JP2002265863A - Coating material for airbag and airbag - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating material for an airbag to form an airbag stable for a long period without causing the blocking of the cloth surfaces, sufficiently and quickly expandable over a wide temperature range from a low temperature to a high temperature and having light weight. SOLUTION: The coating material contains a polyurethane as a film-forming component. The polyurethane is produced by using a diol component consisting of a compound having a fluorine-containing side chain and expressed by general formula 1 (RF is a 1-20C perfluoroalkyl or alkenyl; X is a 1-10C alkylene, alkenylene or alkylenephenoxy; Y is none or O, NH or R0 -NH (R0 is a 1-6C alkylene); Z is none or N(R')R (R is a 1-20C alkylene; R' is H or a 1-6C alkyl; R1 and R2 are each a bivalent organic group; R3 is a diisocyanate residue) or the above compound and a polysiloxane having active hydrogen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating material used for manufacturing an airbag of an airbag device which is mounted on an automobile and protects an occupant from an impact in the event of a collision. The present invention relates to a coating material for an airbag containing a thermoplastic polyurethane.

[0002]

2. Description of the Related Art Airbag devices have become widespread as devices for protecting occupants from the impact of a car collision. This device
It is mounted on the dashboard (instrument panel) in the center of the steering wheel or in front of the passenger seat, inflates instantly when the vehicle receives an unexpected impact, etc., forming an air cushion, and occupants in the driver's seat and passenger seat It plays a role in mitigating the impact on the work.

An airbag device for a driver's seat is provided at the center of a steering wheel, and has a structure for inflating a retainer, an airbag attached to the retainer, the airbag, and deploying the airbag between the driver and the steering wheel. The airbag is composed of a gas generator (inflator) and a module cover that covers the airbag, and the airbag is folded and stored. When a vehicle collides, high-pressure gas is generated from the inflator, and the airbag instantly expands and deploys in the driver's seat while tearing the module cover. On the other hand, in a passenger airbag device provided on a dashboard, an airbag and an inflator are attached to a container, and a module cover is attached so as to cover an opening of the container. This module cover may be referred to as a lid or a deployment door. In the event of a vehicle collision, the inflator operates to inflate the airbag, which is pushed by the inflating airbag to open the module cover indoors, and the airbag is largely deployed toward the passenger seat.

[0004] Airbags currently used are all made of cloth. For example, airbags made by laminating silicone rubber on a woven fabric of synthetic fibers such as polyester and polyamide (Japanese Patent Application Laid-Open No. 63-78744, JP-A 2-2
No. 70654) and an air bag using a silicone emulsion composition or a silicone latex composition as a treatment composition without using an organic solvent from the viewpoint of a working environment (Japanese Patent Application Laid-Open Nos. 56-16553 and 54-54). 131
661, JP-A-5-98579, and U.S. Pat. No. 3,817,894) have been proposed.

[0005]

However, the silicone polymers in these proposals have poor mechanical strength,
It is necessary to add an inorganic filler or to increase the thickness of the film in order to obtain strength enough to withstand the impact when the module cover is opened. As a result, it has been a drawback that the airbag becomes heavier and the storage space in the folded state becomes larger than expected.

[0006] The airbag must be stored in a folded state in the device, and must be immediately inflated and expanded by gas generated from the gas generator due to an impact. In addition, the temperature inside the vehicle to which the device is mounted may reach from an extremely low temperature of -40 ° C. to a high temperature close to 100 ° C., and it is necessary to stably deploy the air bag under any conditions. However, since the conventional airbag fabric laminated with the silicone polymer has a large surface tackiness and a high coefficient of friction, the base fabric surfaces are blocked by long-term storage, and the development of the airbag is hindered. There is fear. In order to solve the above-mentioned drawbacks, an airbag (Japanese Unexamined Patent Publication (Kokai) No. 6-33378) in which a woven fabric is coated with a polycarbonate urethane resin has been devised, but the effect of preventing blocking is not sufficient.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to manufacture an airbag which can be deployed quickly and sufficiently over a wide temperature range from extremely low to high temperature and has a light weight. It is to provide a possible airbag coating material. The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a specific diol having a perfluoroalkyl group or a perfluoroalkenyl group (these groups are referred to as R _f groups), Fluorine using fluorine-containing polysiloxane or fluorine and silicon-containing polyurethane is excellent in low-temperature properties, non-adhesiveness at high temperatures, and mechanical strength. The above-mentioned object is achieved by using this polyurethane as a film-forming component of a coating material. Was achieved.

[0008]

The above object is achieved by the present invention described below. That is, in the present invention, at least a fluorine-containing diol compound represented by the following general formula [1] or a polysiloxane compound having at least one active hydrogen-containing group as a film-forming component is synthesized as a part of a raw material component. It is a coating material for airbags containing thermoplastic polyurethane. Wherein R _f is a perfluoroalkyl group or a perfluoroalkenyl group having 1 to 20 carbon atoms;
Is an alkylene group having 1 to 10 carbon atoms which may have a substituent (may have O, S, or N atoms in the group); an alkenylene group which may have a substituent (-CH =
CH— (CH ₂ ) _n — (n = 1 to 10)) or Or Y is nothing, -O -, - NH-, or -R ₀ -N
H- (R ₀ is an alkylene group having 1 to 6 carbon atoms),
Z is nothing or is -N (R ') R- (R is an alkylene group having 1 to 20 carbon atoms, R' is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), ₁ and R ₂ are 2
R ₃ is a residue of an aliphatic, cycloaliphatic or aromatic diisocyanate. ]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the present invention. The coating material for an airbag of the present invention comprises, as a film-forming component, at least a side chain derived from the fluorine-containing compound represented by the above general formula [1], or a polysiloxane compound containing this side chain and active hydrogen. It is characterized by containing a thermoplastic polyurethane having a polysiloxane segment to be derived in a main chain or a side chain (hereinafter, simply referred to as polyurethane). Here, "polyurethane" is a general term for polyurethane, polyurea and polyurethane-polyurea.

[0010] The polyurethane is prepared by using the above-mentioned diol having one end having an R _f group (a perfluoroalkyl group or a perfluoroalkenyl group having 1 to 20 carbon atoms), or an active hydrogen-containing polysiloxane compound, and a diisocyanate. Can be obtained by a usual method for producing a polyurethane, which is reacted in the presence of a chain extender as necessary. First, a method for producing a diol having one end having an _Rf group used for producing the polyurethane used in the present invention will be described.

As a conventionally known method for producing a diol having one end having an R _f group (a compound having two hydroxyl groups at one end of a molecule), there is a method according to the following reaction formula. Each of the above-mentioned conventional methods for producing a diol having one end having an R _f group and other production methods requires multiple steps,
Therefore, a diol having a high purity and having a _Rf group at one terminal is expensive, and there is a problem in practical use on an industrial scale. However. The method developed by the present inventors described below is an excellent method without such problems.

This method can be manufactured, for example, by the following steps. B) First, an _Rf group and an active hydrogen-containing group (eg, a hydroxyl group)
And a diisocyanate (b) is reacted with NCO / OH ≒ 2 (equivalent ratio)
A fluorine-containing compound (c) having one free isocyanate group in the molecule is obtained. B) Next, the fluorine-containing compound (c) and the dialkanolamine (d) are selectively reacted with the isocyanate group at a temperature of 50 ° C. or lower by utilizing the difference in reactivity between the amino group and the hydroxyl group with respect to the isocyanate group. By reacting the group with an amino group, a diol having one end having a general formula [1] R _f group can be obtained. In this example, Y is -O-.

[0013] (In the formula, R _f , R _{1 to} R ₃ , X and Z are as defined above. Z ₀ is H or a carbon atom having 1 terminal primary or secondary amino group having 1 to 1 carbon atom. And an alkylamino group of 20) Examples of the fluorine compound (a) having an _Rf group and an active hydrogen-containing group used in the present invention include the following compounds.

(1) Alcohol type

(2) Epoxy type The epoxy compound is used by reacting with an active hydrogen-containing compound such as a polyol, polyamide, or polycarboxylic acid so as to have a terminal hydroxyl group.

(3) Amine type

(4) Carboxylic acid type

The fluorine-containing compounds having an _Rf group and an active hydrogen-containing group listed above are examples of preferred compounds used in the present invention, and the present invention is not limited to these examples. Accordingly, not only the above-exemplified compounds but also other known currently commercially available and commercially available compounds can be used in the present invention. Particularly preferred fluorine-containing compounds in the present invention are the alcohol-type fluorine-containing compounds exemplified above.

The diisocyanate (b) used in the present invention
Any known materials can be used, and there is no particular limitation. For example, preferred is toluene-
2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3
-Phenylenediisocyanate, 4-chloro-1,3-
Phenylenediisocyanate, 4-butoxy-1,3-
Phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4'-methylenebis (phenyl isocyanate) (MDI), judylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalenedi isocyanate, benzidine diisocyanate, o- Aromatic diisocyanates such as nitrobenzidine diisocyanate, 4,4-diisocyanate dibenzyl;

Aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4-methylene bis (cyclohexyl) Isocyanate), 1,5-tetrahydronaphthalenediisocyanate, isophorone diisocyanate, alicyclic diisocyanates such as hydrogenated MDI and hydrogenated XDI, or the reaction of these diisocyanates with low molecular weight polyols or polyamines so that the terminals become isocyanates. Naturally, a polyurethane prepolymer obtained by the above method can also be used.

The dialkanolamine (d) used in the present invention includes compounds represented by the following general formula. (Wherein R ₂ , R ₃ and Z ₀ are the same as described above. Preferred R ₂ and R ₃ are divalent groups containing an aliphatic, alicyclic or aromatic ring having 1 to 12 carbon atoms.) And these groups may contain O, N, or S atoms as a linking group therein.) Preferred are, for example, diethanolamine, dipropanolamine, dihexanolamine, 1-amino Examples include propane glycol, diethanolaminomethylamine, diethanolaminoethylamine, diethanolaminopropylamine and the like.

The method for producing the _Rf group-containing diol represented by the general formula (1) will be described more specifically. First, a fluorine-containing compound (a) having an _Rf group and an active hydrogen-containing group and a diisocyanate (b) are reacted with an equivalent ratio (NCO / OH ≒ 2) in which the reaction product has one free isocyanate group in the molecule. ), In the absence of a solvent or under an organic solvent, a conventional polyurethane polymerization catalyst (for example, organic metal,
0-1 in the presence or absence of a tertiary amine or the like)
The reaction is carried out at 50C, preferably at 20-90C.

Next, the fluorine-containing compound having one free isocyanate group is dropped into the dialkanolamine at a temperature of 50 ° C. or lower, preferably 40 ° C. or lower, more preferably 30 ° C. or lower. Under these conditions, the isocyanate group selectively reacts with the amino group before the hydroxyl group (see Ann.Chem., 562 , 205 (1949)), and is represented by the general formula [1] of the present invention. As a result, a diol having one _Rf group at one end is obtained, and at a low temperature, as the reaction proceeds, a part of the product is precipitated as crystals in an organic solvent. After completion of the reaction, the reaction mixture is poured into a poor solvent such as water, toluene, xylene, or n-hexane to precipitate a reaction product crystal. The unreacted diisocyanate or dialkanolamine can be removed by washing the precipitated crystals at room temperature with a poor solvent (such as an aromatic or aliphatic hydrocarbon), and the R represented by the general formula (1) can be removed.
A high-purity one-terminal diol having an _f group is obtained.

The fluorine-containing polyurethane used in the present invention is obtained by reacting the R represented by the general formula (1) obtained by the above reaction.
It can be obtained by reacting the _f- group-containing diol with the diisocyanate and the diol and / or diamine. As the diol, any of those conventionally used in the production of polyurethane can be used,
There is no particular limitation. For example, ethylene glycol, 1,
Low molecular weight glycols such as 2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol; dibasic acids such as adipic acid, maleic acid, and terephthalic acid; and glycols Polyester diols obtained by subjecting lactones to ring-opening polymerization with glycols; polycarbonate diols; polyether diols such as polytetramethylene glycol, polyethylene glycol, and polypropylene glycol. Can be

As the diamine, any of those conventionally used in the production of polyurethane can be used, and there is no particular limitation. For example, aliphatic diamines such as methylene diamine, ethylene diamine, trimethylene diamine, hexamethylene diamine, octamethylene diamine; phenylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-methylenebis (phenyl Amines), aromatic diamines such as 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl sulfone; and alicyclic diamines such as cyclopentadiamine and cyclohexyldiamine. The chain extender is the above-mentioned low molecular weight diol or diamine, and any of those conventionally used in the production of polyurethane can be used without any particular limitation.

A fluorine-containing polyurethane can be obtained by using these components and using a conventionally known polyurethane production method. The method for producing a polyurethane of the present invention comprises reacting the _Rf group-containing diol represented by the general formula (1), a diisocyanate, and a diol and / or a diamine, if necessary, with a chain extender. The production method is not particularly limited. In addition, the reaction mode is not particularly limited, and any reaction mode such as a block, a solution, and a dispersion may be used. Further, the diol, diamine and diisocyanate are not particularly limited as long as a combination suitable for the object and required performance of the obtained fluorine-containing polyurethane is selected. In the fluorine-containing polyurethane obtained using the _Rf group-containing diol, a fluorine-containing side chain derived from the diol has a urethane bond (—NH—CO—O—) via R ₂ and R ₃ in the molecular chain. And / or a urea bond (—NH—CO—NH—) bonded to the polymer molecular chain. When a diol is used, polyurethane is used. When a diamine is used, polyurea is used. When used in combination, a polyurethane-polyurea is obtained.

The content of the fluorine-containing side chain in the polyurethane molecule is from 3 to 80% by weight, preferably from 3 to 50% by weight, based on the fluorine content based on the R _f group in the polyurethane molecule.
% By weight. If the content of the fluorine-containing side chain is too small, blocking of the polyurethane is apt to occur, and peeling of the coated surface or bursting of the bag in an inflation test at a high temperature tends to occur, and heat resistance is also poor. Conversely, if the fluorine content is too high, the polyurethane becomes hard and the bag development at low temperatures becomes unstable.

In still another embodiment of the present invention, a polysiloxane segment derived from a polysiloxane having at least one active hydrogen-containing group in the fluorine-containing polyurethane is used as a siloxane content in the polyurethane molecule. The use of fluorine and silicon containing polyurethanes in amounts of 1 to 75% by weight is mentioned.

The polysiloxane used in the present invention is a polysiloxane having at least one active hydrogen-containing group in the molecule, for example, an amino group, an epoxy group, a hydroxyl group, a mercapto group or a carboxyl group. Examples thereof include the following compounds.

(1) Amino-modified polysiloxane

(2) Epoxy-modified polysiloxane

(3) Alcohol-modified polysiloxane

[0033]

(4) Mercapto-modified polysiloxane

(5) Carboxyl-modified polysiloxane

The polysiloxanes having an active hydrogen-containing group listed above are preferred compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Therefore, not only the compounds exemplified above, but also other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention. Particularly preferred compounds in the present invention are polysiloxanes having at least one hydroxyl or amino group.

The fluorine- and silicon-containing polyurethane obtained by using a diol having one end at one end having an R _f group, a polysiloxane having at least one active hydrogen-containing group in a molecule, and the above-mentioned other polyurethane component are mainly used. In the chain, together with a segment derived from a diisocyanate similar to that of a conventional polyurethane and a segment derived from a diol and / or a diamine, a fluorine-containing side derived from the fluorine-containing diol represented by the general formula (1) is used. The chains are linked by a urethane bond and / or a urea bond via R ₂ and R ₃ in the molecular chain, and a polysiloxane segment derived from the above polysiloxane has a urethane bond and / or a urea bond in a main chain or a side chain. Is a polyurethane bonded with

The content of the polysiloxane segment in the polyurethane molecule is such that the siloxane content in the molecule is 1 to 75% by weight, preferably 5 to 40% by weight. Introducing the polysiloxane segment into the molecule increases the flexibility of the polyurethane and ensures the deployment of the airbag at low temperatures. If the introduction (content) is too large, the strength of the polyurethane decreases, and a problem arises in that the module cannot withstand an impact when the module cover is opened. The weight-average molecular weight (measured by GPC and in terms of standard polystyrene) of the fluorine or the fluorine- and silicon-containing polyurethane of the present invention is 5,000 to 50.
0000 is preferable, and 30,000 or more is more preferable.
150,000. The fluorine-containing polyurethane of the present invention as described above (hereinafter also referred to as further containing a polysiloxane segment) includes a solution dissolved in an organic solvent, a solution dispersed in water, and a solid content of 100% by weight.
Can be used in the form of pellets.

The coating material for an airbag of the present invention comprises:
It contains at least the above-mentioned fluorine-containing polyurethane as a film-forming component. The form of the coating material may be any of a solution, an aqueous emulsion, and an emulsion,
There is no particular limitation. Since the synthesis solution of the fluorine-containing polyurethane can be used as it is or after being diluted, use in a solution is suitable.

As the film-forming component, a fluorine-containing polyurethane may be used alone or in combination, or may be used in combination with another film-forming polymer. When a fluorine-containing polyurethane and another polymer are used in combination, the fluorine content based on the _Rf group is 3 to 50%, and the content of the polysiloxane segment is as a percentage of the total amount of the fluorine-containing polyurethane and the other polymer. The siloxane content is preferably in the range of 5 to 75% by weight.

Examples of the polymer used in combination with the fluorine-containing polyurethane include polyurethane containing no fluorine or fluorine and silicon (polyether type, polyester type, polycarbonate type, etc.), polyester type elastomer, polyamide type elastomer, styrene type elastomer (SBS type). , SEBS, maleic acid-modified SEBS
Olefin elastomers (EPR, EPDM)
Styrene resin (PS, HIPS, AS, AB)
S, AES, etc.), chlorine polymers (PVC, chlorinated polyethylene, etc.), olefin polymers (PE, P
P, EVA, etc.), ester-based polymers (eg, PET), amide-based polymers (eg, nylon), and the like.

The coating material of the present invention may further comprise a flame retardant, a pigment, an extender pigment, a coloring agent, an inorganic filler, an organic filler, a stabilizer,
Hydrolysis inhibitor, antioxidant, light stabilizer, ultraviolet absorber, lubricant, plasticizer, antistatic agent, surfactant, crosslinking agent,
Known additives such as a foaming agent and an antifoaming agent can be added. The type and amount of these additives are not particularly limited, but the total amount is preferably not more than 50% by weight based on all the film-forming components. The coating material of the present invention is usually
The solid content is used in the range of about 5 to 30% by weight.

When an airbag is manufactured using the coating material of the present invention, for example, vinylon, polyurethane,
The base material is a fiber such as polyester or polyamide or a plain woven fabric of such a fiber, and the amount of application after drying is 10 to 200 g / m.
Apply or impregnate to about ² and dry. In this case, the base material may be cut into a circle in advance, sewn into a bag shape, and then coated with a coating material by dipping or the like. Further, a method of applying a coating material on release paper and drying to form a film, and attaching the peeled film to a base material can also be used. The airbag cuts a circular sheet of a predetermined size from the base cloth on which such a fluorine-containing polyurethane film is laminated, overlaps the non-coated surfaces, and adheres the peripheral portion by, for example, heat sealing, sewing, or the like. It is manufactured by forming a bag body and attaching a gas introduction part to a central part of one surface thereof.

[0044]

Next, the present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following examples, “parts” and “%” are based on weight unless otherwise specified.

Reference Example 1 [Fluorine-containing diol (1-A)
Synthesis of 22.2 parts of isophorone diisocyanate in 50 parts of ethyl acetate in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a reflux condenser and purged with nitrogen, and heated at 60 ° C.
46.4 parts of powdery 2
-(Perfluorooctyl) ethanol was gradually added, and after completion of the addition, the mixture was reacted at 80 ° C. for 3 hours to obtain a perfluoroalkyl group-containing one-terminal isocyanate (A).

Next, 10.5 parts of diethanolamine is mixed with 10 parts of ethyl acetate while stirring at a temperature of 10 ° C. or less, and the solution of the compound (A) is dropped into this solution.
An exothermic reaction is observed with the dropping of the solution (A), but the solution is gradually dropped so that the internal temperature does not exceed 20 ° C. The heterogeneous solution becomes homogeneous as the reaction proceeds. After completion of the dropwise addition, the reaction is continued at room temperature (25 ° C.) for 2 hours. After the completion of the reaction, the reaction product was precipitated by adding toluene to the reaction solution and then dried, and dried to obtain a fluorine-containing diol (1-
A) was obtained as a white powder (yield 95%, melting point 132 ° C., hydroxyl value 138 (theoretical value 142)).

Reference Example 2 [Fluorine-containing diol (1-B)
Synthesis of a white powder of a fluorine-containing diol (1-B) having the following structural formula in the same manner as in Reference Example 1 except that tolylene diisocyanate was used in the same equivalent amount instead of the isophorone diisocyanate used in Reference Example 1. This was obtained (95% yield, melting point: 145 ° C., hydroxyl value: 148 (theoretical value: 151)).

Reference Example 3 A commercially available fluorine-containing diol represented by the following structural formula (1-C) was prepared as a fluorine-containing diol for comparative experiments.

Example 1 30 parts of the fluorinated diol (1-A) of Reference Example 1 and 100 parts of a polycarbonate diol having an average molecular weight of 2,000 (Nipporan 980R: manufactured by Nippon Polyurethane Industry Co., Ltd.)
10 parts of 4-butanediol and 49.3 parts of 4,4'-diphenylmethane diisocyanate were reacted at 80 ° C. in dimethylformamide to obtain a fluorine-containing polyurethane (U
1) was obtained. Average weight molecular weight of the obtained fluorine-containing polyurethane measured by GPC (standard polystyrene conversion value)
(The same applies to the following examples and comparative examples) is 7700.
0, and the fluorine content in the resin was measured by an ion chromatograph (manufactured by Yokogawa Hokushin Electric Co., Ltd.) (the same applies to the following Examples and Comparative Examples).
%Met. The properties of the obtained polyurethane were tested by the following methods (the same applies to other Examples and Comparative Examples).
Table 1 shows the results.

[Test Method of Polyurethane] A test piece was prepared by injection molding using the polyurethane separated from the above polyurethane solution, and the characteristics of the polyurethane were measured by the following methods. (A) Mechanical properties: Measured by a method according to JIS K7311. (B) Temperature characteristics: 100% tensile stress (modulus) at -40 ° C and 100 ° C was measured by a method according to JIS K7311, and the ratio was calculated. (C) Static friction coefficient: The static friction coefficient against an iron wire was measured using a surface property tester (Tribogear TYPE: 14DR, manufactured by Shinto Kagaku Co., Ltd.) under the conditions of a temperature of 25 ° C. and a humidity of 70%. (D) Adhesion: Under the conditions of a pressurized area of 49 cm ² , a load of 3 kg and a temperature of 100 ° C., the sheets are stacked and left for 504 hours, then the load is removed, and after 30 minutes, the sheets are peeled off by hand and adhered. Was evaluated and evaluated according to the following criteria.

The above polyurethane solution (solid content 30%)
Is directly used as a coating material, applied to one side of a 210 denier nylon woven fabric having a woven density of 74 / inch so that the amount of polyurethane after drying is 40 g / m ^2, and the solvent is evaporated in an oven to remove air. A base fabric for a bag was prepared. Cut out two 50cm diameter disks from this base cloth, overlap the non-coated surfaces, sew the periphery,
The above-mentioned coating material was applied to the peripheral portion including the sewn portion and dried to prepare a circular bag. A copper tube was attached to the center of one surface as a gas introduction tube. A total of four airbags using the same polyurethane were produced, and the following inflation test was performed (the same applies to the following Examples and Comparative Examples). Table 1 shows the results.

[Inflation test] Each airbag was folded about 10 cm square in the same
/ 100 cm ² and apply each test temperature (−40 to 1
(00 ° C.) for 168 hours, and after removing the load for 30 minutes, an inflation test was performed. The gas introduction pipe of the airbag and the nitrogen gas cylinder were connected by a pressure-resistant rubber hose via a pressure reducing valve, and nitrogen gas was sent at a stretch to inflate the airbag. At this time, the deployed state of the airbag (the state of inflation in a balloon shape), the surface state after deployment, and the like were observed and evaluated based on the following criteria.

[0053]

Example 2 25 parts of the fluorinated diol (1-A) of Reference Example 1 and a polysiloxane oil having an average molecular weight of 3,200 (KF-600)
2: Shin-Etsu Chemical Co., Ltd.) 10 parts, average molecular weight 20
00 polycarbonate diol (Nipporan 980
R: Nippon Polyurethane Industry Co., Ltd.) 100 parts, 1,
10 parts of 4-butanediol and 48.6 parts of 4,4′-diphenylmethane diisocyanate were reacted at 80 ° C. in dimethylformamide to obtain a solution of a fluorine- and silicon-containing polyurethane (U2). The weight average molecular weight of the obtained polyurethane was 82,000, and the fluorine content was 5.
3%, and the polysiloxane segment content is
The content of siloxane was determined by infrared spectroscopy of K0117 (the same applies to the following Examples and Comparative Examples).
Hereinafter, it is simply referred to as polysiloxane content. ) However, it was 5.2%.

Example 3 25 parts of fluorine-containing diol (1-A), average molecular weight 320
100 parts of polysiloxane oil (KF-6002: manufactured by Shin-Etsu Chemical Co., Ltd.), polytetramethylene ether glycol having an average molecular weight of 2,000 (PTMG-200)
0: manufactured by Sanyo Chemical Industries, Ltd.), 100 parts of 1,4-butanediol, and 55.8 parts of 4,4'-diphenylmethane diisocyanate were reacted in the same manner as in Example 1 to obtain a fluorine- and silicon-containing polyurethane (U3 ) Was obtained. The weight average molecular weight of this polyurethane resin is 7
8000, the fluorine content was 3.5%, and the polysiloxane content was 34.4%. Using this polyurethane solution (solid content: 30%) as it was as a coating material, an airbag was prepared and tested. The test results are shown in Table 1 together with the characteristics of the polyurethane.

Example 4 Fluorine-containing diol (1-A) 100 parts, average molecular weight 32
15 polysiloxane oil (KF-6002: manufactured by Shin-Etsu Chemical Co., Ltd.), 100 parts of polycaprolactone diol having an average molecular weight of 2000 (PLACCEL 220: manufactured by Daicel Chemical Industries, Ltd.), and 4,4′-
43.8 parts of diphenylmethane diisocyanate was reacted in the same manner as in Example 1 to obtain a solution of fluorine and silicon-containing polyurethane (U4). The weight average molecular weight of this polyurethane is 84,000, the fluorine content is 15.8%,
The polysiloxane content was 5.8%. Using this polyurethane solution (solid content: 30%) as it was as a coating material, an airbag was prepared and tested. The test results are shown in Table 1 together with the characteristics of the polyurethane.

Example 5 One-end reactive polysiloxane oil (X) having an average molecular weight of 3700 and 50 parts of the fluorinated diol (1-B) of Reference Example 2
22-176DX: manufactured by Shin-Etsu Chemical Co., Ltd.) 30 parts,
Polycarbonate diol having an average molecular weight of 2000 (Nipporan 980R: manufactured by Nippon Polyurethane Industry Co., Ltd.) 1
00 parts, 1,4-butanediol 10 parts, and 4,4 '
44.9 parts of diphenylmethane diisocyanate was reacted in the same manner as in Example 1 to obtain a solution of fluorine and silicon-containing polyurethane (U5). This polyurethane had a weight average molecular weight of 82,000, a fluorine content of 8.1%, and a polysiloxane component content of 12.0%. Using this polyurethane solution (solid content: 30%) as it was as a coating material, an airbag was prepared and tested. The test results are shown in Table 1 together with the characteristics of the polyurethane.

Example 6 Fluorine-containing diol (1-A) 50 parts, average molecular weight 320
0 amino-modified polysiloxane oil (X22-161)
B: Shin-Etsu Chemical Co., Ltd.) 30 parts, average molecular weight 20
00 polycarbonate diol (Nipporan 980
R: Nippon Polyurethane Industry Co., Ltd.) 100 parts, 1,
10 parts of 4-butanediol and 40.3 parts of 4,4′-diphenylmethane diisocyanate were reacted in the same manner as in Example 1 to obtain a fluorine- and silicon-containing polyurethane (U
The solution of 6) was obtained. The weight average molecular weight of this polyurethane was 79000, the fluorine content was 8.9%, and the polysiloxane content was 13.0%. Using this polyurethane solution (solid content: 30%) as it was as a coating material, an airbag was prepared and tested. The test results are shown in Table 1 together with the characteristics of the polyurethane.

Example 7 100 parts of the fluorinated diol (1-A) of Reference Example 1 and a polysiloxane oil having an average molecular weight of 3,200 (KF-600)
2: Shin-Etsu Chemical Co., Ltd.) 50 parts, average molecular weight 20
00 polycarbonate diol (Nipporan 980
R: manufactured by Nippon Polyurethane Industry Co., Ltd.) 100 parts of dimethylformamide was added so that the solid content was 35%.
Dissolved uniformly. Next, 46.7 parts of 4,4'-diphenylmethane diisocyanate was added and reacted in the same manner as in Example 1 to obtain a fluorine- and silicon-containing polyurethane.
It had a weight average molecular weight of 80,000, a fluorine content of 13.8% and a polysiloxane content of 16.8%.

Next, 35 parts of a polycarbonate-based polyurethane (Resamine CU-9430NL: manufactured by Dainichi Seika Kogyo Co., Ltd., solid content 30%) was added to 100 parts of the above 35% solid content polyurethane solution, and the solid content was 30%. And diluted with methyl ethyl ketone to obtain a coating material containing a polyurethane mixture (U7). The fluorine content in the polyurethane mixture was 11.6%, and the polysiloxane content was 13.0%. An airbag was produced using this coating material (solid content: 30%) and tested. The test results are shown in Table 1 together with the properties of the polyurethane mixture.

Example 8 100 parts of the fluorinated diol (1-A) of Reference Example 1 and a polysiloxane oil having an average molecular weight of 3,200 (KF-600)
2: Shin-Etsu Chemical Co., Ltd.) 50 parts, average molecular weight 20
00 polycaprolactone diol (PLACCEL2
20: manufactured by Daicel Chemical Industries, Ltd.), and dimethylformamide was added to 100 parts thereof so as to have a solid content of 35%, and was uniformly dissolved. Next, 46.7 parts of 4,4'-diphenylmethane diisocyanate was added and reacted in the same manner as in Example 1 to obtain a solution of a fluorine and silicon-containing polyurethane. The weight average molecular weight of this polyurethane measured by GPC was 80000, the fluorine content was 13.8%, and the polysiloxane content was 16.8%.

Next, a polyester-based polyurethane (Resamine ME3612LP: manufactured by Dainichi Seika Kogyo Co., Ltd., solid content 3) was added to 100 parts of the above 35% solid content polyurethane solution.
0%) and 35 parts of polyisocyanate (CORONAT)
EL: Nippon Polyurethane Industry Co., Ltd., solid content 75
%), And the mixture was diluted with methyl ethyl ketone to a solid content of 30% to obtain a solution of a polyurethane mixture (U8). The fluorine content in the polyurethane mixture is 11.
5% and the polysiloxane content was 12.9%. An airbag was produced using this coating material (solid content: 30%) and tested. The test results are shown in Table 1 together with the properties of the polyurethane mixture.

Comparative Example 1 Polycarbonate diol having an average molecular weight of 2,000 (Nipporan 980R: manufactured by Nippon Polyurethane Industry Co., Ltd.) 1
00 parts and 10 parts of 1.4-butanediol have a solid content of 35.
%, And dimethylformamide was added to dissolve uniformly. Next, 40.3 parts of 4,4'-diphenylmethane diisocyanate was added and reacted in the same manner as in Example 1 to obtain a solution of fluorine and silicon-containing polyurethane (U9). The weight average molecular weight of this polyurethane measured by GPC was 82,000, and the fluorine content was 2.7.
% And the polysiloxane content was 2.9%. Using this polyurethane solution (solid content: 30%) as it was as a coating material, an airbag was prepared and tested. The test results are shown in Table 2 together with the characteristics of the polyurethane.

Comparative Example 2 Fluorine-containing diol (1-A) 10 parts, average molecular weight 320
5 parts of polysiloxane oil (KF-6002: manufactured by Shin-Etsu Chemical Co., Ltd.), 100 parts of a polycarbonate diol having an average molecular weight of 2000 (Nipporan 980R: manufactured by Nippon Polyurethane Industry Co., Ltd.), and 10 parts of 1,4-butanediol. In addition, dimethylformamide was added so that the solid content became 35%, and the mixture was uniformly dissolved. Then
4,4'-diphenylmethane diisocyanate 47.3
The reaction was carried out in the same manner as in Example 1 to obtain a solution of fluorine-containing and silicon-containing polyurethane (U10). This polyurethane had a weight average molecular weight of 82,000, a fluorine content of 2.7%, and a polysiloxane content of 2.9%. Using this polyurethane solution (solid content: 30%) as it was as a coating material, an airbag was prepared and tested. The test results are shown in Table 2 together with the characteristics of the polyurethane.

Comparative Example 3 25 parts of fluorine-containing diol (1-C), average molecular weight 320
20 parts of polysiloxane oil (KF-6002: manufactured by Shin-Etsu Chemical Co., Ltd.), 100 parts of polycarbonate diol having an average molecular weight of 2000 (Nipporan 980R: manufactured by Nippon Polyurethane Industry Co., Ltd.), and 10 parts of 1,4-butanediol. In addition, dimethylformamide was added so that the solid content became 35%, and the mixture was uniformly dissolved. Then, 4,4'-diphenylmethane diisocyanate 6
0.2 part was added and reacted in the same manner as in Example 1 to obtain a solution of a fluorine- and silicon-containing polyurethane (U11). The weight average molecular weight of this polyurethane is 77000,
The fluorine content is 5.8% and the polysiloxane content is 9.
3%. This polyurethane solution (solid content 30%)
Was used as a coating material, and an airbag was prepared and tested. The test results are shown in Table 2 together with the characteristics of the polyurethane.

[0066]

[0067]

[0068]

As described above, fluorine in the present invention,
Or, fluorine and silicon-containing polyurethanes have little change in physical properties due to temperature changes, have necessary and sufficient strength at high and low temperatures, and have the characteristic of not sticking at high temperatures, making them ideal as airbag materials It is something. With the above characteristics, the airbag using the polyurethane of the present invention can sufficiently protect the occupant from a low temperature to an extremely high temperature.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 7/04 CER C08J 7/04 CERZ CEZ CEZZ C09D 183/04 C09D 183/04 // C08L 101: 00 C08L 101: 00 (72) Inventor Kazuyuki Hanada 1-7-6 Bakurocho, Nihonbashi, Chuo-ku, Tokyo F-term (reference) 3D054 CC26 CC30 CC45 FF18 4F006 AA19 AA35 AA37 AA38 AB37 CA04 DA04 4F100 AK48 AK51A AL06A AL08A BA02 CC00A DG11B DG12 EH46 GB33 JB16A JK16 JL03 JL13 YY00A 4J034 CA04 CB03 CC01 CC05 CC06 CC12 CC22 CC61 CC62 CC65 CC66 CD01 CD12 HA07 HC03 HC12 HC17 HC22 HC46 HC2 CB CB CB CB CB CB CB CB CB CB CB CB CB CB CB CB CB CB CB HCCB CC021 CC022 CF031 CF032 CQ011 CQ012 DD001 DD002 DG091 DG092 DG111 DG112 DG121 DG122 DG131 D G132 DG171 DG172 DG181 DG182 DH001 DH002 DL051 DL052 DL081 DL082 DL091 DL092 DL151 DL152 DL161 DL162 GA12 MA12 MA14 NA00 NA10 NA11 NA14 PC10

Claims (11)

[Claims] 1. A coating material for an airbag, comprising at least a polyurethane having a side chain derived from a fluorine-containing diol represented by the following general formula [1] as a film-forming component. Wherein R _f is a perfluoroalkyl group or a perfluoroalkenyl group having 1 to 20 carbon atoms;
Is an alkylene group having 1 to 10 carbon atoms which may have a substituent (may have O, S, or N atoms in the group); an alkenylene group which may have a substituent (-CH =
CH— (CH ₂ ) _n — (n = 1 to 10)) or Or Y is nothing, -O -, - NH-, or -R ₀ -N
H- (R ₀ is an alkylene group having 1 to 6 carbon atoms),
Z is nothing or is -N (R ') R- (R is an alkylene group having 1 to 20 carbon atoms, R' is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), ₁ and R ₂ are 2
R ₃ is a residue of an aliphatic, cycloaliphatic or aromatic diisocyanate. ] 2. The fluorine-containing compound represented by the general formula [1], wherein R ₁ and R ₂ are a methylene group having 2 to 4 carbon atoms, Y is an oxygen atom, and the fluorine-containing compound is R
₁ and R ₂ a coating material for an air bag according to claim 1 which is bonded with a urethane bond in the main chain of the polyurethane through. 3. The coating material for an airbag according to claim 1, wherein the R _f -XY— group of the general formula [1] is a group obtained by removing hydrogen from a hydroxyl group of at least one of the following compounds. . 4. The compound of the general formula [1], wherein -ZN (R ₁ O
The coating material for an airbag according to claim 1, wherein the H) (R ₂ OH) group is a group obtained by removing hydrogen from an active hydrogen group bonded to Z ₀ in the following formula. (Wherein R _{1 to} R ₂ are as defined above. Z ₀ is H or an alkylamino group having 1 to 20 carbon atoms and having one primary or secondary amino group at the terminal. .) 5. The content of the side chain derived from the fluorine-containing diol represented by the general formula [1] is such that the fluorine content in the polyurethane molecule is 3 to 80% by weight. 2. The coating material for an airbag according to claim 1. 6. The polyurethane according to claim 1, wherein the polyurethane further comprises a polysiloxane segment derived from a polysiloxane having at least one active hydrogen-containing group in an amount of 1 to 75% by weight as a siloxane content. Airbag coating material. 7. The coating material for an airbag according to claim 6, wherein the active hydrogen-containing group of the polysiloxane is a hydroxyl group or an amino group. 8. The polyurethane having a weight average molecular weight of 5,
The coating material for an airbag according to claim 1, wherein the coating material is 000 to 500,000. 9. The coating material for an airbag according to claim 1, further comprising another resin. 10. An airbag comprising a base cloth coated with the coating material for an airbag according to claim 1. Description: 11. The airbag according to claim 10, comprising a base fabric on which a polyurethane coating crosslinked with a polyisocyanate is formed.