JP6469960B2 - Positive photoresist - Google Patents

Description

  The present invention relates to a positive photoresist.

  In general, a positive photoresist composition uses a photosensitizer having a quinonediazide group such as a naphthoquinonediazide compound and an alkali-soluble resin (for example, a novolac-type phenolic resin). A positive photoresist composition having such a composition exhibits high resolving power due to development with an alkaline solution after exposure. For this reason, this positive photoresist composition is used for the production of semiconductors such as IC and LSI, the production of liquid crystal display screen devices such as LCD, and the production of printing original plates. Further, since the novolac type phenol resin has many aromatic rings, it has high heat resistance against plasma dry etching. Therefore, a large number of positive photoresists containing a novolac type phenol resin and a naphthoquinone diazide photosensitizer have been developed and put to practical use, and have achieved great results (see Patent Document 1).

International Publication No. 2012/115029 Pamphlet

  An object of the present invention is to provide a new and useful positive photoresist.

  The present inventors have surprisingly found that aliphatic polycarbonate can be used as a useful positive photoresist, and have made further improvements to complete the present invention.

That is, the present invention includes, for example, the subject matters described in the following sections.
Item 1.
Positive photoresist containing aliphatic polycarbonate.
Item 2.
Item 2. The positive photoresist according to Item 1, wherein the aliphatic polycarbonate is obtained by polymerization reaction of alkylene oxide and carbon dioxide.
Item 3.
Alkylene oxide is ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, isobutylene oxide, 1-pentene oxide, 2-pentene oxide, 1-hexene oxide, 1-octene oxide, 1-decene oxide, cyclopentene oxide, Cyclohexene oxide, styrene oxide, vinylcyclohexene oxide, 3-phenylpropylene oxide, 3,3,3-trifluoropropylene oxide, 3-naphthylpropylene oxide, 3-phenoxypropylene oxide, 3-naphthoxypropylene oxide, butadiene monooxide, Item 3. It is at least one selected from the group consisting of 3-vinyloxypropylene oxide and 3-trimethylsilyloxypropylene oxide. Positive type photoresist.
Item 4.
(1) A method for producing a patterned film on a substrate, comprising: forming an aliphatic polycarbonate-containing resin layer on a substrate; and (2) irradiating the aliphatic polycarbonate-containing resin layer with light.
Item 5.
Item 5. The method according to Item 4, wherein the step (1) is a step of forming an aliphatic polycarbonate-containing resin layer on the substrate by coating the aliphatic polycarbonate-containing resin on the substrate.
Item 6.
Item 6. The method according to Item 4 or 5, wherein the step (2) is a step of irradiating the aliphatic polycarbonate-containing resin layer with light through a photomask.
Item 7.
A pattern film formed on a substrate,
The pattern of the pattern film is formed of a resin layer present portion and a resin layer absent portion on the substrate,
The end part of the resin layer existing part in contact with the resin layer non-existing part has a protruding structure,
Pattern film.
Item 8.
Item 8. The pattern film according to Item 7, wherein the height of the protruding structure is greater than 1 and less than or equal to 4 times the thickness of the resin layer.
Item 9.
Item 9. The pattern film according to Item 7 or 8, wherein the resin layer is an aliphatic polycarbonate-containing resin layer.
Item 10.
Item 10. The patterned film according to any one of Items 7 to 9, wherein the aliphatic polycarbonate is obtained by polymerization reaction of alkylene oxide and carbon dioxide.
Item 11.
A laminate comprising the pattern film according to any one of Items 7 to 10 on a substrate.

  The pattern film manufactured using the positive photoresist containing the aliphatic polycarbonate of the present invention is formed of a resin layer present portion and a resin layer absent portion on the substrate, and a resin layer in contact with the resin layer absent portion Since the end portion of the existing portion has a protruding structure, a larger amount of wiring material can be filled in the resin non-existing portion of the pattern film than when there is no protruding structure. Then, after the wiring material is filled in the resin-free portion, the resin-existing portion is removed, whereby a fine wiring structure can be formed on the substrate. Since the wiring in the wiring structure has a very large thickness, a large amount of current can flow (that is, the electric capacity is large). Moreover, it is excellent also in heat resistance. For this reason, such a wiring structure is particularly suitable for use in a small device (for example, a power device) that requires a large electric capacity and heat resistance. In addition, since a thick wiring can be produced while suppressing the amount of resin used, it is useful from the viewpoint of cost and environmental considerations.

It is the schematic of the preparation methods of the pattern film which concerns on this invention. It is a schematic sectional drawing of the pattern film which concerns on this invention. It is the schematic which expanded the resin layer absence part vicinity of the pattern film (sectional drawing) which concerns on this invention. It is the schematic which shows the place which filled the wiring material in the pattern film of this invention which has a protrusion structure, and the conventional pattern film which does not have a protrusion structure, and each resin layer absence part, and removed the resin presence part. It is a pattern unevenness | corrugation measurement figure (UV (172 nm) pattern figure of PPC [polypropylene carbonate]) of Example 1. FIG. The film thickness (that is, the thickness of the resin layer existing portion) is about 1.50 μm, and the height of the convex portion (that is, the height of the protrusion structure) is about 2.34 μm. It is a pattern unevenness | corrugation measurement figure (UV (172 nm) pattern figure of EC [ethylcellulose]) of the comparative example 1. The film thickness (that is, the thickness of the resin layer existing portion) is about 0.58 μm, and no protruding structure is observed.

  Hereinafter, the present invention will be described in more detail.

  The present invention relates to a positive photoresist containing an aliphatic polycarbonate.

  The aliphatic polycarbonate used in the present invention is not particularly limited, and for example, those obtained by polymerizing alkylene oxide and carbon dioxide are preferably used. Alkylene oxide and carbon dioxide can be preferably polymerized in the presence of a metal catalyst, for example.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, isobutylene oxide, 1-pentene oxide, 2-pentene oxide, 1-hexene oxide, 1-octene oxide, 1-decene oxide, Cyclopentene oxide, cyclohexene oxide, styrene oxide, vinylcyclohexene oxide, 3-phenylpropylene oxide, 3,3,3-trifluoropropylene oxide, 3-naphthylpropylene oxide, 3-phenoxypropylene oxide, 3-naphthoxypropylene oxide, butadiene Examples thereof include monooxide, 3-vinyloxypropylene oxide and 3-trimethylsilyloxypropylene oxide. Among these alkylene oxides, ethylene oxide and propylene oxide are preferably used, and propylene oxide is more preferably used. These alkylene oxides may be used alone or in combination of two or more.

  Examples of the metal catalyst include an aluminum catalyst and a zinc catalyst. Among these, a zinc catalyst is preferably used because it has a high polymerization activity in the polymerization reaction between alkylene oxide and carbon dioxide, and among the zinc catalysts, an organic zinc catalyst is preferably used.

  Examples of the organic zinc catalyst include organic zinc catalysts such as zinc acetate, diethyl zinc, and dibutyl zinc; primary amines, divalent phenols, divalent aromatic carboxylic acids, aromatic hydroxy acids, aliphatic dicarboxylic acids, and fatty acids. And an organic zinc catalyst obtained by reacting a compound such as a group monocarboxylic acid with a zinc compound. Among these organozinc catalysts, an organozinc catalyst obtained by reacting a zinc compound, an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid is preferably used because it has higher polymerization activity. Here, the organic zinc catalyst obtained by reacting a zinc compound, an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid will be described in more detail.

  Specific examples of the zinc compound include inorganic zinc compounds such as zinc oxide, zinc hydroxide, zinc nitrate and zinc carbonate; organic zinc compounds such as zinc acetate, diethyl zinc and dibutyl zinc. Among these zinc compounds, zinc oxide and zinc hydroxide are preferably used from the viewpoint of obtaining an organic zinc catalyst having high catalytic activity. These zinc compounds may be used alone or in combination of two or more.

  Specific examples of the aliphatic dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and the like. Among these aliphatic dicarboxylic acids, glutaric acid and adipic acid are preferably used from the viewpoint of obtaining an organozinc catalyst having high activity. In addition, these aliphatic dicarboxylic acids may be used alone or in combination of two or more.

  The proportion of the aliphatic dicarboxylic acid used is usually preferably 0.1 to 1.5 mol, more preferably 0.5 to 1.0 mol, per 1 mol of the zinc compound.

  Specific examples of the aliphatic monocarboxylic acid include formic acid, acetic acid, propionic acid and the like. Among these aliphatic monocarboxylic acids, formic acid and acetic acid are preferably used from the viewpoint of obtaining an organozinc catalyst having high activity. These aliphatic monocarboxylic acids may be used alone or in combination of two or more.

  The use ratio of the aliphatic monocarboxylic acid is preferably 0.0001 to 0.1 mol, and more preferably 0.001 to 0.05 mol, with respect to 1 mol of the aliphatic dicarboxylic acid.

  The method for reacting the zinc compound, the aliphatic dicarboxylic acid and the aliphatic monocarboxylic acid is not particularly limited, and these may be reacted simultaneously, or the aliphatic dicarboxylic acid or the aliphatic monocarboxylic acid may be reacted. After reacting either one with the zinc compound first, the reaction product and the other may be reacted successively.

  Moreover, when reacting the said zinc compound, aliphatic dicarboxylic acid, and aliphatic monocarboxylic acid, you may use a solvent from a viewpoint of performing reaction smoothly. The solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include aromatic hydrocarbon solvents such as benzene, toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; dimethyl carbonate and diethyl Carbonate solvents such as carbonate and propylene carbonate; acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphotriamide and the like can be mentioned. Among these solvents, aromatic hydrocarbon solvents such as benzene, toluene and xylene are preferably used from the viewpoint of easy recycling of the solvent.

  It is preferable that the usage-amount of the said solvent is 500-10000 mass parts with respect to 100 mass parts of zinc compounds from a viewpoint of performing reaction smoothly.

  Although the reaction temperature at the time of making the said zinc compound, aliphatic dicarboxylic acid, and aliphatic monocarboxylic acid react is not specifically limited, It is preferable that it is 20-110 degreeC, and it is more preferable that it is 50-100 degreeC. preferable. The reaction time for reacting the zinc compound, the aliphatic dicarboxylic acid, and the aliphatic monocarboxylic acid varies depending on the reaction temperature. preferable.

  The organozinc catalyst thus obtained is used in a polymerization step in which carbon dioxide and alkylene oxide are reacted with each other isolated by a conventional method such as filtration after the completion of the reaction or without being isolated. be able to. For example, in the use of the organozinc catalyst, when it is used in the state of being contained in the reaction solution without being isolated, sufficient water that may adversely affect the reaction between carbon dioxide and alkylene oxide is sufficiently obtained. It is preferable to remove it.

  As a particularly preferable organic zinc catalyst, an organic zinc catalyst obtained by reacting zinc oxide, glutaric acid and acetic acid can be exemplified.

  The amount of the metal catalyst used for the polymerization reaction of alkylene oxide and carbon dioxide is preferably 0.001 to 20 parts by mass, and 0.01 to 10 parts by mass with respect to 100 parts by mass of alkylene oxide. More preferably.

  In the polymerization reaction, the method of reacting alkylene oxide and carbon dioxide in the presence of a metal catalyst is not particularly limited. For example, the alkylene oxide, the metal catalyst, and, if necessary, the reaction solvent are added to an autoclave. After charging and mixing, there is a method in which carbon dioxide is injected and reacted.

  The reaction solvent used as necessary in the polymerization reaction is not particularly limited, and various organic solvents can be used. Specific examples of the organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; chloromethane, methylene dichloride, and the like. , Chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, ethyl chloride, trichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, chloro Halogenated hydrocarbon solvents such as benzene and bromobenzene; carbonate solvents such as dimethyl carbonate, diethyl carbonate, and propylene carbonate.

  It is preferable that the usage-amount of the said reaction solvent is 300-10000 mass parts with respect to 100 mass parts of alkylene oxide from a viewpoint of making reaction smooth.

  The working pressure of carbon dioxide used in the polymerization reaction is not particularly limited, but is usually preferably 0.1 to 20 MPa, more preferably 0.1 to 10 MPa, and 0.1 to 5 MPa. More preferably.

  Although the polymerization reaction temperature in the said polymerization reaction is not specifically limited, It is preferable that it is 30-100 degreeC, and it is more preferable that it is 40-80 degreeC. The polymerization reaction time varies depending on the polymerization reaction temperature and cannot be generally specified, but it is usually preferably 2 to 40 hours.

  After completion of the polymerization reaction, an aliphatic polycarbonate can be obtained by, for example, filtering off by filtration or the like, washing with a solvent or the like if necessary, and drying.

  The number average molecular weight of the aliphatic polycarbonate used in the present invention is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, still more preferably 20,000 to 200,000. 000, more preferably 30,000 to 100,000, and particularly preferably 40,000 to 80,000. In addition, the number average molecular weight is prepared by preparing a chloroform solution having an aliphatic polycarbonate concentration of 0.5% by mass and using a high performance liquid chromatograph, and comparing it with polystyrene having a known number average molecular weight measured under the same conditions. Is a value obtained by calculating the molecular weight. The measurement conditions of the high performance liquid chromatograph are as follows.

Model: HLC-8020
Column: GPC column (trade name of Tosoh Corporation, TSK GEL Multipore HXL-M)
Column temperature: 40 ° C
Eluent: Chloroform Flow rate: 1 mL / min

  Particularly preferred aliphatic polycarbonates used in the present invention include polyethylene carbonate, polypropylene carbonate, polybutylene carbonate and the like.

  Moreover, in this invention, an aliphatic polycarbonate can be used individually by 1 type or in combination of 2 or more types.

  The positive photoresist containing the aliphatic polycarbonate of the present invention may be composed only of the aliphatic polycarbonate, or may contain components other than the aliphatic polycarbonate as long as the effects of the present invention are not impaired. Examples of the component other than the aliphatic polycarbonate include a resin known to be used as a positive photoresist, and more specifically, for example, a novolac phenol resin. When a novolac type phenol resin is used, it is also preferable to use a compound having a quinonediazide group such as a naphthoquinonediazide compound that works as a photosensitizer.

  The present invention is a method for producing a patterned film on a substrate, comprising (1) a step of forming an aliphatic polycarbonate-containing resin layer on the substrate, and (2) a step of irradiating the aliphatic polycarbonate-containing resin layer with light. Is also included.

  In the step (1), the method of forming the aliphatic polycarbonate-containing resin layer on the substrate is not particularly limited, but a method of coating the aliphatic polycarbonate-containing resin on the substrate can be preferably exemplified. The aliphatic polycarbonate-containing resin may be composed only of the aliphatic polycarbonate, and may contain components other than the aliphatic polycarbonate as long as the effects of the present invention are not impaired in addition to the aliphatic polycarbonate. As such a component, for example, the same components as those described for the positive photoresist containing the aliphatic polycarbonate can be used. More preferably, the aliphatic polycarbonate-containing resin layer can be formed using a positive photoresist containing the aliphatic polycarbonate of the present invention.

  The coating method is not particularly limited, but a method in which an appropriate amount of an aliphatic polycarbonate-containing resin is applied to the center of the substrate and then the substrate is rotated using a spin coater and uniformly applied to the entire substrate can be preferably exemplified. In application, it is preferred to dissolve the aliphatic polycarbonate-containing resin in a solvent to obtain an aliphatic polycarbonate-containing resin solution, which is used. Such a solvent is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, dimethyl carbonate, diethyl carbonate, propylene carbonate, ethyl lactate and the like. . Of these, ethylene glycol monoethyl ether acetate is preferred. Although the density | concentration of an aliphatic polycarbonate containing resin solution is not restrict | limited in particular, For example, the solution whose aliphatic polycarbonate containing resin density | concentration is 5-20 mass (m / m)% can be illustrated.

  The substrate to be used is not particularly limited, and for example, a silicon wafer, non-alkali glass, a metal plate, a heat-resistant film such as polyethylene terephthalate, polyimide, polyethylene 2,6-naphthalate, or the like can be preferably used.

  In the step (2), when irradiating light, it is preferable to use a photomask to irradiate the aliphatic polycarbonate-containing resin layer through the photomask. As is well known, when a pattern film having a particularly fine pattern is produced, the pattern film can be easily produced by using a photomask having the pattern. A photomask made of a known material can be used.

The light used here is not particularly limited as long as it is a known light used in a positive photoresist, but visible light or ultraviolet light can be preferably used, and ultraviolet light is more preferable. More specifically, the wavelength is preferably about 10 to 450 nm, and more preferably about 100 to 400 nm. More specifically, a high pressure mercury lamp light source, there can be exemplified a low-pressure mercury lamp, KrF excimer laser, ArF excimer laser, or a light to F ₂ excimer laser (see Table 1).

  In the present invention, since the aliphatic polycarbonate-containing resin layer is decomposed by light irradiation and the decomposition product can be volatilized, the resin layer can be removed without performing a special resin removal operation after light irradiation.

  An outline of a method for producing the above pattern film is shown in FIG. Moreover, the outline of the pattern film | membrane on the produced board | substrate is shown in FIG. As shown in FIG. 2, the pattern of the pattern film is formed of a resin layer existing portion and a resin layer nonexistent portion on the substrate.

  According to the method for producing a pattern film on the substrate of the present invention, and when the pattern film is produced using the positive photoresist containing the aliphatic polycarbonate of the present invention, the resin of the obtained pattern film The end portion of the resin layer existing portion in contact with the layer nonexistent portion has a protruding structure.

  A schematic diagram showing this more specifically is shown in FIG. FIG. 3 is an enlarged schematic view of the vicinity of the resin layer absent portion of the pattern film (cross-sectional view) on the substrate. In FIG. 3, the protrusion structure is expressed as “convex part”, the height of the protrusion structure is expressed as “convex part height”, and the thickness of the resin layer existing portion (corresponding to the thickness of the resin layer before light irradiation) is “film "Thickness". As can be seen from the figure, the convex height is the height from the top surface of the film to the convex vertex. Therefore, the height from the upper surface of the substrate to the top of the convex portion is the sum of the film thickness and the convex portion height.

  The protrusion structure preferably has a height (convex height) that is greater than 1 and less than or equal to 4 times, more preferably 1.2 to 3 times, and even more preferably 1.3 times the thickness of the resin layer. ~ 2.5 times.

  In addition, the thickness of the resin layer existing portion (the thickness of the resin layer before light irradiation) (film thickness) is preferably about 0.1 to 100 μm, more preferably about 0.2 to 50 μm, and 0.5 to 20 μm. More preferably, the degree is more preferably about 1 to 10 μm.

  Since the pattern film has such a protruding structure, a resin-existing portion of the pattern film can be filled with a larger amount of wiring material than when there is no protruding structure. Then, after the wiring material is filled in the resin-free portion, the resin-existing portion is removed, whereby a fine wiring structure can be formed on the substrate. Since the wiring in the wiring structure has a very large thickness, a large amount of current can flow (that is, the electric capacity is large). Moreover, it is excellent also in heat resistance. For this reason, such a wiring structure is particularly suitable for use in a small device (for example, a power device) that requires a large electric capacity and heat resistance. In addition, since a thick wiring can be produced while suppressing the amount of resin used, it is useful from the viewpoint of cost and environmental considerations.

  In addition to the above steps (1) and (2), the present invention also includes a method for producing a wiring structure, further comprising the step of (3) filling a wiring material into a resin layer-existing portion of the obtained pattern film. To do. It is preferable that the manufacturing method of the wiring structure further includes a step of (4) removing the resin layer existing portion after or simultaneously with the step (3). In particular, as described below, when the wiring material is filled and then heated to harden the wiring material, the resin layer existing portion can be removed simultaneously by heating, which is preferable.

  As the wiring material, metal fine particle ink is suitable. The metal fine particle ink is obtained by dispersing metal fine particles (preferably nano-sized particles) in a solvent. In order to improve the dispersibility of the metal particles, a dispersant may be attached to the surface of the metal fine particles. Such metal fine particle ink can also be purchased and used. For example, metal nano pastes (NPS series, NPG series) commercially available from Harima Chemical Industry can be used. Examples of the metal include silver, gold, platinum, copper, nickel, palladium, lead, titanium, barium, boron, aluminum, zinc, tungsten, indium tin oxide (ITO), and alloys thereof. Silver is particularly preferable. The metal fine particles can be used alone or in combination of two or more.

  As a method for filling the wiring material in the resin layer absent portion, a method of filling the resin fine particle ink into the resin layer absent portion by inkjet is preferable. It is preferable that the wiring material hardens after filling. For example, when metal fine particle ink is used as a wiring material, the ink can be hardened (sintered) by heating. The heating is performed, for example, at about 250 to 300 ° C. until the ink is hardened.

  After filling (and solidifying) the wiring material, it is preferable to remove the resin layer existing portion. The removal method is not limited as long as the removal is possible, but particularly when the wiring material is solidified by heating, the resin layer existing portion is decomposed and removed by heating. It is particularly preferable that heating is performed later to solidify the wiring material and remove the resin layer existing portion at the same time.

  Further, the solidification method can be appropriately set depending on the wiring material to be used, and examples thereof include high-frequency irradiation, plasma irradiation, microwave irradiation, light irradiation, and solidification by pressure application.

  In addition, this invention also includes the laminated body provided with the pattern film | membrane of this invention on a board | substrate which can be manufactured as mentioned above.

  The present invention will be specifically described below with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples.

[Evaluation method]
The number average molecular weight of the aliphatic polycarbonate obtained by the following production example was measured as follows. Moreover, the following method was used for the coating method in the following Example and comparative example, the pattern formation method, and the unevenness | corrugation degree measuring method.

(1) Number average molecular weight of aliphatic polycarbonate A chloroform solution having an aliphatic polycarbonate concentration of 0.5% by mass was prepared and measured using a high performance liquid chromatograph. After the measurement, the molecular weight was calculated by comparing with polystyrene having a known number average molecular weight measured under the same conditions. The measurement conditions are as follows.

Model: HLC-8020
Column: GPC column (trade name of Tosoh Corporation, TSK GEL Multipore HXL-M)
Column temperature: 40 ° C
Eluent: Chloroform Flow rate: 1 mL / min

(2) Coating method of resin solution A silicon wafer (2 inches) was prepared as a substrate and divided into four equal parts. Using a plasma cleaner (manufactured by Yamato Kagaku Co., Ltd., trade name: Plasma Dry Cleaner PDC210), the divided silicon wafer was subjected to a surface treatment to obtain a test silicon wafer.

  A test silicon wafer was set on a spin coater (manufactured by Active Co., Ltd., model: ACT-220D), an appropriate amount of resin solution was applied to the center of the wafer, and then the spin coater was applied at 500 rpm × 10 sec. + Acceleration 15 sec. +1500 rpm × 20 sec. And evenly applied.

  After the application, the solvent was removed with a hot plate at 120 ° C. for 30 minutes to prepare a coated substrate.

(3) Pattern formation method A UV irradiation apparatus (172 nm, manufactured by Ushio Electric Co., Ltd.) provided with a hot plate apparatus by placing a metal mask on which an exposure pattern of 100 μm × 100 μm is formed on the coated substrate prepared in (2) Excimer irradiation unit, head-on type). The irradiation atmosphere was adjusted to N ₂ : O ₂ = 50: 50, the hot plate was set to 100 ° C., and UV irradiation was performed for 30 minutes. The resin was decomposed and volatilized by the irradiation.

(4) Concavity and convexity evaluation method About the uneven | corrugated shape and thickness of the pattern obtained by (3), it measured using the film thickness measuring apparatus (The Kosaka Laboratory Co., Ltd. make, brand name: fine shape measuring machine surfcorder SE300).

[Production Example 1] (Production of organozinc catalyst)
In a 300 mL four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, zinc oxide 8.1 g (100 mmol), glutaric acid 12.7 g (96 mmol), acetic acid 0.1 g ( 2 mmol) and 130 g (150 mL) of toluene. Next, after the inside of the reaction system was replaced with a nitrogen atmosphere, the temperature was raised to 55 ° C., and the reaction was performed by stirring at the same temperature for 4 hours. Thereafter, the temperature was raised to 110 ° C., and the mixture was further stirred for 4 hours at the same temperature for azeotropic dehydration to remove only moisture, and then cooled to room temperature to obtain a reaction solution containing an organozinc catalyst.

  As a result of measuring IR using an apparatus (trade name: AVATAR360) manufactured by Thermo Nicolet Japan Co., Ltd. for an organozinc catalyst obtained by separating a part of this reaction solution and filtering, the peak based on the carboxylic acid group is I was not able to admit.

[Production Example 2] (Production of polypropylene carbonate)
After replacing the inside of a 1 L autoclave system equipped with a stirrer, a gas introduction tube, and a thermometer with a nitrogen atmosphere in advance, 8 mL of a reaction solution containing an organozinc catalyst obtained by the same method as in Production Example 1 (organozinc catalyst) 1 g), 131 g (200 mL) of hexane, and 46.5 g (0.80 mol) of propylene oxide. Next, carbon dioxide was added under stirring to replace the inside of the reaction system with a carbon dioxide atmosphere, and carbon dioxide was charged until the inside of the reaction system became 1.5 MPa. Thereafter, the temperature was raised to 60 ° C., and a polymerization reaction was carried out for 6 hours while supplying carbon dioxide consumed by the reaction.

  After completion of the reaction, the autoclave was cooled and depressurized, filtered, and dried under reduced pressure to obtain 80.8 g of polypropylene carbonate.

  The obtained polypropylene carbonate could be identified from the following physical properties.

IR (KBr): 1742, 1456, 1381, 1229, 1069, 787
(All units are cm ⁻¹ , indicating the wave number at which the absorption peak was observed)

  Moreover, the number average molecular weight of the obtained polypropylene carbonate was 52,000.

[Production Example 3] (Production of polyethylene carbonate)
Proceeding in the same manner as in Production Example 2 except that 46.5 g (0.80 mol) of propylene oxide was changed to 35.2 g (0.80 mol) of ethylene oxide, 69 g of polyethylene carbonate was obtained.

  The obtained polypropylene carbonate could be identified from the following physical properties.

IR (KBr): 1740, 1448, 1386, 1219, 1029, 787
(All units are cm ⁻¹ , indicating the wave number at which the absorption peak was observed)

  Moreover, the number average molecular weight of the obtained polyethylene carbonate was 60,000.

  In addition, IR (KBr) of polypropylene carbonate and polyethylene carbonate was measured using the apparatus (brand name: AVATAR360) by Thermo Nicolet Japan.

[Example 1]
In a 100 mL separable flask equipped with a stirrer, 90 g of diethylene glycol monoethyl ether acetate and 10 g of polypropylene carbonate obtained by the method of Production Example 2 were charged and dissolved by stirring to obtain 100 g of a uniform 10% by mass resin solution. Obtained.

  The obtained resin solution was applied to a substrate (silicon wafer), irradiated with UV to form a pattern film, and the unevenness of the pattern film was measured. The results are shown in Table 2 and FIG.

[Example 2]
In Example 1, instead of 10 g of polypropylene carbonate, 100 g of a 10% by mass resin solution was obtained in the same manner as in Example 1 except that 10 g of polyethylene carbonate obtained by the method of Production Example 3 was used.

  The obtained resin solution was applied to a substrate (silicon wafer), irradiated with UV to form a pattern film, and the unevenness of the pattern film was measured. The results are shown in Table 2.

[Example 3]
In Example 1, 10 g was used in the same manner as in Example 1 except that 5 g of polypropylene carbonate obtained by the method of Production Example 2 and 5 g of polyethylene carbonate obtained by the method of Production Example 3 were used instead of 10 g of polypropylene carbonate. 100 g of a mass% resin solution was obtained.

  The obtained resin solution was applied to a substrate (silicon wafer), irradiated with UV to form a pattern film, and the unevenness of the pattern film was measured. The results are shown in Table 2.

[Example 4]
In Example 1, 100 g of a 20% by mass resin solution was obtained in the same manner as in Example 1 except that 90 g of diethylene glycol monoethyl ether acetate was changed to 80 g and 10 g of polypropylene carbonate was changed to 20 g.

  The obtained resin solution was applied to a substrate (silicon wafer), irradiated with UV to form a pattern film, and the unevenness of the pattern film was measured. The results are shown in Table 2.

[Comparative Example 1]
In Example 1, in place of 10 g of polypropylene carbonate, 100 g of a 10% by mass resin solution was obtained in the same manner as in Example 1 except that 10 g of ethyl cellulose (manufactured by Nisshin Kasei Co., Ltd., trade name: Etcel 45) was used. .

  The obtained resin solution was applied to a substrate (silicon wafer), irradiated with UV to form a pattern film, and the unevenness of the pattern film was measured. The results are shown in Table 2 and FIG.

[Comparative Example 2]
In Example 1, instead of 10 g of polypropylene carbonate, 100 g of a 10% by mass resin solution was obtained in the same manner as in Example 1 except that 10 g of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., trade name: ESREC BL-5) was used. Obtained.

  The obtained resin solution was applied to a substrate (silicon wafer), irradiated with UV to form a pattern film, and the unevenness of the pattern film was measured. The results are shown in Table 2.

[Comparative Example 3]
In Example 1, instead of 10 g of polypropylene carbonate, 100 g of a 10% by mass resin solution was obtained in the same manner as in Example 1 except that 10 g of polymethyl methacrylate (trade name: Sumipex MGS, manufactured by Sumitomo Chemical Co., Ltd.) was used. Obtained.

  The obtained resin solution was applied to a substrate (silicon wafer), irradiated with UV to form a pattern film, and the unevenness of the pattern film was measured. The results are shown in Table 2.

[Comparative Example 4]
In Example 1, instead of 10 g of polypropylene carbonate, 10 g was used in the same manner as in Example 1 except that 10 g of a copolymer of ethyl acrylate and methyl methacrylate (trade name: Paraloid B75, manufactured by Dow Chemical Co., Ltd.) was used. 100 g of a mass% resin solution was obtained.

  The obtained resin solution was applied to a substrate (silicon wafer), irradiated with UV to form a pattern film, and the unevenness of the pattern film was measured. The results are shown in Table 2.

[Comparative Example 5]
Example 1 is the same as Example 1 except that 90 g of diethylene glycol monoethyl ether acetate is replaced with 95 g of pure water, and 10 g of polypropylene carbonate is replaced with 5 g of hydroxyethyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Metrols SHV-W). Similarly, 100 g of a 5% by mass resin solution was obtained.

  The obtained resin solution was applied to a substrate (silicon wafer), irradiated with UV to form a pattern film, and the unevenness of the pattern film was measured. The results are shown in Table 2.

[Example 5]
Silver nanopaste (manufactured by Harima Kasei Co., Ltd., NPS-J) is dispensed with a needle-type dispenser (manufactured by Applied Microsystem, XD- 2000S).

  The obtained silver nanopaste-filled pattern film was placed on a hot plate at 280 ° C., the silver nanopaste was sintered and the pattern film was thermally decomposed to create a circuit pattern (wiring structure).

  The wiring height of the obtained circuit pattern was measured by the above-described unevenness evaluation method, and the results are shown in Table 3.

[Comparative Example 6]
In Example 5, except that the pattern film used was changed from Example 1 to the pattern film obtained by the same method as in Comparative Example 1, the same processing was performed. As a result, the silver nanopaste overflowed, and a circuit pattern could be created. None (Table 3).

[Comparative Example 7]
In Comparative Example 6, a circuit pattern was prepared in the same manner except that the amount of silver nanopaste applied was reduced to 1/3. The wiring height of the obtained circuit pattern was measured by the above-described unevenness evaluation method, and the results are shown in Table 3.

Claims (12)

Look-containing aliphatic polycarbonates obtained by polymerization reaction and carbon dioxide alkylene oxide,
A positive photoresist for decomposing by light irradiation to form a pattern film for filling a wiring material having a protruding structure at an end of a resin layer existing portion in contact with a resin layer absent portion . Alkylene oxide is ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, isobutylene oxide, 1-pentene oxide, 2-pentene oxide, 1-hexene oxide, 1-octene oxide, 1-decene oxide, cyclopentene oxide, Cyclohexene oxide, styrene oxide, vinylcyclohexene oxide, 3-phenylpropylene oxide, 3,3,3-trifluoropropylene oxide, 3-naphthylpropylene oxide, 3-phenoxypropylene oxide, 3-naphthoxypropylene oxide, butadiene monooxide, it is at least one selected from the group consisting of 3-vinyl-oxy propylene oxide and 3-trimethylsilyloxy propylene oxide, to claim 1 Positive type photoresist of the placement. The positive photoresist according to claim 1, wherein the aliphatic polycarbonate is at least one selected from the group consisting of polyethylene carbonate, polypropylene carbonate, and polybutylene carbonate. (1) forming a resin layer containing an aliphatic polycarbonate obtained by polymerization reaction of alkylene oxide and carbon dioxide on a substrate;
(2) irradiating the aliphatic polycarbonate-containing resin layer with light, decomposing the aliphatic polycarbonate, and creating a pattern film having a protrusion structure at the end of the resin layer existing portion in contact with the resin layer absent portion ; And (3) A method of manufacturing a wiring structure, including a step of filling a wiring material into a resin-free portion of the pattern film obtained in the step (2). Alkylene oxide is ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, isobutylene oxide, 1-pentene oxide, 2-pentene oxide, 1-hexene oxide, 1-octene oxide, 1-decene oxide, cyclopentene oxide, Cyclohexene oxide, styrene oxide, vinylcyclohexene oxide, 3-phenylpropylene oxide, 3,3,3-trifluoropropylene oxide, 3-naphthylpropylene oxide, 3-phenoxypropylene oxide, 3-naphthoxypropylene oxide, butadiene monooxide, 5. At least one selected from the group consisting of 3-vinyloxypropylene oxide and 3-trimethylsilyloxypropylene oxide. The method of mounting. The method according to claim 4, wherein the aliphatic polycarbonate is at least one selected from the group consisting of polyethylene carbonate, polypropylene carbonate, and polybutylene carbonate. The method according to any one of claims 4 to 6, wherein step (1) is a step of forming an aliphatic polycarbonate-containing resin layer on the substrate by coating the aliphatic polycarbonate-containing resin on the substrate. The method according to any one of claims 4 to 7, wherein the step (2) is a step of irradiating the aliphatic polycarbonate-containing resin layer with light through a photomask. further,
(4) The method in any one of Claims 4-8 including the process of removing the resin layer presence part of a pattern film. The method according to claim 9, wherein the removal of the resin layer existing portion of the pattern film is performed by heating. The positive photoresist according to claim 1 , wherein the wiring material is a metal fine particle ink. The method according to claim 4 , wherein the wiring material is a metal fine particle ink.

Images