JP2003146790A - Gas generating agent composition and gas generating member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To generate microgases with high gas generation power from microareas and to intermittently shut off or change the direction of the liquid flow continuously discharged from a nozzle with high accuracy. SOLUTION: The gas generating composition is composed of a gas generating agent and a light absorbent and can generate the gases in the microareas by microheating sources. The gas generating member can be obtained by forming a tight contact layer 2 and a gas generating layer 3 containing the gas generating agent (nitrocellulose, etc.), and the light absorbent (carbon black, etc.), and having >=20 μm thickness on the surface of a supporting body 1. The tight contact layer 2 firmly sticks the supporting body 1 and the gas generating layer 3. A coating layer 4 may be formed on the surface of the gas generating layer 3 in order to hold gaseous pressure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention utilizes a gas generating composition, a gas generating member, and a gas generating member useful for selectively applying a chemical liquid such as a resist by ejecting a gas from a minute portion. Regarding the coating method.

[0002]

2. Description of the Related Art In a semiconductor manufacturing process, a substrate is coated with a photosensitive material and exposed, developed and etched to form a predetermined pattern. JP 2000-
In Japanese Patent Publication No. 79366, a liquid ejecting unit that is disposed above a substrate to be processed in which a film formation region and a non-film forming region are set, and that continuously ejects a constant amount of liquid onto the substrate to be processed,
When a moving unit for relatively moving the substrate to be processed and the liquid ejecting unit and a state in which the liquid is moved by the moving unit and is supplied from the liquid ejecting unit to the non-film formation region, A film forming apparatus has been proposed which includes a liquid blocking unit for blocking the supply of the liquid to the non-film forming region.
In this document, a gas generating material (such as nitrocellulose) that reacts with light to generate a gas, a light emitting portion for irradiating the light, and the gas generating material by reflecting light from the light emitting portion. And a liquid supply nozzle for ejecting a liquid onto the substrate to be processed. The light is emitted from the light emitting unit to generate a gas from the gas generating material to supply the liquid. It is also described that the dropping direction of the liquid dropped from the nozzle is changed and the liquid having the changed dropping direction is recovered in the liquid recovery unit. By using this film forming apparatus, a liquid film such as a resist or an insulating material can be selectively applied to a substrate to be processed to form a film having a flat surface even if there is a step on the surface.

However, in this apparatus, the gas generating force of the gas generating material is small, and a minute amount of liquid flow discharged from the nozzle (for example, liquid flow in microliter units) is intermittently changed in direction, and the film is formed with high accuracy. It is difficult to control the thickness.

On the other hand, in JP-A-7-40674 and JP-A-7-68962, a photosensitive layer containing nitrocellulose, a black colorant (such as carbon black) and a binder is formed on a support, and a laser is used. It is disclosed that the irradiated area is thermally decomposed by light to form pits or a predetermined pattern to manufacture a printing plate material. In this photosensitive layer, the energy of the laser light is absorbed by the black colorant and converted into heat, whereby pits corresponding to the laser light can be formed.

However, even with this method, the amount of gas generation and the gas generation force are small, and it is not sufficient for a liquid flow direction changing mechanism. Moreover, since a large amount of soot is generated, it cannot be used in a process requiring high cleanliness (for example, a semiconductor manufacturing process).

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a gas generant composition which produces a large amount of gas and a large gas generating power even when the energy application site is minute, and a gas generating composition using this composition. It is to provide a member and a liquid application method.

Another object of the present invention is to generate a minute gas with a high gas generating force from a minute portion and to interrupt or change the direction of a liquid flow continuously discharged from a nozzle with high accuracy and intermittently. Another object of the present invention is to provide a gas generating composition useful for the above, a gas generating member using the composition, and a coating method.

Still another object of the present invention is to provide a gas generating composition capable of suppressing contamination even when gas is generated, a gas generating member using the composition, and a coating method.

[0009]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned objects, the present inventors have formed a gas generating layer composed of a gas generating agent and a light absorbing agent in close contact with a support. Then, the ignition energy generated by the irradiation of the laser beam can be held by the gas generating layer that is in close contact with the support, and the gas can be ejected at a high gas pressure even if the heating region is minute, and the flow direction of the fluid can be changed. The present invention has been completed by finding that the change can be made with high precision.

That is, the gas generating member of the present invention is a gas generating member capable of generating gas at a minute portion by a minute heating source, and is formed in close contact with the support and at least the support. And a gas generating layer composed of a gas generating agent and a light absorbing agent. In this gas generating member, when the irradiation energy of laser light is E1 and the kinetic energy of a flying or flying object is E2, the energy efficiency E2 / E1 is about 0.1 to 50. In the gas generating member, an adhesion layer (or an intermediate layer) may be interposed between the support and the gas generation layer, and the adjacent support and the gas generation layer may be brought into close contact with each other. The gas generating member includes, for example, a support composed of a base material capable of transmitting laser light, an adhesion layer formed on the surface of the support, and a gas generation layer formed on the surface of the adhesion layer. The adhesive layer may be a non-light-absorbing layer that does not substantially contain a light absorber and is in close contact with the support and the gas generating layer. This adhesion layer may be composed of a polymer-type gas generating agent having film forming properties. Further, the gas generating layer may be composed of a light absorbing layer containing a polymer type gas generating agent having film forming properties and a light absorbing agent. Examples of the gas generating agent include a polymer type gas generating agent having a film forming property and a low molecular weight or oligomer type gas generating agent. For example, the gas generating agent may include at least nitrocellulose.

In such a gas generating member, the thickness of the gas generating layer is usually 20 μm or more. The thickness of the adhesive layer is usually 1 μm or more.

Further, the gas generating layer is not limited to a single layer and may be composed of a plurality of layers. For example, the gas generating layer includes a light absorbing layer (or an energy absorbing layer) composed of a gas generating agent and a light absorbing agent, and a coating layer (or a load layer or a pressure holding layer) formed on the light absorbing layer. You may comprise.

The present invention also includes a gas generating composition which is composed of at least a gas generating agent and a light absorbing agent and which is capable of generating gas at a minute portion by a minute heating source. This composition is a composition capable of generating a gas upon irradiation with laser light, and is composed of a polymer-type gas generating agent having film-forming properties and at least one selected from a plasticizer and a light absorber. Good.

Further, the present invention is a method for applying the liquid by intermittently interrupting the flow of the liquid ejected from the nozzle, wherein a minute heating source selected from a laser beam and a thermal head is operated. A method of applying a liquid by changing the flow direction by a gas generated from a minute portion of the gas generating member, irradiating laser light to ignite the gas generating layer on the side of the support, and a minute portion of the gas generating layer corresponding to the irradiated portion. It also includes a method of ejecting gas at a part and flying a minute part of the gas generation layer.

[0015]

1 is a schematic sectional view showing an example of a gas generating member of the present invention. In this example, the gas generating member has a high heat resistance and is formed on the surface of the transparent support 1 composed of a base material (a glass substrate, a plastic film or the like) which can transmit laser light, and the support 1. And an adhesive layer 2 transparent to laser light, a gas generating layer 3 formed on the surface of the adhesive layer and composed of at least a gas generating agent and a light absorbing agent, and formed on the surface of the gas generating layer. And a coating layer (load layer or pressure holding layer) 4 for holding the generated gas pressure.

The adhesion layer 2 is composed of a polymer-type gas generating agent and a plasticizer having a film-forming property, which does not substantially contain a light absorbing agent, and the support 1 and the gas generating layer 3 are in close contact with each other. It is formed as a light absorption layer. The gas generating layer 3 is composed of a polymer-type gas generating agent having film forming properties, a plasticizer, and a light absorbing agent, and is formed as a light absorbing layer for laser light. Further, the coating layer 4 is the adhesion layer 2
And is formed as an inactive layer against laser light.

In order to improve the adhesiveness between the support 1 and the gas generating layer 3, the adhesive layer 2 and the gas generating layer 3 have substantially the same composition (polymer type gas generating layer) except for the light absorber. Agent and plasticizer). The plasticizer is composed of a plasticizer that functions as a gas generating agent described later.

In such a gas generating member, when the laser beam is irradiated from the side of the support 1, the gas generating layer 3 absorbs the energy of the laser beam and ignites to generate gas. Since the gas generation layer 3 is in close contact with the support 1 by the adhesion layer 2, this gas is restricted from diffusing and propagating in the interface direction between the adhesion layer 2 and the gas generation layer 3. Moreover, depending on the elastic modulus of the coating layer, the generated gas pressure is held by the coating layer 4 until a predetermined pressure is reached. Therefore, while maintaining a high gas pressure, the gas can be ejected at a high pressure from a minute portion corresponding to the laser light irradiation portion. The gas generation layer 3
It is presumed that the ignition of 1 occurs near the interface with the adhesion layer 2. Further, the support 1 also functions as a firebreak zone, and the coating layer 4 functions as a pressure holding layer.

The gas generating member may be composed of a support and a gas generating layer in close contact with the support,
The gas generating layer may be in direct contact with the support, or may be in indirect contact via the contact layer, as described above. That is, the adjacent support and gas generating layer may be in close contact with each other by an adhesion layer (adhesive layer or intermediate layer) interposed between the support and the gas generating layer. Further, the gas generating layer is a laminated structure composed of a plurality of layers, for example,
It may have a laminated structure of a light absorbing layer (energy absorbing layer) composed of a gas generating agent and a light absorbing agent, and a coating layer formed on the light absorbing layer, and a single layer structure may be formed. You may have.

FIG. 2 is a schematic sectional view showing another gas generating member of the present invention. In this example, a transparent support 11 composed of a base material through which laser light can pass, an adhesion layer 12 formed on the surface of the support 1 and transparent or inert to laser light, and the adhesion Gas generating layer 1 formed on the surface of the layer and composed of at least a gas generating agent and a light absorbing agent
3 and 3. The gas generation layer 13 is formed thicker than the gas generation layer 3 of FIG. 1 in order to maintain a higher gas pressure in the gas generation layer.

Even in such a gas generating member, the gas pressure generated by the irradiation of the laser beam can be held by the gas generating layer 13 having a large thickness, so that the gas can be jetted at a high pressure as described above.

The adhesion strength between the support (or the adhesion layer) and the gas generation layer is such that the gas generated in the gas generation layer is prevented from propagating toward the interface between the support (or the adhesion layer) and the gas generation layer. It suffices if it is possible. Usually, the cohesive failure of the gas generating layer occurs at or near the interface between the support (or the adhesion layer) and the gas generating layer whose pressure has been increased by the irradiation of laser light.

Further, in the present invention, it seems that a part of the film (at least the gas generating layer) corresponding to the laser light irradiation site flies or scatters as the gas is ejected. When the irradiation energy of the laser beam is E1 and the kinetic energy of the flying or scattered object is E2, the energy efficiency E2 / E1 = 0.1 to 50, preferably 0.
Energy efficiencies of 5-30, more preferably 1-30 and especially values above 1 (1.5-20) can be obtained. It is presumed that this is because the gas generating layer is ignited by the laser light, and a larger amount of energy is generated with the combustion.

Examples of the support include various base materials, for example, inorganic base materials such as glass, ceramics and metal foils, plastics (polyester resins such as polyalkylene terephthalate, polyamide resins, polycarbonate resins and cellulose acetate). Examples thereof include organic base materials such as cellulose derivatives, styrene-based resins, (meth) acrylic-based resins, hydrocarbon-based resins, polyimide-based resins, etc., and composite base materials thereof.

The support can be selected according to the kind of the minute heating source, and when the minute heating source is light energy such as laser light, a light-transmittable substrate (eg, glass, polyethylene terephthalate, polybutylene terephthalate). When a micro heating source is a thermal head, a heat resistant substrate (for example, polyethylene terephthalate, polybutylene terephthalate, etc.) can be used. A heat-resistant resin such as a polyester resin may be used, and the heat-resistant substrate may be subjected to a mold release treatment in order to prevent fusion with the thermal head.

Further, in order to improve the adhesion to the adhesion layer or the gas generating agent layer, the surface of the support may be subjected to surface activation treatment such as corona discharge treatment or plasma treatment.

The form of the support or base material can be selected according to the application, and may be in the form of film or sheet, plate or disk. The thickness of the film- or sheet-like support or substrate is not particularly limited, and is, for example, 5 to 200.
0 μm, preferably 10 to 200 μm (for example, 15 to
It can be appropriately selected from the range of about 150 μm).

The adhesion layer is not always necessary as long as the adhesion between the support and the gas generating layer is high. The adhesion layer is, for example, a surface treatment with a coupling agent such as a silane coupling agent or a titanium coupling agent, an undercoat agent, an anchor coating agent or an adhesive agent depending on the type of the support and the gas generating layer. It may be subjected to an adhesive treatment or an undercoat treatment. Examples of undercoat agents and adhesives include
Examples thereof include an epoxy resin composition, a urethane resin composition, an acrylic resin composition, a vinyl acetate resin composition, polyethyleneimine, and a rubber composition (polybutadiene-containing composition etc.). The adhesive layer usually does not contain an energy absorbing agent (light absorbing agent) in many cases. When the light or heat energy absorber is not substantially contained, the adhesion layer is not limited to the undercoating agent or the adhesive component, but may be a gas generating agent (a low molecular weight gas generating agent or a polymer type having a film forming property). Gas generating agent).

Further, the gas generating layer is composed of at least a gas generating agent and a light absorbing agent, and may be formed as an energy absorbing layer (light absorbing layer). The gas generating agent includes a polymer type gas generating agent having a film forming property, a low molecular weight or oligomer type gas generating agent, and the like, and these components can be used alone or in combination of two or more kinds.

The gas generating agent may be a substance that generates a large amount of gas by decomposition or combustion, and such a gas generating agent is often used as a raw material for explosives, explosives, detonators and the like. Examples of the gas generating agent include nitrogen-containing compounds (eg, guanidine derivatives, tetrazole derivatives, nitro compounds, nitrate ester compounds, nitramine compounds, azide compounds, etc.).

More specifically, examples of the gas generating agent include the following compounds, which may be a low molecular type or oligomer type gas generating agent or a polymer type gas generating agent.

Guanidine derivative: For example, nitroguanidine (NQ), guanidine nitrate (GN), dicyandiamide (DCDA), aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate (T).
AGN), nitroaminoguanidine, guanidine perchlorate and other tetrazole derivatives: for example, tetrazole, 5-aminotetrazole (5-AT), 5-hydrazinotetrazole, 5-cyanotetrazole, 5-hydroxytetrazole, 2-methyl- 5-amino-tetrazole, guanylaminotetrazole, bitetrazole derivative [eg bitetrazole diammonium salt (BHT-2NH
3), bitetrazole (BHT), aminoguanidinium bitetrazole, calcium bitetrazole, guanidinium bitetrazole, etc.], azotetrazole derivatives [eg, azotetrazole diammonium salt, etc.], tetracene and other triazine derivatives: eg, melamine , Trihydrazinotriazine (THT), dinitroamelin (DNAM)
Hydrazine derivative: For example, carbohydrazide (CD
H) etc.

Triazole derivatives: for example, 3-nitro-1,2,4-triazol-5-one (NTO), 1
-Amino-1,2,3-triazole, 3-amino-
1,2,4-triazole, 4-amino-1,2,4-
Triazole, 1,2,3-triazole, 1,2,4
-Dicyanamide derivative such as triazole: for example, sodium dicyanamide, ammonium dicyanamide and the like.

Nitramine compounds: For example, nitroguanidine (NQ), trimethylene trinitroamine (RD
X), tetramethylene tetranitroamine (HMX),
Ethylene dinitramine (EDNA), hexanitrohexaazaisourtitanium (CL-20), 1,4-dinitroglycoluril (DINGU), 2-nitroimino-5-nitro-hexahydro-1,3,5-triazine (NNHT), 1,3,3-trinitroazetidine (TNAZ), 1,3,5,5-tetranitrohexahydropyrimidine (DNNC), 1,3,3,5,7,7
-Hexanitro-1,5-diazacyclooctane (HN
DZ) etc.

Nitro compounds: For example, trinitrotoluene (TNT), dinitrotoluene (DNT), dinitronaphthalene (DNN), hexanitrostilbene (HN)
S), diaminotrinitrobenzene (DATB), triaminotrinitrobenzene (TATB), tetryl, picric acid, diazodinitrophenol (DDNP), tricinate, nitrourea, bis-2,2-dinitropropyl acetal / formal (BDNPA / F). ), 1,
4,5,8-Tetranitro-1,4,5,8-tetraazadecalin (TNAD), 2,6-diamino-3,5-
Dinitropyrazine-1-oxide (LLM-105),
2,4-dinitroimidazole (2,4-DNI),
5,7-Diamino-4,6-dinitrobenzofuroxane (CL-14), 1,1 ′-[methylenebis (oxy)] bis [2-fluoro-2,2-dinitroethane]
(FEFO), dinitroazoxyfurazan (DNA
F), aminonitrofurazan (ANF), 7-amino-
4,6-dinitrobenzofuroxan (ADNBF),
4,6-Dinitrobenzofuroxan potassium salt (KDN
BF), 1,1-diamino-2,2-dinitroethylene (FOX-7) and the like.

Nitrate compound: Nitroglycerin (NG), polyhydric alcohol nitrate [eg, trimethylolethane trinitrate (TMET)
N), pentaerythritol trinitrate (Pet)
rin), pentaerythritol tetranitrate (PETN), nitroglycol, butanetriol trinitrate (BTTN), triethylene glycol dinitrate (TEGDN), diethylene glycol dinitrate (DEGDN), etc.], nitratoethyl nitramine (DETN) NENA), alkyl nitratoethyl nitramines [methyl-2-nitratoethyl-nithramine (MeNENA), ethyl-2-nitratoethyl-nithramine (EtNENA), n-butyl-2-nitratoethyl-nithramine (BuNEA), etc.], polyglycidyl Nitrate (PGN), Nitrocellulose (N
C), cellulose acetate nitrate (CAN),
Cellulose nitrate carboxymethyl ether (C
NC) etc.

Azide compounds: For example, sodium azide, lead azide, bis (1,3-diazide-2-propyl) -succinate (BAPS), bis (1,3-diazido-2-propyl) -adipinate ( BAPA), bis (1,3-diazido-2-propyl) -sebacate (BAPSe), azido polymer [glycidyl azide polymer (GAP), 3,3-bis (azidomethyl) oxetane (BAMO), 3-azidomethyl-3- Methyl oxetane (AMMO), 3-nitratomethyl-3-methyl oxetane (NIMMO), bis-3,3-nitratomethyl oxetane (BNMO), BAMO / AMMO copolymer, BAMO / THF (tetrahydrofuran) copolymer, GAP / THF copolymer etc.] etc.

Nitrate: Other compounds such as guanylurea nitrate, ethylenediamine dinitrate, hydroxylammonium nitrate (HAN), triethanolammonium nitrate (TEAN), monomethylhydrazine nitrate, monomethylamine nitrate (MMAN), for example Hydrazinium nitroformate (HNF), ammonium dinitramide (AD
N), azodicarbonamide (ADCA), 3,6-diamino-1,2,4,5-tetrazine-1,4-di-N
-Oxide (LAX-112), diaminoazofurazan (DAAF), diaminoazoxyfurazan (DAAO)
F), N-guanylurea-dinitramide (FOX-1)
2) etc.

These gas generating agents can be used alone or in combination of two or more kinds. Preferred gas generating agents are nitroguanidine (NQ), triaminoguanidine nitrate (TAGN), 5-aminotetrazole (5-AT),
Bitetrazole diammonium salt (BHT-2NH
3), trihydrazinotriazine (THT), carbohydrazide (CDH), trimethylenetrinitroamine (RDX), tetramethylenetetranitroamine (HM
X), ethylenedinitramine (EDNA), hexanitrohexaazaisourtitanium (CL-20), trinitrotoluene (TNT), dinitrotoluene (DNT),
Hydrazinium nitroformate (HNF), ammonium dinitramide (ADN), nitrocellulose (N
C), cellulose acetate nitrate (CAN),
Cellulose nitrate carboxymethyl ether (C
NC), azido polymers such as glycidyl azide polymer (GAP), nitroglycerin (NG), trimethylolethane trinitrate (TMETN). The gas generant is usually at least nitrocellulose (N
Often includes C). The nitrogen content of nitrocellulose can be selected from the range of 6.7 to 14.1%, and is usually about 10 to 13.5% (particularly 11 to 13.5%).

Among these gas generating agents, polymer type gas generating agents (or gas generating agents functioning as binders) having film-forming property include cellulose derivatives [nitrocellulose (NC), cellulose acetate nitrate (CAN), Cellulose nitrate carboxymethyl ether (CNC) etc.], polyvinyl tetrazole derivative [poly (1-vinyl-5-aminotetrazole),
Poly (2-vinyl-5-aminotetrazole), poly (1-vinyltetrazole), poly (2-vinyltetrazole), poly (1-methyl-5-vinyltetrazole), poly (2-methyl-5-vinyltetrazole) ) Etc.], polyaminotriazole derivatives [polymethylene-
4-amino-1,2,4-triazole, polyethylene-4-amino-1,2,4-triazole, polypropylene-4-amino-1,2,4-triazole, polybutylene-4-amino-1,2, 4-triazole, polypentamethylene-4-amino-1,2,4-triazole, polyhexamethylene-4-amino-1,2,4-triazole, polyheptamethylene-4-amino-1,
2,4-triazole, polyoctamethylene-4-amino-1,2,4-triazole, polynonamethylene-4
-Amino-1,2,4-triazole, polydecamethylene-4-amino-1,2,4-triazole and other polyalkylene-4-amino-1,2,4-triazoles, etc.], azide polymer [glycidyl azide Polymer (G
AP), 3,3-bis (azidomethyl) oxetane (B
AMO), 3-azidomethyl-3-methyloxetane (AMMO), 3-nitratomethyl-3-methyloxetane (NIMMO), bis-3,3-nitratomethyloxetane (BNMO), BAMO / AMMO copolymer,
BAMO / THF (tetrahydrofuran) copolymer, G
AP / THF copolymer and the like]. These gas generating agents having film forming properties can be used alone or in combination.

The gas generant may be a compound that functions as a plasticizer. Examples of the gas generating agent (high energy plasticizer) that functions as a plasticizer include nitrate ester compounds [NG, TMETN, Petrin, PETN,
Nitroglycol, BTTN, TEGDN, DEGD
N, NENA, etc.], alkyl nitratoethyl nitramines [MeNENA, EtNENA, BuNENA, etc.], azide compound [glycidyl azide polymer plasticizer (GAP plasticizer), BAPS, BAPA, BAPSe
Etc.] and nitro compounds [BDNPA / F etc.] and the like.

The gas generating agent may be used in combination with a binder that does not easily decompose or burn regardless of whether or not it has a film forming property. As the binder, various resins capable of forming a film can be used. For example, not only a resin soluble in a solvent (organic solvent, water, a mixed solvent of water and an organic solvent), but also a solventless binder can be used. is there. A diluent may be used in combination with the solventless binder. The binder may be a thermoplastic resin, a thermosetting resin or a photocurable resin.

Examples of the binder include cellulose derivatives [cellulose esters such as cellulose acetate (CA), cellulose acetate propionate and cellulose acetate butyrate (CAB), methyl cellulose (MC), ethyl cellulose (EC), sodium carboxymethyl cellulose). (CMC-Na), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), cellulose ethers such as hydroxypropyl methyl cellulose, etc.], styrene resin [polystyrene (PS), styrene such as styrene-methyl methacrylate copolymer] And a (meth) acrylic monomer copolymer, styrene-acrylonitrile copolymer, etc.], acrylic resin [polymethylmethacrylate (PMMA)] Methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate-acrylic acid ester copolymer, polyacrylamide, etc.], vinyl chloride resin [polyvinyl chloride (PVC), vinyl chloride-vinyl acetate copolymer, etc.] , Vinyl resins [ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, polyvinyl acetate, cyclopentadiene polymer, etc.), polyvinyl alcohol (PV
A), ethylene-vinyl alcohol copolymer, etc.], rubber or elastomer [acrylic rubber, butadiene rubber,
Styrene-butadiene rubber, etc.], polyester resin (polyalkylene terephthalate copolyester, polyalkylene naphthalate copolyester, polyalkylene adipate resin, etc.), polyurethane resin (polyester polyurethane, polyether polyurethane, etc.), polyamide Resin (polyamide 11, polyamide 12, polyamide 611, homopolyamide such as polyamide 612, nylon 6/11, nylon 6 /
12, copolyamides such as nylon 66/11 and nylon 66/12), epoxy resins [bisphenol A type epoxy resins etc.], vinyl ester resins [adducts of epoxy resin and (meth) acrylic acid etc.], Diallyl phthalate resin, thermosetting polyurethane resin,
Examples include silicone resins, polyimide resins, thermosetting acrylic resins, polysaccharides or their derivatives (starch, guar gum, gum arabic, sodium alginate, etc.). Furthermore, examples of the photocurable resin include epoxy (meth) acrylate, polyurethane (meth) acrylate, and polyester (meth) acrylate. The thermosetting resin can be cured using a commonly used curing agent, and the photocurable resin can be cured using a photopolymerization initiator. These binders can be used alone or in combination of two or more.

Examples of the polymer or oligomer capable of forming a cured film in combination with a curing agent include, for example, hydroxy-terminated polybutadiene (HTPB), carboxy-terminated polybutadiene (CTPB), hydroxy-terminated polyethylene (HTPE), azide polymer (GAP, BAM).
O, AMMO, NIMMO, BNMO, BAMO / AM
MO copolymers, BAMO / THF (tetrahydrofuran) copolymers, GAP / THF copolymers, etc.) can also be exemplified.

When a gas generating agent having a film-forming property is used as the binder, the gas generating layer may be formed of the gas generating agent. When a binder which is difficult to decompose or burn is used as the binder, the content of the gas generating agent is , Binder 1
The amount is 10 to 1000 parts by weight, preferably 20 to 500 parts by weight, and more preferably 50 to 200 parts by weight, relative to 00 parts by weight. Further, the ratio of the non-film forming gas generating agent to the gas generating agent (binder) having film forming property can be selected from the same range as above.

The gas generating layer and the gas generating composition can generate gas by various energy, for example, irradiation of light (laser light etc.) or action of heat. Such a composition may include an energy absorber (a light absorber and / or a heat absorber).

The light absorber can be selected according to the wavelength of the light beam, and may be a colorant such as white, yellow, orange, red, blue, green, violet and black. A typical light absorber is a black colorant (carbon black, black dye, etc.).
Further, examples of the heat absorbing agent include an infrared absorbing agent and the like, and a black colorant may be used like the light absorbing agent.

The content of the light absorber is, for example, 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight, relative to 100 parts by weight of the gas generating agent.

Further, the gas generating layer and the gas generating composition of the present invention may contain a plasticizer in order to impart plasticity. This plasticizer may be composed of a gas generating agent as described above, or may be an ordinary plasticizer (non-gas generating plasticizer).

Examples of usual plasticizers include phthalate ester plasticizers [dialkyl phthalates such as diethyl phthalate, dibutyl phthalate and dioctyl phthalate], acetate plasticizers [triacetin, acetyl triethyl citrate, etc.], adipic acid Plasticizers [dialkyl adipates such as dibutyl adipate and dioctyl adipate], butylphthalyl butyl glycolate, methylphthalyl ethyl glycolate (MPE
G), ethylphthalylethyl glycolate (EPE
G), camphor, etc. can be illustrated.

These plasticizers can be used alone or in combination of two or more kinds. The amount of the plasticizer (including the plasticizer as the gas generating agent) used is, for example, 1 to 100 parts by weight, preferably 1 to 70 parts by weight (for example, 1 to 50 parts by weight) with respect to 100 parts by weight of the gas generating agent. ), And may be about 5 to 100 parts by weight (for example, 10 to 50 parts by weight).

The gas generating layer and the gas generating composition are usually composed of an energy absorbing agent (especially a light absorbing agent) and a gas generating agent (especially a polymer type gas generating agent having a film forming property). It is often composed of at least one selected from film-forming aids (particularly, plasticizers).

Further, as described above, the gas generating layer and the gas generating composition may contain a curing agent depending on the kind of the binder. Examples of the curing agent include polyisocyanate compounds [hexamethylene diisocyanate (HMDI), 2,4-toluene diisocyanate (T
DI), dimerisocyanate (DDI), isophorone diisocyanate (IPDI), etc.], polyamine compounds, polyvalent carboxylic acids, epoxy compounds and the like.

The gas generating layer and the gas generating composition may contain an oxidant in order to improve the ignitability and combustibility and increase the calorific value. Examples of the oxidant include chlorate, perchlorate, nitrate, nitrite and the like,
These salts may be salts with ammonia, alkali metals, alkaline earth metals and transition metals. Specific oxidizing agents include, for example, NH ₄ ClO ₄ , NH ₄ NO ₃ , and KC.
lO ₄ , NaClO ₄ , KNO ₃ , NaNO ₃ , Sr (NO
₃ ) ₂ and basic copper nitrate (BCN) can be exemplified. These oxidizing agents can be used alone or in combination of two or more kinds.

The content of the oxidizing agent is, for example, 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the binder (including the gas generating agent having film forming property).
More preferably, it is about 1 to 20 parts by weight.

The gas generating layer and the gas generating agent composition may contain a combustion catalyst in order to improve the ignitability and the burning rate. Examples of the combustion catalyst include metal oxides (iron oxide, copper oxide, etc.), chromates (copper chromite, ammonium dichromate, etc.) and the like.
These combustion catalysts can be used alone or in combination of two or more.

The amount of the combustion catalyst used is, for example, 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight, more preferably about 1 to 10 parts by weight, relative to 100 parts by weight of the gas generating agent. .

The gas generating layer and the gas generating composition are, for example, to improve the stability of the gas generating agent,
It may contain a stabilizer. In particular, in order to improve the stability in a system containing a nitrate ester compound, it is useful to add a stabilizer. Examples of such stabilizers include amine stabilizers (diphenylamine, 2-nitrodiphenylamine, etc.), ethyl centrallite, resorcinol and the like.

The gas generating layer and the gas generating composition are composed of a cross-linking agent (ammonium benzoate, trimethylolpropane (TMP), melamine resin, etc.), an antioxidant (phenylisopropyl-P-phenylenediamine (trade name: Nocrac 810-). NA) and the like).
Further, in order to enhance the bond between the oxidant and the binder, the composition may include a binder (eg, 1,2-tris (2-methylaziridenyl) phosphine oxide (trade name).
MAPO) etc.) may be contained. Furthermore, in order to improve ignitability and combustibility, or to efficiently generate a large amount of heat with combustion, the gas generating layer and the gas generating agent composition have a metal component (for example, aluminum, magnesium,
Zirconium, titanium, silicon iron, aluminum-magnesium alloy, boron, etc.) may be contained.

The gas generating layer and composition of the present invention are
If necessary, various additives such as stabilizers (antioxidants, ultraviolet absorbers, etc.), fillers, antistatic agents, antiblocking agents, flame retardants, surfactants and the like may be contained.

When the gas generating layer is composed of an energy absorbing layer (light absorbing layer) and a coating layer, the energy absorbing layer can be formed in the same manner as the gas generating layer, and the coating layer is an inorganic film (metal vapor deposition film). , A vapor-deposited film of a metal compound such as silica or alumina), but it may be formed in the same manner as a non-conductive coating, particularly the adhesion layer, or a resin coating. . As the resin, for example, various film-forming resins described in the section of the binder can be used. Typical resins include cellulose derivatives (cellulose esters such as cellulose acetate), acrylic resins (such as methyl methacrylate resin containing methyl methacrylate as a main component), styrene resins (styrene-acrylonitrile copolymer, etc.). ), Vinyl resin [ethylene-vinyl acetate copolymer, ethylene- (meth)]
Acrylic ester copolymer, polyvinyl acetate, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer, etc.], rubber or elastomer, polyester resin (polyalkylene terephthalate copolyester, polyalkylene naphthalate copolyester,
Polyalkylene adipate resin, etc., polyurethane resin (polyester polyurethane, etc.), epoxy resin [bisphenol A type epoxy resin, etc.], vinyl ester resin [adduct of epoxy resin with (meth) acrylic acid, etc.], Examples include thermosetting polyurethane resins, silicone resins, polyimide resins, and photocurable resins.

In order to adjust the characteristics of the coating (flexural modulus, tensile modulus, etc.), the coating may contain various additives such as a plasticizer, a curing agent or a crosslinking agent, and a stabilizer (antioxidant, ultraviolet ray, etc.) as necessary. Absorber, etc.), filler, colorant, antistatic agent, antiblocking agent, flame retardant, surfactant and the like.

In order to improve the adhesion between the adhesive layer and the gas generating layer, the adhesive layer and the gas generating layer may contain the same or the same component. For example, the adhesion layer may be composed of a film-forming gas generating agent such as nitrocellulose, and the second layer may be composed of a film-forming gas generating agent such as nitrocellulose and a light absorber. Further, in such a combination, when the adhesiveness of the adhesive layer to the support is low, the adhesive layer may contain an adhesiveness improver. Furthermore, in order to improve the adhesion between the adhesion layer and the gas generating layer, at least the vicinity of the interface between the adhesion layer and the gas generating layer, except for the presence or absence of the light absorber, composition of substantially the same component ratio. It may be formed of a material. For example, the adhesion layer is formed of a composition containing a film-forming gas generating agent and an adhesion improving agent in a specific ratio, and the gas generating agent is formed of a composition obtained by adding a light absorber to the composition of the adhesion layer. You may. The adhesiveness improver may be, for example, the plasticizer, the silane coupling agent, the coupling agent such as the titanium coupling agent, the undercoating agent, the anchor coating agent or the adhesive agent.

The thickness of each layer can be appropriately selected. For example, the thickness of the adhesion layer is within a range in which the support and the gas generating layer can be adhered, for example, 1 μm or more (for example, 1 to 200 μm, preferably 2 to 100 μm, More preferably 3 to 70 μ
It can be selected from the range of about m). When a gas generating agent (polymer type gas generating agent or the like) is used, the thickness of the adhesion layer is, for example, 10 μm or more (for example, 10 to 100 μm, preferably 20 to 100 μm, more preferably 25 to 70).
μm).

In the gas generating member, the thickness of the gas generating layer (or the total of the energy absorbing layer (light absorbing layer) and the coating layer) has a great influence on the gas ejection property. That is, depending on the bending elastic modulus and / or the tensile elastic modulus of the gas generating layer, the gas pressure that can be retained in the gas generating layer can be controlled, and if the thickness of the gas generating layer is small, the generated gas pressure cannot be retained, If the thickness of the gas generating layer is too thick, the gas ejection property may be impaired. Therefore, the thickness of the gas generating layer is usually 10 μm or more (for example, 10 to 250 μm).
m, preferably 20 to 200 μm, more preferably 2
5 to 150 μm), and usually 20
μm or more (for example, 20 to 250 μm, preferably 25
˜200 μm, more preferably about 30 to 100 μm).

When the adhesion layer is formed, the total thickness of the adhesion layer and the gas generating layer is usually 20 to 250.
μm, preferably 40 to 200 μm, more preferably 50 to 150 μm, and usually 60 to 150 μm.
It is a degree.

When the gas generating layer is composed of the light absorbing agent (energy absorbing layer) and the coating layer, the minimum thickness of the light absorbing layer (energy absorbing layer) is 1 μm (preferably 5 μm).
m, and more preferably 10 μm).

The gas generating member and the gas generating composition of the present invention can generate gas at a minute portion by a minute heating source. As the minute heating source, for example, laser light (YAG laser, semiconductor laser, etc.), a thermal head, or the like can be used, and a gas can be generated or ejected from a minute hot spot with large energy. The area of the heating area (hot spot) is not particularly limited, and is, for example, 0.1 μmφ
The diameter is 10 mmφ, preferably 1 μmφ to 1 mmφ, and more preferably about 5 to 500 μmφ.

The amount of gas generated by the gas generating layer and the gas generating composition is 1 × 10 ^{−3 to} 6 × 10 ⁻² mol per 1 g,
It is preferably 1 × 10 ^{-2 to} 6 × 10 ^-2 mol, and more preferably 2 × 10 ^{-2 to} 6 × 10 ^-2 mol.

The gas generating member of the present invention, as described above,
A minute heating source can heat a minute area of the gas generating layer to release or eject the gas at a high gas pressure. Therefore, the gas generating member of the present invention is useful for intermittently interrupting the flow of a fluid such as a liquid discharged from a discharge port such as a nozzle with a gas that is emitted or ejected or changing the flow direction of the fluid. is there. Particularly, in a method of intermittently interrupting or changing the flow of a liquid discharged from a discharge port to apply a liquid to a base processing substrate, a minute heating source is caused to act on the gas generating member, The generated gas is useful for changing the flow direction of the liquid and applying the liquid. In addition, when a minute heating source is actuated (laser light irradiation, etc.), the gas generation layer on the support side ignites,
It is also possible to eject gas at a minute portion of the gas generation layer corresponding to the irradiation portion and fly the minute portion of the gas generation layer.

With such a method, it is possible to form a coating film having a uniform thickness on a substrate having a step even when a coating region and a non-coating region are set. For example, in semiconductor process manufacturing, a metal thin film, an interlayer insulating film, or the like formed on a semiconductor substrate is utilized by using a lithography technique and an etching technique such as reactive ion etching (RIE). When a primary pattern with steps is formed, an interlayer insulating film is formed on the primary pattern, and a secondary pattern is formed using a lithography technique and an etching technique such as RIE,
When a step is formed in the upper interlayer insulating film according to the step of the primary pattern, exposure failure or the like occurs in the lithography process used for forming the secondary pattern, and the yield is reduced. On the other hand, in the present invention, while scanning the substrate on which the primary pattern is formed, the coating region and the non-coating region corresponding to the primary pattern are made to correspond, and in the non-coating region, the gas pressure is used to apply the coating agent. By changing the flow direction, the coating area can be selectively coated, and a coating film having a uniform thickness can be formed.

The gas generating member is usually movable relative to the substrate to be processed, and is movable together with the discharge port (or nozzle) of the fluid (or coating material). The form of the gas generating member is not particularly limited, and for example,
It may be in the form of a film or sheet, or a tape.
Further, in order to renew the heating area by the minute heating source, it is preferable that the gas generating member is movable relative to the minute heating source. For example, by using a reel or a sprocket hole formed in a gas generating member, a tape-shaped gas generating member that can be wound or unwound is formed, and a minute heating source (such as a laser light irradiation position or a thermal head position) On the other hand, the heating region of the tape-shaped gas generating member may be moved regularly (or periodically).

Further, the direction of the gas flow generated from the gas generating member is a direction transverse to the flow direction of the liquid (or the coating material), for example, an orthogonal direction, an obliquely downward direction, an obliquely upward direction, or the like. A gas stream can be ejected.

The type of liquid is not particularly limited, and various film formability coating agents such as photoresist, insulating material, reflective material, low dielectric constant material, high dielectric material, and wiring material can be exemplified. The type of solvent in the coating agent is not particularly limited, and may be an aqueous solvent or an organic solvent. The width of the liquid flow (coating width) may be any as long as the flow direction can be changed by the gas pressure without impairing the coating efficiency due to the scanning operation, for example, 10 to 1000 μm.
It may be about m.

INDUSTRIAL APPLICABILITY The present invention is effective for manufacturing a functional component (semiconductor, liquid crystal substrate, etc.) obtained by finely processing a substrate or substrate having an uneven surface, particularly a substrate having a step portion on the surface.

[0076]

According to the present invention, since the gas generating layer which is in close contact with the support is provided, the gas generation amount and the gas generating force can be improved even if the energy application site is minute.
Therefore, it is possible to generate a minute gas with a high gas generating force from a minute portion, and to interrupt or change the direction of the liquid flow continuously discharged from the nozzle with high accuracy and intermittently. Further, even if gas is generated, pollution can be suppressed.

[0077]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples. In the following examples,
"Part" indicates "part by weight". Each test method is as follows.

(1) Laser Light Irradiation Test The laser light irradiation test was conducted using the apparatus shown in FIG.
That is, using the laser device (argon laser) 21 connected to the power source 29, the exposure time of the shutter 22 is set to 1/500 seconds, and the gas generating member 25 is
Laser light (power 600mW, laser beam diameter about 200
μm). A beam sampler 23 and a condenser lens 24 are arranged in the optical path. A change in the amount of laser light transmitted through the gas generating member 25 was measured by the oscilloscope 28, and a graph shown in FIG. 4 [time (horizontal axis)]
With the voltage value of the signal detected by the photo sensor 26a and amplified by the amplifier 27a]. This change in voltage value means a change in light amount. In order to measure the irradiation start time of the laser light, a part of the laser light is reflected by the beam sampler 23, the light quantity of the reflected light is detected by the photo sensor 26b, and the amplifier 27b is used.
It is amplified by and recorded as reference light.

Since it takes a little time to completely open the shutter from the closed state, the time when the light quantity of the reference light reaches 50% of the maximum value is defined as the laser light irradiation start time T1. . When the gas generating member is irradiated with laser light and the gas generating layer of the gas generating member burns to open holes, transmitted light is observed. Similarly to the case of the reference light, the time T2 when the transmitted light was observed was set to the time when the light amount of the transmitted light reached 50% of the maximum value. Then, the ignition delay time ΔT = T2-T1 of the gas generating member was set.

(2) Observation with a microscope The state of the gas generating member irradiated with laser light was observed with a microscope according to the above (1) Laser light irradiation test.

(3) Water Droplet Scattering Test In order to investigate the scattering state of water droplets, as shown in FIG. 5, a water stream 3 discharged vertically from a nozzle 31 having a hole diameter of 40 μm.
The gas generating material member 35 was installed at a distance of 0.5 mm from 1a. When the gas generating member 35 is irradiated with laser light (power of 600 mW, laser beam diameter of about 200 μm), the gas generating member violently ejects gas, and the ejected gas scatters the water stream 31a as water droplets. The scattered water droplets are horizontally arranged on the opposite side of the gas generating member 35 via the water flow 31a and horizontally fall on the glass plate 32 colored with the red pigment 32a, leaving a trace. The distance from the hanging water stream to the trace was defined as the water droplet scattering distance. 20
Irradiation with laser light was performed and the result was observed.

(4) Generation Gas Velocity Measurement Test Using Piezoelectric Element In the apparatus shown in FIG. 3, the same method as in the laser light irradiation test of (1) above is used except that a piezoelectric element is used instead of the photosensor 26a. Time, detected by the piezoelectric element,
Also, a graph showing the relationship with the voltage value of the signal amplified by the amplifier is obtained (see FIG. 6). This change in voltage value means a change in light amount and sound pressure. Further, in order to measure the irradiation start time of the laser light, a part of the laser light was reflected by a beam sampler and recorded as reference light in the same manner as in the laser light irradiation test of (1) above. Since it takes a little time for the shutter to be completely opened after it is closed, the gap between when the reference light amount reaches 50% of the maximum value,
It was defined as the laser light irradiation start time. The sound pressure was measured when the gas generating member was irradiated with laser light and gas was ejected from the gas generating member. The time when the sound pressure measurement was started was the place where the voltage change suddenly started on the chart, and could be easily determined. Then, (time when the sound pressure was started to be measured)-(laser light irradiation start time) was taken as the arrival time of the gas generated from the gas generating member. After obtaining data in which the distance between the gas generating member and the piezoelectric element was changed, the velocity of the generated gas was calculated.

Example 1 [Coating liquid for adhesion layer / coating layer] Nitrocellulose (NC,
Nitrohemie Wimis, mixed cotton type I grade C) 6 parts, trimethylolethane trinitrate (TMETN, NOF Corporation) 4 parts, ethyl acetate 9
0 part was placed in an Erlenmeyer flask and stirred at room temperature using a magnetic stirrer for about 3 hours. The mixed liquid became a colorless and transparent viscous liquid. This mixed solution was used after standing for 1 hour or more in order to remove air bubbles mixed in with stirring.

[Coating liquid for gas generating layer] Carbon black (C, manufactured by Mitsubishi Chemical Corporation, Mitsubishi Carbon Black MCF
88, average particle diameter 18 nm) 1 part and ethyl acetate 90 parts were put in an Erlenmeyer flask, and the carbon black was dispersed in ethyl acetate by applying vibration for 30 minutes using an ultrasonic cleaner. To this dispersion liquid, the nitrocellulose (NC)
6 parts and 4 parts of the above trimethylolethane trinitrate (TMETN) were further added, and the mixture was stirred at room temperature for about 3 hours using a magnetic stirrer. The mixed liquid was a black viscous liquid, and this mixed liquid was used after being left for 1 hour or more in order to remove bubbles mixed with stirring.

[Production of Gas Generating Member] Using a film applicator, length 24 mm × width 60 mm × thickness 15
A film having a three-layer structure was formed on 0 μm glass. The adhesive layer was formed by applying the adhesive layer coating liquid on glass, allowing it to stand at room temperature, and drying it. For the gas generating layer, the coating liquid for gas generating layer is applied on the adhesion layer and left at room temperature,
It was formed by drying. Further, the coating layer, the coating liquid for the coating layer is applied on the gas generating layer, and allowed to stand at room temperature,
It was formed by drying. The final composition and thickness of each layer are as follows.

Support layer Glass 150 μm Adhesion layer NC / TMETN (6 parts / 4 parts) 60 μm Gas generation layer NC / TMETN / C (6 parts / 4 parts / 1 part) 15 μm Coating layer NC / TMETN (6 parts / 4 parts) ) 60 μm The obtained gas generating member was subjected to a laser light irradiation test (1) and data was obtained with an oscilloscope. As a result, the curve of the transmitted light was sharp as shown in FIG. Rising, the transmitted light was not attenuated. The ignition delay time was in the range of 400 to 440 μs, the average value of 10 times was 416 μs, and it was confirmed that intense combustion occurs with high reproducibility with a very short ignition delay time.

Observation of the gas generating member irradiated with the laser beam with a microscope revealed that the laser beam irradiated part had an average hole diameter of 452 μm.
It was confirmed that the m hole was open. Further, it was found from observation of scattered objects that spherical plano-convex lens-like fine particles were generated and scattered by combustion.

Further, the gas generating member was subjected to a water droplet scattering condition observation test (3), and when the glass plate was observed after being irradiated with laser light 20 times, the number of traces of water droplets was 20. The average flying distance was 2.8 mm. Most of the traces of the water droplets were present within the range of the spread angle of about 90 °. It was shown that the gas generating member has a force sufficient to scatter the water stream as water droplets.

Further, the gas generating member was subjected to the generated gas velocity measurement test (4) and irradiated with laser light to obtain data. When the distance between the gas generating member and the piezoelectric element is 1.8 mm, the arrival time of the gas generated from the gas generating member is 36 mm.
When the distance was 1 μs and the distance was 4.8 mm, the gas arrival time was 368 μs, and when the distance was 7.8 mm, the gas arrival time was 382 μs. The generated gas velocity calculated from these data is about 300m
Was / s.

Example 2 Using a film applicator, length 24 mm × width 6
A film having a two-layer structure was formed on glass having a thickness of 0 mm and a thickness of 150 μm. The adhesive layer was formed by applying the adhesive layer coating liquid prepared in Example 1 on glass, leaving it at room temperature and drying it, and the gas generating layer was used for the gas generating layer prepared in Example 1. The coating liquid was applied onto the adhesion layer, left standing at room temperature and dried. The composition and thickness of the final film are as follows.

Support layer glass 150 μm Adhesion layer NC / TMETN (6 parts / 4 parts) 60 μm Gas generation layer NC / TMETN / C (6 parts / 4 parts / 1 part) 75 μm Laser light irradiation test of the obtained gas generation member When subjected to (1) and obtained data with an oscilloscope, the curve of the transmitted light rises violently as in the case shown in FIG. 4, and the transmitted light is not attenuated even after 10 irradiations. The ignition delay time was in the range of 488 to 514 μs, and the average value of 10 times was 501 μs. It was confirmed that intense combustion occurs reproducibly with a very short ignition delay time.

When the laser-irradiated gas generating member was observed with a microscope, an average hole diameter of 3 was observed at the laser-irradiated portion.
It was confirmed that a hole of 84 μm was opened. Further, it was found from observation of scattered objects that spherical plano-convex lens-like fine particles were generated and scattered by combustion.

Example 3 Using a film applicator, length 24 mm × width 6
On a 0 mm × 125 μm thick OHP (for overhead projector) sheet, a film having a three-layer structure (adhesion layer, gas generation layer and coating layer) was formed in the same manner as in Example 1.
The film formed was easily peelable from the OHP sheet, so the film peeled from the OHP sheet was tested. The composition and thickness of the final film are as follows.

Support layer Glass 150 μm Adhesion layer NC / TMETN (6 parts / 4 parts) 100 μm Gas generation layer NC / TMETN / C (6 parts / 4 parts / 1 part) 10 μm Coating layer NC / TMETN (6 parts / 4 parts) ) 50 μm The obtained gas generating member was subjected to a laser light irradiation test (1), and data was obtained with an oscilloscope. The curve of the transmitted light rises violently as in the case shown in FIG. 4, and the transmitted light was not attenuated 10 times during the 10th irradiation. The ignition delay time was in the range of 374 to 400 μs, the average value of 10 times was 385 μs, and intense combustion was obtained with high reproducibility with a very short ignition delay time.

Further, when the gas generating member irradiated with the laser beam was observed with a microscope, it was confirmed that holes having an average hole diameter of 376 μm were formed in the laser beam irradiated portion. Also,
By observing the scattered matter, it was found that the spherical plano-convex lens-like fine pieces were generated by combustion and scattered.

Example 4 A mixed solution of 6 parts of the nitrocellulose (NC), 4 parts of glycidyl azide polymer (GAP, manufactured by 3M (3M), GAP plasticizer L-12616, molecular weight about 700), and 90 parts of ethyl acetate was added. Using a film applicator, it was applied on a glass having a length of 24 mm × a width of 60 mm × a thickness of 150 μm and dried to form an adhesion layer having a thickness of 60 μm.

On the surface of this adhesive layer, 6 parts of the nitrocellulose (NC) and glycidyl azide polymer (GAP) were formed.
4 parts, 1 part of carbon black (C, Mitsubishi carbon black MCF88), and 90 parts of ethyl acetate were applied to the gas generation layer coating solution to form gas generation layers having different thicknesses in the range of 10 to 70 μm. When the ignition delay time was measured in the same manner as above, the results shown in Table 1 were obtained.

[0098]

[Table 1]

Example 5 A mixed solution of 6 parts of the nitrocellulose (NC), 4 parts of the glycidyl azide polymer (GAP) and 90 parts of ethyl acetate was used in a length of 24 mm by using a film applicator.
It was applied on a glass having a width of 60 mm and a thickness of 150 μm and dried to form an adhesive layer having a thickness different from that of 0 to 60 μm.

On the surface of this adhesive layer, 6 parts of the nitrocellulose (NC) and the glycidyl azide polymer (GA
P) 4 parts, carbon black (C, Mitsubishi carbon black MCF88) 1 part, and ethyl acetate 90 parts were applied to the gas generating layer coating solution to form a gas generating layer having a thickness of 60 μm. When the ignition delay time was measured in the same manner as above, the results shown in Table 2 were obtained.

[0101]

[Table 2]

Example 6 [Support coating liquid] Cellulose acetate (CA, manufactured by Daicel Chemical Industries, Ltd., VAC) 7 parts, diethyl phthalate (DEP, reagent manufactured by Wako Pure Chemical Industries, Ltd.) 3 parts, acetic acid 90 parts of methyl (manufactured by Nacalai Tesque, Inc.) was placed in an Erlenmeyer flask and stirred at room temperature for about 3 hours using a magnetic stirrer. The mixed liquid became a colorless and transparent viscous liquid. This mixed solution was used after standing for 1 hour or more in order to remove air bubbles mixed in with stirring.

[Production of Gas Generating Member] Using a film applicator, length 24 mm × width 60 mm × thickness 15
A 3-layer structure film (support layer, adhesion layer, gas generation layer) was formed on a 0 μm glass plate. The support layer was formed by applying the coating solution for a support on glass, allowing it to stand at room temperature, and drying it. The adhesive layer was formed by applying the coating liquid for an adhesive layer prepared in Example 1 on the support layer, leaving it at room temperature and drying it, and the gas generating layer was formed by the gas generating layer prepared in Example 1. It was formed by applying the coating liquid for a coating on the adhesion layer, allowing it to stand at room temperature, and drying. The formed film was peeled from the glass and then subjected to the test. The peeled support layer functions as a support layer. The final composition and thickness of each layer are as follows.

Supporting layer CA / DEP (7 parts / 3 parts) 100 μm Adhesion layer NC / TMETN (6 parts / 4 parts) 30 μm Energy absorbing layer NC / TMETN / C (6 parts / 4 parts / 1 part) 40 μm Obtained When the gas generating member was subjected to the laser light irradiation test (1) and data was obtained with an oscilloscope, the curve of the transmitted light was sharply raised in 10 times of irradiation, 10 times, as shown in FIG. The transmitted light was not attenuated. The average ignition delay time was 10 times 455 μs, and it was confirmed that violent combustion occurs with high reproducibility with a very short ignition delay time.

Example 7 [Production of Gas Generating Member] A film having a three-layer structure (support layer, adhesion layer, gas generating layer) was formed on a glass plate having a length of 24 mm, a width of 60 mm and a thickness of 150 μm using a film applicator. ) Was formed. The support layer was formed by applying the support coating solution prepared in Example 6 on glass, leaving it at room temperature, and drying it. For the adhesive layer, the adhesive layer coating liquid prepared in Example 4 was applied onto the support layer and left standing at room temperature,
The gas generating layer was formed by drying, and the gas generating layer was formed by applying the coating liquid for gas generating layer prepared in Example 4 on the adhesion layer, allowing it to stand at room temperature, and drying. The formed film was subjected to a test after being peeled from the glass. The final composition and thickness of each layer are as follows.

Support layer CA / DEP (7 parts / 3 parts) 90 μm Adhesion layer NC / GAP (6 parts / 4 parts) 20 μm Gas generating layer NC / GAP / C (6 parts / 4 parts / 1 part) 30 μm The obtained gas generating member was subjected to a laser light irradiation test (1) and data was obtained with an oscilloscope. As a result, the curve of the transmitted light was the same as that shown in FIG. It rose violently and the transmitted light was not attenuated.
The average ignition delay time was 10 times 431 μs, and it was confirmed that violent combustion occurs with high reproducibility with a very short ignition delay time.

Example 8 [Production of Gas Generating Member] Biaxially oriented polypropylene (OPP) film having a length of 24 mm × width of 60 mm × thickness of 40 μm (Pyrene Film-OT manufactured by Toyobo Co., Ltd.)
A film having a two-layer structure (adhesion layer and gas generation layer) was formed on P2161). The adhesion layer uses a bar coater,
Urethane adhesive [Takeda Pharmaceutical Co., Ltd. mixed two-component type laminating agent Takelac (main agent A-385 and curing agent A-5
A mixture of 0 and 6: 1 (weight ratio)]] on the biaxially oriented polypropylene film as a support,
It was formed by heating at 80 ° C. for 10 seconds and then leaving it at 40 ° C. for 1 day. The gas generating layer was formed by applying the coating liquid for gas generating layer prepared in Example 4 on the adhesion layer using a film applicator, allowing it to stand at room temperature, and drying. The final composition and thickness of each layer are as follows.

Support Biaxially oriented polypropylene film 40 μm Adhesion layer Two-liquid mixing type laminating agent Takelac 1 μm Gas generating layer NC / GAP / C (6 parts / 4 parts / 1 part) 20 μm Laser irradiation of the obtained gas generating member When subjected to the test (1) (however, the laser light power was 1500 mW) and the data was obtained with an oscilloscope, the curve of the transmitted light was the same as that shown in FIG. , And the transmitted light was not attenuated. The average ignition delay time was 10 times 408 μs, and it was confirmed that intense combustion occurs with high reproducibility with a very short ignition delay time.

Example 9 [Production of Gas Generating Member] Using a film applicator, a polyethylene terephthalate (PET) film having a length of 24 mm × a width of 60 mm × a thickness of 75 μm (manufactured by Teijin DuPont Films Co., Ltd., Melinex Easy Adhesion Type) A film having a two-layer structure (adhesion layer and gas generation layer) was formed thereon. The adhesive layer was formed by applying the adhesive layer coating liquid prepared in Example 4 on a polyethylene terephthalate film, leaving it at room temperature, and drying it.
The coating liquid for gas generating layer prepared in Example 4 was applied onto the adhesion layer, allowed to stand at room temperature and dried.
The final composition and thickness of each layer are as follows.

Support Polyethylene terephthalate (PET) film 75 μm Adhesion layer NC / GAP (6 parts / 4 parts) 10 μm Gas generating layer NC / GAP / C (6 parts / 4 parts / 1 part) 40 μm Obtained gas generating member Was subjected to the laser light irradiation test (1) (however, the laser light power was 1000 mW) and the data was obtained with an oscilloscope. The curve of the transmitted light was shown in FIG. Similarly to the above, the light stood up sharply and the transmitted light was not attenuated. The average ignition delay time was 10 times 423 μs, and it was confirmed that intense combustion occurs with high reproducibility with a very short ignition delay time.

Example 10 [Coating Solution for Adhesion Layer / Coating Layer] Nitrocellulose 8
Part, 2 parts of dibutyl phthalate (DBP, manufactured by Nacalai Tesque, Inc., reagent Nacalai first grade), and 90 parts of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) are placed in an Erlenmeyer flask, and a magnetic stirrer is used at room temperature. I worshiped for about 3 hours. The mixed liquid became a colorless and transparent viscous liquid. This mixed solution was used after standing for 1 hour or more in order to remove air bubbles mixed in with stirring.

[Coating liquid for gas generating layer] Carbon black (C, Mitsubishi Carbon Black MC manufactured by Mitsubishi Chemical Corporation)
F88 (particle diameter 18 nm) (1 part) and ethyl acetate (90 parts) were placed in an Erlenmeyer flask and shaken for 30 minutes using an ultrasonic cleaner to disperse carbon black in ethyl acetate. To this dispersion, 8 parts of nitrocellulose and 2 parts of dibutyl phthalate were further added, and the mixture was stirred at room temperature using a magnetic stirrer for about 3 hours. The mixed liquid was a black viscous liquid, and this mixed liquid was used after being left for 1 hour or more in order to remove bubbles mixed with stirring.

[Production of Gas Generating Member] Using a film applicator, length 24 mm × width 60 mm × thickness 15
A 3-layer structure film (adhesion layer, gas generation layer and coating layer) was formed on 0 μm glass. The adhesive layer was formed by applying the adhesive layer coating liquid on glass, allowing it to stand at room temperature, and drying it. The gas generating layer is formed by applying the prepared coating liquid for gas generating layer on the adhesion layer, leaving at room temperature and drying, and the coating layer is prepared by coating the prepared coating liquid for coating layer on the gas generating layer. It was formed by coating the composition on a substrate, leaving it at room temperature, and drying it. The final composition and thickness of each layer are as follows.

Support layer Glass 150 μm Adhesion layer NC / DBP (8 parts / 2 parts) 63 μm Gas generation layer NC / DBP / C (8 parts / 2 parts / 1 part) 16 μm Coating layer NC / DBP <8 parts / 2 parts ) 62 μm The obtained gas generating member was subjected to a laser light irradiation test (1) (however, the laser light power was 1500 mW), and data was obtained with an oscilloscope. The curve of transmitted light was 10 times during 10 times irradiation. In both cases, as in the case shown in FIG. 4, the light rises sharply and the transmitted light is not attenuated. The ignition delay time has an average value of 575 μs for 10 times, and it was confirmed that violent combustion occurs with high reproducibility with a very short ignition delay time.

Example 11 [Gas Generating Layer Coating Liquid] 1 part of carbon black (C, Mitsubishi carbon black MCF88 particle size 18 nm manufactured by Mitsubishi Chemical Co., Ltd.) and 90 parts of ethyl acetate were placed in an Erlenmeyer flask, and ultrasonic cleaner was used. Give a vibration for 30 minutes using
Carbon black was dispersed in ethyl acetate. Add 8 parts of nitrocellulose and 2 parts of dibutyl phthalate to this dispersion.
Section, trimethylenetrinitroamine (RDX, manufactured by Nippon Koki Co., Ltd., US military standard MIL-DTL-398
2 parts (D compatible grade) was further added, and the mixture was stirred at room temperature using a magnetic stirrer for about 3 hours. The mixed liquid was a black viscous liquid, and this mixed liquid was used after being left for 1 hour or more in order to remove bubbles mixed with stirring.

[Production of Gas Generating Member] Using a film applicator, length 24 mm × width 60 mm × thickness 15
A 3-layer structure film (adhesion layer, gas generation layer and coating layer) was formed on 0 μm glass. The adhesive layer was formed by coating the adhesive layer coating liquid prepared in Example 10 on glass, allowing it to stand at room temperature, and drying it. The gas generating layer is formed by applying the prepared gas generating layer coating liquid on the adhesion layer, leaving it at room temperature and drying, and the coating layer is the coating liquid for coating layer prepared in Example 10. Was applied on the gas generating layer, left standing at room temperature and dried. The final composition and thickness of each layer are as follows.

Support layer Glass 150 μm Adhesion layer NC / DBP (8 parts / 2 parts) 60 μm Gas generation layer NC / DBP / C / RDX (8 parts / 2 parts / 1 part / 2 parts) 15 μm Coating layer NC / DBP ( 8 parts / 2 parts) 60 μm The obtained gas generating member was subjected to a laser light irradiation test (1) (however, the laser light power was 1200 mW) and data was obtained with an oscilloscope. The curve of the transmitted light was 10 As in the case shown in FIG. 4, the ten times during the irradiation of 10 times, the rising was sharp and the transmitted light was not attenuated. The ignition delay time averaged 10 times was 488 μs, and it was confirmed that violent combustion occurs with high reproducibility with a very short ignition delay time.

Example 12 [Coating liquid for gas generating layer] 1 part of carbon black (C, Mitsubishi carbon black MCF88 particle size 18 nm manufactured by Mitsubishi Chemical Co., Ltd.) and 90 parts of ethyl acetate were placed in an Erlenmeyer flask, and an ultrasonic cleaner was used. Give a vibration for 30 minutes using
Carbon black was dispersed in ethyl acetate. Add 8 parts of nitrocellulose and 2 parts of dibutyl phthalate to this dispersion.
And 3 parts of nitroguanidine (NQ, US military standard MIL-N-494B compatible grade manufactured by Chugoku Kayaku Co., Ltd.) were further added, and the mixture was stirred at room temperature for about 3 hours using a magnetic stirrer. The mixed liquid is a black viscous liquid, and after leaving it for 1 hour or more to remove air bubbles mixed with stirring, using this mixed liquid, a [gas-producing member] film applicator was used to measure a length of 24 mm. A film having a two-layer structure (adhesion layer, gas generation layer) was formed on glass having a width of 60 mm and a thickness of 150 μm. The adhesive layer was formed by coating the adhesive layer coating liquid prepared in Example 10 on glass, allowing it to stand at room temperature, and drying it. The gas generating layer was formed by applying the prepared coating solution for gas generating layer on the adhesion layer, leaving it at room temperature, and drying. The final composition and thickness of each layer are as follows.

Support layer glass 150 μm Adhesion layer NC / DBP (8 parts / 2 parts) 60 μm Gas generation layer NC / DBP / C / NQ (8 parts / 2 parts / 1 part / 3 parts) 75 μm Obtained gas generation member Was subjected to a laser light irradiation test (1) (however, the laser light power was 1200 mW) and data was obtained with an oscilloscope. The curve of the transmitted light was shown in FIG. Similarly to the above, the light stood up sharply and the transmitted light was not attenuated. The average ignition delay time of 10 times was 503 μs, and it was confirmed that intense combustion occurs with high reproducibility with a very short ignition delay time.

Example 13 [Gas generating layer coating solution] 1 part of carbon black (C, Mitsubishi carbon black MCF88 particle size 18 nm manufactured by Mitsubishi Chemical Co., Ltd.) and 90 parts of ethyl acetate were placed in an Erlenmeyer flask, and an ultrasonic cleaner was used. Give a vibration for 30 minutes using
Carbon black was dispersed in ethyl acetate. Add 8 parts of nitrocellulose and 2 parts of dibutyl phthalate to this dispersion.
Part, bitetrazole diammonium salt (BHT-2NH
3, 3 parts by Toyo Kasei Kogyo Co., Ltd.) was added, and the mixture was stirred at room temperature for about 3 hours using a magnetic stirrer. The mixed liquid was a black viscous liquid, and this mixed liquid was used after being left for 1 hour or more to remove air bubbles mixed in with stirring.

[Production of Gas Generating Member] Using a film applicator, length 24 mm × width 60 mm × thickness 15
A two-layer structure film (adhesion layer, gas generation layer) was formed on 0 μm glass. The adhesive layer was formed by coating the adhesive layer coating liquid prepared in Example 10 on glass, allowing it to stand at room temperature, and drying it. The gas generating layer is prepared by coating the prepared gas generating layer coating solution on the adhesion layer and leaving it at room temperature.
It was formed by drying. The final composition and thickness of each layer are as follows.

Support layer glass 150 μm Adhesion layer NC / DBP (8 parts / 2 parts) 60 μm Gas generation layer NC / DBP / C / BHT-2NH3 (8 parts / 2 parts / 1 part / 3 parts) 75 μm Obtained gas The generation member was subjected to the laser light irradiation test (1) (however, the laser light power was 1200 mW) and the data was obtained with an oscilloscope. The curve of the transmitted light is shown in FIG. Just as it was done, it rose vigorously and the transmitted light was not attenuated. The ignition delay time was 498 μs on average for 10 times, and it was confirmed that intense combustion occurs with high reproducibility with a very short ignition delay time.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of a gas generating member of the present invention.

FIG. 2 is a schematic cross-sectional view showing another example of the gas generating member of the present invention.

FIG. 3 is a schematic view showing an apparatus used for a laser light irradiation test of an example.

FIG. 4 is a graph showing the relationship between time and light intensity obtained in the laser light irradiation test of the example.

FIG. 5 is a schematic view showing an apparatus used for the water droplet scattering test of the example.

FIG. 6 is a graph showing the relationship between time and voltage value obtained in the generated gas velocity measurement test of the example.

[Explanation of symbols] 1, 11 ... Support 2, 12 ... Adhesion layer 3, 13 ... Gas generating layer 4 ... coating layer

Continued front page    (72) Inventor Mikio Yoneda             1903-3 Yogohama, Aboshi-ku, Himeji City, Hyogo Prefecture

Claims (13)

[Claims] 1. A gas generating member capable of generating gas at a minute portion by a minute heating source, which is formed in close contact with a support, and at least a gas generating agent and a light absorbing agent. A gas generating member comprising a configured gas generating layer. 2. When the irradiation energy of the laser beam is E1 and the kinetic energy of a flying or flying object is E2, E2 /
The gas generating member according to claim 1, wherein E1 is 0.1 to 50. 3. The gas generating member according to claim 1, wherein the adjacent support and the gas generating layer are in close contact with each other by the adhesion layer. 4. A support comprising a base material capable of transmitting laser light, an adhesion layer formed on the surface of the support, and a gas generating layer formed on the surface of the adhesion layer. The gas generating member according to claim 1, wherein the adhesive layer is a non-light absorbing layer that does not substantially contain a light absorbing agent and is in close contact with the support and the gas generating layer. 5. The gas generating agent according to claim 1, wherein the gas generating agent is composed of at least one component selected from a polymer type gas generating agent having film forming property and a low molecular weight or oligomer type gas generating agent. Element. 6. The gas generating member according to claim 1, wherein the gas generating agent contains at least nitrocellulose. 7. The gas generating member according to claim 1, wherein the gas generating layer has a thickness of 20 μm or more. 8. The gas generating member according to claim 3, wherein the adhesion layer has a thickness of 1 μm or more. 9. The gas generating layer according to claim 1, wherein the gas generating layer comprises a light absorbing layer composed of a gas generating agent and a light absorbing agent, and a coating layer formed on the light absorbing layer. Gas generating member. 10. A gas generating composition comprising at least a gas generating agent and a light absorbing agent, and capable of generating gas at a minute portion by a minute heating source. 11. A composition capable of generating a gas when irradiated with laser light, which is composed of a polymer-type gas generating agent having film-forming properties and at least one selected from a plasticizer and a light absorber. The gas generant composition according to claim 10. 12. A method for applying a liquid by intermittently interrupting the flow of a liquid discharged from a nozzle, wherein a minute heating source selected from a laser beam and a thermal head is operated. A method of applying a liquid by changing the flow direction by a gas generated from a minute portion of a gas generating member. 13. A method of irradiating a laser beam to ignite a gas generating layer on the side of a support, ejecting gas at a minute portion of the gas generating layer corresponding to the irradiated portion and flying a minute portion of the gas generating layer. 12. The method according to 12.