JP2002265554A - Airbag - Google Patents

Abstract

(57) [Problem] To provide a thermoplastic polyurethane air bag which solves the conventional problems and can be quickly and sufficiently developed in a wide range from extremely low temperature to high temperature. SOLUTION: An airbag made of a polyurethane having a fluorine-containing side chain or a polysiloxane segment and a fluorine-containing side chain as shown below in a molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an airbag for an airbag device which is mounted on a vehicle and protects an occupant from an impact in a collision. More specifically, the present invention relates to a high-performance airbag made of fluorine or fluorine and silicone-modified thermoplastic polyurethane. Related to airbags.

[0002]

2. Description of the Related Art An airbag device is widely used as a device for protecting an occupant from the impact of a vehicle collision. This device is installed in the center of the steering wheel (streering wheel) or on the dashboard in front of the passenger seat, and when the vehicle receives an unexpected impact, it instantly expands to form an air cushion, and the driver and passenger seats It plays a role in reducing the impact on passengers.

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 an automobile collides, gas is generated from the inflator, and the airbag inflates instantly 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 (instrument panel), 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. When a vehicle collides, the inflator operates to inflate the airbag, the module cover pushed by the inflating airbag opens to the indoor side, and the airbag expands largely toward the indoor.

[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]

In each of these conventional airbags, since the base synthetic fiber woven fabric is coated, the adhesion between the fiber and the coating material is insufficient, or the sewn portion is sewn. To increase the tear strength of
Further, there is a problem that measures must be taken such as attaching a rubber tape such as a silicone rubber in order to enhance confidentiality. Furthermore, there is a disadvantage that the sewing process is time-consuming and economically disadvantageous.

As a method for eliminating the trouble of sewing, for example, an airbag made of a thermoplastic polymer such as polyvinyl chloride, polyurethane, or polyamide has been devised (see Japanese Patent Application Laid-Open No. 4-266544). However, in the above-mentioned thermoplastic polymer airbag, the bag becomes too hard in a low temperature range (for example, −40 ° C.), or the strength of the polymer is reduced in a high temperature range (for example, + 100 ° C.) or the surface is sticky. Folded bags may stick and become poorly deployed.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned conventional problems and to provide a thermoplastic polyurethane air bag which can be developed sufficiently quickly in a wide range from a very low temperature to a high temperature. The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a perfluoroalkyl group or a perfluoroalkenyl group (these groups are represented by R _f
Called a group. ) Or a fluorine- or fluorine- and silicon-containing thermoplastic polyurethane synthesized using a diol having one end or a polysiloxane having an active hydrogen-containing group, has excellent low-temperature properties, non-adhesion at high temperatures, and mechanical strength. It has been found that the above objects are achieved by producing an airbag with polyurethane.

[0008]

The above object is achieved by the present invention described below. That is, the present invention comprises a thermoplastic polyurethane synthesized using a fluorine-containing diol compound represented by the following general formula [1] or a polysiloxane compound having the same and at least one active hydrogen-containing group as a raw material component. It is an airbag. 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 airbag of the present invention comprises a side chain derived from the fluorine-containing compound represented by the general formula [1] or a polysiloxane segment derived from a polysiloxane compound having the side chain and an active hydrogen-containing group. It is characterized by being mainly composed of a thermoplastic polyurethane having a main chain or a side chain. Here, "polyurethane" is a general term for polyurethane, polyurea and polyurethane-polyurea.

[0010] Such a polyurethane can be obtained by an ordinary polyurethane production method in which a diol having one end having an R _f group, or an active hydrogen-containing compound, and a diisocyanate are reacted, if necessary, in the presence of a chain extender. Can be. First, a method for producing a diol having one terminal having a perfluoroalkyl group or a perfluoroalkenyl group (hereinafter referred to as 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. All of the above-mentioned conventional methods for producing a diol having a single terminal having an R _f group require many steps, and therefore, R
_One- terminal diols having an _f group are expensive and have problems in practical use on an industrial scale, but the method described below is an excellent method developed by the present inventors without such problems. is there.

The one-terminal diol having an R _f group used for producing the polyurethane used in the present invention can be produced, for example, by the following steps. B) First, an _Rf group and an active hydrogen-containing group (eg, a hydroxyl group)
Is reacted with diisocyanate (b) at a molar ratio of NCO / OH モ ル 2 to obtain a fluorine-containing compound (c) having one free isocyanate group in the molecule. 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 an R _f group represented by the general formula [1] 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), judile 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 an O, N, or S atom as a linking group therein.) Preferred are, for example, diethanolamine,
Examples thereof include dipropanolamine, dihexanolamine, 1-aminopropane glycol, diethanolaminomethylamine, diethanolaminoethylamine, and diethanolaminopropylamine.

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, an 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 the R represented by the general formula (1) of the present invention. _A diol having one end having an _f group is obtained, and at a low temperature, as the reaction proceeds, a product is partially precipitated as a crystal 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, and octamethylene diamine; phenylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-methylene bis (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 by using the _Rf group-containing diol, the fluorine-containing side chain has a urethane bond (—NH—CO—O—) and / or urea in the molecular chain via R ₂ and R _3. Join (-
NH-CO-NH-), a polyurethane is obtained when a diol is used, a polyurea is used when a diamine is used, and a polyurethane-polyurea is obtained when a diol and a diamine are used in combination. .

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.
%, More preferably 5 to 25% by weight. If the content of the fluorine-containing side chain is too small, blocking of the polyurethane is likely to occur, and in an inflation test at a high temperature, excessive expansion and rupture become inferior to heat resistance, and if too large, the polyurethane becomes hard, Bag deployment 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. 1 to 75% by weight, preferably 3 to
An airbag is formed using a fluorine-containing polyurethane containing 50% by weight, more preferably 3 to 20% by weight.

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

(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 terminal 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 chain is bonded to the molecular chain via a urethane bond and / or a urea bond via R ₂ and R ₃ , and the polysiloxane segment derived from the above polysiloxane is bonded to the main chain via a urethane bond and / or a urea bond. Polyurethane.

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 3 to 50% by weight, more preferably 3 to 20% by weight. is there. The introduction of the polysiloxane segment increases the flexibility of the polyurethane and ensures the operation of the airbag at low temperatures. If the introduction (content) is too small, the above effect becomes insufficient, while if it is too large, the strength of the polyurethane decreases, and the problem that the airbag cannot withstand the impact at the time of tearing occurs. Further, the weight average molecular weight (measured by GPC and in terms of standard polystyrene) of the fluorine-containing polyurethane of the present invention is preferably from 5,000 to 500,000, more preferably from 30,000 to 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. It can be used in the form of pellets or the like.

Such a fluorine-containing thermoplastic polyurethane may be used in a blend with another thermoplastic polymer. Examples of the polymer to be blended include a polyester elastomer, a polyamide elastomer, and a styrene elastomer (SBS, SEBS, maleic acid-modified SEBS, etc., olefin elastomers (EP
R, EPDM, etc.), styrene resins (PS, HIPS,
AS, ABS, AES, etc.), chlorine-based polymers (PVC,
Chlorine-based polyethylene, etc.), olefin-based polymer (P
E, PP, EVA, etc.), ester polymers, amide polymers and the like.

Further, a flame retardant, a pigment, an extender, a colorant,
Inorganic fillers, organic fillers, stabilizers, hydrolysis inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, plasticizers, antistatic agents, surfactants, crosslinking agents, foaming agents, defoamers, etc. Known additives may be added.

When another polymer is blended with the fluorine-containing polyurethane, the fluorine content based on the _Rf group is 3 to 50%, and the siloxane content is the ratio to the total amount of the fluorine-containing polyurethane and the other polymer. The polysiloxane segment content (as siloxane content) is preferably in the range of 5 to 75% by weight. When the above various additives are used, the amount of the additives is preferably not more than 50% by weight based on the weight of the polyurethane.

In producing an air bag comprising the fluorine-containing thermoplastic polyurethane of the present invention, for example, the fluorine-containing thermoplastic polyurethane of the present invention or a polyurethane composition obtained by blending another polymer or additive with this polyurethane is used. For example, one molded into a film or sheet by a T-die extrusion method, or one obtained by blow molding or injection molding is used. The airbag is obtained in this manner, usually from 0.1 to 2.
From a film or sheet having a thickness of about 0 mm, a circle having a predetermined size is cut, and two sheets are laminated and the peripheral portions are bonded together by fusion (heat sealing) or use of an adhesive. It is manufactured by attaching a gas introduction part to one surface by any means.

[0042]

EXAMPLES Next, the present invention will be described more specifically with reference to Reference Examples, Polymerization Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. Further, “parts” and “%” in the following examples 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 used as a fluorine-containing diol for comparative experiments.

Production Example 1 30 parts of the fluorinated diol (1-A) of Reference Example 1 and 100 parts of a polycarbonate diol having a mean 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 100 ° C. to obtain a fluorine-containing polyurethane (U1). The weight average molecular weight (standard polystyrene conversion value) of the obtained fluorinated polyurethane measured by GPC was 77000, and the fluorine content in the polyurethane was measured by an ion chromatograph (manufactured by Yokogawa Hokushin Electric Co., Ltd.). 5%. In addition, the measuring method of the weight average molecular weight and the fluorine content of the polyurethane is the same in the following examples.

Production Example 2 25 parts of the fluorinated diol (1-A) of Reference Example 1 and a polysiloxane oil having an average molecular weight of 3200 (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 100 ° C. to obtain a fluorine- and silicon-containing polyurethane (U2).
The weight average molecular weight of the obtained fluorine and silicon-containing polyurethane was 82,000 (standard polystyrene conversion value), and the fluorine content was 5.3%. The polysiloxane segment content was expressed as a siloxane content measured by infrared spectroscopy according to JIS K0117, and it was 5.2%. Similarly, in the following examples, the siloxane content measured by the above JIS method is defined as the siloxane segment content, and simply referred to as the polysiloxane content.

Production 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: 100 parts of Sanyo Kasei Kogyo Co., Ltd.), 10 parts of 1,4-butanediol, and 55.8 parts of 4,4′-diphenylmethane diisocyanate were reacted in the same manner as in Production Example 1 to obtain a fluorine- and silicon-containing polyurethane (U3 ) Got. The weight average molecular weight of this polyurethane is 78,000,
Fluorine content is 3.5%, polysiloxane content is 3
It was 4.4%.

Production Example 4 100 parts of fluorine-containing diol (1-A), 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 Production Example 1 to obtain a fluorine- and silicon-containing polyurethane (U4). The weight average molecular weight of this polyurethane was 84,000, the fluorine content was 15.8%, and the polysiloxane content was 5.8%.

Production Example 5 50 parts of the fluorinated diol (1-B) of Reference Example 2 and a one-terminal reactive polysiloxane oil having an average molecular weight of 3700 (X
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 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 content of 12.0%.

Production 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 Production Example 1 to obtain a fluorine- and silicon-containing polyurethane (U6).
I got The weight average molecular weight of this polyurethane is 7900
0, the fluorine content was 8.9%, and the polysiloxane content was 13.0%.

Production Example 7 100 parts of the fluorine- and silicon-containing polyurethane (U2) obtained in Production Example 2 and a polyamide elastomer (PAE1
200: Ube Industries, Ltd.) 10 parts were melt-mixed with an extruder to obtain a fluorine- and silicon-containing polyurethane composition (U7). The content of fluorine in this polyurethane composition was 4.8%, and the content of polysiloxane was 4.7%.
Met.

Production Example 8 100 parts of the fluorine- and silicon-containing polyurethane (U5) obtained in Production Example 5 and 20 parts of SEBS (styrene-ethylene-butylene-styrene) (Tufprene M1593: hydrogenated SBS manufactured by Asahi Kasei Corporation) Was melt-mixed with an extruder to obtain a fluorine- and silicon-containing polyurethane composition (U8). The fluorine content in this polyurethane composition was 6.8%, and the polysiloxane content was 10.0.
%Met.

Comparative Production Example 1 Polycarbonate diol having an average molecular weight of 2000 (Nipporan 980R: manufactured by Nippon Polyurethane Industry Co., Ltd.) 1
00 parts, 10 parts of 4-butanediol, and 4,4 '
-Diphenylmethane diisocyane resin (U9) was obtained.
The weight average molecular weight of this polyurethane was 80,000.

Comparative Production Example 2 10 parts of fluorine-containing diol (1-A), average molecular weight 320
5 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.), 10 parts of 1,4-butanediol, and 47.3 parts of 4,4'-diphenylmethane diisocyanate was added and reacted in the same manner as in Production Example 2.
A fluorine and silicon containing polyurethane (U10) was obtained.
The polyurethane had a weight average molecular weight of 82,000, a fluorine content of 2.7%, and a polysiloxane content of 2.9%.
Met.

Comparative Production 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 2,000 (Nipporan 980R: manufactured by Nippon Polyurethane Industry Co., Ltd.), 10 parts of 1,4-butanediol, and 60.2 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 (U11) solution. The weight average molecular weight of this polyurethane is 7700
0, the fluorine content was 5.8%, and the polysiloxane content was 9.3%.

Examples 1 to 8 and Comparative Examples 1 to 3 The characteristics of the polyurethanes obtained in Production Examples 1 to 8 and Comparative Production Examples 1 to 3 and the performance of an actual airbag were evaluated. The test items and methods are as follows, and the results are shown in Tables 1 and 2.

Test method (1) Polyurethane property test A test piece of each polyurethane resin was prepared by injection molding.
Various characteristics were measured by the following methods. (A) Mechanical properties: Measured by a method according to JIS K7311. (B) Temperature characteristics: 100% modulus values at −40 ° C. and 100 ° C. were 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: Pressing surface 49 cm ² , load 3 kg, temperature 1
After the sheets were stacked and left for 504 hours under the condition of 00 ° C., the load was removed, and after leaving for 30 minutes, the sheets were peeled off and observed for the presence or absence of adhesion, and evaluated according to the following criteria.

(2) Inflation test Each polyurethane was extruded (T-die) to a thickness of 5
The sheet was processed into a sheet having a thickness of 00 to 600 μm to produce an airbag. Two circular sheets having a diameter of 50 cm were cut from the above sheet. One center part is about 5cm in diameter of the same sheet
Was reinforced from both sides by a circular sheet, and a copper tube was attached thereto as a gas introduction tube. Two circular sheets were stacked, the peripheral edge was heat-sealed at 200 ° C., and further reinforced with polyurethane sealing tape to produce an airbag. A total of four airbags were produced using the same polyurethane. Fold each airbag about 10 cm square in the same way,
A load of 6 kg / 100 cm ² was applied, and each test temperature (-4
(0 to 100 ° C.) for 168 hours, and after the load was removed 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.

[0061]

[0062]

[0063]

[0064]

As described above, the fluorine of the present invention or
Fluorine and silicon-containing polyurethanes are characterized by little change in physical properties due to temperature changes, have necessary and sufficient strength at high and low temperatures, and have no sticking problem at high temperatures. It is the best one. 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.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kazuyuki Hanada 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Dainichi Seika Kogyo Co., Ltd. F-term (reference) 3D054 CC26 FF01 FF16 FF17 4J034 BA02 BA09 CA04 CA12 CB01 CB03 CC03 CC12 CC22 CC45 CC52 CC62 CD01 CD12 DA01 DB01 DB04 DC02 DC12 DC35 DC43 DD06 DM01 DM04 DM08 DR04 HA01 HA07 HC03 HC06 HC12 HC13 HC17 HC22 HC46 HC52 HC61 HC64 HC71 HC73 JA44 QB10 QB14 QC08 RA12

Claims (10)

[Claims] 1. An airbag comprising a polyurethane having a side chain derived from a fluorine-containing diol represented by the following general formula [1]. 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
The airbag according to claim 1 which is bonded with a urethane bond in the main chain of the polyurethane through the ₁ and R _2. 3. The R _f -XY group of the above general formula [1] is:
The airbag according to claim 1, which is a group obtained by removing hydrogen from a hydroxyl group of at least one of the following compounds. 4. The airbag according to claim 1, wherein the ZN (R ₁ OH) (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 airbag according to claim 1, wherein the content of the side chain represented by the general formula [1] is such that the fluorine content in the polyurethane molecule is 3 to 80% by weight. 6. The polyurethane further comprises polysiloxane segments derived from a polysiloxane having at least one active hydrogen-containing group in an amount such that the siloxane content in the polyurethane is from 1 to 75% by weight. 2. The airbag according to 1. 7. The 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 airbag according to claim 1, wherein the number of the airbag is from 000 to 500,000. 9. The airbag according to claim 1, further comprising another resin. 10. The airbag according to claim 1, wherein the polyurethane is crosslinked with a polyisocyanate.