JP2014026107A - Method for manufacturing photosensitive element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a photosensitive element, in which temperature of a coating liquid can be varied as desired within the range from 15°C to 45°C, and by which qualities and thickness of a photosensitive element are maintained uniform in a width direction thereof at a set temperature and the appearance of a photosensitive element is improved, thereby to obtain a photosensitive element having uniform thickness.SOLUTION: A method for manufacturing a photosensitive resin element is provided, including steps of: (1) supplying a photosensitive resin liquid at a temperature controlled to be within ±0.25°C allowance with respect to a target temperature set in the range from 15°C to 45°C, to a coating device including a die head set on a trestle and a backup roll arranged along a longitudinal axis of the die head; and (2) discharging the photosensitive resin liquid from the coating device onto a substrate film set on the backup roll and applying the photosensitive resin liquid to the substrate film to obtain a photosensitive element.

Description

  The present invention relates to a method for producing a photosensitive element, and the like.

  Conventionally, in order to manufacture a photosensitive element such as a photosensitive resin laminate, a coating apparatus for applying a photosensitive resin liquid to a substrate has been used. In addition, using a device that includes a backup roll and a die head equipped with a slit and a maneuver as a coating device, the coating accuracy of the photosensitive resin solution is maintained in a method of applying the photosensitive resin solution to the substrate with high accuracy. In view of the above, the photosensitive element is generally produced at the same temperature as the temperature at which the die head and the backup roll are manufactured (for example, room temperature, more specifically 23 ° C. to 25 ° C.).

  For example, as a prior art, Patent Document 1 describes a method of suppressing thermal deformation of a die by keeping the die head within a range of room temperature ± 2 ° C. Patent Document 2 describes a method of suppressing thermal deformation of a die by forming the die with a material having a low coefficient of thermal expansion.

JP 2003-285343 A JP 7-328509 A

  However, in the manufacturing process of the photosensitive element, the photosensitive resin liquid is prepared in a preparation tank, the photosensitive resin liquid is applied to the film with a predetermined thickness, dried, and then wound up to form a roll-shaped photosensitive element. Is used, so-called batch production is adopted, so that not only the viscosity of the photosensitive resin solution is adjusted according to the amount of solvent added, but also the viscosity of each batch, the viscosity of the batch For the purpose of changing, etc., it is also necessary to manufacture a photosensitive element that controls the viscosity by the temperature of the photosensitive resin liquid and has uniform coating accuracy in the width direction.

  In addition, the photosensitive resin liquid may be decolored with time, but the lower the temperature, the lower the decoloring speed. Therefore, it is necessary to produce the photosensitive resin liquid at a low temperature if the composition is quickly decolored. ing. In this regard, even if the photosensitive resin liquid can be applied with high accuracy at room temperature (23 ° C. to 25 ° C.), if the temperature of the photosensitive resin liquid becomes too high or too low, Or, a low temperature liquid may enter and the straightness of the die head may become non-uniform due to thermal expansion or low temperature shrinkage, and in such a case, the thickness distribution of the coating film may not be uniform.

  In other words, the method described in Patent Document 1 means that the room temperature is set to the same temperature as the die head. When applied to the manufacture of a photosensitive element, it is essential that the photosensitive element is manufactured in a clean room from the viewpoint of foreign matter management. For example, it is about 45 degrees at a high temperature, and at a low temperature. Controlling the room temperature to be about 15 degrees requires very large energy. Furthermore, from the viewpoint of ease of work, it is not practical for an operator to work at high or low temperatures as described above while wearing clean clothes.

  Regarding the method described in Patent Document 2, not only the types of materials are limited, but it is extremely difficult to manufacture all of the backup rolls and die head peripheral devices from specific materials. At a high temperature around 45 ° C., a uniform film thickness may not be obtained due to thermal expansion.

  Moreover, the method which sets the temperature of the photosensitive resin liquid to target temperature by making a preparation tank and the conventional supply piping into a double pipe with a jacket, and letting warm water etc. pass through the inside of the jacket can be considered. However, in this method, time and energy are lost until the temperature of the photosensitive resin solution is stabilized at the beginning of the batch, and the temperature of the photosensitive resin solution is ± 0 even when the accuracy is high with respect to the target temperature. Since it can only be controlled within the range of 5 ° C, a photosensitive resin layer having a uniform thickness cannot be obtained, or when the photosensitive resin liquid is heated to a high temperature, There is still room for improvement in that the quality of the photosensitive resin solution deteriorates because it stays for a long time.

  Accordingly, an object of the present invention is to provide a method for producing a photosensitive element in which the thickness of the photosensitive element is kept uniform in the width direction.

As a result of diligent research and experiments, the present inventor has found that the above problem can be solved by controlling the temperature of the photosensitive resin liquid, which is the material of the photosensitive element, within a specific range and supplying it to the coating apparatus. The present invention has been completed.
That is, the present invention is as follows.

[1] The following steps:
(1) A photosensitive resin solution adjusted within an error range of ± 0.25 ° C. with respect to a target temperature set within a range of 15 ° C. to 45 ° C., along a die head installed on a gantry and a longitudinal axis of the die head And (2) discharging the photosensitive resin liquid from the coating device onto a base film placed on the backup roll, and supplying the coating film to the base film. Applying the photosensitive resin solution to obtain a photosensitive element;
The manufacturing method of the photosensitive element containing this.

  [2] The temperature adjustment in the step (1) is performed by a jacket type heat exchanger including a static mixer and a plurality of tubes attached to the photosensitive resin solution supply unit and the supply unit. [1] The method described in 1.

  [3] The method according to [1] or [2], wherein the photosensitive resin liquid has a viscosity at 25 ° C. of 500 cps to 5000 cps.

  [4] The temperatures of the die head and the backup roll are adjusted within an error range of ± 0.25 ° C. with respect to a target temperature set within a range of 15 ° C. to 45 ° C., respectively. [3] The method according to any one of [3].

  [5] The surface of the die head toward the backup roll has a straightness error range of 1 μm or less per meter as a distribution in the width direction, and a surface roughness Rz of 0.25 μm or less. ] The method of any one of [4].

  [6] Any one of [1] to [5], wherein the temperature of the gantry is adjusted within an error range of ± 0.25 ° C. with respect to a target temperature set within a range of 15 ° C. to 45 ° C. The method according to item.

  [7] The method according to any one of [1] to [6], wherein a means for releasing a dimensional change due to thermal expansion or cooling contraction is disposed on the bearing of the die head.

  [8] The method according to any one of [1] to [7], wherein a temperature difference between the photosensitive resin liquid and the die head is adjusted within a range of ± 0.25 ° C.

  [9] The temperature difference between the photosensitive resin liquid, the die head, and the backup roll is adjusted within a range of ± 0.25 ° C., according to any one of [1] to [7]. Method.

  [10] Any one of [1] to [7], wherein a temperature difference between the photosensitive resin liquid, the die head, the backup roll, and the mount is adjusted within a range of ± 0.25 ° C. The method according to item.

[11] For the sum of the total solids of the photosensitive resin composition:
(A) 10% by mass to 90% by mass of the alkali-soluble polymer;
(B) 5% by mass to 70% by mass of a compound having an ethylenically unsaturated bond; and (C) 0.01% by mass to 20% by mass of a photopolymerization initiator;
The method according to any one of [1] to [10], wherein the photosensitive resin composition is dissolved in a solvent to obtain the photosensitive resin liquid.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the photosensitive element with which the thickness of the photosensitive element is kept uniform in the width direction is provided.

It is a block diagram which shows the system for manufacturing a photosensitive element. It is a perspective view of the heat exchanger in embodiment of this invention. It is sectional drawing of the heat exchanger in the cutting line III-III of FIG. It is sectional drawing of the heat exchanger in the cutting line IV-IV of FIG. It is a perspective view which shows the positional relationship of the backup roll, die head, and die head mount frame in embodiment of this invention.

  The best mode for carrying out the present invention (hereinafter abbreviated as “embodiment”) will be described in detail below. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

In the embodiment, the method for producing the photosensitive resin element includes the following steps:
(1) A photosensitive resin solution adjusted within an error range of ± 0.25 ° C. with respect to a target temperature set within a range of 15 ° C. to 45 ° C., along a die head installed on a gantry and a longitudinal axis of the die head And (2) discharging the photosensitive resin liquid from the coating device onto a base film placed on the backup roll, and supplying the coating film to the base film. Applying the photosensitive resin solution to obtain a photosensitive element;
including.

  A photosensitive element refers to a substance that changes its properties by receiving light. The photosensitive element may be in various forms such as a film, a plate, a sheet, a roll, and a molded article, and may include, for example, a photosensitive resin or a material that includes a photosensitive resin. More specifically, a layer made of photosensitive resin (hereinafter referred to as “photosensitive resin layer”) is applied by applying a liquid containing photosensitive resin (hereinafter referred to as “photosensitive resin liquid”) to a substrate such as a film. And a photosensitive resin laminate obtained by laminating to a substrate is preferable as the photosensitive element. Further, a photosensitive resin roll obtained by further laminating and winding a protective material (for example, a protective film, an interleaf paper film, etc.) on the exposed portion of the photosensitive resin laminate, It is more preferable as a photosensitive element, and a dry film roll in which the entire photosensitive resin roll or the photosensitive resin layer portion is dried is particularly preferable.

The photosensitive resin liquid is composed of the following components (A) to (C):
(A) 10% by mass to 90% by mass of the alkali-soluble polymer with respect to the total solid content of the photosensitive resin composition;
(B) 5% by mass to 70% by mass of the compound having an ethylenically unsaturated double bond based on the total solid content of the photosensitive resin composition; and (C) a photopolymerization initiator as the photosensitive resin composition. 0.01% by mass to 20% by mass with respect to the total solid content of
It is preferable to prepare by dissolving a photosensitive resin composition containing a solvent.

  In the embodiment, in order to achieve the step (1), a photosensitive resin solution supply means (for example, a feeder, a tube, etc.) and a means for adjusting the temperature of the photosensitive resin solution (for example, a photosensitive resin solution). Any means comprising at least a cold temperature control device, etc.) can be used. Preferably, the temperature adjustment in the step (1) is performed by a photosensitive resin solution supply unit and a jacket type heat exchanger attached to the supply unit, and the jacket type heat exchanger includes a static mixer and a plurality of heat exchangers. Preferably it includes a tube.

  In the jacket type heat exchanger including the static mixer and the plurality of tubes, it is preferable to optimize the number of tubes from the viewpoint of appropriately controlling the pressure loss. For this purpose, the jacketed multi-tube heat exchanger can include preferably 10 or more, more preferably 15 or more, and even more preferably 19 tubes. For example, in FIG. 3, a heat exchanger having 19 tubes 9 and an outer wall 8 is shown.

  A static mixer is a static mixer (for example, a line mixer) that can stir and mix fluid without the need for a drive unit, and can stir and mix fluid sequentially by individual elements installed in the line. . If a plurality of elements are installed in the line, they preferably have different shapes in order to divide, convert or invert the fluid. In FIG. 4, the photosensitive resin liquid that passes through the plurality of tubes 9 is shown as a flow A of the coating solution, and a static mixer that includes a plurality of elements is incorporated. It can be stirred and mixed as it passes.

  From the viewpoint of uniformizing the temperature of the photosensitive resin liquid that passes through the jacket-type multitubular heat exchanger, the static mixer is preferably mounted on more than half of the plurality of tubes included in the heat exchanger, More preferably, all the tubes are mounted.

  In order to adjust the temperature of the heat exchanger, it is preferable to pass a medium such as water, pure water, antifreeze, or oil through the jacket. In FIG. 1 it is shown that the medium is circulated between the heat exchanger 4 and the high-precision temperature control unit 5. FIG. 4 shows the inlet and outlet of the pipe 10 for circulating the medium, and the medium flow B, and the medium supplied from the high-precision temperature control unit 5 is passed from the vicinity of the jacket outlet, A convection circulation system for returning to the high-precision temperature control unit 5 again from the vicinity of the inlet is preferably used.

From the viewpoint of improving the uniformity of the coating film thickness and improving the accuracy of the thickness in the width direction of the photosensitive resin layer, the temperature of the photosensitive resin liquid is an error of ± 0.25 ° C. with respect to the target temperature. It is preferable to adjust within the range, and it is more preferable to adjust within the error range of ± 0.1 ° C. In general, the target temperature is preferably determined within a range of 15 ° C. to 45 ° C., and preferably equal to the temperature of the die head (ie, die head temperature = target temperature).
In the present embodiment, “an error range of ± X ° C.” means that the absolute value of the temperature difference between the temperatures measured for a plurality of measurement objects is X ° C. or less.

  It is preferable that the temperature of the photosensitive resin solution is measured by one or a plurality of resistance thermometers arranged upstream and / or downstream of the heat exchanger. For example, in FIG. 1, in the system for manufacturing a photosensitive element, one resistance temperature detector 18 is arranged upstream of the heat exchanger 4, and two resistance temperature detectors 18 are connected to the heat exchanger 4. It is shown that it is arranged further downstream.

  The jacket type heat exchanger including a static mixer and a plurality of tubes is preferably disposed upstream of the process of applying the photosensitive resin liquid in the system for manufacturing the photosensitive element. For example, in FIG. 1, it is shown that the heat exchanger 4 is arranged upstream of a coating apparatus having a die head 6 and a backup roll 7. In addition, the jacket type heat exchanger including the static mixer and the plurality of tubes is preferably disposed within about 5 m by linear distance from the coating apparatus, and more preferably within about 3 m. FIG. 1 shows the positional relationship between the coating apparatus having the die head 6 and the backup roll 7 and the heat exchanger 4, and more specifically, the linear distance W between the heat exchanger 4 and the die head 6 is about 5 m. Or less, more preferably about 3 m or less, and particularly preferably about 1 m or less.

  The viscosity of the photosensitive resin liquid is preferably 500 cps to 5000 cps, and more preferably 500 cps to 2000 cps. When the viscosity of the photosensitive resin liquid is 5000 cps or less, it is preferable that the beat is formed well in the gap between the backup roll and the upper surface of the die head (hereinafter referred to as “clearance”), so that no streak-like defects are generated. Thus, it is preferable that the viscosity of the photosensitive resin liquid is 500 cps or more because the coating liquid is prevented from leaking toward the base material in the clearance and no streak-like defects are generated.

  The temperature of the die head and the backup roll is preferably adjusted within an error range of ± 0.25 ° C. with respect to the target temperature determined within the range of 15 ° C. to 45 ° C., and an error of ± 0.10 ° C. More preferably, it is adjusted within the range. The temperatures of the die head and the backup roll are each preferably 14.75 ° C. or higher because the occurrence of condensation and the like can be suppressed. On the other hand, the temperatures of the die head and the backup roll are 45.25 ° C. and lower, respectively. It is preferable because the instruments in the coating apparatus can be used appropriately.

  A method for adjusting the temperature of the die head and the backup roll within an error range of ± 0.25 ° C. with respect to the target temperature is not particularly limited, but the temperature can be adjusted by connecting a cooling / cooling device to the die head and the backup roll in a circulating manner. A means for adjusting is preferable. In FIG. 5, in order to improve the temperature distribution of the backup roll 7, it is shown that the backup roll 7 has a cooling / temperature adjusting medium passage 13 through a rotary joint 12 therein. More specifically, the backup roll 7 may have an arbitrary form of the cooling / controlling medium passage 13 through the rotary joint 12 therein. For example, the cooling / controlling medium passage 13 may be spiral, cylindrical, angular It may be cylindrical. Furthermore, it is preferable that the cooling / controlling medium passage 13 has a spiral shape. On the other hand, in FIG. 5, in order to improve the temperature distribution of the die head 6 including the slit 15 and the manifold 16, the die head 6 preferably has two cold temperature control medium passages 17 penetrating the die head 6 in the longitudinal direction. As described above, it is shown that four or more are more preferable. It should be understood that the temperature control device (not shown) can be in fluid communication with the temperature control medium passage 13 or the temperature control medium passage 17.

  In addition, in order to prevent the gantry for installing the die head from being deformed by thermal expansion / shrinkage, and to improve the accuracy of the die head arranged on the gantry, the temperature of the gantry is in the range of 15 ° C to 45 ° C. It is preferable to adjust within an error range of ± 0.25 ° C. with respect to the target temperature determined in the above, and it is more preferable to adjust within an error range of ± 0.10 ° C. with respect to the target temperature. More specifically, the temperature of the die head gantry can be adjusted by installing a means for supplying a cooling / heating medium inside or outside the die head gantry. For example, in FIG. 5, the die head pedestal 11 preferably has a cooling / temperature adjusting medium passage 17 penetrating the die head pedestal 11 in the longitudinal direction in order to flow a medium supplied in a circulating manner from a cooling / temperature adjusting device (not shown). Is shown to have 2 or more, more preferably 4 or more.

  It is preferable that the surface of the die head facing the backup roll (for example, the upper surface of the die head) has a straightness error range of 1 μm or less per meter as a widthwise distribution. The straightness error range is expressed as a thickness change (maximum value−minimum value) per 1 m in the width direction of the die head surface. It is preferable that the straightness error range of the die head surface is 1 μm or less because the accuracy of the clearance becomes uniform in the width direction and a photosensitive element having a uniform thickness can be obtained. The error range of the straightness of the die head surface is more preferably about 0.5 μm.

  In addition, the surface facing the backup roll of the die head (for example, the upper surface of the die head) has a surface roughness Rz of 0.25 μm from the viewpoint of suppressing generation of a fine streak-like thickness distribution during application of the photosensitive resin liquid. Or less, more preferably 0.20 μm or less, and particularly preferably 0.15 μm or less.

The temperature difference between the temperature of the photosensitive resin solution and the temperature of the die head is preferably within a range of ± 0.25 ° C., and more preferably within an error range of ± 0.10 ° C.
The temperature difference between the temperature of the photosensitive resin solution, the temperature of the die head, and the temperature of the backup roll is preferably within an error range of ± 0.25 ° C., more preferably an error of ± 0.10 ° C. Within range.
Further, the temperature difference between the temperature of the photosensitive resin liquid, the temperature of the die head, the temperature of the backup roll, and the temperature of the gantry is preferably within an error range of ± 0.25 ° C., more preferably ± 0. Within the error range of 10 ° C.
Adjusting the temperature of the photosensitive resin solution, the temperature of the die head, the temperature of the backup roll, and / or the temperature of the gantry within the above error range can make the thickness of the photosensitive element more in the width direction. It is suitable from the viewpoint of keeping it uniform.

  Further, the temperature of the die head is preferably measured by one or a plurality of thermocouples attached to the die head body. The plurality of thermocouples can be attached on the die head surface at any direction and interval. For example, FIG. 5 shows that a plurality of thermocouples 19 are arranged on the side surface of the die head 6 in parallel in two rows along the longitudinal direction of the side surface at equal intervals of 50 mm.

  Moreover, it is preferable that the temperature of a backup roll and a mount is measured by applying a sensor (for example, infrared temperature sensor etc.) to each of a backup roll and a mount. The sensor can be applied to any part of the object to be measured, in any direction and at a distance, in a contact or non-contact manner. For example, in FIG. 5, in order to measure the temperature of the backup roll 7, an infrared temperature sensor is applied to a plurality of measurement points 20 set at equal intervals at a pitch of 100 mm along the longitudinal direction of the backup roll 7. On the other hand, in order to measure the temperature of the gantry 11, a plurality of measurement points 20 in which infrared temperature sensors are set in parallel in two rows along the longitudinal direction of the side surface of the gantry 11 and at equal intervals of 100 mm pitch. Is shown to apply.

  In the embodiment, it is preferable to dispose a means for releasing a dimensional change due to thermal expansion or cooling contraction in the bearing of the die head. When the die head is held by a bearing, this means is preferably achieved by a mechanism capable of absorbing the deformation amount of the die head that thermally expands and contracts by cooling at high and low temperatures, respectively. More specifically, as a mechanism capable of absorbing the deformation amount of the die head, for example, a linear guide provided under a bearing part can be cited. As a simpler mechanism, there is a method of absorbing the deformation amount of the die head by fixing the bearing only on one side and opening the other side.

  In the above-described embodiment, the temperature of the coating solution can be arbitrarily changed within a range of 15 ° C. to 45 ° C. in the method for manufacturing a photosensitive element. In addition, the photosensitive element having a uniform thickness can be provided by keeping the quality and thickness of the photosensitive element uniform in the width direction at the set temperature and improving the appearance of the photosensitive element. .

  In the above-described embodiment, in the method for manufacturing a photosensitive element, not only a means for arbitrarily changing the temperature of the coating solution within a range of 15 ° C. to 45 ° C. in a short time is provided, but also the thickness at the set temperature. There is also provided a photosensitive element having a uniform thickness and quality distribution in the width direction, an excellent appearance, and a uniform thickness. It is also possible to provide means for improving the thickness accuracy of the photosensitive resin layer obtained by applying and drying the photosensitive resin liquid.

  Furthermore, in the above-described embodiment, the photosensitive element can be produced at a higher temperature (for example, 45 ° C.) than the conventional method such as coating at about 23 ° C., so that the temperature can be increased without adding a solvent. It is possible to reduce the viscosity of the photosensitive resin solution, thereby reducing the amount of solvent used and suppressing the material cost. On the other hand, since the photosensitive element can be manufactured at a lower temperature (for example, 15 ° C.) than the conventional method, streaky defects are eliminated from the applied thin film, and the rate of decrease in the viscosity of the photosensitive resin liquid relative to the amount of solvent used The photosensitive element can be manufactured at a high speed without causing a reduction in production rate due to the addition of a solvent, thereby reducing time and energy.

The embodiment will be described more specifically with reference to examples and comparative examples, but the embodiment is not limited to the following examples unless it exceeds the gist. The parameters shown in the examples and comparative examples were measured by the following methods:
<Temperature of photosensitive resin liquid>
As shown in FIG. 1, the temperature is measured at three resistance thermometers (manufactured by Okazaki Manufacturing Co., Ltd.) installed upstream and downstream of the jacket type heat exchanger and immediately before the die coater, and the average value of each temperature is photosensitized. The temperature of the conductive resin liquid was used.
<Die head temperature>
As shown in FIG. 5, along the longitudinal direction of the die head side surface, the temperature was measured with a plurality of thermocouples (manufactured by Chino Co., Ltd.) arranged in parallel in two rows and at equal intervals of 50 mm, and the average of each temperature The value was the die head temperature.
<Backup roll temperature>
As shown in FIG. 5, an infrared temperature sensor (manufactured by Edox Co., Ltd.) is applied to a plurality of measurement points set at equal intervals at a pitch of 100 mm along the longitudinal direction of the backup roll, and each temperature is measured. Was the backup roll temperature.
<Stage temperature>
As shown in FIG. 5, an infrared temperature sensor (manufactured by Edox Co., Ltd.) is applied to a plurality of measurement points set in parallel in two rows along the longitudinal direction of the side surface of the gantry and at equal intervals of 100 mm. The temperature was measured, and the average value of each temperature was taken as the temperature of the gantry.
<Acid equivalent of resin>
Hiranuma Sangyo Co., Ltd. Hiranuma automatic titrator (COM-555) was used, and the acid equivalent of the resin was measured by potentiometric titration using a 0.1 mol / L aqueous sodium hydroxide solution.
<Weight average molecular weight of resin>
Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) was used to determine the weight average molecular weight of the resin.

<Preparation example 1 of photosensitive resin liquid>
The compound shown below was mixed and the photosensitive resin liquid was prepared.
Methyl ethyl ketone solution of terpolymer of methyl methacrylate 50% by mass, methacrylic acid 25% by mass and styrene 25% by mass (solid content concentration 35%, weight average molecular weight 50,000, acid equivalent 344, dispersity 3.1) ... Polyethylene glycol dimethacrylate with 254 parts by mass of bisphenol A on each side added with an average of 2 moles of ethylene oxide (NK Sell BPE-200, Shin-Nakamura Chemical Co., Ltd.)
... Dimethacrylate of polyalkylene glycol in which propylene oxide and ethylene oxide are added in an average of 2 moles each on both ends of 15 parts by weight bisphenol A, respectively.
... 30 parts by mass β-hydroxypropyl-β '-(acryloxy) propyl phthalate
... 5 parts by mass of trioxyethyltrimethylolpropane triacrylate (NK Nakamura Chemical Co., Ltd. NK ester A-TMPT-3EO)
... 5 parts by mass 4,4'-bis (diethylamino) benzophenone
... 0.3 parts by mass 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer
... 3 parts by weight diamond green (Eizen (registered trademark) DIAMOND manufactured by Hodogaya Chemical Co., Ltd.)
GREEN GH)
... 0.15 parts by mass leuco crystal violet
... 0.4 parts by mass

<Photosensitive resin liquid preparation example 2>
A solvent (methyl ethyl ketone) was further added to the photosensitive resin solution prepared in Preparation Example 1, and the mixture was stirred in a preparation tank at a temperature of 30 ° C. and a stirring rotation speed of 55 rpm for 4 hours to obtain a new photosensitive resin solution.

<Experiment 1>
The temperature of the backup roll and the die head is kept at 23 ° C. (room temperature), the temperature of the photosensitive resin solution is changed, and the 16 μm thick PET film (manufactured by Toray Industries, Inc.) has a width of 1600 mm with a width of 1650 mm. After coating and drying, a polyethylene film (manufactured by Tamapoly Co., Ltd.) was bonded to obtain a photosensitive element having a three-layer structure. As an evaluation item, a thickness variation in the width direction was measured using a rotary caliper (manufactured by Meisho Co., Ltd.), and as a quality survey, transmittance was measured by a spectrophotometer (manufactured by Shimadzu Corporation) to confirm a hue change. In the quality survey, when no color development or gelation was observed, the evaluation was “good”. In addition, the thickness variation evaluation was performed according to the following criteria (the same applies to the following experiments 2 to 4):
When dry thickness is 30 μm ×: 5.0% or more Δ: 2.1% to 4.9%
○: 1.0% to 2.0%
A: 0.1% to 0.9%
In addition, about the change of the temperature of the photosensitive resin liquid, the temperature control method which makes a preparation tank and liquid feeding piping double, and the method of arrange | positioning the heat exchanger shown by FIGS. And compared. The experimental results are shown in Table 1 below.

  It can be seen from Table 1 that good results can be obtained when a heat exchanger is incorporated in the liquid feed line and the temperature difference between the backup roll and die head and the coating liquid is within ± 0.25 ° C. More specifically, the photosensitive resin solution generally deteriorates with time when the temperature is 35 ° C. or higher. Therefore, when the temperature is adjusted with a conventional compounding tank and a double pipe of the piping, the time that is maintained at 35 ° C. or longer is long. It is confirmed that the color changes or gels. On the other hand, when the heat exchanger shown in FIGS. 2 to 4 is arranged immediately before the coating apparatus, the temperature of the photosensitive resin liquid can be instantaneously changed immediately before the coating apparatus. It is confirmed that the time during which the photosensitive resin solution is maintained at a temperature of 35 ° C. or more can be extremely reduced by applying the photosensitive resin solution immediately after the preparation.

<Experiment 2>
When the temperature of the photosensitive resin solution is adjusted to 15.00 ° C. using the heat exchanger shown in FIGS. 2 to 4 and the temperatures of the backup roll and the die head are as shown in Table 2 below, The resin solution was applied, and the thickness variation in the width direction was measured using a rotary caliper (manufactured by Meisei Co., Ltd.).

  From Table 2, it was confirmed that when the temperature of the backup roll and the die head was ± 0.25 ° C. or less with respect to the temperature of the photosensitive resin liquid, a good thickness distribution was obtained.

<Experiment 3>
As shown in Table 3 below, the temperature of the die head frame is adjusted, or the presence or absence of means for escaping the thermal expansion or cooling shrinkage of the die head is confirmed and evaluated in the same manner as in Experiments 1 and 2, and the temperature of the die head frame is adjusted. It was confirmed that a more uniform thickness distribution in the width direction could be obtained by implementing both the means and the means for releasing the thermal expansion or cooling shrinkage of the die head.

<Experiment 4>
As shown in Table 4 below, when the straightness or surface roughness of the die head upper surface was changed and the thickness variation and appearance of the photosensitive element were evaluated in the same manner as in Experiments 1 to 3, the straightness of the die head upper surface was 1.0 μm. It was confirmed that the best results were obtained when the surface roughness was within the range of 0.2 μm.

  The photosensitive element according to the embodiment has high sensitivity and high resolution, so that a printed wiring board, a flexible substrate, a lead frame substrate, a chip-on-film (COF) substrate, a semiconductor package substrate, a transparent electrode for liquid crystal It can be used for the production of conductor patterns such as liquid crystal TFT wiring and plasma display panel (PDP) electrodes.

DESCRIPTION OF SYMBOLS 1 Mixing tank 2 Pump 3 Filter 4 Heat exchanger 5 High-precision temperature control unit 6 Die head 7 Backup roll 8 Outer wall 9 Tube 10 Tube for circulating a medium 11 Die head mount 12 Rotary joint 13 Cooling temperature control medium passage 14 Die head upper surface 15 Slit 16 Maneuver 17 Cooling medium passage 18 Resistance thermometer 19 Thermocouple 20 Measurement point of infrared temperature sensor A Flow of coating liquid B Flow of medium W Linear distance between heat exchanger and die head

Claims (11)

The following steps:
(1) A photosensitive resin solution adjusted within an error range of ± 0.25 ° C. with respect to a target temperature set within a range of 15 ° C. to 45 ° C., along a die head installed on a gantry and a longitudinal axis of the die head And (2) discharging the photosensitive resin liquid from the coating device onto a base film placed on the backup roll, and supplying the coating film to the base film. Applying the photosensitive resin solution to obtain a photosensitive element;
The manufacturing method of the photosensitive element containing this.   The temperature adjustment in the step (1) is performed by a jacket type heat exchanger including a static mixer and a plurality of tubes attached to the photosensitive resin solution supply unit and the supply unit. Method.   The method according to claim 1 or 2, wherein the photosensitive resin solution has a viscosity at 25 ° C of 500 cps to 5000 cps.   The temperatures of the die head and the backup roll are adjusted within an error range of ± 0.25 ° C with respect to a target temperature determined within a range of 15 ° C to 45 ° C, respectively. 2. The method according to item 1.   The surface of the die head facing the backup roll has a straightness error range of 1 μm or less per meter as a lateral distribution, and a surface roughness Rz of 0.25 μm or less. The method of any one of these.   6. The method according to claim 1, wherein the temperature of the gantry is adjusted within an error range of ± 0.25 ° C. with respect to a target temperature defined within a range of 15 ° C. to 45 ° C. 6. .   The method according to any one of claims 1 to 6, wherein a means for releasing a dimensional change due to thermal expansion or cooling contraction is arranged on a bearing of the die head.   The method according to any one of claims 1 to 7, wherein a temperature difference between the photosensitive resin liquid and the die head is adjusted within a range of ± 0.25 ° C.   The method according to any one of claims 1 to 7, wherein a temperature difference between the photosensitive resin liquid, the die head, and the backup roll is adjusted within a range of ± 0.25 ° C.   The method according to any one of claims 1 to 7, wherein a temperature difference between the photosensitive resin liquid, the die head, the backup roll, and the mount is adjusted within a range of ± 0.25 ° C. . For the total solid content of the photosensitive resin composition:
(A) 10% by mass to 90% by mass of the alkali-soluble polymer;
(B) 5% by mass to 70% by mass of a compound having an ethylenically unsaturated bond; and (C) 0.01% by mass to 20% by mass of a photopolymerization initiator;
The method of any one of Claims 1-10 which melt | dissolves the photosensitive resin composition containing in a solvent, and obtains the said photosensitive resin liquid.

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