KR20190018037A - Photosensitive resin laminate roll - Google Patents

Abstract

Provided is a photosensitive resin laminate roll capable of simply removing foreign matters from a cross section of a photosensitive resin laminate roll when releasing the roll. This photosensitive resin laminated body roll is a photosensitive resin laminated body roll in which a laminated photosensitive resin layer is wound in a roll on a core and the roll end face protective member is disposed so as to come into contact with the end face of the wound photosensitive resin laminate, Comprises a pressure-sensitive adhesive composition on the side in contact with the roll section, and the photosensitive resin laminate includes at least a support layer and a photosensitive resin layer laminated on the support layer.

Description

[0001] PHOTOSENSITIVE RESIN LAMINATE ROLL [0002]

The present invention relates to a photosensitive resin laminate roll.

BACKGROUND ART [0002] Conventionally, several aspects are disclosed as a packing of a photosensitive element. For example, there is disclosed a wrapping in which a cross-sectional protective member is disposed to protect a roll cross section (Patent Document 1).

Japanese Laid-Open Patent Publication No. 2005-41537

A 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 face of a roll of a photosensitive resin laminate when a roll is unwound.

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

[One]

The photosensitive resin laminate is wound in a rolled form on the core,

A roll of a photosensitive resin laminated body in which a roll section protecting member is arranged so as to come into contact with an end face of a wound photosensitive resin laminate,

Wherein the roll section protection member has a pressure-sensitive adhesive composition on a side in contact with the roll section,

Wherein the photosensitive resin laminate comprises at least a support layer and a photosensitive resin layer laminated on the support layer.

[2]

A photosensitive resin laminated body roll according to [1], characterized in that it is covered with a light-shielding sheet.

[3]

The photosensitive resin laminated body roll according to [2], wherein the light-shielding sheet is cylindrical.

[4]

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

The roll-side protection member is a ring-shaped sheet provided on an end face of a photosensitive resin laminate wound in a roll form, and the ring-shaped sheet is inserted into the projection of the winding core through the insertion hole. Photosensitive resin laminate roll.

[5]

The photosensitive resin laminated body 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]

Wherein the ring-shaped sheet is provided so as to be in the air in a state of being projected horizontally, and the tip end of the ring-shaped sheet which is farthest from the flat plate in a portion in the air of the ring- (4), wherein the ratio of H / R is 0.06 to 0.59, wherein a distance between the contacting surface and the contacting surface is defined as a bending distance H (mm), and a half of the outer diameter of the ring- Or the photosensitive resin laminate roll described in [5].

[7]

The photosensitive resin laminated body roll according to any one of [1] to [6], wherein the adhesive strength between the cross-sectional protective member and the low-density polyethylene film is from 5 gf / inch to 250 gf / inch.

[8]

The photosensitive member according to any one of [1] to [7], which is characterized in that the substrate of the rolled section protection member is a non-fogged, low fogged, synthetic paper, Resin laminate roll.

[9]

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

[10]

The photosensitive resin laminated body roll according to [9], wherein the alkali-soluble polymer containing a carboxyl group is a copolymer of styrene or a derivative thereof.

[11]

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

[12]

The photosensitive resin laminated body roll according to any one of [9] to [11], wherein the photopolymerization initiator is a hexaaryl biimidazole or a derivative thereof.

[13]

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

[14]

Wherein the pressure-sensitive adhesive composition contains a pressure-sensitive adhesive and particles, wherein at least 50 mass% of the particles have a diameter of 80 to 120% of a thickness of the pressure-sensitive adhesive composition applied, and the content of the particles is 100 parts by mass The photosensitive resin laminated body roll according to any one of [1] to [13], wherein the photosensitive resin layer is in the range of 5 to 30 parts by weight.

[15]

A process for producing a photosensitive resin laminate roll in which a photosensitive resin laminate is wound in a roll in a winding manner and the roll end face protection member is brought into contact with the end face of the wound photosensitive resin laminate,

The length of the winding 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 rolled section protection member,

And a pressure-sensitive adhesive composition on the side in contact with the roll section,

The photosensitive resin laminate wound in a rolled state is provided in a state in which it is divided into one or a plurality of parts, and after the photosensitive resin laminate is wound on the roll, the inner diameter of the photosensitive resin laminate is 1 to 1.1 times Characterized in that it is a ring-shaped sheet,

A method for producing a photosensitive resin laminate roll.

[16]

The method of producing a photosensitive resin laminated body roll according to [15], wherein the ring-shaped sheet has an inner diameter of 1.001 to 1.1 times as large as the outer diameter of the winding core, and is inserted through the projection of the winding core.

[17]

Wherein the ring-shaped sheet is provided so as to be in the air in a state of being projected horizontally, and the tip end of the ring-shaped sheet which is farthest from the flat plate in a portion in the air of the ring- (15), wherein H / R is 0.06 to 0.59, where B (mm) is the bending distance of the contacting side, and R Or the photosensitive resin laminate roll according to [16].

[18]

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

[19]

A method for packing a photosensitive resin laminate roll, characterized in that a photosensitive resin laminate roll is produced by the method according to any one of [15] to [18] and further covered with a tubular light shielding sheet.

[20]

1. A ring-shaped sheet for a film roll in which a film is wound in a roll-

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 core, and

Wherein the ring-shaped sheet has a pressure-sensitive adhesive composition on a side contacting the end face of the wound film and in contact with the end face, wherein the pressure-

Ring top sheet.

[21]

The above-mentioned film is a ring-shaped sheet described in [20], which is a laminate of photosensitive resin.

[22]

Wherein the ring-shaped sheet is provided so as to be in the air in a state of being projected horizontally, and the tip end of the ring-shaped sheet which is farthest from the flat plate in a portion in the air of the ring- (20), wherein H / R is from 0.06 to 0.59, where B (mm) is the bending distance between the contacting surface and R (mm) Or the ring-shaped sheet according to [21].

[23]

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

[24]

The ring-shaped sheet according to any one of the items [20] to [23], characterized by having a base material which is made of a nonwoven fabric, a low density paper or a laminate of paper and a resin base material.

[25]

The photosensitive resin composition according to any one of claims 21 to 24, characterized in that the photosensitive resin layer is a layer comprising 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 a copolymer of 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 comprises hexaaryl biimidazole or a derivative thereof.

[29]

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

[30]

Wherein the pressure-sensitive adhesive composition contains a pressure-sensitive adhesive and particles, wherein at least 50 mass% of the particles have a diameter of 80 to 120% of a thickness of the pressure-sensitive adhesive composition applied, and the content of the particles is 100 parts by mass The ring-shaped sheet according to any one of the items [20] to [29], wherein the weight ratio is 5 parts by weight to 30 parts by weight.

[31]

A film roll comprising a ring-shaped sheet according to any one of [20] to [30], which is covered with a light-shielding sheet.

By using the photosensitive resin laminate roll of the present invention, it is possible to easily remove foreign matter from the end face of the photosensitive resin laminate roll when releasing the roll.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic view of an embodiment of a photosensitive resin laminate roll in which a photosensitive resin laminate is wound in a roll on a core, and a roll-end protection member is disposed so as to contact the end face of the wound photosensitive resin laminate.
2 is a view showing the folding distance H and half R of the outer diameter of the ring-shaped sheet.
Fig. 3 shows a schematic view of an embodiment of a photosensitive resin laminate roll covered with a tubular light-shielding sheet.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the present invention (hereinafter abbreviated as "an embodiment") will be described in detail. The present invention is not limited to the following embodiments, and various modifications may be made within the scope of the present invention.

In the photosensitive resin laminate roll, a laminate of photosensitive resin laminate in the form of a long belt (strip-shaped) is wound around the core in the longitudinal direction thereof, and the roll end protection member is wound around the end face of the wound photosensitive resin laminate Side end side of the sieve) of the photosensitive resin laminated body roll.

Fig. 1 shows a schematic view of an embodiment of such a photosensitive resin laminate roll 10. As shown in Fig. Here, 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 water, Is wound on the core (2). Then, the roll end surface protection member 3 is disposed in contact with both end faces of the wound photosensitive resin laminate. Here, the roll section 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 a dry film resist or a dry film photoresist is also included in the photosensitive resin laminate.

The supporting layer may be one which supports the photosensitive resin layer. As the supporting layer to be used, it is preferable that the support layer is transparent to transmit light emitted from the exposure light 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, a polymethyl methacrylate copolymer film, a polystyrene film, A polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films may be stretched if necessary. 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 more preferable, and a haze value of 1 or less is even more preferable. Although the thickness of the support layer is advantageous from the viewpoints of image forming property and economical efficiency, the thickness of the support layer is preferably 10 to 30 占 퐉 in view of maintaining heat shrinkage upon coating the photosensitive resin composition layer. For example, GR19 and GR16 manufactured by Teijin DuPont Film Co., Ltd., R310-16 and R340G16 manufactured by Mitsubishi Plastics, FB40 (16 탆 film thickness) manufactured by Toray Polyester Film Co., Thickness).

The protective layer can be easily peeled off because the protective layer is sufficiently smaller than the support layer in adhesion to the photosensitive resin layer. For example, a polyethylene film, a polypropylene film, a stretched polypropylene film and the like 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 thickness of the protective layer is preferably 10 to 100 mu m, more preferably 10 to 50 mu m. For example, GF-18, GF-818, and GF-858 manufactured by Tama Polyol Co., Ltd. can be mentioned.

The photosensitive resin layer can be laminated by applying a photosensitive resin composition to a support layer and drying the solution. The thickness of the photosensitive resin layer is preferably 5 to 100 占 퐉, and more preferably 50 占 퐉. The closer the thickness of the photosensitive resin layer is to 5 mu m, the higher the resolution, and the closer to 100 mu m the film strength is, the better it can be selected depending on the application.

As a method for producing the photosensitive resin laminate, a conventionally known method can be employed. For example, a photosensitive resin composition used for a photosensitive resin layer is mixed with a solvent to prepare a photosensitive resin composition combination solution. The base resin composition is applied to the support layer using a bar coater or a roll coater, followed by drying. Is laminated on the photosensitive resin layer. It is preferable that the photosensitive resin composition combination liquid is added at a temperature of 25 ° C to 500 to 4000 mPa · s by adding a solvent. Examples of the solvent include solvents such as methyl ethyl ketone, acetone, ethanol, methanol, propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and toluene in combination with a photosensitive resin composition in terms of viscosity, drying composition, residual solvent amount, And the like. Then, a photosensitive resin laminate can be prepared by laminating a protective layer on the photosensitive resin layer.

The photosensitive resin laminate is rolled up into a long winding shape and used as a roll. The winding length is not particularly limited, but is preferably 320 m or less in view of the weight of the roll and ease of handling. Since a large number of substrates that can be laminated with a single photosensitive resin laminate roll are more efficient, the winding length from the viewpoint of productivity is preferably 100 m or more.

(Reverence)

Sometimes called core, also called core. The shape thereof is not particularly limited, but may be cylindrical or circular. Since the photosensitive resin laminate is used as an etching or plating resist, and further as a permanent pattern for an electronic material, it is preferable that a process not oscillating is performed, and a plastic resin is preferable. The material of the plastic resin is preferably light, excellent in strength, and does not oscillate. 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 is preferably 2 to 5 inches, and more preferably 3 inches in diameter when the photosensitive resin laminate roll is mounted on the laminator. The length of the winding core (the length in the axial direction when the cylindrical or circumferential winding core is used) may be the same or shorter than the width of the photosensitive resin laminate. However, when the photosensitive resin laminate is wound, It is preferable that the length is larger than the width of the photosensitive resin laminate so as to secure a suitable protrusion. So that the ring-shaped sheet is inserted so as to be inserted into the projecting portion. Also, a bearing called a core holder may be fitted to the protruding portion, and the photosensitive resin laminate roll may be kept hanging in the air so that the roll does not move.

(Roll section protection member)

The roll section protection member is arranged to contact the end face of the wound photosensitive resin laminate. The shape is not particularly limited and may be any shape as long as it covers at least a part of the end surface of the roll in contact with the end surface in a predetermined area. However, among them, the projecting portion of the winding is inserted into contact with the end surface of the wound photosensitive resin laminate It is preferable that the sheet is a ring-shaped sheet. Further, it is preferable that the photosensitive resin laminate roll is a ring phase having a width enough to substantially cover substantially the entire cross section of the roll of the photosensitive resin laminate. The roll section protection member may be used only at one end of the wound photosensitive resin laminate, but is preferably used at both ends.

When the roll section protecting member is a ring-shaped sheet, its ring inner diameter is preferably slightly larger than the outer diameter of the winding core so that it can be inserted into the winding core and used. Further, the center of the ring-shaped sheet slightly deviates from the center of the winding core, so that the outer periphery of the ring-shaped sheet comes out slightly from the outer periphery of the wound photosensitive resin laminate. It is preferable that the outer diameter of the ring-shaped sheet is slightly larger than the outer diameter of the ring-shaped ring in view of facilitating the removal of the ring-shaped sheet. Concretely, the ring inner diameter is preferably 1.001 times or more of the outer diameter of the core, because it does not adhere to the core at the time of installation. More preferably 1.005 times or more, and further preferably 1.01 times or more. From the viewpoint of protecting the entire roll cross section and removing foreign matter, the ring inner diameter is preferably 1.1 times or less, more preferably 1.05 times or less, more preferably 1.03 times or less of the outer diameter of the winding core.

The ring outer diameter is preferably 0.99 times or more, more preferably 1 time or more, of the outer diameter of the photosensitive resin laminate wound in the roll so as to cover the end face of the photosensitive resin laminate roll. The outer diameter of the ring is preferably 1.1 times or less the outer diameter of the photosensitive resin laminate roll from the viewpoint of suppressing the adhesion to the wrapping material such as the light-shielding cylindrical tube covering the photosensitive resin laminate roll, 1.05 times or less, and more preferably 1.03 times or less.

The base material of the roll section protection member may be any one of a polyester, a polyethylene terephthalate, a polyphenylene sulfide, a polypropylene, and a nylon which are each made of an unoriented, stretched or biaxially stretched film and a low density polyethylene, a high density polyethylene, a hard polyvinyl chloride, Plastic resins such as soft polyvinyl chloride, cellophane, acetate, cellulose triacetate, polystyrene, polycarbonate, polyimide and the like, antistatic-treated paper, anti-vibration treated surface paper, clean paper, Resins, synthetic paper, and the like. Since the photosensitive resin laminate is used as an etching or plating resist, and further as a permanent pattern for an electronic material, it is preferable that a process not oscillating is performed. From the viewpoint of less generation of static electricity, good followability to the cross section, excellent removability of foreign matters, and excellent mounting property, the base material is preferably a paper having an anti-vibration treatment, an anti-vibration treated top paper, a clean paper, Synthetic resin, and synthetic resin are preferably used as the material. It is preferable that the synthetic paper mainly contains polypropylene.

In the case where the base material is an anti-vibration treated paper, an anti-vibration treated top paper, a clean paper, and a paper and a plastic resin are laminated, the thickness of the base material is preferably 50 to 500 μm. From the viewpoint of mountability, 50 mu m or more is preferable, and from the viewpoint of cross-sectional trackability and removability of foreign matter, 500 mu m or less is preferable. More preferably 60 to 200 占 퐉, and still more preferably 60 to 150 占 퐉.

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

Wherein said ring-shaped sheet is provided on a horizontally protruding flat plate so that said ring-shaped sheet is halfway in the air, and a tip end of said ring-shaped sheet which is farthest from said flat plate in a portion existing in the air of said ring- H / R is preferably in the range of 0.06 to 0.59 when the bending distance H (mm) is a distance between the surface of the ring-shaped sheet contacting the ring-shaped sheet and R (mm) . From the viewpoint of the roll section mounting property of the ring-shaped sheet, it is preferably 0.59 or less. More preferably, it is 0.5 or less, and more preferably 0.45 or less. It is preferably 0.06 or more from the viewpoint of trackability to the cross-section of the roll and removability of foreign matter. More preferably 0.1 or more, and even more preferably 0.15 or more.

The method of measuring the bending distance H is as follows. First, as shown in Fig. 2, a ring-shaped sheet 3 is provided on a substantially flat plate 7 projecting in a substantially horizontal direction (direction perpendicular to the vertical direction). At this time, the surface provided with the adhesive is directed upward so as not to be attached 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 the substantially straight short side existing at the end of the flat plate. When fixed, it may be fixed with a fixing member 8 as shown in Fig. At this time, the ring-shaped seat 3 is affected by factors other than gravity, so that it is not bent or bent. The distance in the vertical direction between the tip end of the ring-shaped sheet most distant from the short side of the flat plate and the imaginary plane formed by the surface in contact with the ring-shaped sheet of flat plate in the air- . The measurement site shall be Fuji-shi, Shizuoka.

(Pressure-sensitive adhesive composition)

The pressure-sensitive adhesive composition is prepared by using a known pressure-sensitive adhesive composition so that there is no residue on the end face of the photosensitive resin film when the roll-end protection member is peeled off and the photosensitive resin is not adhered to the roll- .

Among them, it is preferable to contain an acrylic resin from the viewpoints of foreign matter removal and releasability. When the photosensitive resin composition is a photosensitive resin composition containing a carboxyl group-containing alkali-soluble polymer, an addition polymerizable monomer, and a photopolymerization initiator, and the pressure-sensitive adhesive composition contains an acrylic resin, a viewpoint capable of highly removing both foreign matter and releasability .

The pressure-sensitive adhesive composition preferably contains particles, wherein 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 mass Is preferably 5 parts by weight to 30 parts by weight. The diameter of the particles was observed by microscopic observation, and the maximum diameter of any 100 particles was observed and calculated as an average value thereof.

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. , More preferably 90 to 110%, further preferably 100%.

The particles usually have a single particle size, which is theoretically possible, but is often difficult to obtain in practice. It is preferable that the particle size distribution is as narrow as possible, that is, it has a sharp particle size curve.

It is preferable that 50 mass% or more of the total amount of the pressure-sensitive adhesive is a diameter of 80 to 120% of the thickness of the pressure-sensitive adhesive. More preferably 70% by mass or more, and more preferably 80% by mass or more from the viewpoint of the balance between releasability and tackiness.

The content of the particles is preferably 5 parts by weight to 30 parts by weight per 100 parts by weight of the pressure-sensitive adhesive. In the case of pasting, 5 parts by weight or more is preferable from the viewpoint of the dropping of air bubbles, and 30 or less is preferable from the viewpoint of adhesiveness. More preferably 10 parts by weight to 25 parts by weight. The material of the particles is preferably 15 to 30 parts by weight in the case of glass and 5 to 25 parts by weight in the case of plastic.

The material of the particle is preferably plastic or inorganic material. Examples of the plastics include polymethacrylate, polyethylene methacrylate, polystyrene, polystyrene acrylic, polyethylene, polypropylene, polystyrene butadiene, polystyrene divinylbenzene, polyurethane, polybenzoguanamine, . Examples of the inorganic material include glass, silica (silicate mineral), and calcium carbonate.

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

The adhesion strength between the cross-sectional protective member and the low-density polyethylene film is preferably 5 gf / inch to 250 gf / inch, more preferably 50 gf / inch to 240 gf / inch from the viewpoint of foreign matter removal and mountability.

The adhesive force is measured in the following manner. That is, the low-density polyethylene film (LDPE) sheet is affixed to the surface of the cross-sectional protective 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. is used. It is cut into 1 inch wide and 15 cm long desk, and humidity is adjusted at relative humidity 50% and 23 degrees Celsius for 11 hours. A tensile test is carried out at a tensile speed of 100 mm / min. At a load cell of 1 kg, Tensilon RTM-500 manufactured by ORIENTECH CORPORATION. At this time, the sample's cross-sectional protective member is chucked (fixed) at the bottom of the tensilon, and the low-density polyethylene film is chucked (fixed) at the tensile portion. In the tensile test, an integral average of the load is taken in a section of 10 mm to 50 mm in height, and an average of the number of times of the test is taken as an adhesive value.

(Method for producing photosensitive resin laminate roll)

The photosensitive resin laminate roll is preferably covered with a light-shielding sheet from the viewpoint of suppressing light sensitivity during adhering and transportation of foreign matters. The light-shielding sheet may be called a light-shielding film. The light-shielding sheet can be covered by winding it on the photosensitive resin laminate roll. As shown in Fig. 3, in the case where the light shielding sheet 9 is cylindrical, it is preferable that the light shielding sheet 9 can be covered by inserting the photosensitive resin roll 1 in the cylinder. 3, when the length of the barrel is longer than that of the winding 2 of the photosensitive resin laminate roll 1, the portion longer than the winding core 2 is fitted into the inside of the winding core, It is preferable because it can further suppress.

The light-shielding sheet is preferably a polyethylene material from the viewpoint that the photosensitive resin laminate roll can be protected from, for example, contact with a lightweight drop or a slight contact with a packaging container. The film thickness is preferably 10 占 퐉 or more from the viewpoint of maintaining an appropriate strength and suppressing pinholes, and is preferably 300 占 퐉 or less from the viewpoint of handling. More preferably 20 to 200 占 퐉, and still more preferably 30 to 130 占 퐉. Black is preferable for increasing the 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 core holders formed with convex portions to be fitted with the cores. It is possible to prevent the photosensitive resin laminate from contacting with the bottom wall 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.

When the photosensitive resin laminate roll is covered with the light-shielding sheet, if the core holder is further mounted with the longer portion of the light-shielding sheet inserted into the core than the core of the light-shielding sheet with the sandwiched portion interposed therebetween, It is preferable.

(Photosensitive resin composition)

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

From the viewpoint that when the ring-shaped sheet is peeled off from the roll section, the amount of the residue remaining on the roll surface is small and the adhesion of the photosensitive resin composition to the ring-shaped sheet is also reduced, it is preferable that the photosensitive resin composition includes (a) desirable.

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

The alkali-soluble polymer (a) containing a carboxyl group preferably contains an α, β-unsaturated carboxyl group-containing monomer as a polymerization component, preferably has an acid equivalent weight of 100 to 600 and a weight average molecular weight of 5,000 to 500,000 Do. The carboxyl group in the alkali-soluble polymer containing a carboxyl group is necessary because the photosensitive resin composition has developability or peelability with respect to a developer or release agent comprising an aqueous alkaline solution. The acid equivalent means the mass of an alkali-soluble polymer having one equivalent of carboxyl groups therein. A more preferable lower limit of the acid equivalent is 250, and a more preferable upper limit is 450. The acid equivalent of the alkali-soluble polymer containing a carboxyl group (a) is preferably from 0.01 to 10 parts by weight, more preferably from 0.01 to 10 parts by weight, more preferably from 0.1 to 50 parts by weight, Is preferably 100 or more from the viewpoint of ensuring the compatibility of the photosensitive resin composition of the present invention and is preferably 600 or less in that development and releasability are improved. The measurement of the acid equivalent was carried out by potentiometric titration using 0.1 mol / l sodium hydroxide by using a Hirunuma automatic titrator (COM-555) manufactured by Hiranuma Industrial Co., Ltd.

The weight average molecular weight of the alkali-soluble polymer containing a carboxyl group (a) is preferably 5,000 to 500,000. The weight average molecular weight is preferably not less than 5,000 from the standpoint of maintaining the thickness of the photosensitive resin laminate uniformly to obtain resistance to a developing solution and also from the point that the edge fuse is suppressed, . The edge fuse is a phenomenon in which the photosensitive resin composition exudes from the end face of the roll when the photosensitive resin laminate is wound in a roll form. The light-sensitive resin composition that has permeated may adhere to the photosensitive resin composition exuded from the photosensitive resin layer of another adjacent layer through the support layer protective layer in the roll state. When the laminated photosensitive resin laminate of the roll-like photosensitive resin composition is laminated, the laminated photosensitive resin composition, that is, the edge-fused photosensitive resin composition, may peel off from the end face to scatter as a resist chip. When a resist chip is attached to a substrate after lamination, it is attached to a mask for exposure, exposed and cured, and in the case of a negative resist, exposure is cut off, 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 the present specification means the weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.).

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

Differential refractometer: RI-1530

Pump: PU-1580

D: DG-980-50

Column oven: CO-1560

Column: KF-8025, KF-806Mx2, KF-807

Eluent: THF.

(a) the alkali-soluble polymer containing a carboxyl group is preferably a (co) polymer containing as a component at least one monomer selected from the first or second monomer to be described later.

The first monomer is a carboxylic acid or an acid anhydride having one polymerizable unsaturated group in the molecule. Examples thereof include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride and maleic acid ester. Among them, (meth) acrylic acid is particularly preferable.

The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. (Meth) acrylate, isopropyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl , Esters of vinyl alcohol 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 preferable, and it is particularly preferable to use styrene from the viewpoint of resolution.

(a) The alkali-soluble polymer containing a carboxyl group can be obtained by mixing a monomer as described above and adding a radical polymerization initiator such as benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide or the like to a solution prepared by diluting the monomer with a solvent such as acetone, methyl ethyl ketone, or isopropanol, It is preferable that azo isobutyronitrile is added in an appropriate amount and the mixture is heated and stirred. The synthesis may be 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 level. As the synthesizing means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

Particularly preferred alkali-soluble polymers (a) containing carboxyl groups are those wherein the copolymerization ratio of the first monomer and the second monomer is 10 to 60% by mass of the first monomer and 40 to 90% by mass of the second monomer, Preferably, the content of the first monomer is 15 to 35 mass% and the content of the second monomer is 65 to 85 mass%.

More specific examples of the alkali-soluble polymer (a) containing a carboxyl group include a polymer containing methyl methacrylate, methacrylic acid and styrene as copolymer components, methyl methacrylate, methacrylic acid and n-butyl acrylate as copolymerizable components , And polymers containing benzyl methacrylate, methyl methacrylate, and 2-ethylhexyl acrylate as copolymer components.

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

(b) an 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 ethylenic unsaturated group. From the viewpoints of high resolution, edge fusing and tentability, it is preferable to use at least one bisphenol A (meth) acrylate compound as the addition polymerizable monomer (b).

In the present specification, the bisphenol A (meth) acrylate compound means a compound having a carbon-carbon unsaturated double bond derived from a (meth) acryloyl group or a (meth) acryloyl group and -C6H4-C -C6H4- group. Specific examples thereof include dimethacrylates of polyethylene glycol (NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.) in which ethylene oxide is added in an average of 2 units on both ends of bisphenol A or bisphenol A, (NK Ester BPE-500, manufactured by Shin Nakamura Chemical Co., Ltd.) having ethylene oxide added with ethylene oxide, an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide were added to both ends of bisphenol A Dimethacrylates of one polyalkylene glycol, and dimethacrylates of polyalkylene glycols obtained by adding ethylene oxide of 15 units on average and propylene oxide of 2 units on average at both ends of bisphenol A, respectively.

As the addition polymerizable monomer (b), known compounds having at least one ethylenic unsaturated group in addition to the above-mentioned compounds can be used. For example, there can be mentioned 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, half of phthalic anhydride and 2-hydroxypropyl acrylate A reaction product of an ester compound and propylene oxide (trade name: OE-A 200, manufactured by Nippon Catalysts & Chemicals, Inc.)

(Meth) acrylate, 4-n-octylphenoxypentapropylene glycol acrylate, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di Di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate and pentaerythritol penta (meth) (Meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane, hexamethylene diisocyanate and nonapropylene glycol monomethacrylate Polyfunctional (meth) acrylate containing a urethane group such as urethane of urethane group, and polyfunctional (meth) acrylate of isocyanuric acid ester compound. These may be used alone, or two or more of them may be used together, or may be used in combination with a bisphenol A (meth) acrylate compound.

The content of the addition polymerizable monomer (b) 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 addition polymerizable monomer (b) is 5% by mass or more from the viewpoints of resolution, adhesion and copper line formation, and 75% by mass or less from the viewpoint of flexibility of the cured film.

(c) a photopolymerization initiator

As the photopolymerization initiator (c), those ordinarily used as photopolymerization initiators for photosensitive resins can be suitably used, and hexaaryl bisimidazole (hereinafter also referred to as triarylimidazolyl dimer) is preferably used .

Examples of the triarylimidazolyl dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (hereinafter referred to as 2,2'-bis (2-chlorophenyl) (4,4 ', 5,5'-tetraphenyl-1,1'-bisimidazole), 2,2', 5-tris (o- chlorophenyl) -4- Diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylimidazolyl dimer ,

(O-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4- dimethoxyphenyl) -imidazolyl (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'- 4-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer,

(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'- (3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'- -Trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer,

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

Tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2, 2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ' , 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 .

Particularly, the 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 alone or in combination of two or more. The acridine compound, the pyrazoline compound, and the like may be used in combination.

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

9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- , 9- (4-tert-butylphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- Pyridine, 9- (4-chlorophenyl) acridine,

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

Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert- butylphenyl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert- butylphenyl) phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazolene are preferred.

Examples of the photopolymerization initiator other than the above include 2-ethyl anthraquinone, octaethyl anthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2-methyl-1, 4-naphthoquinone, 2,3-dimethyl anthraquinone, and 3-chloro -2-methyl anthraquinone, and the like,

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

Benzyl dimethyl ketal, benzyl diethyl ketal, a combination of thioxanthones and alkyl aminobenzoic acids, 1-phenyl-1,2-propanedione-2-O-benzoin oxime, And oxime esters such as 2- (O-ethoxycarbonyl) oxime.

Examples of the combination of the thioxantho acids and alkylaminobenzoic acids described above include a combination of ethyl thioxanthone and ethyl dimethyl aminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethyl aminobenzoate, and a combination of isopropylthio And a combination of ethyl xanthone and dimethylaminobenzoate. N-arylamino acid may also be used. Examples of the N-aryl amino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among them, N-phenylglycine is particularly preferable.

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, more preferably 0.05% by mass, more preferably 0.1% The preferable upper limit is 15% by mass, and the more preferable upper limit is 10% by mass. The content of the photopolymerization initiator (c) is 0.01 mass% or more from the viewpoint of obtaining sufficient sensitivity at the time of photopolymerization by exposure, and the light is sufficiently emitted from the bottom of the photosensitive resin composition And is not more than 30% by mass from the viewpoint of obtaining good resolution and adhesion.

(e) Other additives

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

When the coloring material is contained, the amount of the coloring material to be added is preferably 0.001 to 1% by mass based on the total solid content of the photosensitive resin composition. When the addition amount of the coloring material is 0.001% by mass or more, there is an effect of improving the handling property, and when it is 1% by mass or less, the storage stability is maintained.

In addition, a coloring agent may be contained in the photosensitive resin composition so that a visible image can be given by exposure. Examples of such a coloring dye include a leuco dye or a combination of a fluoro dye and a halogen compound.

Examples of the leuco dyes include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leuco malachite green], and fluororan dyes . Among them, when Loico crystal violet is used, the contrast is preferably good.

Examples of the halogen compound include amides such as amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzene bromide, methylene bromide, tribromomethylphenylsulfone, tetrabromocarbon, tris (2,3-dibromo Propyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, .

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

In order to improve the thermal stability and storage stability of the photosensitive resin composition, it is preferable to incorporate at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles into the photosensitive resin composition Do.

Examples of such a radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert- -Cresol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis Salts, and diphenylnitrosamine.

Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene- Benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2- hydroxyethyl) aminomethylene- .

Carboxybenzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, (N, N- dibutylamino) carboxybenzotriazole Aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, N- (N, N- N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole.

The total addition amount of the radical polymerization inhibitor, the benzotriazoles and / or the carboxybenzotriazoles is preferably 0.001 to 3% by mass, more preferably 0.05% by mass, more preferably 0.05 to 3% by mass based on the total solid content of the photosensitive resin composition The preferred upper limit is 1% by mass. The total amount added 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 the sensitivity.

Other plasticizers may be added to the photosensitive resin composition, if necessary. Examples of such plasticizers include compounds obtained by modifying bisphenol A with polyalkylene oxide.

In addition, sorbitan derivatives such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan oleate, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, phthalic acid esters such as diethyl phthalate , o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetylcitrate, tri-n-propylcitrate citrate, and tri-n-butyl acetylcitrate. Particularly, sorbitan derivatives and polyalkylene glycols are preferably used.

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

Example

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

First, the method for producing samples for evaluation in the examples and comparative examples will be described first, followed by evaluation methods for the obtained samples and evaluation results thereof. Here, a ring-shaped sheet is used as the roll-end-surface protecting member.

(Examples 1 to 12 and Comparative Example 1)

1. Preparation of sample for evaluation

The samples for evaluation in the examples and comparative examples were produced as follows.

≪ Preparation of Photosensitive Resin Laminate >

(The abbreviations in Table 1 are as shown in Table 2) and the solvent were thoroughly stirred and mixed to prepare a photosensitive resin composition combination liquid , And a polyethylene terephthalate film (R310, manufactured by Mitsubishi Resin Co., Ltd.) having a thickness of 16 mu m was prepared as a support, and the solution of the photosensitive resin composition was uniformly coated on the surface of the polyethylene terephthalate film using a die coater and dried , A photosensitive resin layer was formed. The thickness of the photosensitive resin layer was 15 mu m. Subsequently, a 33 占 퐉 -thick polyethylene film (GF-858 manufactured by Tama Poly Co., Ltd.) as a protective layer was laminated on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to form the photosensitive resin laminate 1, .

A photosensitive resin laminate (2 to 6) was obtained in the same manner as in the photosensitive resin laminate (1) except that the composition 1 was used as the composition 2 to 6 in the photosensitive resin laminate (1) . The photosensitive resin laminate (1) was prepared in the same manner as in the photosensitive resin laminate (1) except that the composition 1 was used as the composition 7 to 10 and the photosensitive resin layer was made to have a thickness of 10 탆, To obtain laminated bodies (7 to 10).

≪ Preparation of photosensitive resin laminate roll >

As the ring-shaped sheet, the sheets shown in Tables 3 to 5 were used. In the pressure-sensitive adhesive composition containing the acrylic resin of the ring-shaped sheet, the pressure-sensitive adhesive composition of ErieruTak NS80 / SBG85S / re-exfoliation (manufactured by Eriertexcel Co., Ltd.) was used as it is unless otherwise specified.

For the samples F and G, the pressure-sensitive adhesive composition was adjusted as follows. That is, B-1 and M-8 shown in Table 2 were blended so as to have a solid content ratio of 45:55 and 40:60, and the coating was applied to the substrate so as to have a dry thickness of 15 μm and dried.

The photosensitive resin laminate 1 was slit with a width of 495 mm and wound in an ABS resin core (core) having an inner diameter of 77 mm, an outer diameter of 88 mm and a length of 530 mm by 300 m. The outer diameter of the photosensitive resin laminate wound in a roll form was 180 mm.

Shaped stainless steel lock holder designed so that the other end was fixed and held horizontally, the photosensitive resin laminated body wound around the core and held in a roll-like state was held.

A photosensitive resin laminate rolled in a cylindrical light-shielding polyethylene tube having an outer diameter of 500 mm, a length of 800 mm and a thickness of 80 占 퐉 was covered.

The photosensitive resin laminate on the roll coated with the light-shielding polyethylene tube was peeled from the lock holder, and a roll was installed on a cushion designed to fix the roll with a width of 330 mm and a height of 100 mm.

One end of the light-shielding polyethylene tube was folded back, and a cross-section of the rolled photosensitive resin laminate was exposed to attach a ring-shaped sheet. A ring-shaped sheet was attached to the other end in the same manner to produce a photosensitive resin laminate roll (1).

A light-shielding polyethylene tube was inserted into the core, and a core holder designed to fit the core with the core in a convex shape was mounted, and the photosensitive resin roll (1) was packed.

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 removing property

The ring-shaped sheet was peeled from the photosensitive resin laminate roll, and it was confirmed whether or not the foreign substance adhered to the ring-shaped sheet. And ranked as follows.

A: Foreign matter adhered to the ring sheet. Another adhesive tape was pasted on the roll section to peel off, but adhesion of the foreign matter could not be confirmed.

?: The foreign substance was adhered to the ring-shaped sheet, but another adhesive tape was pasted on the end face of the roll and peeled off. As a result, adherence of foreign matter to the adhesive tape was confirmed.

X: No foreign matter adhered to the ring-shaped sheet. Adhesion of foreign matter was confirmed by sticking another adhesive tape to the roll section and peeling it off.

(2) Mountability of the ring seat

The rolls were prepared as described in < Production of photosensitive resin laminate roll >, and the mountability when the ring-shaped film was mounted on the roll section was ranked as follows.

A: The ring-shaped sheet could be easily mounted. It could be attached without wrinkles when it was attached to the roll section.

?: The ring-shaped sheet was stuck to the lock holder or the core, requiring time for mounting. When pasting to the roll section, some wrinkles or air entered.

X: The ring-shaped sheet was stuck to the lock holder or the core, requiring time for mounting. The ring-shaped sheet is stretched and deformed or torn when the ring-shaped sheet pasted to an undesired point is peeled and reapplied, making it difficult to attach the ring-shaped sheet to the roll section.

(3) Packing material of ring sheet

A roll was prepared as described in < Production of photosensitive resin laminate roll >, which was then loosened. It was observed whether the ring sheet was attached to the end face in the same manner as in the case of the back mounting, and ranked as follows.

∘: Mounted in the same way as when mounted.

DELTA: When the roll is released, the ring-shaped sheet is attached to the light-shielding cylindrical polyethylene sheet, and there is a point where the ring-shaped sheet is peeled off from a part of the end surface.

X: When the roll was released, the ring-shaped sheet was attached to the light-shielding cylindrical polyethylene sheet and peeled together with the light-shielding cylindrical polyethylene sheet.

(4) Removability of the ring sheet

After the roll was prepared as described in " Production of photosensitive resin laminate roll ", the roll was loosened, and the ring-shaped sheet was peeled off with a hand made of resin gloves. The workability at the time of peeling was ranked as follows.

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

DELTA: Time required for peeling of the ring sheet for 5 seconds or more.

(5) Number of foreign substances

Fourteen photosensitive resin laminate rolls were prepared as described in < Production of photosensitive resin laminate roll >. The foreign substances were removed from the cross sections of all the rolls, and a total of four foreign substances were adhered to the roll cross section at random among these. Thereafter, a ring-shaped sheet was attached to all the rolls and peeled off, and the foreign substances adhering to the rolls were counted.

A photosensitive resin laminate roll was prepared in the same manner as in the case of the photosensitive resin laminate roll (1) except that the photosensitive resin laminate (1) was a photosensitive resin laminate (2 to 6) This was used 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 the same results as those in the case of using the photosensitive resin laminate roll (1) were obtained.

A photosensitive resin laminate roll (1) was obtained in the same manner as in the photosensitive resin laminate (1) except that the photosensitive resin laminate (1) was a photosensitive resin laminate (7 to 10) , A photosensitive resin laminate roll was prepared and used as a photosensitive resin laminate roll (7 to 10). The outer diameter of the photosensitive resin laminate wound in the roll form was 176 mm. Evaluation of (1) to (5) using photosensitive resin rolls (7 to 10) gave the same results as in the case of using the photosensitive resin laminate roll (1).

Industrial availability

The photosensitive resin laminate roll described above is useful for processing precision instruments and electronic materials because foreign matters are easily removed when rolls are unrolled, and is also useful as a permanent pattern to be inserted into precision instruments and electronic materials.

1: photosensitive resin laminate
2: Reason
3: Roll section 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 laminate roll

Claims (31)

The photosensitive resin laminate is wound in a rolled form on the core,
A roll of a photosensitive resin laminated body in which a roll section protecting member is arranged so as to come into contact with an end face of a wound photosensitive resin laminate,
Wherein the roll section protection member has a pressure-sensitive adhesive composition on a side in contact with the roll section,
Wherein the photosensitive resin laminate comprises at least a support layer and a photosensitive resin layer laminated on the support layer,
Photosensitive resin laminate roll. The method according to claim 1,
Wherein the light-shielding sheet is covered with a light-shielding sheet. 3. The method of claim 2,
Wherein the light-shielding sheet is cylindrical. The method according to claim 1,
The length of the winding core is longer than the width of the photosensitive resin laminate,
Wherein the roll protection member is a ring-shaped sheet provided on an end face of the photosensitive resin laminate wound in a roll form, and the ring-shaped sheet is provided by inserting the protrusion of the winding core. 5. The method of claim 4,
Wherein the inner diameter of the ring-shaped sheet is 1 to 1.1 times the outer diameter of the winding core. 5. The method of claim 4,
Wherein the ring-shaped sheet is provided so as to be in the air in a state of being projected horizontally, and the tip end of the ring-shaped sheet which is farthest from the flat plate in a portion in the air of the ring- Wherein a ratio of H / R is 0.06 to 0.59, where B (mm) is the bending distance of the contact side, and R (mm) is the half of the outer diameter of the ring-shaped sheet. role. The method according to claim 1,
Wherein the adhesive force between the cross-sectional protective member and the low-density polyethylene film is 5 gf / inch to 250 gf / inch. The method according to claim 1,
Wherein the substrate of the rolled section protection member is formed by blending a non-fogged spot, a low fogging spot, a synthetic paper, or a paper and a resin base material. 9. The method according to any one of claims 1 to 8,
Wherein the photosensitive resin layer is a layer comprising a photosensitive resin composition containing an alkali-soluble polymer containing a carboxyl group, an addition polymerizable monomer, and a photopolymerization initiator. 10. The method of claim 9,
Wherein the alkali-soluble polymer containing a carboxyl group is a copolymer of styrene or a derivative thereof. 10. The method of claim 9,
Wherein the addition polymerizable monomer contains a bisphenol A (meth) acrylate compound. 10. The method of claim 9,
Wherein the photopolymerization initiator comprises hexaaryl biimidazole or a derivative thereof. 9. The method according to any one of claims 1 to 8,
Wherein the pressure-sensitive adhesive composition comprises an acrylic resin. 9. The method according to any one of claims 1 to 8,
Wherein the pressure-sensitive adhesive composition contains a pressure-sensitive adhesive and particles, wherein at least 50 mass% of the particles have a diameter of 80 to 120% of a thickness of the pressure-sensitive adhesive composition applied, and the content of the particles is 100 parts by mass To 5 parts by weight to 30 parts by weight per 100 parts by weight of the photosensitive resin composition. A process for producing a photosensitive resin laminate roll in which a photosensitive resin laminate is wound in a roll in a winding manner and the roll end face protection member is brought into contact with the end face of the wound photosensitive resin laminate,
The length of the winding 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 rolled section protection member,
And a pressure-sensitive adhesive composition on the side in contact with the roll section,
The photosensitive resin laminate wound in a rolled state is provided in a state in which it is divided into one or a plurality of parts, and after the photosensitive resin laminate is wound on the roll, the inner diameter of the photosensitive resin laminate is 1 to 1.1 times Characterized in that it is a ring-shaped sheet,
A method for producing a photosensitive resin laminate roll. 16. The method of claim 15,
Wherein the inner diameter of the ring-shaped sheet is 1.001 to 1.1 times as large as the outer diameter of the core, and the projections of the core are passed through the core. 16. The method of claim 15,
Wherein the ring-shaped sheet is provided so as to be in the air in a state of being projected horizontally, and the tip end of the ring-shaped sheet which is farthest from the flat plate in a portion in the air of the ring- Wherein a ratio of H / R is 0.06 to 0.59, where B (mm) is the bending distance of the contact side, and R (mm) is the half of the outer diameter of the ring-shaped sheet. A method of manufacturing a roll. 16. The method of claim 15,
Wherein the adhesion between the ring-shaped sheet and the low-density polyethylene film is from 5 gf / inch to 250 gf / inch. A method for packing a photosensitive resin laminate roll, characterized in that a photosensitive resin laminate roll is produced by the method according to any one of claims 15 to 18 and further covered with a tubular light shielding sheet. 1. A ring-shaped sheet for a film roll in which a film is wound in a roll-
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 core, and
Wherein the ring-shaped sheet is in contact with an end face of the wound film,
And a pressure-sensitive adhesive composition is provided on the side in contact with the end face,
Ring top sheet. 21. The method of claim 20,
The film is a ring-shaped sheet, which is a laminate of photosensitive resin. 21. The method of claim 20,
Wherein the ring-shaped sheet is provided so as to be in the air in a state of being projected horizontally, and the tip end of the ring-shaped sheet which is farthest from the flat plate in a portion in the air of the ring- Wherein the ratio H / R is 0.06 to 0.59, where B (mm) is the bending distance of the contacting side, and R (mm) is the half of the outer diameter of the ring-shaped sheet. 21. The method of claim 20,
Wherein the adhesive strength to the low-density polyethylene film is 5 gf / inch to 250 gf / inch. 21. The method of claim 20,
Wherein the base sheet is made of a nonwoven fabric, a low density paper, a synthetic paper, or a paper base and a resin base material. 25. The method according to any one of claims 21 to 24,
Wherein the photosensitive resin layer is a layer comprising a photosensitive resin composition containing an alkali-soluble polymer containing a carboxyl group, an addition polymerizable monomer, and a photopolymerization initiator. 26. The method of claim 25,
Wherein the alkali-soluble polymer containing a carboxyl group is a copolymer of styrene or a derivative thereof. 26. The method of claim 25,
Wherein the addition polymerizable monomer contains a bisphenol A (meth) acrylate compound. 26. The method of claim 25,
Wherein the photo polymerization initiator comprises hexaaryl biimidazole or a derivative thereof. 25. The method according to any one of claims 20 to 24,
Wherein the pressure-sensitive adhesive composition comprises an acrylic resin. 25. The method according to any one of claims 20 to 24,
Wherein the pressure-sensitive adhesive composition contains a pressure-sensitive adhesive and particles, wherein at least 50 mass% of the particles have a diameter of 80 to 120% of a thickness of the pressure-sensitive adhesive composition applied, and the content of the particles is 100 parts by mass And 5 to 30 parts by weight per 100 parts by weight of the total weight of the ring-shaped sheet. A film roll comprising the ring-shaped sheet according to any one of claims 20 to 24, which is covered by a light-shielding sheet.

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