JP4299642B2 - Pattern formation method - Google Patents

Description

  The present invention relates to a pattern forming method, and more particularly to pattern formation of a heat extinguishing resin film and pattern formation of various materials using the pattern as a mask.

  Currently, in the manufacture of semiconductor devices, a resist pattern is formed by photolithography, and various materials such as conductor films, semiconductor films, or insulator films used in semiconductor devices are formed by etching using the resist pattern as a mask. (For example, refer nonpatent literature 1.). Further, using this resist pattern as a plating mask, a metal film pattern such as copper (Cu) or gold (Au) is formed. This pattern formation method by photolithography is currently the most widely used method for pattern formation, such as the manufacture of various display devices other than the manufacture of semiconductor devices, as well as the manufacture of micromachines.

  Pattern formation by this photolithography technique will be described with reference to FIGS. 6 and 7 are cross-sectional views in the order of steps showing a resist pattern formation by a photolithography technique and a pattern formation method when an insulating film is processed using the resist pattern as an etching mask.

  As shown in FIG. 6A, an insulator film 102 is deposited with silicon oxide on a semiconductor substrate 101 on which various semiconductor elements (not shown) are formed, and a coating process using a photolithography technique is performed on the insulator film 102. Then, a resist film 103 is formed. Here, the resist film 103 is a so-called photosensitive resin and is formed as follows. That is, a resist coating solution obtained by dissolving a polymer or the like made of a photosensitive resin composition in a solvent is spin-coated on the insulator film 102 of the semiconductor substrate 101 that is a semiconductor wafer. Then, after this spin coating, pre-baking is performed at a temperature of 100 ° C. or less to remove unnecessary solvents. In this way, the resist film 103 is formed.

  Next, as shown in FIG. 6B, in the exposure process of the photolithography technique, a normal reduced projection is performed using a reticle 106 formed of a quartz glass substrate 104 and a light-shielding film pattern 105 formed on the surface thereof as a photomask. Exposure light 107 is irradiated by exposure, and pattern exposure transfer is performed on the resist film 103. In this way, an optical pattern transfer region 103 a is formed in a predetermined region of the resist film 103. Then, a heat treatment called PEB (Post Exposure Bake) is performed. Here, the recent exposure light 107 is an ArF excimer laser (wavelength: about 193 nm), and the resist film 103 is made of a so-called chemically amplified resist.

  Next, in the development step of the photolithography technique, the semiconductor substrate 101 in the semiconductor wafer state is immersed in a developer. Alternatively, it is exposed to a developer shower. In this way, as shown in FIG. 6C, the optical pattern transfer region 103a is removed by development to form a resist pattern. Further, post-baking is performed at a temperature of about 120 ° C., and a resist mask 108 is formed on the insulator film 102. This is a case where the resist is a positive resist. In contrast, in the case of a negative resist, the optical pattern transfer region 103a remains by the development, and other regions are removed.

  Next, as shown in FIG. 7A, the insulating film 102 is etched by dry etching using plasma using the resist mask 108 as an etching mask. Then, an opening 109 is formed in the insulator film 102.

Next, as shown in FIG. 7B, the resist mask 108 is removed by ashing in oxygen (O ₂ ) plasma in a resist mask peeling step. In this way, a pattern of the insulator film 102 having the opening 109 is formed. Here, the opening 109 is normally a via hole for wiring connection using the insulating film 102 as an interlayer insulating film of the wiring.

Semiconductor Handbook Compilation Committee, “Semiconductor Handbook”, Second Edition, Ohm Co., Ltd., May 25, 1994, p. 198-199

  In recent years, in pattern formation in semiconductor devices, the pattern dimension has been reduced to 100 nm or less. With the miniaturization of the pattern, semiconductor devices are becoming increasingly highly integrated, multifunctional, and high performance.

  However, the miniaturization of the dimensions in the pattern formation requires the sophistication in the coating process, the exposure process, the development process or the peeling process as described above in the photolithography technique, and the manufacturing cost in the pattern formation of the semiconductor device is reduced. Increase.

  Conventionally, in the formation of resist masks by photolithography technology, the above coating process, exposure process, and development process have been the foundation of photolithography technology. Will not change. The resist mask peeling process is also the same. And the advancement of the technology described above inevitably causes an increase in the cost of pattern formation. Therefore, it is desired to develop a new technique that is completely different from the conventional technique, which can achieve both high accuracy of the pattern formation technique and low cost of the technique.

  The present invention has been made in view of the above circumstances, and provides a pattern forming method capable of providing a new technique in pattern formation, simplifying the series of techniques described above, and reducing the cost of the pattern formation technique. The purpose is to provide.

  In order to achieve the above object, the pattern forming method of the present invention includes a step of forming a heat extinguishing resin film on the surface of the substrate to be processed, and selectively irradiating the heat extinguishing resin film with thermal energy. Removing the heat extinguishing resin film in the thermal energy irradiation region to form a pattern of the heat extinguishing resin film. The selective thermal energy irradiation to the heat extinguishing resin is performed by a direct drawing method using a laser beam or an electron beam.

  Alternatively, the pattern forming method of the present invention includes a step of forming a heat extinguishing resin film on the surface of the substrate to be processed, and a step of exposing and transferring the pattern formed on the photomask to the heat extinguishing resin film by irradiation of exposure light The heat extinguishing resin film is subjected to heat treatment after the exposure transfer, and the heat extinguishing resin film in the region not exposed to the exposure light in the exposure transfer process is selectively extinguished to Forming a pattern. Here, in the exposure transfer step, the heat extinguishing resin film in the region irradiated with the exposure light is crosslinked and photocured.

  The temperature in the heat treatment is higher than the temperature at which the heat extinguishing resin film in the region not irradiated with the exposure light decomposes and disappears, and the heat extinguishing resin film in the region irradiated with the exposure light decomposes and disappears. Set lower than temperature.

With such a configuration, in the case of forming a pattern using a conventional resist film, the resist development process that is essential after direct pattern writing or exposure transfer on the resist film is completely eliminated. The formation is greatly simplified and the cost of pattern formation technology is reduced.

  In the pattern forming method of the present invention, preferably, the heat extinguishing resin film is a material that decomposes and disappears by heating. Further preferably, the heat extinguishing resin film is made of a polyoxyalkylene resin composition having a crosslinkable silyl group. Preferably, the entire surface is irradiated with light after the pattern of the heat extinguishing resin film is formed.

  With such a configuration, unlike the conventional photolithography technique, the work efficiency is improved, the cost of the pattern forming technique can be reduced, and a highly accurate pattern forming technique can be realized.

  In the pattern forming method of the present invention, the pattern of the heat extinguishing resin is selectively etched by using the pattern of the heat extinguishing resin as an etching mask of the substrate to be processed, and then subjected to heat treatment to form the pattern of the heat extinguishing resin. Disassemble and remove.

  Further, in the pattern forming method of the present invention, a step of forming a conductor film on the entire surface from the upper part of the pattern of the heat extinguishing resin formed on the surface of the substrate to be processed by the sputtering method, and the heat extinguishing by performing the heat treatment A step of decomposing and extinguishing the conductive resin and lifting off the conductive film to form a pattern of the conductive film.

  In the pattern forming method of the present invention, a step of plating a metal film on the surface of the substrate to be processed using the pattern of the heat extinguishing resin as a mask for electrolytic plating, and a heat treatment to decompose and extinguish the heat extinguishing resin. And forming a pattern of the metal film.

  By adopting such a configuration, pattern formation of various materials used in the manufacture of semiconductor devices and the like is greatly simplified, and the manufacturing cost is greatly reduced.

  And preferably in the pattern formation method of this invention, the said heat processing are performed at the temperature of 150 to 250 degreeC by oxygen atmosphere. Alternatively, the heat treatment is performed at a temperature of 200 ° C. to 250 ° C. in a nitrogen atmosphere.

  According to the present invention, the pattern forming method is greatly simplified as compared with the pattern forming method by the conventional photolithography technique, and it becomes possible to increase the accuracy of the pattern forming technique of various materials and to reduce the cost of the technique. And the manufacturing cost of a semiconductor device etc. can be reduced significantly.

  The most significant feature of the present invention is that a material having a characteristic different from that of a resist which is a conventional photosensitive resin, that is, a heat extinguishing resin is used in pattern formation. Although this material will be described in detail later, when the material film is subjected to a heat treatment at an appropriate temperature, the film has a characteristic that it undergoes thermal decomposition and disappears completely.

(First embodiment)
A first embodiment of the present invention will be described with reference to FIG. FIG. 1 is a cross-sectional view in order of steps showing a pattern formation method of an etching mask using the above-described heat extinguishing resin film and a pattern formation method for processing an insulator film using the same.

Here, in order to form a heat extinguishing resin film, for example, an extinguishing resin coating solution in which a polyoxypropylene resin having a crosslinkable silyl group and a diacylphosphine oxide compound were dissolved in a solvent was used.

  As shown in FIG. 1A, an insulator film 2 is deposited with silicon oxide on a semiconductor substrate 1 on which various semiconductor elements (not shown) are formed, and the above-described extinction property is formed on the insulator film 2. A resin coating solution is applied by spin coating. Then, after this spin coating, pre-baking is performed at a temperature of 100 ° C. or less to remove unnecessary solvent. In this way, the heat extinguishing resin film 3 having a film thickness of about 1 μm is formed. Here, in this application | coating process, it can carry out under normal fluorescent lamp irradiation. On the other hand, the coating process of the conventional photolithography technique needs to be performed in a special processing chamber that completely blocks ultraviolet light.

  Next, as shown in FIG. 1B, in a so-called direct drawing method, a carbon dioxide laser is used as a light source, and a laser beam 4 having a high energy density is irradiated in a short time. The laser beam 4 is a heat beam, and heat energy is applied to the heat extinguishing resin film 3 so that the temperature of the irradiated region is about 200 ° C. to 250 ° C. With this thermal energy, the heat extinguishing resin film 3 in the irradiated region is thermally decomposed and disappears. Thus, the pattern of the heat extinguishing resin film 3 is formed, and the etching mask 5 is formed.

  On the other hand, in the conventional resist film, in this direct writing, the functional group in the resist is exposed and the base resin of the resist changes. That is, the base resin copolymerization is cut (positive type) or the polymerization is accelerated (negative type). In this way, a pattern is formed through dissolution of the base resin after being changed by the light irradiation in the development step.

  In this way, in the present invention, the development step as in the conventional photolithography technique becomes unnecessary, and the cost for pattern formation can be greatly reduced.

  Next, as shown in FIG. 1C, light irradiation 6 is performed on the entire surface, and the composition constituting the heat extinguishing resin film 3 patterned as the etching mask 5 is crosslinked and photocured to be etched. A mask 5a is formed. The light source that can be used for the light irradiation is not particularly limited as long as the light source includes a wavelength at which the polyoxyalkylene resin composition is exposed to light and begins to cure. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure Examples include mercury lamps, excimer lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, sodium lamps, halogen lamps, xenon lamps, fluorescent lamps, sunlight, and electron beam irradiation devices. These light sources may be used independently and may use 2 or more types together. The etching mask 5a photocured from the etching mask 5 by this light irradiation is improved in dry etching resistance described below, and functions sufficiently as a mask for dry etching.

  Next, as shown in FIG. 1D, the insulator film 2 is etched by dry etching using plasma using the etching mask 5a as a mask. Then, an opening 7 is formed in the insulator film 2.

  Next, as shown in FIG. 1 (e), in the oxygen atmosphere or nitrogen atmosphere, heat treatment at a temperature of about 150 ° C. to 250 ° C. is performed in the former, and heat treatment at a temperature of about 200 ° C. to 250 ° C. is performed in the latter case. . By such heat treatment, the etching mask 5a made of heat extinguishing resin is thermally decomposed and completely disappeared and removed. Here, the atmosphere of the heat treatment may be dry air. In this manner, a pattern formation of the insulator film 2 having the opening 7 is formed on the semiconductor substrate 1.

The etching mask 5a of the present invention can be removed by using a simple oven as an apparatus to be used, and the removal method is very simple, as compared with the conventional ashing removal in plasma. Thus, the removal after use as an etching mask becomes very simple, so that the cost of pattern formation is greatly reduced.
Moreover, if it heats under reduced pressure, it can remove more efficiently.

  In the above embodiment, thermal energy may be given by an electron beam instead of the laser beam. In addition, as the laser light source, a UV laser light source or an excimer laser light source may be used.

(Second Embodiment)
Next, a second embodiment of the present invention will be described with reference to FIG. FIG. 2 is a sectional view showing a lift-off mask pattern formation using the heat extinguishing resin film and a conductor film pattern formation process such as wiring using the lift-off mask pattern. Here, the same components as those described in the first embodiment are denoted by the same reference numerals.

  Also in this embodiment, in order to form a heat extinguishing resin film, an extinguishing resin coating solution in which the above-described polyoxypropylene resin having a crosslinkable silyl group and a diacylphosphine oxide compound are dissolved in a solvent is used.

  In the same manner as described in the first embodiment, an insulator film 2 is deposited on the semiconductor substrate 1 with silicon oxide as shown in FIG. Spin the extinct resin coating solution. Then, after this spin coating, pre-baking is performed at a temperature of about 80 ° C. to remove unnecessary solvents. In this way, the heat extinguishing resin film 3 having a thickness of about 1.5 μm is formed.

  Next, as shown in FIG. 2B, a laser beam 4 which is a heat beam is irradiated by a direct drawing method. Here, a YAG laser is used as the light source. And heat energy is provided with respect to the heat extinction resin film 3, and the temperature of an irradiation area | region shall be about 200 degreeC. In this case, heat accumulates on the surface of the insulator film 2 made of silicon oxide having poor heat conductivity, so that the heat extinguishing resin film 3 is easily thermally decomposed as it approaches the insulator film 2. Then, a lift-off mask 9 having a lift-off opening 8 having a reverse taper cross-sectional shape as shown in FIG. 2B can be formed.

  In the same manner as described in the first embodiment, even in this case, in the formation of the lift-off mask 9 having the lift-off opening 8, a development process as in the conventional photolithography technique is completely unnecessary. For this reason, as described above, the cost for pattern formation can be greatly reduced.

  Next, in the same manner as described in the first embodiment, the entire surface is irradiated with light 6 as shown in FIG. 2C, and the heat extinguishing resin film 3 patterned as the lift-off mask 9 is formed. Are lifted and a photo-cured lift-off mask 9a is formed.

  Next, as shown in FIG. 2D, using the lift-off mask 9a as a mask, for example, a conductor film 10 such as tungsten (W) having a film thickness of about 0.5 μm is formed by sputtering. Here, it is preferable to use a collimated sputtering method with high straightness. In this case, since the lift-off mask 9a has a reverse taper shape, the conductor film 10 deposited on the lift-off mask 9a and the conductor film deposited in the lift-off opening 8 and serving as the wiring 11 are shown in FIG. As shown in 2 (d), they are formed separately.

Next, in an oxygen atmosphere or a nitrogen atmosphere, heat treatment at a temperature of about 200 ° C. is performed in the former, and heat treatment at a temperature of about 250 ° C. is performed in the latter case. By such heat treatment, the lift-off mask 9a made of the heat extinguishing resin is thermally decomposed and disappears, and the lift-off mask 9a
The upper conductive film 10 is lifted off and removed. Through such a lift-off process of the present invention, the wiring 11 is formed on the insulator film 2 on the semiconductor substrate 1 as shown in FIG.

  Here, in the conventional lift-off technique, the lift-off mask is formed from a resist film. In the lift-off process, the lift-off mask made of a resist film is dissolved and removed in a chemical solution of an organic solvent. By dissolving and removing the lift-off mask, the conductor film deposited on the lift-off mask is lifted off and removed to form wiring.

  In the present invention, since the chemical solution is not used as in the conventional lift-off process as described above, the operation becomes safe and the workability is improved. This reduces the pattern formation cost. Note that when the light amount of the YAG laser is changed, a reverse taper may not be formed, but lift-off is possible.

(Third embodiment)
Next, a third embodiment of the present invention will be described with reference to FIGS. 3 and 4 are cross-sectional views in the order of steps showing the pattern formation of the etching mask using the heat extinguishing resin film and the method of forming the pattern of the semiconductor film using the same. Here, the same components as those described in the first embodiment are denoted by the same reference numerals.

  Also in this embodiment, in order to form a heat extinguishing resin film, the polyoxypropylene resin having a crosslinkable silyl group and a diacylphosphine oxide compound described above are used as a solvent in the same manner as in the first and second embodiments. A dissolved extinguishing resin coating solution is used.

  As shown in FIG. 3A, a thermal oxide film (not shown) is formed on the surface of the semiconductor substrate 1, and a semiconductor thin film 12 such as a polycrystalline silicon film is deposited on the thermal oxide film. The extinct resin coating solution as described above is spin-coated. Then, after this spin coating, pre-baking is performed at a temperature of about 80 ° C. to remove unnecessary solvents. In this way, the heat extinguishing resin film 3 having a thickness of about 1 μm is formed.

  Next, as shown in FIG. 3B, the same processing as the exposure process of the conventional photolithography technique is performed. That is, the reticle 15 comprising the quartz glass substrate 13 and the light-shielding film pattern 14 formed on the surface thereof is used as a photomask, and the exposure light 16 is irradiated by normal reduction projection exposure, and the above-described heat extinguishing resin film 3 pattern is transferred by exposure. I do. In this way, the photocured region 3 a is formed in a predetermined region of the heat extinguishing resin film 3. Here, an ArF excimer laser (wavelength: about 193 nm) is used as the exposure light 16.

  Next, heat treatment is performed at a temperature of about 150 ° C. in an oxygen atmosphere. By this heat treatment, the heat extinguishing resin in the region other than the photocuring region 3a in the heat extinguishing resin 3 is thermally decomposed and completely disappeared. In the heat extinguishing resin film 3, the photocured region 3 a remains as it is without being thermally decomposed at the temperature of about 150 ° C. In this way, as shown in FIG. 3C, the pattern of the heat extinguishing resin film 3 is formed, and the etching mask 17 is formed on the semiconductor film 12. What is important here is that the temperature of the heat treatment is higher than the temperature at which the heat extinguishing resin film 3 in the region not exposed to the exposure light 16 decomposes and disappears, and the heat extinguishing resin in the region irradiated with the exposure light 16 The temperature is set lower than the temperature at which the film 3, that is, the photocured region 3a is decomposed and disappears.

On the other hand, in the conventional pattern formation of a resist film, as described above, in the step of FIG. 6B, the functional group in the resist is exposed and the base resin of the resist changes. That is, the base resin copolymerization is cut (positive type) or the polymerization is accelerated (negative type). In this way, a pattern is formed through dissolution of the base resin after being changed by the light irradiation in the development step.

  Thus, even in this case, the development step as in the conventional photolithography technique is not required, and the cost for pattern formation can be greatly reduced.

  Next, as shown in FIG. 4A, the semiconductor thin film 12 is etched by dry etching using plasma using the etching mask 17 as a mask. In this way, for example, the gate electrode 18 is formed.

  Next, as shown in FIG. 4B, heat treatment is performed at a temperature of about 200 ° C. to 250 ° C. in a nitrogen atmosphere. By such heat treatment, the etching mask 17 made of heat extinguishing resin is thermally decomposed and completely disappeared and removed. Here, the atmosphere of the heat treatment may be dry air. In this way, the gate electrode 18 is formed on the semiconductor substrate 1 by pattern formation of the semiconductor thin film 12.

Also in this case, the removal of the etching mask 17 is extremely simple compared with the conventional ashing removal in plasma, and the cost of pattern formation is greatly reduced.
Here, as the extinguishing resin coating solution, a solution obtained by adding a photocurable resin based on polypropylene glycol diacrylate may be used. Thereby, a photocrosslinkable material is added, and the extinction temperature T1 of the exposed region is selectively increased above the extinction temperature T0 of the non-exposed region,
If heating is performed at a temperature T (T: T0 <T <T1), a resist pattern can be easily formed.
After the processing, the resist pattern can be removed by heating to T (T: T> T1).

(Fourth embodiment)
Next, a fourth embodiment of the present invention will be described with reference to FIG. FIG. 5 is a cross-sectional view in the order of steps showing a pattern formation method of a plating mask using the heat extinguishing resin film and a pattern formation method of a metal film such as a bump using the same. Here, the same components as those described in the first embodiment are denoted by the same reference numerals.

  Also in this embodiment, in order to form a heat extinguishing resin film, an extinguishing resin coating solution in which the above-described polyoxypropylene resin having a crosslinkable silyl group and a diacylphosphine oxide compound are dissolved in a solvent is used.

  As shown in FIG. 5A, an insulator film 2 is deposited with silicon oxide on a semiconductor substrate 1 on which various semiconductor elements (not shown) are formed, and a thin Cu layer is formed by sputtering. A power supply layer 19 is formed on the film 2. Then, the extinction resin coating solution as described above is spin-coated, and a plating mask 21 having a plating opening 20 is formed by the same method as described with reference to FIG. Further, in the same manner as described in the first embodiment, the entire surface of the plating mask 21 is irradiated with light to form a heat extinguished resin film patterned as the plating mask 21. Are crosslinked and photocured.

  Next, a plating treatment is performed in a plating bath containing a plating solution containing divalent copper ions as a plating solution, for example, a copper sulfate aqueous solution containing about 5 to 200 g / L (liter) of copper ions. By this plating process, as shown in FIG. 5B, the copper electrode 22 is formed so as to be embedded in the plating opening 20. In this plating step, the plating mask 21 that has been subjected to the above-described photocuring treatment does not swell with the plating solution, and the pattern does not change.

  Next, as shown in FIG.5 (c), the heat processing of the temperature of 200 to 250 degreeC is performed in nitrogen atmosphere. By this heat treatment, the plating mask 21 made of heat extinguishing resin is thermally decomposed and completely disappeared and removed. Here, the atmosphere of the heat treatment may be dry air. In this way, a metal film pattern formed of the copper electrode 22 is formed on the insulator film 2 on the semiconductor substrate 1. The thin power feeding layer 19 is removed by dry etching or ion milling in a later step.

  The plating mask 21 made of the heat extinguishing resin can be applied to the case of gold (Au) plating as well as copper plating. By forming such a metal film pattern, bumps or wirings can be formed on the semiconductor chip.

  As described above, by using the plating mask made of the heat extinguishing resin of the present invention, the cost of forming the pattern of the metal film is greatly reduced.

  The present invention is not limited to the above-described embodiment, and the embodiment can be appropriately changed within the scope of the technical idea of the present invention. In the above-described embodiment, the case of manufacturing a semiconductor device has been described. Although the case of dry etching in the etching process has been described, the present invention can be applied to the case of wet etching.

  Below, the heat extinction resin used by this invention is explained in full detail. Examples of the heat extinguishing resin used in the present invention include polymethylene malonic acid diester, polybutylene, nitrocellulose, α-methylstyrene polymer, propylene carbonate polymer, poly (meth) acrylic acid alkyl ester, carboxylic acid dihydrazide and diisocyanate. Copolymers, peroxides of these polymers, etc., and plasticizers such as dibutyl phthalate and dioctyl phthalate, and softeners such as xylene oil, terpene oil, and paraffin wax, if necessary. That have been given tackiness. Polybutene and polylauryl methacrylate can also be used as the heat extinguishing resin.

Furthermore, this inventor discovered that the heat extinction resin film which consists of polyoxyalkylene resin lose | disappears rapidly by heating at 150-260 degreeC.
Although it does not specifically limit as said polyoxyalkylene resin, 95% or more of mass lose | disappears within 10 minutes by heating to predetermined temperature in 150-350 degreeC by oxygen atom content 15-55 mass%. Those that do are preferred.
The polyoxyalkylene resin means both uncrosslinked and crosslinked ones.
The polyoxyalkylene resin is not particularly limited, and examples thereof include a polymer containing polyalkylene glycol or polyoxyalkylene as a segment.

Although it does not specifically limit as said polyalkylene glycol, For example, polyoxypropylene glycol, polyoxyethylene glycol, polyoxytetramethylene glycol etc. are mentioned. Among them, it is preferable to use as polyoxypropylene, polyoxyethylene, polyoxytetramethylene or a mixed resin of polyoxypropylene and polyoxyethylene and / or polyoxytetramethylene, and the inclusion of polyoxypropylene in the mixed resin The rate is more preferably 50% by mass or more. If such a mixed resin is used, the temperature at which it disappears and the time until it disappears can be adjusted by adjusting the mixing ratio of the resin. Moreover, when it is used as a mixed resin with solid polyoxyethylene glycol and / or polyoxytetramethylene glycol, there is no adhesiveness, and the properties can be widely changed from a hot melt type resin layer to an adhesive layer.

  The polyoxyalkylene segment in the copolymer containing polyoxyalkylene as a segment means a segment having two or more repeating units represented by the following general formula (1).

In the formula (1), n represents an integer of 1 or more, and R ¹ⁿ and R ²ⁿ are n-th substituents, which are hydrogen, alkyl group, aryl group, alkenyl group, hydroxyl group, carboxyl group, epoxy group, amino group The substituent obtained by combining 1 or more types selected from the group which consists of group, an amide group, an ether group, and ester group is represented.

  When the number of repeating units represented by the general formula (1) is one, it becomes difficult to completely extinguish the heat extinguishing resin film by heating. Further, even when the segment having two or more repeating units represented by the general formula (1) has no crosslinking point and is a gel-like resin crosslinked by another segment, the polyoxy group is crosslinked between the crosslinking points. When an alkylene segment is present, it can be used for the heat extinguishing resin film of the present invention. Furthermore, the copolymer containing the polyoxyalkylene as a segment may be connected in a chain form using a chain extender.

  The polymer containing the polyoxyalkylene as a segment is not particularly limited. For example, polymethylene glycol (polyacetal), polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, polybutylene glycol, and a plurality thereof Including those segments. Moreover, the polyurethane, polyester, polyamide, polyimide etc. which are obtained from this are mentioned. Further, (meth) acrylic polymers having a polyoxyalkylene segment in the graft chain, vinyl polymers such as polystyrene, and the like can be mentioned. These resins may be used in combination.

The number average molecular weight of the polyoxyalkylene resin is preferably 5,000 to 5,000,000. When the number average molecular weight is lower than 500, the volatility becomes strong and it may be difficult to handle stably. On the other hand, if it exceeds 5 million, the cohesive force is excellent, but it may be difficult to quickly disappear due to the entanglement effect.
Specifically, the number average molecular weight is appropriately selected according to the method aspect of the present invention.

In order to form a heat extinguishing resin film on the surface of a substrate to be processed using the polyoxyalkylene resin, a method of applying and drying a resin composition containing the polyoxyalkylene resin, or a polyoxyalkylene having a crosslinkable functional group is used. Examples thereof include a method in which a resin composition containing an alkylene resin and a crosslinking agent is applied, dried if necessary, and the crosslinking functional group and the crosslinking agent are reacted to be crosslinked and cured.
Examples of the polyoxyalkylene resin having a crosslinkable functional group include polyoxyalkylene glycol having a crosslinkable functional group or a polymer having a crosslinkable functional group containing polyoxyalkylene as a segment.

  The crosslinkable functional group possessed by the polymer containing the polyalkylene glycol or polyoxyalkylene as a segment is not particularly limited. For example, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an oxetanyl group, an acid anhydride group, Examples thereof include a carboxyl group, a hydroxyl group, and a polymerizable unsaturated hydrocarbon group. Among them, it is preferably at least one selected from a hydrolyzable silyl group, an isocyanate group, an epoxy group, an oxetanyl group, an acid anhydride group, a carboxyl group, a hydroxyl group, and a polymerizable unsaturated hydrocarbon group. It is more preferably at least one selected from a reactive silyl group, an epoxy group, and an oxetanyl group, and a hydrolyzable silyl group is more preferable. These crosslinkable functional groups may be used alone or in combination of two or more.

  Among the above-mentioned polymers containing a polyalkylene glycol having a hydrolyzable silyl group or a polyoxyalkylene as a segment, for example, MS polymer S--is a trade name MS polymer manufactured by Kaneka Chemical Co., Ltd. 203, S-303, S-903, etc., as silyl polymers, silyl SAT-200, MA-403, MA-447, etc., EPION as EP103S, EP303S, EP505S, etc., Exstar ESS-2410, ESS manufactured by Asahi Glass Co., Ltd. -2420, ESS-3630, and the like.

  The polymer containing the above-mentioned polyalkylene glycol or polyoxyalkylene having an isocyanate group as a segment is, for example, a diisocyanate such as 1,6-hexamethylene diisocyanate, TDI, MDI, and polypropylene glycol, and the molar amount of isocyanate is larger than the molar amount of hydroxyl group. It can be obtained by, for example, urethanization reaction under the above conditions.

  Examples of commercially available polymers containing the above-described polyalkylene glycol or polyoxyalkylene having an epoxy group as a segment include Epolite series manufactured by Kyoeisha Chemical Co., Ltd.

Examples of the polymerizable unsaturated hydrocarbon group include a (meth) acryloyl group and a styryl group.
Examples of the polymer containing a polyalkylene glycol or polyoxyalkylene having a polymerizable unsaturated group such as the (meth) acryloyl group or styryl group as a segment include α, ω-di (meth) acryloyloxypolypropylene glycol, α , Ω-di (meth) acryloyloxypolyethylene glycol, α- (meth) acryloyloxypolypropylene glycol, α- (meth) acryloyloxypolyethylene glycol, and the like. Among these, commercially available products include, for example, Nippon Oil & Fats Bremer Series, Shin Nakamura Chemical Co., Ltd. NK Ester M Series, Shin Nakamura Chemical Co., Ltd. NK Ester AMP Series, Shin Nakamura Chemical Co., Ltd. NK Ester BPE Series, New Nakamura Chemical Co., Ltd. NK Ester A Series, Shin-Nakamura Chemical Co., Ltd. NK Ester APG Series, Toa Gosei Co., Ltd. Aronix M-240, Toa Gosei Co., Ltd. Aronix M-245, Toa Gosei Co., Ltd. Aronix M-260, Toa Gosei Co., Ltd. Aronix M-270, Daiichi Kogyo Seiyaku PE Series, Daiichi Kogyo Seiyaku BPE Series, Daiichi Kogyo Seiyaku BPP Series, Kyoeisha Chemical Company Light Ester 4EG, Kyoeisha Chemical Company Light Ester 9EG, Kyoeisha Chemical Company Light Ester 14EG, Kyoeisha Chemical Light Acrylate MTG-A, Kyoei Kagaku Light Acrylate DPM-A, Kyoeisha Chemical Co., Ltd. Light Acrylate P-200A, Kyoeisha Chemical Co., Ltd. Light Acrylate 9EG, include Kyoeisha Chemical Co., Ltd. Light Acrylate BP-EPA or the like.

Below, the said crosslinking agent is demonstrated.
The cross-linking agent is not particularly limited as long as it is a cross-linking agent that cross-links the cross-linkable functional group of the polymer. For example, it reacts with the cross-linkable functional group of the polymer containing the polyalkylene glycol or polyoxyalkylene as a segment. Thus, the crosslinkable functional group possessed by the polymer itself having the effect of being incorporated into the structure of the crosslinked product (hereinafter also referred to as the crosslinking agent (1)) and the polymer containing the polyalkylene glycol or polyoxyalkylene as a segment. Some have a function as a catalyst for reacting groups (hereinafter, also referred to as a crosslinking agent (2)). Moreover, there exists a crosslinking agent (3) which has an effect | action of both said crosslinking agent (1) and crosslinking agent (2).

Although it does not specifically limit as a crosslinking agent (1), Specifically, the following are mentioned.
A cross-linking agent for cross-linking a polymer containing a polyalkylene glycol or polyoxyalkylene having an oxetanyl group as a segment, for example, a photocationic initiator or a thermal cation initiator that generates an acid by ultraviolet rays or visible light.

  A cross-linking agent for cross-linking a polymer containing the above-mentioned isocyanate group-containing polyalkylene glycol or polyoxyalkylene as a segment, for example, a plurality of active hydrogens such as a compound having a plurality of hydroxyl groups and a compound having a plurality of amino groups The compound which has is mentioned. Examples of the compound having a plurality of hydroxyl groups include ethylene glycol, butylene glycol, glycerin, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, pentaerythritol, and polyester polyol. Examples of the compound having a plurality of amino groups include hexamethylene diamine, tetramethylene diamine, and α, ω-diaminopropylene glycol.

Although it does not specifically limit as a crosslinking agent (2), Specifically, the following are mentioned.
As a crosslinking agent for crosslinking the hydrolyzable silyl group, for example, a photoreactive catalyst having a functional group represented by the following formula (2), a photocation initiator that generates an acid by ultraviolet light or visible light, an organometallic compound , Amine compounds, acidic phosphates, tetraalkylammonium halides (halides: fluoride, chloride, bromide, iodide), organic acids such as carboxyl groups, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid. Especially, the photoreactive catalyst which has a functional group represented by following formula (2) is suitable.

In the formula (2), m represents an integer of 2 to 5, Y (m) represents an atom of group IVB, VB or VIB of the periodic table, Z represents a hydrogen group, a hydrocarbon group, a mercapto group, amino Represents a group, a halogen group, an alkoxyl group, an alkylthio group, a carbonyloxy group or an oxo group.

The photoreaction catalyst having a functional group represented by the above formula (2) may have a plurality of different functional groups represented by the above formula (2).
Examples of the functional group represented by the general formula (2) include two carbonyl groups bonded to an atom represented by Y (m) selected from the group consisting of oxygen, sulfur, nitrogen, phosphorus and carbon. And a compound having a hydrocarbon group or an oxide group represented by Z according to the valence of the atom represented by Y (m).

Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, and an aromatic hydrocarbon group. These hydrocarbon groups have a substituent such as an amino group, a hydroxyl group, an ether group, an epoxy group, a polymerizable unsaturated group, a urethane group, a urea group, an imide group, and an ester group as long as the object of the present invention is not impaired. You may do it. Further, different hydrocarbon groups may be used in combination.

  The photoreaction catalyst having the functional group represented by the general formula (2) may be a cyclic compound. Examples of such a cyclic compound include compounds having one or two or more of the same or different functional groups represented by the general formula (2) in the cyclic chain. Furthermore, a compound in which a plurality of the same or different cyclic compounds are bonded with an appropriate organic group, a bicyclic compound containing at least one or more of the same or different cyclic compounds as a unit, and the like can also be used. .

As the photoreaction catalyst having the functional group represented by the general formula (2), when the atom represented by Y (m) is an oxygen atom, for example, acetic anhydride, propionic anhydride, butyric acid Anhydride, isobutyric acid anhydride, valeric acid anhydride, 2-methylbutyric acid anhydride, trimethylacetic acid anhydride, hexanoic acid anhydride, heptanoic acid anhydride, decanoic acid anhydride, lauric acid anhydride, myristic acid anhydride, Palmitic anhydride, stearyl anhydride, docosanoic anhydride, crotonic anhydride, acrylic anhydride, methacrylic anhydride, oleic anhydride, linoleic anhydride, chloroacetic anhydride, iodoacetic anhydride, Dichloroacetic anhydride, trifluoroacetic anhydride, chlorodifluoroacetic anhydride, trichloroacetic anhydride, pentafluoropropionic anhydride, heptafluoro Tyric anhydride, succinic anhydride, methyl succinic anhydride, 2,2-dimethyl succinic anhydride, isobutyl succinic anhydride, 1,2-cyclohexanedicarboxylic anhydride, hexahydro-4-methylphthalic anhydride, Itaconic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, maleic anhydride, 2-methylmaleic anhydride, 2,3- Dimethylmaleic acid anhydride, 1-cyclopentene-1,2-dicarboxylic acid anhydride, glutaric acid anhydride, 1-naphthyl acetic acid anhydride, benzoic acid anhydride, phenylsuccinic acid anhydride, phenylmaleic acid anhydride, 2, 3-diphenylmaleic anhydride, phthalic anhydride, 4-methylphthalic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 4,4 '-(hexafluoropropylidene) diphthalic anhydride, 1,2,4,5-benzenetetracarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,4,5,8 -Naphthalenetetracarboxylic acid anhydride and the like; As a copolymer of maleic acid anhydride and a compound having a radical polymerizable double bond, for example, maleic acid anhydride and (meth) acrylate copolymer, maleic acid anhydride and Examples include styrene copolymers and copolymers of maleic anhydride and vinyl ether. Of these, commercially available products include, for example, Adeka Hardner EH-700, Adeka Hardner EH-703, Adeka Hardner EH-705A manufactured by Asahi Denka Co., Ltd .; RIKACID MH-700, RIKACID MH-700H, RIKACID MH, RIKACID SH, RIKARESIN TMEG; Hitachi Chemical HN-5000, HN-2000; A Sumicure MS manufactured by Sumitomo Chemical Co., Ltd.

As a photoreaction catalyst having a functional group represented by the general formula (2), when the atom represented by Y (m) is a nitrogen atom, for example, succinimide, N-methylsuccinimide, α , Α-dimethyl-β-methyl succinimide, α-methyl-α-propyl succinimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-tert-butylmaleimide, N-laurylmaleimide N-cyclohexylmaleimide, N-phenylmaleimide, N- (2-chlorophenyl) maleimide, N-benzylmaleimide, N- (1-pyrenyl) maleimide, 3-methyl-N-phenylmaleimide, N, N′-1, 2-phenylene dimaleimide, N, N′-1,3-phenylene dimaleimide, N, N′-1,4-phenylene dimale N, N ′-(4-methyl-1,3-phenylene) bismaleimide, 1,1 ′-(methylenedi-1,4-phenylene) bismaleimide, phthalimide, N-methylphthalimide, N-ethylphthalimide, N-propyl phthalimide, N-phenyl phthalimide, N-benzyl phthalimide, pyromellitic acid diimide and the like can be mentioned.

As the photoreaction catalyst having the functional group represented by the general formula (2), when the atom represented by Y (m) is a phosphorus atom, for example, bis (2,6-dimethoxybenzoyl) -2 , 4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

As the photoreaction catalyst having the functional group represented by the general formula (2), when the atom represented by Y (m) is a carbon atom, for example, 2,4-pentanedione, 3-methyl- 2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3-chloro-2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1 , 5,5,5-hexafluoro-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1-benzoylacetone, dibenzoylmethane, and other diketones; dimethylmalo Acid ester, diethyl malonate, dimethyl methyl malonate, polycarboxylic acid esters such as tetraethyl 1,1,2,2-ethanetetracarboxylic acid; methyl acetylacetonate, ethylacetylacetonate α- carbonyl such as methyl propionylacetate - acetic acid esters and the like.

  Among the photoreaction catalysts having the functional group represented by the general formula (2), diacylphosphine oxide or a derivative thereof is particularly preferably used because the residue after disappearance is extremely small.

  As a preferable use amount of the photoreaction catalyst having the functional group represented by the general formula (2), a polymer containing 100 parts by weight of the polyalkylene glycol or polyoxyalkylene having a hydrolyzable silyl group as a segment is used. 0.01 parts by weight with respect to parts, and the preferred upper limit is 30 parts by weight. When the amount is less than 0.01 parts by weight, photoreactivity may not be exhibited. When the amount exceeds 30 parts by weight, a polymer containing a polyalkylene glycol or polyoxyalkylene having a hydrolyzable silyl group as a segment is contained. The light transmittance of the composition is lowered, and even when irradiated with light, only the surface may be crosslinked and cured, and the deep part may not be crosslinked or cured. A more preferred lower limit is 0.1 parts by weight, and a more preferred lower limit is 20 parts by weight.

  Examples of the organometallic compound include dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin laurate) oxide, dibutyltin bisacetylacetonate, and dibutyltin bis (monoester maleate). And tin compounds such as tin octylate, dibutyltin octoate and dioctyltin oxide, and alkyloxytitanates such as tetra-n-butoxy titanate and tetraisopropoxy titanate.

  As a crosslinking agent for crosslinking a polymer containing a polyalkylene glycol or polyoxyalkylene having a polymerizable unsaturated group as a segment, for example, a thermal radical initiator such as a peroxide or an azo compound; light by ultraviolet rays or visible light Radical initiator; an initiator system comprising a combination of a thermal or photo radical initiator and a compound having a plurality of mercapto groups.

Examples of the thermal radical initiator include diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide, tert-butyl hydroperoxide, and the like. Hydroperoxides, α, α′-bis (tert-butylperoxy-m-isopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, dialkyl peroxides such as tert-butyl cumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3; ketone peroxides, Oxyketer , Organic peroxides such as diacyl peroxides, peroxydicarbonates, peroxyesters, or 2,2′-azobisisobutyronitrile, 1,1 ′-(cyclohexane-1-carbonitrile ), 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and the like.

Examples of the photo radical initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α'-dimethylacetophenone, methoxyacetophenone, and 2,2-dimethoxy. 2-acetophenone derivative compounds such as 2-phenylacetophenone; benzoin ether compounds such as benzoin ethyl ether and benzoin propyl ether; ketal derivative compounds such as benzyldimethyl ketal; halogenated ketones; acyl phosphine oxides; acyl phosphonates; Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone; Bis (2,4,6-trimethyl Benzoyl) -phenylphosphine oxide bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; bis (η5-cyclopentadienyl) -bis (pentafluorophenyl) -titanium, bis (Η5-Cyclopentadienyl) -bis [2,6-difluoro-3- (1H
-Pyrid-1-yl) phenyl] -titanium; anthracene, perylene, coronene, tetracene, benzanthracene, phenothiazine, flavin, acridine, ketocoumarin, thioxanthone derivatives, benzophenone, acetophenone, 2-chlorothioxanthone, 2,4-dimethyl Examples include thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone and the like. These may be used alone or in combination of two or more.

  As a crosslinking agent for crosslinking a polymer containing the above-mentioned polyalkylene glycol or polyoxyalkylene having an epoxy group as a segment, for example, a photocation initiator that generates an acid by ultraviolet light or visible light, a thermal cation initiator, an amine compound-based curing Agents, amide-based curing agents, acid anhydride-based curing agents, mercapto-based curing agents, thermal latent curing agents such as ketimine and DICY, and photoamine generators having a carbamoyloxyimino group.

Examples of the photocation catalyst include iron-allene complex compounds, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, pyridinium salts, aluminum complexes / silanol salts, and trichloromethyltriazine derivatives. Among these, as anions of onium salts and pyridinium salts, for example, SbF ₆ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ ,
Examples thereof include BF ₄ ⁻ , tetrakis (pentafluoro) borate, trifluoromethane sulfonate, methane sulfonate, trifluoroacetate, acetate, sulfonate, tosylate, and nitrate. Among these photocationic catalysts, those commercially available include, for example, Irgacure 261 (Ciba Geigy), Optmer SP-150 (Asahi Denka Kogyo), Optomer SP-151 (Asahi Denka Kogyo), Optomer SP-170 (Asahi Denka Kogyo), Optomer SP-171 (Asahi Denka Kogyo), UVE-1014 (General Electronics), CD-1012 (Sartomer), Sun-Aid SI-60L (Sanshin) Chemical Industry Co., Ltd.), Sun Aid SI-80L (manufactured by Sanshin Chemical Industry Co., Ltd.), Sun Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.), CI-2064 (manufactured by Nippon Soda Co., Ltd.), CI-2639 (manufactured by Nippon Soda Co., Ltd.) ), CI-2624 (Nippon Soda Co., Ltd.), CI-2481 (Nippon Soda Co., Ltd.), RHODORSIL PHOTOINITIATOR 2074 (manufactured by Rhone-Poulenc), UVI-6990 (manufactured by Union Carbide), BBI-103 (
Midori Kagaku), MPI-103 (Midori Chemical), TPS-103 (Midori Chemical), MDS-103 (Midori Chemical), DTS-103 (Midori Chemical), NAT-103 (Midori Chemical) Midori Chemical Co., Ltd.), NDS-103 (Midori Chemical Co., Ltd.) and the like. These photocationic catalysts may be used alone or in combination of two or more.

Examples of the thermal cation curing agent include ammonium salts having at least one alkyl group, sulfonium salts, iodonium salts, diazonium salts, boron trifluoride / triethylamine complexes, and the like. As counter anions of these salts, for example, SbF ₆ ⁻
, PF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , tetrakis (pentafluoro) borate, trifluoromethanesulfonate, methanesulfonate, trifluoroacetate, acetate, sulfonate, tosylate, nitrate and the like.

  Examples of the photoamine generator include a compound having a carbamoyloxyimino group, a cobaltamine complex, carbamate-o-nitrobenzyl, o-acyloxime, and the like.

  Although it does not specifically limit as a crosslinking agent (3), (alpha), omega-diamino polyoxypropylene etc. are mentioned.

  A resin composition containing a polyoxyalkylene resin having a crosslinkable functional group and a crosslinker is a polymer containing, as a segment, a polyalkylene glycol or polyoxyalkylene having a crosslinkable functional group, as long as the object of the present invention is not impaired. A compound having a functional group passing through the same reactive intermediate may be contained as a copolymerizable or co-crosslinkable component. In addition, a compound having a crosslinkable or polymerizable functional group via a reactive intermediate different from a polymer containing a polyalkylene glycol or polyoxyalkylene having a crosslinkable functional group as a segment is a copolymerizable or cocrosslinkable component. You may contain as. Furthermore, you may contain the compound which has these two types of functional groups simultaneously.

Examples of the copolymerizable or co-crosslinkable component include compounds having a radical polymerizable unsaturated group. Examples of such a compound having a radically polymerizable unsaturated group include styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert. -Compounds having a styryl group such as butoxystyrene and divinylbenzene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate Isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hexanediol di (meth) Acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Rate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 2-hydroxybutyl (meth)
Acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-3-methylbutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, 2-[(meth) acryloyloxy] ethyl 2-hydroxyethylphthalic acid, 2-[(meth) acryloyloxy] ethyl 2-hydroxypropylphthalic acid, a compound represented by the following formula (3), the following formula Examples include compounds having a (meth) acryloyl group such as the compound represented by (4).

Examples of the copolymerizable or co-crosslinkable component include compounds having an epoxy group. Examples of such an epoxy group-containing compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, cresol epoxy resin, aliphatic cyclic epoxy resin, Brominated epoxy resin, rubber modified epoxy resin, urethane modified epoxy resin, glycidyl ester compound, epoxidized polybutadiene, epoxidized SBS (SBS indicates poly (styrene-co-butadiene-co-styrene) copolymer), etc. Can be mentioned.

  Examples of the copolymerizable or co-crosslinkable component include compounds having an isocyanate group. Examples of such a compound having an isocyanate group include xylylene diisocyanate, toluylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, 1,6-hexamethylene diisocyanate, and phenylmethane diisocyanate.

The resin composition containing a polyoxyalkylene resin having a crosslinkable functional group and a crosslinking agent is imparted with fast curability by containing 30% by mass or less of a compound having a polymerizable unsaturated group.
Although it does not specifically limit as a polymerizable unsaturated group of the compound which has a polymerizable unsaturated group, For example, a styryl group, an acryloyl group, a methacryloyl group, a vinyl ester group, a vinyloxy group etc. can be mentioned.

  Although it does not specifically limit as a compound which has the said styryl group, For example, styrene, indene, alpha-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxy Examples thereof include styrene and divinylbenzene.

  Examples of the compound having an acrylic group or a methacryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meta ) Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, Benzyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) ) Acrylate, hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, Urethane acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy -3-methylbutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-[(meth) acryloyloxy] ethyl-2-hydroxyethyl-phthalic acid, 2 -[(Meth) acryloyloxy] ethyl-2-hydroxypropyl-phthalic acid and the like.

  Examples of the compound having a vinyl ester group include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, and vinyl cinnamate.

  Examples of the compound having a vinyloxy group include n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloro Ethyl vinyl ether, ethylene glycol butyl vinyl ether, triethylene glycol methyl vinyl ether, benzoic acid (4-vinyloxy) butyl, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4- Diol-divinyl ether, hexane-1,6-di -Divinyl ether, cyclohexane-1,4-dimethanol-divinyl ether, di (4-vinyloxy) butyl isophthalate, di (4-vinyloxy) butyl glutarate, di (4-vinyloxy) butyl trimethylolpropane succinate Trivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane-1,4-dimethanol-monovinyl ether, diethylene glycol monovinyl ether, 3-aminopropyl vinyl ether, 2- (N, N- Diethylamino) ethyl vinyl ether, urethane vinyl ether, polyester vinyl ether, and the like.

The viscosity of the resin composition containing the above polyoxyalkylene resin or the resin composition containing a polyoxyalkylene resin having a crosslinkable functional group and a crosslinking agent is not particularly limited, but is 1 to 5 million mPa · s at 20 ° C. It is preferable that it is s. Specifically, the viscosity can be selected and prepared in accordance with the aspect of the present invention.
For example, in the present invention, in order to form a heat extinguishing resin film by a spin coating method, a pulling method, a dipping method, etc., the viscosity of the resin composition at 20 ° C. is 1 to 100 mPa · s.
It is preferable that
In the present invention, in order to form the heat extinguishing resin film by a brush coating method or the like, it is preferable that the viscosity of the resin composition at 20 ° C. is 500 to 100,000 mPa · s.
In the present invention, in order to form the heat extinguishing resin film by a screen printing method or the like, the resin composition preferably has a viscosity at 20 ° C. of 20 to 1000 mPa · s.

  A method for forming a heat extinguishing resin film on the surface of a substrate to be treated using the resin composition is not particularly limited, and examples thereof include known methods such as a solvent casting method, an extrusion coating method, a calendar method, and a UV coating polymerization method. This method can be used.

  As a method by the solvent casting method, for example, a resin as a raw material in a solvent, and additives such as a crosslinking agent and a filler are dissolved and dispersed as necessary, and the resulting solution is cast on the surface of the substrate to be processed, And the like.

  Examples of the method based on the hot melt coating method include a method in which a raw material resin and, if necessary, additives such as a crosslinking agent and a filler are heated and mixed and dispersed, and hot melt coating is performed through a T die or the like.

  As a method by UV coating polymerization, for example, a raw material resin having a photocrosslinkable functional group, an initiator or a crosslinker selected according to the crosslinkable functional group, and various additives such as a filler as necessary are mixed. The method of irradiating the light which can activate a photoinitiator, etc., can be mentioned, applying the composition obtained.

  Examples of the lamp used for the light irradiation include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp. In this case, when the photocationic polymerization initiator contains light in the wavelength region that is exposed to light, the light can be cut and irradiated as appropriate with a filter or the like.

  In the case of the UV coating polymerization method, a sensitizer may be added to the raw material composition in advance. Examples of the sensitizer include anthracene derivatives and thioxanthone derivatives.

  In addition, as a method by the thermal polymerization method, for example, a raw material resin having a thermally crosslinkable functional group, an initiator or a crosslinker selected according to the crosslinkable functional group, and various additives such as a filler as necessary are mixed. The method of heating or superposing | polymerizing or crosslinking the prepared composition, etc. is mentioned. Examples of the heating method in this case include a hot plate, a heating press device, a drying oven, a heat gun, an infrared heating device, a dielectric heating device, an induction heating device, and an ultrasonic heating device. When a plurality of crosslinkable functional groups are used depending on the purpose, a plurality of production methods may be used in combination.

In addition, the resin composition containing the polyoxyalkylene resin having a crosslinkable functional group and a crosslinking agent is crosslinked and cured by applying energy for crosslinking or the like to obtain a crosslinked cured product. Examples of the crosslinking and curing of the fat composition include thermal crosslinking by heat and photocrosslinking by light.
However, in the case of thermal crosslinking, caution is required because the polyoxyalkylene resin in the composition may decompose and disappear due to overheating. For these reasons, photocrosslinking is preferred for crosslinking and curing the composition.

  When the composition is crosslinked and cured by photocrosslinking, a method of irradiating light capable of activating the crosslinking reaction of the composition can be exemplified.

Examples of the lamp used for the light irradiation include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp. In this case, when the photocationic polymerization initiator includes light in a wavelength region that is exposed to light, the light can be appropriately cut and irradiated by a filter or the like.
Further, when a resin composition containing a polyoxyalkylene resin having a crosslinkable functional group and a crosslinking agent is crosslinked and cured by photocrosslinking, a sensitizer may be added to the composition. Examples of the sensitizer include anthracene derivatives and thioxanthone derivatives.

  Moreover, when the said resin composition is bridge | crosslinked and hardened by thermal crosslinking, the method of heating this resin composition, an apparatus, etc. can be mentioned. Examples of the heating method and apparatus in this case include a hot plate, a heating press apparatus, a drying oven, a heat gun, an infrared heating apparatus, a dielectric heating apparatus, an induction heating apparatus, and an ultrasonic heating apparatus.

  Moreover, the resin composition containing a polyoxyalkylene resin having a crosslinkable functional group and a crosslinking agent includes a crosslinkable functional group containing a polyoxyalkylene glycol or polyoxyalkylene having a crosslinkable functional group as a segment. It is possible to partially cross-link a polymer having a polymer with a cross-linking agent into a microgel form.

The resin composition containing a polyoxyalkylene resin and the resin composition containing a polyoxyalkylene resin having a crosslinkable functional group and a crosslinking agent may contain a liquid resin. By containing a liquid resin, the extinction start temperature of the heat extinguishing resin film formed by the resin composition can be lowered, and can be rapidly extinguished at 150 ° C. or higher. The liquid resin is not particularly limited as long as it is a compound having a boiling point of 100 ° C. or higher in consideration of maintaining the shape of the heat extinguishing resin film and the extinction temperature. For example, polyethylene glycol oligomer, polypropylene oligomer, polytetramethylene glycol oligomer , Dioctyl phthalate, dibutyl phthalate, glycerin monooleate and the like.

  In addition, the resin composition includes titanium oxide, alumina, colloidal calcium carbonate, heavy calcium carbonate, barium carbonate, magnesium carbonate, silica, surface-treated silica, calcium silicate, anhydrous silicon, hydrous silicon, mica, surface-treated mica, and talc. , Clay, surface treatment talc, boron nitride, alumina nitride, carbon nitride, carbon black, white carbon, short glass fiber, glass beads, glass balloons, shirasu balloons, acrylic beads, polyethylene beads, etc. . By containing these, the cohesive force of the sheet or the cured product is improved. However, since these always become inorganic residues, the content should be kept to the minimum necessary.

Furthermore, the resin composition may contain a silane coupling agent.
Examples of the silane coupling agent include vinyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and 3-aminopropyl. Trimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Triethoxysilane, N, N′-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (triethoxysilyl) propyl] ethylenediamine, N, N′-bis- [ 3- (Trimethoxy Silyl) propyl] hexaethylenediamine, N, N′-bis- [3- (triethoxysilyl) propyl] hexaethylenediamine, and the like.

Moreover, the said resin composition may contain a titanium coupling agent.
Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl-n-dodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphite) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraisopropyl bis (ditri). Decyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridodecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl And tri (N-aminoethyl-aminoethyl) titanate.

  Further, the above resin composition is rosin-based, rosin ester-based, disproportionated rosin ester-based, hydrogenated rosin ester-based, polymerized rosin ester-based, terpene resin-based, terpene phenol resin-based, aromatic A modified terpene resin-based, C5 / C9 petroleum resin-based, hydrogenated petroleum resin-based, phenol resin-based, coumarone-indene resin-based, ketone resin-based, or xylene resin-based tackifier resin may be contained.

Further, the heat extinguishing resin film formed in the method of the present invention can contain a decomposition accelerator or a decomposition retarder so that the decomposition rate and the decomposition temperature can be appropriately controlled according to the use mode. .
The decomposition accelerator is not particularly limited, but an azo compound such as azodicarbonamide,
Heavy metal compounds such as iron sulfate, sodium nitrate and cobalt naphthenate; carboxylic acids such as oxalic acid, linolenic acid and ascorbic acid; hydroquinone, peroxide, azo compound and tin oxide.
The peroxide is not particularly limited, and may be an inorganic peroxide or an organic peroxide. Specific examples of the inorganic peroxide include potassium persulfate, sodium persulfate, ammonium persulfate, potassium perchlorate, sodium perchlorate, ammonium perchlorate, and potassium periodate.

Although it does not specifically limit as an organic peroxide, When storage stability is required for the heat extinction resin film formed in the method of this invention, the thing whose 10-hour half-life temperature is 100 degreeC or more is suitable. . Examples of the organic peroxide having a 10-hour half-life temperature of 100 ° C. or more include P-menthane hydroxy peroxide, diisopropylbenzene hydroxy peroxide, 1,1,3,3-tetramethylbutyl hydroxy peroxide, cumene hydroxyperoxide. Hydroxyl peroxides such as oxide, t-hexyl hydroxy peroxide, t-butyl hydroxy peroxide; dicumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropylbenzene), 2,5-dimethyl −
2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t -Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis ( t-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-
Peroxyketals such as di-t-butylperoxycyclohexyl) propane; t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy3,5,5-trimethylhexanoate, t -Butyl peroxylaurate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t-butyl peroxyisopropyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2 , 5-bis (m-benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, bis-t-butylperoxyisophthalate, t-butylperoxyallyl monocarbonate and other peroxyesters Etc.

The azo compound is not particularly limited. Specifically, azobisisobutyronitrile (AIBN), 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2- Azobis (2-cyclopropylpropionitrile), 2,2-azobis (2-methylbutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile) and the like can be mentioned.
By containing the peroxide and the azo compound, it is also possible to suppress the generation of carbide residues after heating and extinguishing the heat extinguishing resin layer formed in the present invention. Among peroxides, organic peroxides are preferred because generation of ash residues can be suppressed.

Although it does not specifically limit as said decomposition retarder, A mercapto compound, an amine compound, organic tin, an organic boron, etc. are mentioned.
The mercapto compound is not particularly limited, and specific examples include propanethiol, butanethiol, pentanethiol, 1-octanethiol, dodecanethiol, cyclopentanethiol, cyclohexanethiol, 1,3-propanediol, and the like. it can.
The amine compound is not particularly limited, and specific examples include propylamine, butylamine, hexylamine, dodecylamine, isopropylamine, hexamethylenediamine, cyclohexylamine, benzylamine, aniline, methylaniline and the like. .
Although it does not specifically limit as said organic tin, Specifically, dimethyltin dilaurate, dibutyltin diurarate, dibutyltin dioctate, dibutyltin diacetate, dibutyltin bis (2,4-pentanedione), dilauryltin dilaurate, etc. are included. Can be mentioned.
Although it does not specifically limit as said organic boron, Specifically, a trimethyl borate, a tripropyl borate, a tributyl borate, a trimethoxyboroxine, a trimethylene borate etc. can be mentioned.

  In the heat extinguishing resin film formed in the present invention, the content of the decomposition accelerator and the decomposition retarder is not particularly limited and is appropriately selected depending on the use mode and the like. It is preferable to contain 1-10 mass% with respect to a heat extinction resin film.

  Further, the heat extinguishing resin film formed in the present invention is under a reduced pressure at a predetermined temperature of 150 to 300 ° C. in an atmosphere containing oxygen and at a predetermined temperature of 150 to 350 ° C. in an anaerobic atmosphere. Then, it disappears by heating at a predetermined temperature of 150 to 350 ° C. within 5 minutes. By utilizing such a characteristic that the decomposition temperature range changes depending on the difference in the atmosphere during heating, the present invention can be appropriately used for various aspects.

  Further, the heat extinguishing resin film formed in the present invention further contains an anti-sagging agent, an antioxidant, an anti-aging agent, an ultraviolet absorber, a solvent, a fragrance, a pigment, a dye, etc., depending on the application and usage. May be.

It is sectional drawing of the order of the process of pattern formation for demonstrating the 1st Embodiment of this invention. It is sectional drawing of the process order of the pattern formation for demonstrating the 2nd Embodiment of this invention. It is sectional drawing of the process order of the pattern formation for demonstrating the 3rd Embodiment of this invention. It is sectional drawing of the pattern formation process order following the said process. It is sectional drawing of the partial process order of the pattern formation for demonstrating the 4th Embodiment of this invention. It is sectional drawing of the process order of the pattern formation for demonstrating the prior art. It is sectional drawing of the pattern formation process order following the said process.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Insulator film 3 Heat extinction resin film 3a Photocuring area | region 4 Laser beam 5, 5a, 17 Etching mask 6 Light irradiation 7 Opening 8 Lift-off opening 9, 9a Lift-off mask 10 Semiconductor film 11 Wiring 12 Semiconductor film 13 Quartz glass substrate 14 Light-shielding film pattern 15 Reticle 16 Exposure light 18 Gate silicon layer 19 Feed layer 20 Plating opening 21 Plating mask 22 Copper electrode

Claims (11)

A process of forming a heat extinguishing resin film on the surface of the substrate to be processed, and selectively irradiating the heat extinguishing resin film with thermal energy to extinguish the heat extinguishing resin film in the thermal energy irradiation region and thereby extinguish the heat. Forming a pattern of a conductive resin film , wherein the heat extinguishing resin film is made of a polyoxyalkylene resin composition having a crosslinkable silyl group . The pattern forming method according to claim 1, wherein the selective thermal energy irradiation to the heat extinguishing resin is performed by a direct drawing method using a laser beam or an electron beam. A step of forming a heat extinguishing resin film on the surface of the substrate to be processed; a step of exposing and transferring a pattern formed on a photomask to the heat extinguishing resin film by irradiation of exposure light; and the heat extinguishing property after the exposure transfer. A process comprising: heat-treating the resin film, and selectively annihilating the heat-extinguishing resin film in a region not exposed to the exposure light in the exposure transfer step to form a pattern of the heat-extinguishing resin film A pattern forming method, wherein the heat extinguishing resin film comprises a polyoxyalkylene resin composition having a crosslinkable silyl group . 4. The pattern forming method according to claim 3, wherein in the exposure transfer step, the heat extinguishing resin film in the region irradiated with the exposure light is crosslinked and photocured. The temperature in the heat treatment is higher than the temperature at which the heat extinguishing resin film in the region not irradiated with the exposure light is decomposed and disappeared, and the temperature at which the heat extinguishing resin film in the region irradiated with the exposure light is decomposed and extinguished. 5. The pattern forming method according to claim 3, wherein the pattern forming method is set to a low value. 6. The pattern forming method according to claim 1 , wherein the entire surface is irradiated with light after the pattern of the heat extinguishing resin film is formed. Using the heat extinguisher resin pattern as an etching mask of the substrate to be processed, the substrate to be processed is selectively etched, and then heat treatment is performed to decompose and remove the pattern of the heat extinguishing resin. The pattern formation method in any one of Claims 1 thru | or 6 . Forming a conductive film over the entire surface of the heat extinguishing resin pattern formed on the surface of the substrate to be processed by sputtering; and applying heat treatment to decompose and extinguish the heat extinguishing resin; The pattern forming method according to claim 1 , further comprising a step of lifting off the body film to form a pattern of the conductor film. A metal film comprising: a step of plating a metal film on the surface of the substrate to be processed using the pattern of the heat extinguishing resin as a mask for electroplating; and a step of applying heat treatment to decompose and extinguish the heat extinguishing resin. The pattern forming method according to claim 1, wherein the pattern is formed. The pattern forming method according to claim 7 , wherein the heat treatment is performed at a temperature of 150 ° C. to 250 ° C. in an oxygen atmosphere. The pattern forming method according to claim 7 , wherein the heat treatment is performed at a temperature of 200 ° C. to 250 ° C. in a nitrogen atmosphere.

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