JP4842029B2 - Method for forming precision fine space, and method for manufacturing member having precision fine space - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a precision minute space having a regular shape and regular volume, a method for producing a member having the precision minute space having the regular shape and the regular volume, etc. <P>SOLUTION: In the precision minute space forming method including a process for placing a film on a substrate having a precision minute recess, in the film placing process, the film is placed while the pressure per unit contact area of a contact part where the substrate and the film are brought into contact is controlled to be constant to form the precision minute space having the regular shape and the regular volume. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

The present invention relates to the production how member having a method of forming the precision fine space formed by laying a film on the substrate, and a precision fine space having a precision fine concave portion, and more particularly the base and film the method of forming the precision fine space laying while controlling the pressure per unit contact area of the contact portion in contact with the constant relates to the production how member having, and precision fine space.

  2. Description of the Related Art In recent years, in the industrial field, attention has been paid to a technique for obtaining various actions by forming a precise fine space in various products and further forming a member having this fine space. For example, a precise fine space is formed in a semiconductor device, a technique using an air layer existing in this space as a dielectric layer, and a large number of fine fine spaces are formed to generate pressure electrically or thermally inside. Technologies such as a liquid ejecting apparatus that incorporates elements and ejects a liquid such as ink filled in a precise fine space quantitatively and continuously have been developed.

  As a method for forming such a precise fine space, for example, Patent Document 1 discloses a method for forming a continuous fine fine space of an ink pool for supplying ink to an ink pressure chamber, and forming a side wall of each space. A method of forming a precise fine space by laminating a plurality of plate-like members having large and small holes and integrating them with an adhesive is disclosed.

For example, in Patent Document 2, a metal layer is formed on a resin film, the metal layer is intermittently removed using sandblasting and etching, and a plate member is bonded so as to surround the obtained recess. Thus, a method for forming an ink pressure chamber is disclosed.
JP 2001-63052 A Japanese Patent Laid-Open No. 11-342607

  However, the conventional method for forming a precise fine space has a problem that the number of parts to be used is large and the manufacturing accuracy is severe, so that the number of manufacturing steps is increased. Furthermore, the selectivity of the material to be used is narrow, and as a result, it has been difficult to improve the production efficiency and the production cost.

  In order to solve such a problem, a film that becomes a top plate portion is laid on a base material having a precision fine recess formed on the surface, and is laid by using a contact member in order to lay the film. A method for forming a fine space has been proposed.

  However, since the unit contact area of the contact portion that is in contact with the base material and the film differs between the central portion and the peripheral portion of the base material, even if the moving speed of the contact portion is constant, the central portion and the peripheral portion of the base material There is a problem that the shape and volume of the precise fine space in the part are not constant. That is, in the central part of the base material, even if it is a precise fine recess as shown in FIG. 1B, the unit contact area of the contact part in contact with the base material and the film is in the peripheral part of the base material. Since it becomes high, there is a tendency to apply more pressure than necessary, and the film enters the fine fine recess as shown in FIG. In particular, when the precise fine space is used as a liquid ejection head or the like, the shape and volume of the precise fine space are required to be constant. Moreover, when forming a fine fine space after putting a part etc. in a fine fine recessed part, it will cause defects, such as a film and a part contacting and a part not working. Therefore, it is ideal that all the fine fine spaces in the substrate have a shape in which the film does not erode into the fine fine spaces as shown in FIG. On the other hand, when the pressure per unit contact area of the contact portion where the substrate and the film are in contact with each other is reduced, the center portion of the substrate has a precision fine recess as shown in FIG. The adhesive strength with the film becomes weak, and the film peels off.

In view of the above problems, the present invention aims to provide a manufacturing how the member shape and volume of the precision fine space has a constant der Ru forming method of precision fine space, and precision fine space To do.

  The present inventors have made extensive studies to solve the above problems. As a result, the pressure per unit contact area of the contact portion where the substrate and the film are in contact with each other is found to be constant so that the film does not enter the precision fine recess, and the present invention has been completed. . More specifically, the present invention provides the following.

  In the method for forming a precise fine space having a step of laying a film on a substrate having a precision fine recess, the step of laying the film is per unit contact area of the contact portion where the substrate and the film are in contact with each other. The above-mentioned problem can be solved by a method for forming a precise fine space, which is a step of laying while controlling the pressure to be constant.

  In the above formation method, by laying while controlling the pressure per unit contact area of the contact portion where the substrate and the film are in contact with each other, a precise fine space in the peripheral portion of the substrate and the center portion of the substrate The shape and volume of the precise fine space in can be made constant. The “base material having a precision fine recess” means a base material on which at least one precision fine recess is formed on the surface.

  Here, “pressure per unit contact area” means that the pressure applied to the contact portion when the substrate and the film are brought into contact with each other in order to lay the film on the substrate. The pressure divided by the area.

  The above-mentioned problem can also be solved by a photosensitive laminated film, which is a film used in the above-described method for forming a precise fine space, wherein a photosensitive composition layer and a support film are laminated.

  By using the photosensitive laminated film, deformation of the photosensitive composition layer can be prevented, and a precise fine space having a certain shape and volume can be efficiently provided.

  In the method for producing a member having a precision fine space having a step of laying a film on a substrate having a precision fine recess, the step of laying the film is a contact portion where the substrate and the film are in contact with each other The above-mentioned problem can also be solved by a method for producing a member having a precise fine space, which is a step of laying while maintaining a constant pressure per unit contact area.

  According to the method for producing a member having a fine fine space of the present invention, the shape and volume of the fine fine space in the peripheral portion of the base material and the precise fine space in the central portion of the base material can be made constant.

  According to the present invention, by controlling the pressure per unit contact area of the contact portion where the substrate and the film are in contact with each other, the fine fine recesses in the central portion and the fine fine recesses in the peripheral portion are controlled. It became possible to control the shape and volume of the precise fine space to be constant. As a result, a precise fine space having a constant shape and volume can be efficiently formed, and a member having a precise fine space having a constant shape and volume can be efficiently produced.

  Moreover, according to this invention, after laying the photosensitive laminated | multilayer film on a base material, it came to be able to form easily the top-plate part excellent in dimensional accuracy by making it photocure. In addition, by using the photosensitive composition layer as the top plate part, high sensitivity, small volume shrinkage at the time of heat curing, good dimensional stability, and multifunctional fine space can be easily formed. Can now.

  The present invention is characterized in that the pressure per unit contact area of the contact portion where the substrate and the film are in contact is controlled to be constant. As a result, it has become possible to solve the problem that the shape and volume of the precise fine space obtained from the fine fine recesses in the central part of the substrate and the fine fine recesses in the peripheral part cannot be controlled to be constant. Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. For convenience of explanation, the case where the film is a photosensitive laminated film will be described. However, even if a film other than the photosensitive laminated film is used, the present invention can be implemented by the same manufacturing method and forming method, etc. It is not intended to limit the purpose.

  FIG. 2 is a diagram showing the overall flow of the method for forming a fine fine space and the method for producing a member having a fine fine space according to the present invention.

  The base material 3 having the precision fine recess 31 is placed on the stage 1. The photosensitive composition layer 42 in the photosensitive laminated film 4 becomes a top plate portion of the precision fine recess 31, and the photosensitive laminated film 4 is a photosensitive composition layer 42 and a support film that supports the photosensitive composition layer 42. 41 and a protective film 43 for protecting the photosensitive composition layer 42 are laminated. Further, on the stage 1, a contact member 2 for laying the photosensitive laminated film 4 on the substrate 3 is provided. In order to lay the photosensitive laminated film 4 on the substrate 3, the contact member 2 may be press-contacted as necessary.

  The precision fine recess 31 formed on the base material 3 can be formed by using a known method as appropriate according to the purpose of use, etc., but it has high sensitivity and small volume shrinkage during heat curing. In order to form a good precision fine space, it is preferable to form the precision fine recess 31 by a photoresist pattern.

  Although the height (depth) of the precision fine recessed part 31 is not specifically limited, It is preferable that it is 0.1 micrometer-1 mm, and a shape etc. are not specifically limited. Moreover, although the precision fine recessed part 31 can be changed suitably according to a use purpose etc., it is a recessed part 1 mm or less in width and 1 mm or less in depth. A member having a precise fine space is mainly formed in an electronic component, for example, a liquid discharge head such as a SAW filter, an ink jet head, a resist droplet discharge head, a DNA droplet discharge head, a micro pump, a micro It can be used for optical arrays, micro switches, micro relays, optical switches, micro flow meters, pressure sensors, and the like.

  The protective film 43 that protects the photosensitive composition layer 42 is peeled off halfway to expose the photosensitive composition layer 42, and the contact member 2 lays the photosensitive laminated film 4 on the substrate 3. The contact member 2 is not particularly limited in shape and the like as long as the photosensitive laminated film 3 can be laid on the substrate 2, but it is preferable to use a roller from the viewpoint of work efficiency and the like.

  FIG. 3 is a diagram illustrating a state in which the photosensitive laminated film 4 is laid on the base material 3 while the contact member 2 moves on the base material 3 and the photosensitive laminated film 4 under pressure. When the contact member 2 is moved from the point (starting point) at which the contact portion between the base material 3 and the photosensitive laminated film 4 (not shown) is started to the center portion of the base material 3, the pressure of the contact portion Is constant, the pressure per unit contact area of the contact portion in contact with the photosensitive laminated film 4 gradually decreases. That is, when the contact portion reaches the center portion of the substrate 3, the pressure per unit contact area of the contact portion in contact with the photosensitive laminated film 4 is minimized. Therefore, if the pressure of the contact portion is gradually increased from the starting point to the center portion, the pressure per unit contact area of the contact portion in contact with the photosensitive laminated film 4 can be controlled to be constant.

  On the other hand, when the contact portion reaches the center of the base material 3 and is moved to the point (end point) where the laying of the photosensitive laminated film 4 is finished on the base material 3, the base material is gradually increased when the pressure of the contact portion is constant. 3 and the pressure per unit contact area of the contact portion in contact with the photosensitive laminated film 4 is increased. That is, when the contact portion reaches the end point of the substrate 3, the pressure per unit contact area of the contact portion in contact with the photosensitive laminated film 4 becomes maximum. Therefore, if the pressure at the contact portion is gradually reduced from the central portion to the end point, the pressure per unit contact area of the contact portion in contact with the photosensitive laminated film 4 can be controlled to be constant.

  FIG. 3 illustrates the case where the base material 3 has a circular shape, but the base material 3 is not limited to a circular shape, and the base material 3 and the photosensitive property gradually move from the starting point toward the center. The pressure per unit contact area of the contact portion in contact with the laminated film 4 is increased, and the unit contact area of the contact portion in which the base material 3 and the photosensitive laminated film 4 are gradually in contact from the center to the end point. What is necessary is just to make the hit pressure small.

The pressure per unit contact area of the contact portion where the substrate 3 and the photosensitive laminated film 4 are in contact with each other is 0 in order to obtain a member having a precise fine space and a precise fine space as shown in FIG. 0.1 to 1 MPa / cm ² is preferable, and 0.3 to 0.6 MPa / cm ² is more preferable. By setting the pressure per unit contact area of the contact portion where the substrate 3 and the photosensitive laminated film 4 are in contact to be 0.1 MPa / cm ² or more, as shown in FIG. It is possible to prevent a precise fine space from being formed due to insufficient adhesion with the photosensitive laminated film 4. On the other hand, by setting the pressure per unit contact area of the contact portion where the base material 3 and the photosensitive laminated film 4 are in contact to 1 MPa / cm ² or less, as shown in FIG. It is possible to prevent the photosensitive laminated film 4 from entering.

  The moving speed of the contact member 2 when laying the photosensitive laminated film 4 on the base material 3 can be appropriately changed according to the number of precision fine recesses 31 included in the base material 3. It is preferably 5 m / min. By setting the moving speed of the contact member 2 to 0.1 m / min or more, it is possible to prevent the photosensitive laminated film 4 from entering the precise fine space as shown in FIG. The shape and volume of the fine space can be made constant. On the other hand, by setting the moving speed of the contact member 2 to 1 m / min or less, a precise fine space is not formed due to insufficient adhesion between the base material 3 and the photosensitive laminated film 4 as shown in FIG. Can be prevented, and the volume of the plurality of precision fine spaces can be made constant.

  The temperature (roller temperature) of the contact member 2 and the temperature of the stage 1 when laying the base material 3 and the photosensitive laminated film 4 are appropriately changed according to the number of precision fine recesses 31 provided in the base material 3. However, it is preferably 20 to 80 ° C. By setting each temperature to 20 ° C. or more, it is possible to prevent a precise fine space from being formed due to insufficient adhesion between the base material 3 and the photosensitive laminated film 4 as shown in FIG. The shape and volume of the plurality of precision fine spaces can be made constant. On the other hand, by setting each temperature to 80 ° C. or less, it is possible to prevent the photosensitive laminated film 4 from entering the precise fine space as shown in FIG. Can be made constant.

  After laying the photosensitive laminated film 4 on the substrate 3 with the contact member 2, the excess photosensitive laminated film 4 not in close contact with the substrate 3 is cut off. The substrate 3 to which the photosensitive laminated film 4 is in close contact is taken out from the stage 1, the photosensitive composition layer 42 is exposed through the support film 41, and then heat-treated to cure the photosensitive composition layer 42. Thereafter, the support film 41 is peeled from the cured photosensitive composition layer 42, and the cured photosensitive composition layer 42 is main-cured by reheating, and a top plate portion is formed on the precision fine recess 32, A precise fine space is formed. The curing temperature for curing the photosensitive composition layer 42, the heating temperature for heat treatment, and the like can be appropriately changed according to the substance used for the photosensitive composition layer 42 and the like. Moreover, the process which heat-processes and hardens the photosensitive composition layer 42 as needed, such as when forming precise fine space using other than the photosensitive laminated | multilayer film 4, can be skipped.

  In the photosensitive laminated film 4 used in the present invention, the photosensitive composition layer 42 becomes a top plate portion of the precision fine recess 31, and further, the photosensitive composition layer 42 is exposed, cured, etc., and thus has excellent dimensional accuracy. A member having a precise fine space can be manufactured.

  As described above, the photosensitive laminated film 4 used in the present invention is laminated in the order of the support film 41, the photosensitive composition layer 42, and the protective film 43. As the protective film 43, various known films such as a polyethylene terephthalate film, a polypropylene film, and a polyethylene film can be used, and these may be used alone or in combination.

  The photosensitive composition constituting the photosensitive composition layer 42 is preferably a chemically amplified negative photosensitive resin composition.

  A photosensitive resin composition comprising a polyfunctional epoxy resin and a cationic polymerization initiator as a photosensitive resin composition constituting the photosensitive composition layer 42 suitably used for the photosensitive laminated film 4 of the present invention. It is preferable that By combining the polyfunctional epoxy resin and the cationic polymerization initiator, it is possible to form a precise fine space with high sensitivity and small volume shrinkage during heat curing. Various combinations of these are possible, but in particular, an 8-functional bisphenol A novolac type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name: Epicoat 157S70) and 4- {4- (2-chloro A combination with benzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (Asahi Denka Kogyo Co., Ltd., trade name: Adekaoptomer SP-172) is most preferred.

  The cationic polymerization initiator has a high generation efficiency of cations by irradiation of radiation, so it may be contained in a relatively small amount. By combining with the polyfunctional epoxy resin, the sensitivity of the photosensitive composition layer 42 can be greatly increased. it can. In addition, the cationic polymerization initiator has a specific compatibility with a polyfunctional epoxy resin, in particular, a polyfunctional epoxy resin that can efficiently attack the epoxy group in the molecule of the polyfunctional bisphenol A novolac type epoxy resin to advance the polymerization. Therefore, it has an excellent effect. Furthermore, this combination has the effect of reducing volume shrinkage of the photosensitive composition layer 42 during heat curing. Therefore, if the photosensitive composition layer 42 using such a photosensitive resin composition is used, it is possible to form a top plate portion of a precision fine space with excellent dimensional accuracy, and to have a certain shape and volume. It is possible to manufacture a member having a precise fine space by forming a precise fine space and having a certain shape and volume.

  The cationic polymerization initiator contained in the photosensitive composition layer 42 generates cations upon irradiation with radiation such as ultraviolet rays, far ultraviolet rays, excimer lasers such as KrF and ArF, X-rays, and electron beams. A compound that can serve as a polymerization initiator, specifically, at least one selected from aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, aromatic phosphonium salts, and silanol / aluminum complexes. These may be used alone or in combination.

  As the cationic polymerization initiator, more specifically, as an aromatic sulfonium salt-based cationic polymerization initiator, for example, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (4-benzoylphenylthio) ) Phenylbis (4-hydroxyethyloxyphenyl) sulfonium hexafluoroantimonate, 4- (4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (4-benzoylphenylthio) phenyl Bis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- {4- (3-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate 4- (4-benzoylphenylthio) phenylbis (4-methylphenyl) sulfonium hexafluoroantimonate, 4- (4-benzoylphenylthio) phenylbis (4-hydroxyethylphenyl) sulfonium hexafluoroantimonate, 4- { 4- (4-hydroxyethyloxybenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- {4- (4-hydroxyethyloxybenzoyl) phenylthio} phenyldiphenylsulfonium hexafluoroantimonate, 4 -{4- (4-hydroxyethyloxybenzoyl) phenylthio} phenylbis (4-hydroxyethyloxyphenyl) sulfonium hexafluoroantimonate, 4- (4- Zoylphenylthio) phenylbis (4-methoxyethoxyphenyl) sulfonium hexafluoroantimonate, 4- {4- (3-methoxybenzoyl) phenylthio} phenyldiphenylsulfonium hexafluoroantimonate, 4- {4- (3-methoxycarbonyl) Benzoyl) phenylthio} phenyldiphenylsulfonium hexafluoroantimonate, 4- {4- (2-hydroxymethylbenzoyl) phenylthio} phenyldiphenylsulfonium hexafluoroantimonate, 4- {4- (4-methylbenzoyl) phenylthio} phenylbis ( 4-fluorophenyl) sulfonium hexafluoroantimonate, 4- {4- (4-methoxybenzoyl) phenylthio} phenylbis (4-fluorophenyl) Sulfonium hexafluoroantimonate, 4- {4- (4-fluorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- {4- (2-methoxycarbonylbenzoyl) phenylthio} phenylbis ( 4-fluorophenyl) sulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- ( Diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl 4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, Triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (di (4- (2 -Hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (di (4- (2-hydroxyethoxy) )) Phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) can be given borate. Among these compounds, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (4-benzoylphenylthio) phenylbis (4-hydroxyethyloxyphenyl) sulfonium hexafluoroantimonate, 4- (4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- {4- (3 -Chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate is more preferable, “Adekaoptomer SP-172” [4- {4- ( -Chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate] “Adekaoptomer SP-170” manufactured by Asahi Denka Kogyo Co., Ltd. is preferably used, and these may be used alone or in combination. May be used.

  Examples of the iodonium salt-based cationic polymerization initiator include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, and bis (dodecylphenyl) iodonium hexafluoro. Phosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) Phenyl iodonium hexafluorophosphate, 4-methylphenyl-4- (1-mes Ruethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate Etc. Among these compounds, Ciba Specialty Chemicals “DI-1” and “DI-2” are preferably used, and a plurality of these may be used in combination.

  Examples of diazonium salt-based cationic polymerization initiators include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate, which are used alone. It may be used in combination.

  When the composition ratio of the cationic polymerization initiator in the photosensitive composition layer 42 is too high, development of the photosensitive composition layer 42 becomes difficult. Conversely, when the composition ratio is too low, the photosensitive composition layer 42 Curing time by radiation exposure of 42 becomes long. Considering these, the composition ratio of the cationic polymerization initiator is preferably 0.1% to 10%, and more preferably 0.5% to 5%.

  The photosensitive resin composition constituting the photosensitive composition layer 42 may further contain a polymer linear bifunctional epoxy resin for improving film formability.

  The photosensitive resin composition constituting the photosensitive composition layer 42 can further contain a naphthol type sensitizer. When the sensitivity is high, if there is a gap between the mask and the resist surface, the resulting resin pattern will become thicker than the mask as a result of exposure, but it contains a naphthol type sensitizer. Therefore, this fat phenomenon can be suppressed without lowering the sensitivity. It is preferable to add the naphthol type sensitizer in this manner because an error of the resist pattern dimension with respect to the mask pattern dimension can be suppressed.

  Examples of the naphthol type sensitizer include 1-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, and the like. From the viewpoint of the effect of suppressing the resist thickness without reducing the sensitivity. -Preferably naphthol is used.

  When the composition ratio of the naphthol type sensitizer in the photosensitive composition layer 42 is too high, it is not preferable from the viewpoint that a reverse taper shape is obtained and the line width is too thin. Considering these, the composition ratio of the naphthol type sensitizer is preferably 0 to 10%, and more preferably 0.1 to 3%.

  The photosensitive resin composition constituting the photosensitive composition layer 42 can further contain a solvent. The sensitivity of the photosensitive composition layer 42 can be increased by containing a solvent. Examples of such a solvent include propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”), methyl isobutyl ketone (hereinafter referred to as “MIBK”), butyl acetate, methyl amyl ketone (2-heptanone), and ethyl acetate. , And methyl ethyl ketone (hereinafter referred to as “MEK”), and the like. These may be used alone or in combination.

  In the case of a liquid resist, it is preferable to use γ-butyrolactone as a solvent because the solvent reacts and is taken into the resist. In consideration of forming into a dry film, the wettability with the substrate 3 and the surface From the point of tension, it is preferable to use PGMEA, MIBK, butyl acetate, MEK or the like.

  The photosensitive resin composition constituting the photosensitive composition layer 42 can further contain an oxetane derivative and an epoxy derivative. When formed into a dry film, by containing an oxetane derivative or an epoxy derivative, the flexibility of the photosensitive composition layer 42 before curing can be increased without lowering the physical properties of the photosensitive composition layer 42 after curing. . Such an oxetane derivative is not particularly limited. For example, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [[(3-ethyl-3-oxetanyl) methoxy] methyl] benzene, di [1- Ethyl (3-oxetanyl)] methyl ether and the like, and a plurality of these may be used in combination. Examples of such epoxy derivatives include bisphenol A type epoxy resins and bisphenol F type epoxy resins having an average molecular weight of 7000 or less, preferably 2000 or less, more preferably 1000 or less. Specific examples include bisphenol A type epoxy resin (“Epicoat 828” average molecular weight 380 manufactured by Japan Epoxy Resin Co., Ltd.).

  The photosensitive composition layer 42 used in the photosensitive laminated film 4 of the present invention may further contain miscible additives as desired, for example, additional resins, plasticizers, stabilizers, colorings for improving pattern performance. As necessary, known agents, surfactants and the like can be added and contained.

  Although the thickness of the photosensitive composition layer 42 can be appropriately changed according to the purpose of use and the like, it is preferably 2 to 500 μm, and more preferably 5 to 200 μm.

  In order to obtain the photosensitive laminated film 4 from the photosensitive composition layer 42, the photosensitive composition layer 42 is formed into a dry film shape with both surfaces protected by a resin film, and has a desired precision fine recess 31 before pattern exposure. You may make it stick on a member.

  The support film 41 supports the photosensitive composition layer 42 until the photosensitive composition layer 42 is completely cured before being exposed. That is, deformation of the photosensitive composition layer 42 is prevented. Therefore, it is necessary to have a predetermined heat shrinkage rate, a predetermined thickness, and a predetermined haze value.

  As the support film 41, it is preferable to use a resin film having a longitudinal shrinkage ratio of 0.01 to 1% by heating at 100 ° C. for 30 minutes, and a longitudinal shrinkage ratio by heating at 150 ° C. of 30 minutes of 4% or less. It is more preferable to use a resin film having a longitudinal shrinkage rate of 3% or less by heating at 200 ° C. for 10 minutes. In addition, a deformation | transformation of the photosensitive composition layer 52 can be prevented by making a vertical contraction rate into 0.01 to 1% or more. Moreover, it is preferable that the thickness is 6-350 micrometers, and it is more preferable that it is 10-100 micrometers. Furthermore, the haze value is preferably from 0.1 to 5, and more preferably from 0.1 to 3 (at a film thickness of 30 μm). Specifically, polyethylene terephthalate is preferable as the material of the support film 5, and polyethylene, polypropylene, and the like can also be used. The support film 51 is preferably subjected to a release treatment so that it can be easily peeled off as necessary.

  The photosensitive laminated film 4 having the photosensitive composition layer 42 is laid on the substrate 3 having the desired precision fine recesses 31, and the photosensitive composition layer 42 is patterned by radiation without peeling off the supporting film 41. After the exposure and the application of heat to accelerate the curing, the support film 41 is peeled off and developed with a developing solution. When the substrate 3 has the fine fine recesses 31, a good resin pattern faithful to the mask pattern is obtained. It can be formed without depending on the shape. Thereby, it is possible to form a precise fine space having a constant shape and volume, and to manufacture a member having a precise fine space having a constant shape and volume.

  The method for forming a precise fine space and the method for producing a member having a precise fine space according to the present invention may be realized by executing a program prepared in advance by a computer such as a personal computer. This program may be recorded on a computer-readable recording medium such as a hard disk, a CD-ROM, or a DVD, and may be executed by being read from the recording medium by the computer.

  Examples of the present invention will be described below. However, these examples are merely examples for suitably explaining the present invention, and do not limit the present invention.

(Photosensitive composition layer 42)
A photosensitive composition layer 42 was obtained by dissolving and mixing 100 parts by weight of an epoxy resin (JER157s70 manufactured by Japan Epoxy Resin Co., Ltd.) and 3 parts by weight of an acid generator (ADEKA OPTMER SP172 ADEKA Co., Ltd.) in PGMEA. . The film thickness of the photosensitive composition layer 42 was 30 μm.

(Formation of photosensitive laminated film 4)
On the support film 51 having a film thickness of 50 μm made of a polyethylene terephthalate film with a release agent (Purex A53 manufactured by Teijin DuPont Films), the photosensitive composition layer 42 prepared as described above was uniformly applied, and hot air convection was performed. It was dried at 65 ° C. for 5 minutes and at 80 ° C. for 5 minutes by a dryer. Thereafter, a protective film 43 having a film thickness of 25 μm made of a polyethylene terephthalate film with a release agent (Purex A31 manufactured by Teijin DuPont Films) was laminated on the photosensitive composition layer 42 to form a photosensitive laminated film 4.

(Precision of fine space)
A circular substrate 3 having a diameter of 300 mm and having precision fine recesses 31 formed by a photoresist pattern was placed on the stage 1. The precision fine recess 31 had a height (depth) of 30 μm and a width and depth of 100 μm.

Next, the photosensitive laminated film 4 from which the protective film 43 was peeled was placed on the base material 3 having the precision fine recesses 31. A roller is used as the contact member 2, the roller roll temperature is 50 ° C., the moving speed is 0.5 m / min, and the pressure per unit contact area of the roller contacting the substrate 3 and the photosensitive laminated film 4 is constant. The photosensitive laminated film 4 was laid (laminated) on the substrate 3 so as to be. The width of the roller in contact with the photosensitive laminated film 4 at this time is 1 mm, the pressure (P ₁ ) at the start point and the end point is 1 × 10 ⁻³ MPa, and the pressure (P ₂ ) at the center is 0.15 MPa. there were.

The pressure Pa at the point a where the roller moved 50 mm on the substrate 3 was 223.6 × 10 ⁻³ MPa. Further, the contact area Sa of the roller in contact with the photosensitive laminated film 4 at the point where the roller moved 50 mm on the substrate 3 was 223.6 mm ² .

Therefore, by dividing the pressure Pa by the contact area Sa, the pressure per unit contact area of the contact portion where the base material 3 and the photosensitive laminated film 4 are in contact at the point where the roller moves 50 mm on the base material 3 is obtained. When determined, it was 0.1 MPa / cm ² .

The pressure P _{2 at} the center of the substrate 3 was 0.15 MPa, and the contact area S was 300 mm ² . The pressure per unit contact area of the contact portion in contact with the photosensitive laminated film 4 at the point where the roller moves in the center of the substrate 3 is 0.1 MPa / cm ² , and the roller moves over the substrate 3. It turned out that the unit contact area of the contact part which the base material 3 and the photosensitive laminated | multilayer film 4 in the point moved 50 mm is controlled uniformly.

Pattern exposure (proximity, GHI line, exposure amount 400 mJ / cm ² ) is applied to the photosensitive composition layer 42 of the photosensitive laminated film 4 laid on the substrate 3 by using Parallel light aligner (mask aligner: manufactured by Canon Inc.). ) The patterning at this time was performed so that the photosensitive composition layer 42 on the upper portion of the fine fine recess 31 was cured and the fine fine recess 31 was blocked. Then, it heated at 90 degreeC for 5 minute (henceforth "PEB") with the hotplate. After the support film 41 of the photosensitive laminated film 4 was peeled off, development processing was performed for 4 minutes by an immersion method using PGMEA. Next, post-baking was performed at 200 ° C. for 1 hour using an oven to obtain a precision fine space. In this pattern, the upper portion of the precision fine recess 31 was blocked by the cured portion of the photosensitive composition layer 42. When observing the precise fine space with a scanning electron microscope (SEM), all the fine fine spaces in the member were spaces as shown in FIG. 1B, and the shape and volume were constant.

(Comparative example)
This was carried out in the same manner as in the example except that the pressure per unit contact area of the contact portion where the substrate 3 and the photosensitive laminated film 4 were in contact was not controlled to be constant. When observing a precise fine space with a scanning electron microscope (SEM), all the fine fine spaces on the member are not spaces as shown in FIG. 1B but spaces as shown in FIG. 1C. There was also a space as shown in FIG. 1 (a), and the shape and volume of the precise fine space were not constant.

It is a figure showing the shape of precision fine space. It is the figure which showed the flow of the whole process of laying a film on a base material. It is the figure which showed a mode that a contact part lays while moving on a base material and a film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Stage 2 Contact member 3 Base material 31 Precision fine recessed part 4 Photosensitive laminated film (film)
41 support film 42 photosensitive composition layer 43 protective film

Claims (7)

In the method for forming a precise fine space having a step of laying a film to be a top plate portion of the precision fine recess on a substrate having a precision fine recess, the step of laying the film includes the substrate and the film. A method for forming a precise fine space, characterized in that it is a step of laying while maintaining a constant pressure per unit contact area of a contact portion in contact with. The film forming method of the precision fine space according to claim 1, wherein the photosensitive composition layer on the support film is a photosensitive laminate film obtained by laminating. The method of forming the precision fine space according to claim 1 or 2 pressure per unit contact area of the contact portion, characterized in that a 0.1 to 1 MPa / cm ² to said substrate and said film is in contact.   The method for forming a precise fine space according to any one of claims 1 to 3, wherein the precision fine concave portion has a height of 0.1 µm to 1 mm.   5. The method for forming a precise fine space according to any one of claims 1 to 4, wherein the precise fine recess is a precise fine recess formed by a photoresist pattern. On a substrate having the precision microscopic recesses, the rear step of laying the photosensitive laminated film, exposing the photosensitive laminated film, heat treatment is performed to cure the photosensitive composition layer, the precision fine concave portion 3. The method for forming a precise fine space according to claim 2 , further comprising a step of forming a top plate portion on the top to form a precise fine space. In the method of manufacturing a member having a precision fine space, which has a step of laying a film to be a top plate portion of the precision fine recess on a substrate having a precision fine recess, the step of laying the film includes the substrate and A method for producing a member having a precise fine space, characterized in that it is a step of laying while maintaining a constant pressure per unit contact area of a contact portion in contact with the film.

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