighter, stronger, and does not cause dust. A polypropylene (PP) resin, an acrylonitrile-butadiene-styrene (ABS) resin, a nylon resin, a polyvinyl chloride resin or the like can be used, and an ABS resin is preferable. The diameter of the core is not particularly limited, and when the photosensitive resin laminate roll is attached to the bonding machine, it is preferably 2 to 5 inches, more preferably 3 inches in diameter, so as to be attachable to the device. The length of the core (the length in the axial direction when a cylindrical or cylindrical core is used) may be the same as or shorter than the width of the photosensitive resin laminate, but is preferably larger than The length of the width of the photosensitive resin laminate is such that an appropriate protrusion can be secured on both sides when the photosensitive resin laminate is wound up. It is preferable since the annular sheet can be attached so that the protruding portion can be inserted. Further, a bearing called a core holder may be fitted to the projecting portion, and stored in a suspended state so that the photosensitive resin laminate roller does not move.

(roll end face protection member)

The roller end face protection member is disposed in contact with the end surface of the wound photosensitive resin laminate. The shape is not particularly limited as long as it covers at least a part of the end surface of the protective roller in contact with the end surface at a constant area, and it is preferable to insert it in contact with the end surface of the wound photosensitive resin laminate. An annular sheet disposed through the projecting portion of the core. Further, it is preferable to have a ring shape which substantially covers the width of the entire end surface of the photosensitive resin laminate roll. The roll end face protecting member may be used only for one end of the wound photosensitive resin laminate, preferably for both ends.

In the case where the roller end face protection member is an annular sheet, the inner diameter of the ring is preferably slightly larger than the outer diameter of the core to be inserted into the core. Further, the center of the annular sheet is slightly deviated from the center of the core, and the outer periphery of the annular sheet is slightly exposed from the outer periphery of the photosensitive resin laminate wound in a roll shape. Thereby, the annular sheet is easily removed, and therefore it is preferably slightly larger than the outer diameter of the core. Specifically, when the inner diameter of the ring is 1.001 times or more of the outer diameter of the core, it is preferably not adhered to the core at the time of mounting. More preferably, it is 1.005 times or more, and further preferably 1.01 times or more. The inner diameter of the ring is preferably 1.1 times or less, more preferably 1.05 times or less, still more preferably 1.03 times or less, from the viewpoint of protecting the entire end surface of the roll and removing foreign matter.

The outer diameter of the ring is preferably 0.99 times or more, more preferably 1 or more times the outer diameter of the photosensitive resin laminate which is wound into a roll, so as to cover the end faces of the photosensitive resin laminate roll. In addition, from the viewpoint of suppressing the packaging material such as the light-shielding cylindrical tube that covers the photosensitive resin laminated body roll, the outer diameter of the ring is preferably 1.1 times or less the outer diameter of the photosensitive resin laminated body roll. More preferably, it is 1.05 times or less, further preferably 1.03 times or less.

The substrate of the roll end face protection member may be exemplified by polyester, polyethylene terephthalate, polyphenylene sulfide, polypropylene, nylon, unstretched, stretched, and biaxially stretched, respectively; and low density. Polyethylene, high density polyethylene, rigid polyvinyl chloride, soft polyvinyl chloride, cellophane, acetate, cellulose triacetate, polystyrene, polycarbonate Plastic resins such as esters and polyimine; and papers treated with anti-dust treatment, road papers treated with anti-dust treatment, and dust-free paper; and papers obtained by laminating paper with the above-mentioned plastic resins, synthetic paper, and the like. Since the photosensitive resin laminated system is used as an electronic material as an etching or plating resist and a permanent pattern, it is preferable to carry out a process which does not raise dust. From the viewpoints of less generation of static electricity, good followability to the end surface, excellent foreign matter removal property, and excellent mountability, the substrate is preferably a dust-proof paper, a dust-proof processed paper, It is made of dust-free paper and paper and the above-mentioned plastic resin. The synthetic paper is preferably a polypropylene-based material.

When the substrate is a dust-proof paper, a dust-proof paper, a dust-free paper, and a paper and a plastic resin, the thickness of the substrate is preferably 50 to 500 μm. From the viewpoint of the mountability, the thickness is preferably 50 μm or more, and is preferably 500 μm or less from the viewpoint of the followability of the end face and the foreign matter removal property. More preferably, it is 60 to 200 μm, and further preferably 60 to 150 μm.

Regarding the roll end face protecting member, the surface may be embossed from the viewpoint of mold release property and antifouling property. The roller end face protection member has an adhesive composition on the side in contact with the end surface of the photosensitive resin laminate roll. The roll end face protection member is preferably an annular sheet having a circular shape in plan view.

Preferably, the annular sheet is disposed on the horizontally extending flat plate such that the annular sheet is present in the air, and the annular sheet is located in the air in the portion farthest from the flat plate. The distance between the front end of the annular sheet and the surface of the flat plate contacting the annular sheet is defined as a bending distance H (mm), and one half of the outer diameter of the annular sheet is set to R ( When mm), H/R is 0.06~0.59. From the viewpoint of the roll end surface mountability of the annular sheet, it is preferably 0.59 or less. More preferably, it is 0.5 or less, More preferably, it is 0.45 or less. From the viewpoint of the followability of the roll end face and the foreign matter removal property, it is preferably 0.06 or more. More preferably, it is 0.1 or more, More preferably, it is 0.15 or more.

The measurement method of the bending distance H is as follows. First, as shown in Figure 2, The annular sheet 3 is provided on the substantially flat plate 7 which protrudes in the horizontal direction (the direction perpendicular to the vertical direction). At this time, the surface having the adhesive is faced upward so that the annular sheet 3 is not attached to the flat plate 7. The annular sheet is fixed such that one half of the annular sheet 3 is present in the air, and even if the center of the annular sheet 3 reaches the substantially linear end edge existing at the end portion of the flat plate. When it is fixed, it can also be fixed by the fixing member 8 as shown in FIG. At this time, the annular sheet 3 is not warped or bent by the influence of gravity. Using an L-shaped ruler to contact the annular sheet at the front end of the annular sheet which is the farthest from the end of the flat plate in the portion of the annular sheet (the portion exposed from the end portion) The distance in the vertical direction of the imaginary plane formed by the surface was measured. The measurement location is set to Fuji City, Shizuoka Prefecture.

(adhesive composition)

In the adhesive composition, when the roll end face protecting member is peeled off, no paste remains on the end face of the photosensitive resin film, and a known adhesive composition is selected in such a manner that the roll end face protecting member does not adhere to the photosensitive resin when the roll end face protecting member is peeled off.

Among them, from the viewpoint of foreign matter removal property and mold release property, an acrylic resin is preferably contained. Furthermore, it is preferable that the photosensitive resin composition is an alkali-soluble polymer containing a carboxyl group, an addition polymerizable monomer, and photopolymerization from the viewpoint of having a high degree of foreign matter removal property and mold release property. The photosensitive resin composition of the initiator, and the adhesive composition contains an acrylic resin.

The adhesive composition preferably contains particles, and preferably 50% by mass or more of the particles are those having a diameter of 80 to 120% of the coating thickness of the adhesive composition, and the content of the particles is relative to the adhesive 100. The parts by weight are from 5 parts by weight to 30 parts by weight. Further, the diameter of the particles was observed by a microscope, and the maximum diameter was observed for any of the 100 particles, and the average value was calculated.

The diameter of the particles is preferably 80% or more from the viewpoint of mold release property, and is preferably 120% or less from the viewpoint of adhesion. More preferably, it is 90 to 110%, and further preferably 100%.

Particles are usually theoretically a single particle size, but in practice they are mostly difficult to obtain. It is preferred that the particle size distribution be as narrow as possible, i.e., have a steep grain size curve.

It is preferable that 50% by mass or more of the total amount of the adhesive is a diameter of 80 to 120% of the coating thickness of the adhesive. From the viewpoint of the balance between mold release property and adhesiveness, it is more preferably 70% by mass or more, and still more preferably 80% by mass or more.

The content of the particles is preferably from 5 parts by weight to 30 parts by weight based on 100 parts by weight of the adhesive. From the viewpoint of the escape property of the air bubbles in the case of the attachment, it is preferably 5 parts by weight or more, and preferably 30 or less from the viewpoint of adhesion. More preferably, it is 10 parts by weight to 25 parts by weight. In the case where the material of the particles is glass, it is preferably 15 to 30 parts by weight, and in the case of plastic, it is preferably 5 to 25 parts by weight.

The material of the particles is preferably plastic or inorganic. Examples of the plastic include polymethacrylate type, polyethylene methacrylate type, polystyrene type, polystyrene acrylic type, polyethylene type, polypropylene type, and polystyrene-butadiene type. Polystyrene-divinylbenzene-based, polyurethane-based, polybenzoguanamine-based, and melamine-based. Examples of the inorganic material include glass, cerium oxide (cerium phosphate mineral), and calcium carbonate.

The adhesion of the adhesive can be increased by lowering the softening temperature of the composition as a whole or increasing the polarity of the resin component.

The adhesion between the end face 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 property and mountability.

Further, the adhesion was measured in the following manner. That is, a low-density polyethylene film (LDPE) sheet is attached to the surface of the end face protection member on which the layer of the adhesive composition is formed by a hand pressure roller. The low density polyethylene film used was GF-858 manufactured by TAMAPOLY Co., Ltd. It was cut into a short strip having a width of 1 inch and a length of 15 cm, and was subjected to humidity control at a relative humidity of 50% and 23 ° C for 11 hours. Tensile test at a tensile speed of 100 mm/min under a load of 1 kg using Tensilon RTM-500 manufactured by Orientec Co., Ltd. Test. At this time, the end face protection member of the sample was clamped (fixed) under the Tensilon, and the low-density polyethylene film was clamped (fixed) with a tensile portion, and a tensile test was performed. In the tensile test, the integral average of the load was taken in the interval of 10 mm to 50 mm, and the average of the number of times of the test was taken twice, and this was set as the value of the adhesion.

(Manufacturing method of photosensitive resin laminated body roll)

The photosensitive resin laminate roll is preferably coated with a light-shielding sheet from the viewpoint of suppressing adhesion of foreign matter and light absorption during conveyance. The light shielding sheet may also be referred to as a light shielding film. The light-shielding sheet can be coated so as to be wound around a photosensitive resin laminate roll. As shown in FIG. 3, when the light-shielding sheet 9 is in the form of a cylinder, it can be coated by inserting the photosensitive resin roller 1 into the cylinder, which is preferable. Further, when the length of the cylinder is longer than the core 2 of the photosensitive resin laminate roll 1, as shown in Fig. 3, the adhesion of the foreign matter can be further suppressed by folding the portion longer than the core 2 into the core of the core. Sensitive, so better.

The light-shielding sheet is preferably made of polyethylene from the viewpoint of protecting the photosensitive resin laminate roll from, for example, damage from contact with a lightweight drop or slight contact with the package container. The film thickness is preferably 10 μm or more from the viewpoint of maintaining moderate strength and suppressing pinholes, and is preferably 300 μm or less from the viewpoint of workability. More preferably, it is 20 to 200 μm, and further preferably 30 to 130 μm. In order to improve the light blocking property, it is preferably black.

Preferably, the photosensitive resin laminate roll is suspended and fixed by a member called a core seat formed with a convex portion fitted to the winding core. By fixing by suspension, it is possible to prevent the photosensitive resin laminate from coming into contact with the bottom wall surface of the packaging container during transportation. As the core seat, for example, those described in JP-A-2004-42952 and JP-A-2003-89477 can be cited.

When the photosensitive resin laminate roll is covered with a light-shielding sheet, if the portion of the light-shielding sheet longer than the core is folded into the core, and the core portion is further attached via the folded portion, It is preferable to suppress adhesion and sensitization of foreign matter.

(Photosensitive resin composition)

The photosensitive resin composition preferably contains (a) an alkali-soluble polymer having a carboxyl group, (b) an addition polymerizable monomer, and (c) a photopolymerization initiator.

The photosensitive resin composition is preferably a viewpoint that the amount of the paste remaining on the end surface of the roll is small when the annular sheet is peeled off from the end surface of the roll, and the adhesion of the photosensitive resin composition to the annular sheet is also small. Contains the above (a) to (c).

(a) an alkali-soluble polymer containing a carboxyl group

(a) The alkali-soluble polymer having a carboxyl group is preferably a monomer having an α,β-unsaturated carboxyl group as a polymerization component, and the alkali-soluble polymer has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000. The carboxyl group in the alkali-soluble polymer containing a carboxyl group is required to make the photosensitive resin composition developable or releasable to a developing solution or a peeling liquid containing an alkaline aqueous solution. The acid equivalent refers to the mass of the alkali-soluble polymer having one equivalent of a carboxyl group. The lower limit of the acid equivalent is preferably 250, and more preferably, the upper limit is 450. (a) The acid equivalent of the alkali-soluble polymer containing a carboxyl group improves the development resistance, the resolution, and the adhesion, and further secures other components in the solvent or the photosensitive resin composition, especially later (b) The compatibility of the addition polymerizable monomer is preferably 100 or more, and is preferably 600 or less in terms of improvement in developability and peelability. The measurement of the acid equivalent was carried out by a potentiometric titration method using a Pingyu automatic titrator (COM-555) manufactured by Hiranuma Industries Co., Ltd. using 0.1 mol/L of sodium hydroxide.

(a) The weight average molecular weight of the alkali-soluble polymer containing a carboxyl group is preferably from 5,000 to 500,000. With respect to the weight average molecular weight, the thickness of the photosensitive resin laminate is maintained to be uniform and the resistance to the developer is obtained. Further, in terms of suppressing edge melting, it is preferably 5,000 or more, and the developability is maintained. From the viewpoint, it is preferably 500,000 or less. The term "edge melting" refers to a phenomenon in which the photosensitive resin composition oozes from the end surface of the roll when the photosensitive resin laminate is wound into a roll. The photosensitive resin composition which has bleed out adheres to the photosensitive resin composition oozing out from the adjacent photosensitive resin layer via the support layer protective layer in the roll state. Adhesion When the photosensitive resin composition which melts a roll-form photosensitive resin laminated body is laminated, the resin composition is peeled from the end surface, and the resist debris is scattered. If the resist fragments adhere to the laminated substrate, they will adhere to the mask for exposure again, and will be hardened by exposure, and will be blocked in the case of the negative resist, resulting in defect of the pattern.

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

(a) The weight average molecular weight of the alkali-soluble polymer containing a carboxyl group can be measured using a gel permeation chromatograph manufactured by JASCO Corporation, under the following conditions: differential refractometer: RI-1530

Pump: PU-1580

Deaerator: DG-980-50

Column oven: CO-1560

Column: in order, KF-8025, KF-806M×2, KF-807

Dissolution: THF (tetrahydrofuran, tetrahydrofuran).

(a) The alkali-soluble polymer containing a carboxyl group is preferably a (co)polymer containing, as a component, one or more 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 a maleic acid half ester are mentioned. Among them, (meth)acrylic acid is particularly preferred.

The second monomer is a monomer that is non-acidic and has 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, (A) Isobutyl acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (A) Ethyl alcohol esters such as 2-hydroxypropyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, etc. Acrylonitrile, styrene, and a polymerizable styrene derivative. Among them, methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, and benzyl (meth)acrylate are preferred, and styrene is particularly preferably used from the viewpoint of resolution.

(a) The alkali-soluble polymer containing a carboxyl group is preferably synthesized by adding an appropriate amount to a solution obtained by mixing the above monomers and diluting with a solvent such as acetone, methyl ethyl ketone or isopropyl alcohol. The radical polymerization initiator, for example, benzamidine peroxide or azoisobutyronitrile, is heated and stirred. There is also a case where a part of the mixture is dropped into the reaction liquid and synthesized. Further, after the completion of the reaction, a solvent is 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 can also be used.

Further, (a) the copolymerization ratio of the first monomer having a carboxyl group to the second monomer is from 10 to 60% by mass of the first monomer and from 40 to 90% by mass of the second monomer. Further preferably, the first monomer is 15 to 35 mass%, and the second monomer is 65 to 85 mass%.

More specific examples of the (a) alkali-soluble polymer having a carboxyl group include a polymer containing methyl methacrylate, methacrylic acid, and styrene as a copolymerization component, and methyl methacrylate or the like. A polymer of a base polymer of acrylic acid and n-butyl acrylate as a copolymerization component, and a polymer containing benzyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate as a copolymerization component.

The content of the (a) carboxyl group-containing alkali-soluble polymer 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. %. With respect to the content of the (a) carboxyl group-containing alkali-soluble polymer, the alkali developability of the photosensitive resin composition is maintained, and the resist pattern formed by exposure and development has characteristics as a resist, for example, a cover. From the viewpoint of sufficient resistance in the hole, etching, and various plating steps, it is preferably 20% by mass or more, and the photosensitivity before hardening The resin composition and the resist pattern after curing have sufficient flexibility, and are preferably 90% by mass or less.

(b) Addition polymerizable monomer

(b) The addition polymerizable monomer is a compound having at least one polymerizable ethylenically unsaturated bond in the molecule. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group. Further, from the viewpoint of high resolution, edge melting property and capping property, at least one bisphenol A-based (meth) acrylate compound is preferably used as the (b) addition polymerizable monomer.

In the present specification, the bisphenol A-based (meth) acrylate compound means a carbon-carbon unsaturated double bond having a (meth) acryl fluorenyl group or a (meth) acrylonitrile group derived from a double A compound of the phenol A-C6H4-C(CH3)2-C6H4- group. Specific examples include dimethyl acrylate of polyethylene glycol obtained by adding an average of two units of ethylene oxide to both ends of bisphenol A (NK manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Ester BPE-200) or a polyethylene glycol dimethacrylate ester obtained by adding an average of 5 units of ethylene oxide to both ends of bisphenol A (NK Ester BPE, manufactured by Shin-Nakamura Chemical Co., Ltd.) -500), a dialkyl diol obtained by adding an average of 6 units of ethylene oxide to an average of 2 units of propylene oxide at both ends of bisphenol A, and bisphenol A The two ends are respectively added with an average of 15 units of ethylene oxide and an average of 2 units of propylene oxide to form a dialkyl diol methacrylate.

As the (b) addition polymerizable monomer, a known compound having at least one ethylenically unsaturated group may be used in addition to the above compound. For example, 4-mercaptophenyl heptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxy hexaethylene glycol acrylate, phthalic anhydride and acrylic acid a reaction of a half-ester compound of 2-hydroxypropyl ester with propylene oxide (trade name: OE-A 200, manufactured by Nippon Shokubai Chemical Co., Ltd.), 4-n-octylphenoxypentapropylene glycol acrylate, 1,6-hexane Polyoxyalkylene such as alcohol (meth) acrylate, 1,4-cyclohexane diol di(meth) acrylate, polypropylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate Glycol di(meth)acrylate, 2-di (p-hydroxyphenyl)propane di(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol penta(meth)acrylate, trimethylolpropane triglycidyl ether tri(meth)acrylate, 2,2-bis(4-methylpropenyloxypentaethoxyphenyl)propane, hexamethylene diisocyanate and urethane of propylene glycol monomethacrylate containing urethane A polyfunctional (meth) acrylate of an ester group, a polyfunctional (meth) acrylate of an isomeric cyanurate compound, or the like. These may be used alone or in combination of two or more kinds, or 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% by mass, and more preferably 15 to 70% by mass based on the total solid content of the photosensitive resin composition. . The content of the (b) addition polymerizable monomer is 5% by mass or more from the viewpoint of the resolution of the resolution, the adhesion, and the formation of the copper wire, and is 75 in terms of the flexibility of the cured film. Below mass%.

(c) Photopolymerization initiator

As the (c) photopolymerization initiator, a photopolymerization initiator which is generally used as a photosensitive resin can be suitably used, and a hexaarylbisimidazole (hereinafter also referred to as a triaryl imidazolyl dimer) can be preferably used. .

Examples of the triarylimidazolyl dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer (hereinafter also referred to as "2,2'-bis(2-). Chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-bisimidazolium), 2,2',5-tris-(o-chlorophenyl)-4-(3, 4-Dimethoxyphenyl)-4',5'-diphenylimidazolyl dimer, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxybenzene 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'-tetra-(3- Methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetra-(3-methoxy Phenyl)-imidazolyl dimer, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetra-(3- Methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetra-(3-methoxybenzene Imidazolyl dimer, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazole Dimer, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-imidazolyl Polymer, 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'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2 , 2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2 '-Bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'- Bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'- Bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, and 2,2' Bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer.

In particular, the 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer is preferably a photopolymerization initiator having a high effect on the strength of the resolving or hardening resist film, and is preferably used. Use. These may be used alone or in combination of two or more. Further, it may be used together with the following acridine compound, pyrazoline compound or the like.

In a preferred embodiment, an acridine compound or a pyrazoline compound is used as (c) a photopolymerization initiator. Examples of the acridine compound include acridine, 9-phenyl acridine, 9-(4-methylphenyl)acridine, 9-(4-methoxyphenyl)acridine, and 9-(4-hydroxyl group. Phenyl) acridine, 9-ethyl acridine, 9-chloroethyl acridine, 9-methoxyacridine, 9-ethoxy acridine, 9-(4-methylphenyl)acridine, 9-(4-ethylphenyl)acridine, 9-(4-n-propylphenyl)acridine, 9-(4-n-butylphenyl)acridine, 9-(4-tert-butyl Phenyl) acridine, 9-(4-ethoxyphenyl)acridine, 9-(4-ethylphenylphenyl)acridine, 9-(4-dimethylaminophenyl)acridine, 9 -(4-chlorophenyl)acridine, 9-(4-bromophenyl)acridine, 9-(3-methylphenyl)acridine, 9-(3-tert-butylphenyl)acridine, 9-(3-ethylmercaptophenyl Acridine, 9-(3-dimethylaminophenyl) acridine, 9-(3-diethylaminophenyl) acridine, 9-(3-chlorophenyl)acridine, 9-(3) -Bromophenyl)acridine, 9-(2-pyridyl)acridine, 9-(3-pyridyl)acridine, 9-(4-pyridyl)acridine. Among them, 9-phenyl acridine is preferred.

As the pyrazoline compound, 1-phenyl-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-( 4-(benzo Zin-2-yl)phenyl)-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-phenyl-3- (4-biphenyl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-t-octyl -Phenyl)-pyrazoline.

Examples of the photopolymerization initiator other than the above include 2-ethyl hydrazine, octaethyl hydrazine, 1,2-benzopyrene, 2,3-benzopyrene, and 2-phenyl. Bismuth, 2,3-diphenylanthracene, 1-chloroindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-di Anthraquinones such as methyl hydrazine and 3-chloro-2-methyl hydrazine, benzophenone, and misoketone [4,4'-bis(dimethylamino)benzophenone], and 4 , aromatic ketones such as 4'-bis(diethylamino)benzophenone, benzoin ethers such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin, benzoin dimethyl condensate Ketone, benzoin diethyl ketal, 9-oxo sulfur Combination with alkylaminobenzoic acid, 1-phenyl-1,2-propanedione-2-O-benzoin, 1-phenyl-1,2-propanedione-2-(O-B An oxoester such as oxycarbonyl)anthracene.

Furthermore, as the above 9-oxygen sulfur A combination of a class and an alkylaminobenzoic acid, for example, ethyl-9-oxygen sulfide Combination with ethyl dimethylaminobenzoate, 2-chloro-9-oxosulfur Combination with ethyl dimethylaminobenzoate and isopropyl-9-oxosulfur In combination with ethyl dimethylaminobenzoate. Further, an N-arylamino acid can also be used. 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 (c) photopolymerization initiator 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, and more preferably 0.05% by mass, and further preferably 0.05% by mass. A more preferred lower limit is 0.1% by mass, a more preferred upper limit is 15% by mass, and a still more preferred upper limit is 10% by mass. The content of the (c) photopolymerization initiator is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity in the photopolymerization by exposure, and the light is sufficiently transmitted to the photosensitive resin at the time of photopolymerization. The bottom surface of the composition (that is, the portion farther from the light source) has a good resolution and adhesion, and is 30% by mass or less.

(e) Other additives

The photosensitive resin composition may contain various additives in addition to the components (a) to (c) described above. Specifically, for example, a coloring matter such as a dye or a pigment is contained. Examples of the coloring matter include phthalocyanine green, crystal violet, methyl orange, Nero blue 2B, Victoria blue, malachite green, basic blue 20, and diamond green.

When the coloring matter is contained, the amount of the coloring matter 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 coloring matter added is 0.001% by mass or more, the effect of improving the workability is obtained, and when it is 1% by mass or less, the storage stability is maintained.

Further, a coloring agent may be contained in the photosensitive resin composition to impart a visible image by exposure. Examples of the chromogenic dye include a leuco dye or a combination of a fluoran dye and a halogen compound.

For example, as a leuco dye, tris(4-dimethylamino-2-methylphenyl)methane [leuco crystal violet], tris(4-dimethylamino-2-methylphenyl) ) methane [hidden malachite green], and fluoran dye. Among them, in the case of using leuco crystal violet, the contrast is good, so that it is preferable.

Examples of the halogen compound include bromopentane, bromoisopentane, bromoisobutane, dibromoethane, diphenylbromide, dibromon toluene, dibromomethane, tribromomethylphenylhydrazine, and tetra. Carbon bromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro-2,2-bis(p-chloro Phenyl) ethane, hexachloroethane, chlorination Compounds, etc.

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

Further, in order to improve the thermal stability and storage stability of the photosensitive resin composition, it is preferred that the photosensitive resin composition contains a radical polymerization inhibitor, or a benzotriazole or a carboxybenzotriazole. At least one or more compounds of the group consisting of.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, and 2,6-di. Tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6- Tributylphenol), nitrosophenylhydroxylamine aluminum salt, diphenylnitrosamine.

Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis(N-2-ethylhexyl)amino group. Methylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyl) Aminomethylmethylene-1,2,3-benzotriazole.

Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and (N,N-dibutyl). Amino) carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl Aminomethylenecarboxybenzotriazole, N-(N,N-di-2-ethylhexyl)amine-extended ethylcarboxybenzotriazole.

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

The photosensitive resin composition may contain other plasticizers as needed. The plasticizer may, for example, be a compound obtained by modifying bisphenol A with a polyalkylene oxide.

In addition, for example, a sorbitan derivative such as polyoxyethylene sorbitan cinnamate or polyoxyethylene sorbitan oleate, or a polyalkylene glycol such as polyethylene glycol or polypropylene glycol may be used. Phthalates such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl citrate triacetate, acetamidine A plasticizer such as tri-n-propyl citrate or tri-n-butyl citrate. It is especially preferred to use a sorbitol anhydride derivative and a polyalkylene glycol.

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

[Examples]

Hereinafter, the description will be more specifically described in the examples, but the invention is not limited thereto.

First, the preparation methods of the samples for evaluation of the examples and the comparative examples will be described, and then the evaluation methods for the obtained samples and the evaluation results thereof will be disclosed. Here, an annular sheet is used as the roller end face protection member.

(Examples 1 to 12, Comparative Example 1) 1. Production of samples for evaluation

The samples for evaluation in the examples and the comparative examples were produced in the following manner.

<Production of Photosensitive Resin Laminate>

Composition 1 shown in Table 1 below (wherein the number of each component is expressed as a solid matter) The amount of the metering (parts by mass). The abbreviations in Table 1 are prepared by mixing and mixing the solvent with a solvent to prepare a photosensitive resin composition, and preparing a polyethylene terephthalate film having a thickness of 16 μm (manufactured by Mitsubishi Resin Co., Ltd.). R310) As a support, a photosensitive resin composition conditioning liquid is uniformly applied onto the surface of the polyethylene terephthalate film by a die coater and dried to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 15 μm. Then, a polyethylene film (GF-858 manufactured by TAMAPOLY Co., Ltd.) having a thickness of 33 μm was attached to the surface of the uncovered polyethylene terephthalate film of the photosensitive resin layer as a protective layer to obtain a photosensitive resin layer. Body 1.

In the photosensitive resin laminate 1 described above, the composition 1 is prepared in the same manner as the photosensitive resin laminate 1 except that the composition 1 is the composition 2 to 6, and the photosensitive resin laminate 2 is obtained. 6. In the photosensitive resin laminate 1 described above, the composition 1 is used in the same manner as the photosensitive resin laminate 1 except that the composition 1 is 10 to 10 and the thickness of the photosensitive resin layer is 10 μm. The photosensitive resin laminates 7 to 10 were obtained.

<Production of photosensitive resin laminated body roll>

For the annular sheet, the sheets shown in Tables 3 to 5 were used. The adhesive composition containing the acrylic resin of the annular sheet was directly used as an adhesive composition of Elleair Tack NS80/SBG85S/re-peeling (manufactured by Elleair Texel Co., Ltd.) unless otherwise specified.

Regarding the samples F and G, the adhesive composition was adjusted in the following manner. In other words, B-1 and M-8 shown in Table 2 were prepared so as to have a solid content ratio of 45:55 and 40:60, and applied to the substrate so that the film thickness after drying became 15 μm. Dry and adjust.

The photosensitive resin laminate 1 was cut into a strip having a width of 495 mm, and wound on a winding core (core) of an 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 in a roll shape was 180 mm.

The photosensitive resin laminate which is wound around the core and which is in the form of a roll is held by a rod-shaped stainless steel holder which is fixed at the other end and can be kept horizontal.

A photosensitive resin laminate having a roll shape was coated 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 holder, and the roll was placed on a cushion which was designed to have a width of 330 mm and a height of 100 mm and an upper portion bent into a concave shape to fix the roller.

One end of the light-shielding polyethylene tube was folded back to expose the end surface of the roll-shaped photosensitive resin laminate, and an annular sheet was attached. On the other end, the annular sheet was attached in the same manner to form a photosensitive resin laminate roll 1.

The light-shielding polyethylene tube was folded into the core and attached to a core seat which was designed to have a convex shape at the center and fitted to the core, and the photosensitive resin roller 1 was bundled.

2. Evaluation criteria

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

(1) Foreign matter removal

The annular sheet was peeled off from the photosensitive resin laminate roll, and it was confirmed whether the foreign material adhered to the annular sheet. The rating is as follows.

○: Foreign matter adheres to the annular sheet. The other adhesive tape was peeled off from the end surface of the roller, and the adhesion of the foreign matter could not be confirmed.

△: The foreign matter adhered to the annular sheet, but the other adhesive tape was peeled off from the end surface of the roll, and as a result, adhesion of the foreign matter was confirmed on the adhesive tape.

×: Foreign matter was not attached to the annular sheet. When the other adhesive tape is peeled off from the end surface of the roller, adhesion of the foreign matter is confirmed.

(2) Annular sheet mountability

The roll is produced as described in the above <Preparation of photosensitive resin laminated roll>, as follows As described above, the mountability when the annular film is attached to the end surface of the roll is graded.

○: The annular sheet can be simply mounted. It can be attached without wrinkles when attached to the end surface of the roll.

△: The annular sheet is in close contact with the holder or the core, and installation takes time. When attached to the end face of the roll, a part of the wrinkles or air enters.

×: The annular sheet is in close contact with the holder or the core, and installation takes time. When the annular sheet attached to the undesired portion is peeled off and attached again, the annular sheet is elongated and deformed or broken, and it is difficult to adhere to the end surface of the roll.

(3) Adhesiveness of packaging materials of annular sheets

After the roll was produced as described in the above <Preparation of photosensitive resin laminated roll>, it was unwound. It is observed whether or not the annular sheet is attached to the end surface as in the case of unbundling, and is graded as follows.

○: Installed in the same way as during installation.

△: The unbounded sheet was attached to the light-shielding cylindrical polyethylene sheet at the time of unbundling, and a part of the portion peeled off from the end surface.

X: The unbounded sheet was attached to a light-shielding cylindrical polyethylene sheet at the time of unbundling, and was peeled off together with the light-shielding cylindrical polyethylene sheet.

(4) Removal of annular sheet

After the roll was produced as described in the above-mentioned <Preparation of Photosensitive Resin Laminate Roll>, the roll was unwound, and the annular sheet was peeled off by a hand wearing a resin glove. The workability at the time of peeling is graded as follows.

○: The annular sheet can be easily peeled off within 5 seconds.

△: It takes 5 seconds or more for the peeling of the annular sheet.

(5) Number of foreign objects

Four roll-shaped photosensitive resin laminates were produced as described above in the "Production of Photosensitive Resin Laminate Roll". Remove foreign matter from the end faces of all the rolls, making a difference among the 14 The objects were arbitrarily attached to the end faces of the rolls at a total of four places. Thereafter, the annular sheet was attached to all the rolls and peeled off, and the foreign matter adhering to the end faces of the rolls was counted.

A photosensitive resin laminate is produced in the same manner as the photosensitive resin laminate roll 1 except that the photosensitive resin laminate 1 is used as the photosensitive resin laminates 2 to 6 and the sample B is used as the annular sheet. The rolls were set as photosensitive resin laminate rolls 2 to 6. Evaluation of (1) to (5) was carried out using the photosensitive resin rolls 2 to 6, and as a result, the same results as in the case of using the photosensitive resin laminate roll 1 were obtained.

The photosensitive resin laminate 1 was used as the photosensitive resin laminates 7 to 10, and the sample B was used as the annular sheet, and the outer diameter of 180 mm was set to an outer diameter of 176 mm. A photosensitive resin laminate roll was produced in the same manner as the photosensitive resin laminate roll 1 and used as the photosensitive resin laminate roll 7 to 10. The outer diameter of the photosensitive resin laminate which was taken up in a roll shape was 176 mm. Evaluation of (1) to (5) was carried out using the photosensitive resin rolls 7 to 10, and as a result, the same results as in the case of using the photosensitive resin laminate roll 1 were obtained.

[Industrial availability]

Since the photosensitive resin laminate roller can easily remove foreign matter during unbundling, it can be used for processing of precision equipment and electronic materials, and can also be used as a permanent pattern incorporated in precision equipment and electronic materials.

1‧‧‧Photosensitive resin laminate

2‧‧‧Volume core

3‧‧‧Roll end face protection member (annular sheet)

4‧‧‧Support layer

5‧‧‧Photosensitive resin layer

6‧‧‧Protective layer

10‧‧‧Photosensitive resin laminated roller

Claims (27)

A photosensitive resin laminated body roll in which a photosensitive resin laminated body is wound around a winding core and formed into a roll shape, and the roll end face protecting member is placed in contact with an end surface of the wound photosensitive resin laminated body. And the roller end face protection member has an adhesive composition on a side in contact with the end surface of the roller, wherein the length of the winding core is longer than the width of the photosensitive resin laminate, and the roller end face protection member is provided in a roll-like photosensitive The annular sheet of the end surface of the resin laminated body is inserted into the protruding portion of the winding core to be provided with the annular sheet, and the annular sheet is placed horizontally in such a manner that half of the annular sheet is present in the air. In the flat plate, the distance between the front end of the annular sheet which is farthest from the flat plate and the side of the flat plate which is in contact with the annular sheet is the bend in the portion of the annular sheet which is present in the air. When the folding distance is H (mm), when one half of the outer diameter of the annular sheet is R (mm), the H/R is 0.06 to 0.59, and the photosensitive resin laminate includes at least a support layer and a laminate in the support. A photosensitive resin layer on the layer. The photosensitive resin laminate roll of claim 1 is coated with a light-shielding sheet. The photosensitive resin laminate roll of claim 2, wherein the light shielding sheet has a cylindrical shape. The photosensitive resin laminate roll according to any one of claims 1 to 3, wherein the inner diameter of the annular sheet is 1 to 1.1 times the outer diameter of the core. The photosensitive resin laminate roller according to any one of claims 1 to 3, wherein an adhesion of the end face protection member to the low-density polyethylene film is 5 gf/inch to 250 gf/inch. The photosensitive resin laminate roll according to any one of claims 1 to 3, wherein the substrate of the roll end face protection member is a non-dusting paper, a low dust paper, a synthetic paper, or a paper and a resin substrate. By. The photosensitive resin laminate roller according to any one of claims 1 to 3, wherein the photosensitive resin layer is a layer containing a photosensitive resin composition, and the photosensitive resin composition contains an alkali-soluble polymer containing a carboxyl group, A polymerizable monomer, a photopolymerization initiator. The photosensitive resin laminate roll according to claim 7, wherein the alkali-soluble polymer containing a carboxyl group is obtained by copolymerizing styrene or a derivative thereof. The photosensitive resin laminate roll according to claim 7, wherein the addition polymerizable monomer contains a bisphenol A-based (meth) acrylate compound. The photosensitive resin laminate roll of claim 7, wherein the photopolymerization initiator comprises hexaarylbiimidazole or a derivative thereof. The photosensitive resin laminate roll according to any one of claims 1 to 3, wherein the above-mentioned adhesive composition contains an acrylic resin. The photosensitive resin laminate roller according to any one of claims 1 to 3, wherein the adhesive composition contains an adhesive and particles, and 50% by mass or more of the particles is 80% of the coating thickness of the adhesive composition. It is a diameter of ~120%, and the content of the particles is 5 parts by weight to 30 parts by weight with respect to 100 parts by weight of the adhesive. A method for producing a photosensitive resin laminated body roll, which is obtained by winding a photosensitive resin laminated body on a winding core to form a roll and contacting an end surface of the wound photosensitive resin laminated body. A method of manufacturing a photosensitive resin laminate roll having a roll end face protection member, wherein the length of the core is longer than a width of the photosensitive resin laminate, the photosensitive resin laminate comprising at least a support layer and laminated on the support layer On the photosensitive resin layer, The roller end face protection member is provided with an adhesive composition on the side in contact with the end surface of the roller, and is integrally provided or divided into a plurality of portions, and is provided on the end surface of the photosensitive resin laminate which is wound into a roll shape, and is equipped with a roll. An annular sheet having an inner diameter of the roll-shaped photosensitive resin laminate and having an inner diameter of 1 to 1.1 times the outer diameter of the core is provided so that the annular sheet is halfway in the air. On the horizontally extending flat plate, the distance between the front end of the annular sheet which is farthest from the flat plate and the side of the flat plate which is in contact with the annular sheet is located in the portion of the annular sheet which is present in the air. When the bending distance H (mm) is one and a half of the outer diameter of the annular sheet is R (mm), H/R is 0.06 to 0.59. The method for producing a photosensitive resin laminate roller according to claim 13, wherein the inner diameter of the annular sheet is 1.001 to 1.1 times the outer diameter of the core, and is inserted into the protruding portion of the winding core. The method for producing a photosensitive resin laminate roll according to claim 13 or 14, wherein the annular sheet and the low-density polyethylene film have an adhesion of 5 gf/inch to 250 gf/inch. A method of packaging a photosensitive resin laminated body roll, which is characterized in that a photosensitive resin laminate roll is produced by the method according to any one of claims 13 to 15, and further coated with a cylindrical light-shielding sheet. An annular sheet for winding a film onto a core to be a roll-shaped film roll, wherein the length of the core is longer than the width of the film, and the inner diameter of the annular sheet is a core 1 to 1.1 times the outer diameter, and the annular sheet is in contact with the end surface of the wound film, and has an adhesive composition on the side in contact with the end surface, and is inserted into the protruding portion of the winding core. On the film roll, the annular sheet is placed horizontally in such a manner that half of it is in the air. On the extended flat plate, the distance between the front end of the annular sheet which is farthest from the flat plate and the side of the flat plate which is in contact with the annular sheet in the portion of the annular sheet which is present in the air is set as When the bending distance H (mm) is one and a half of the outer diameter of the annular sheet is R (mm), H/R is 0.06 to 0.59. The annular sheet of claim 17, wherein the film is a photosensitive resin laminate. The annular sheet of claim 17 or 18 has an adhesion to the low density polyethylene film of 5 gf/inch to 250 gf/inch. The annular sheet of claim 17 or 18, which has a substrate that is free of dust-proof paper, low-dust paper, synthetic paper, or a paper and a resin substrate. The annular sheet according to claim 18, wherein the photosensitive resin layer is a layer containing a photosensitive resin composition containing an alkali-soluble polymer containing a carboxyl group, an addition polymerizable monomer, and photopolymerization. Starting agent. The cyclic sheet according to claim 21, wherein the alkali-soluble polymer having a carboxyl group is obtained by copolymerizing styrene or a derivative thereof. The cyclic sheet according to claim 21 or 22, wherein the addition polymerizable monomer comprises a bisphenol A-based (meth) acrylate compound. The cyclic sheet of claim 21 or 22, wherein the photopolymerization initiator comprises hexaarylbiimidazole or a derivative thereof. The annular sheet of claim 17 or 18, wherein the above adhesive composition comprises an acrylic resin. The annular sheet according to claim 17 or 18, wherein the adhesive composition contains an adhesive and particles, and 50% by mass or more of the particles are those having a diameter of 80 to 120% of a coating thickness of the adhesive composition. And the content of the particles is from 5 parts by weight to 30 parts by weight based on 100 parts by weight of the adhesive. A film roll which is coated with a light-shielding sheet and which is provided with the annular sheet of any one of claims 17 to 26.