CA1233010A - Wiper blade - Google Patents
Wiper bladeInfo
- Publication number
- CA1233010A CA1233010A CA000475197A CA475197A CA1233010A CA 1233010 A CA1233010 A CA 1233010A CA 000475197 A CA000475197 A CA 000475197A CA 475197 A CA475197 A CA 475197A CA 1233010 A CA1233010 A CA 1233010A
- Authority
- CA
- Canada
- Prior art keywords
- wiper blade
- fluorine
- blade according
- ethylene
- fluorination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/126—Halogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60S—SERVICING, CLEANING, REPAIRING, SUPPORTING, LIFTING, OR MANOEUVRING OF VEHICLES, NOT OTHERWISE PROVIDED FOR
- B60S1/00—Cleaning of vehicles
- B60S1/02—Cleaning windscreens, windows or optical devices
- B60S1/04—Wipers or the like, e.g. scrapers
- B60S1/32—Wipers or the like, e.g. scrapers characterised by constructional features of wiper blade arms or blades
- B60S1/38—Wiper blades
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60S—SERVICING, CLEANING, REPAIRING, SUPPORTING, LIFTING, OR MANOEUVRING OF VEHICLES, NOT OTHERWISE PROVIDED FOR
- B60S1/00—Cleaning of vehicles
- B60S1/02—Cleaning windscreens, windows or optical devices
- B60S1/04—Wipers or the like, e.g. scrapers
- B60S1/32—Wipers or the like, e.g. scrapers characterised by constructional features of wiper blade arms or blades
- B60S1/38—Wiper blades
- B60S2001/3827—Wiper blades characterised by the squeegee or blade rubber or wiping element
- B60S2001/3829—Wiper blades characterised by the squeegee or blade rubber or wiping element characterised by the material of the squeegee or coating thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A wiper blade is disclosed which is produced by molding a wiper blade matrix of ethylene-propylene copolymer (EPM) or ethylene-propylene-diene copolymer (EPDM) and fluorinating the wiper blade matrix thereby causing fluorine atoms be bonded to the carbon atoms of the copolymer in the surface layer of the wiper blade matrix. The wiper blade possesses a small friction coefficient and excels in resistance to aging ozonization; chemicals, abrasion, and permanent deformation.
A wiper blade is disclosed which is produced by molding a wiper blade matrix of ethylene-propylene copolymer (EPM) or ethylene-propylene-diene copolymer (EPDM) and fluorinating the wiper blade matrix thereby causing fluorine atoms be bonded to the carbon atoms of the copolymer in the surface layer of the wiper blade matrix. The wiper blade possesses a small friction coefficient and excels in resistance to aging ozonization; chemicals, abrasion, and permanent deformation.
Description
~233(~
WIPER BLADE
BACKGROUND OF THE INVENTION
1. Field of the Invention:
This invention relates to a wiper blade for wiping the windshield of a vehicle such as automobile, a streetcar, or an aircraft.
WIPER BLADE
BACKGROUND OF THE INVENTION
1. Field of the Invention:
This invention relates to a wiper blade for wiping the windshield of a vehicle such as automobile, a streetcar, or an aircraft.
2. Description of the Prior Art:
The wiser blade used for vehicles is intended to wipe water drops, snow, etc. away the windshield surface by sliding on the windshield surface.
It is, therefore, required to give even wiping to the windshield by being pressed uniformly against the windshield and to operate smoothly an-d avoid emitting objectionable noise by offering low frictional resistance.
t has been customary, therefore, to form the wiper blade with natural rubber, synthetic rubber such as chloroprene rubber, resin such as polye~len thereby to confer us thermoplastic elastomers such as urethane type e].astomer, ox synthetic /
the wiper blade the elasticity high enough for the wiper blade j to slide evenly on the shield surface and, at the same time, ¦ subject the surface of the wiper blade to a treatment of ¦ chlorination or bromination thereby to cause bonding of chlorine atoms or bromide atoms to the carbon atoms in the main chain of the rubber or elastomers and induce degradation of frictional resistance.
The treatment of chlorination or bromination, however, is incapable of amply lowering the frictional resistance.
Particularly, the Cal bond or Cur bond is chemically instable , - 1~33(~
and is readily unbounded by heat, water, ultraviolet light, ozone, oxygen, or chemicals to remove Of or Bra The conventional wiper blade, therefore, is deficient in resistance to the conditions of nature and looses the performance as a wiper blade within a short time.
When the treatment of chlorination, for example, is carried out to a high degree for the purpose of lowering the friction resistance and enhancing the durability, adversely, cracks are produced easily on the surface thereof, the permanent set resistance is reduced and the striped trace remains on the surface thereof after wiping, whereby the wiping properties are lowered.
It is known that the ethylene-propylene copolymer (hereinafter refried to as EM) and the ethylene-propylene-dine copolymer (hereinafter referred to as EPDM) obtained by adding a small amount of a dine compound to EM for enhancing its valcanizability have a remarkable quality in resistance to aging, ozone, chemicals, water and permanent set. The above-mentioned problems, therefore, can be solved, if EM or EPDM may be used as a material for the wiper blade.
Since EM and EPDM are saturated organic high molecular compounds possessing no double bond in the main chains thereof, however, they form neither Cal bond nor Cur bond even if they are subjected to the treatment of chlorination or bromination.
~:3;~0~C~
The present invention is accomplished by studying the fact that fluorine is extremely active and substitutes for the hydrogen atom of the C-F bond to form a C-F bond.
SUMMARY OF THE INVENTION
According to this invention, it is provided that a wiper blade produced by molding a wiper blade matrix of ethylene-propylene copolymer (EM) or ethylene-propylene-diene copolymer (EPDM) and fluoridating the wiper blade matrix thereby causing fluorine atoms to be bonded to the carbon atoms of the aforementioned copolymer in the surface layer of the wiper blade matrix.
- An object of this invention, therefore, is to provide a wiper blade possessing a low friction coefficient and is excellent in resistance to aging, ozone, chemicals, abrasion, and permanent set.
The other and further objects and characteristic features of this invention will become apparent to those skilled in the art from the further disclosure of this invention to be made in the following detailed description of a preferred embodiment and described in the appended claims and various advantages not referred to herein will become obvious to those of ordinary skill in the art through employment of the invention in practice.
Now a preferred embodiment of the invention will be described below in conjunction with concrete experiments.
~;~330~C~
retailed Description of Preferred Embodiments:
A method for the manufacture of a wiper blade according to the present invention will be described. First, a lopper blade matrix Or a prescribed shape is molded of EM or EPDM
as the material. Then the wiper blade matrix so produced is fluorinated to have fluorine atoms bonded to the carbon atoms forming the main chain of the saturated organic high molecular compound (EM or EPDM) in the surface layer of the wiper blade matrix.
In the EM so used, the ethylene content falls in the range of 75 to 50% by weight and the propylene content in the range of 25 to 50% by weight. In the EPDM, the ethylene and propylene contents are in the ranges mentioned above and the dine content is in a minute proportion. Here, the fluorination may be effected in the form of a gaseous-phase reaction or a liquid-phase reaction. The gaseous-phase reaction can be carried our by a method of directly exposing the wiper blade matrix fresh from the molding step to an atmosphere solely Or fluorine gas, an atmosphere formed of fluorine gas mixed with a small amount Or oxygen gas, or an atmosphere prepared by diluting fluorine gas or a mixture of fluorine gas and a small amount of oxygen was with an inert gas such as helium, Argo nor nitrogen. The reaction of this method is ~errormed at a fluorine concentration of 5 to 100%, preferably about 10%, at a temperature in the range of 0 to 100C. An excessively high fluorine concentration is undesirable because cracks occur easily on the surface of the ,., 33(~
wiper blade. As means of effecting the liquid-phase treatment, the method which comprises immersing a wiper blade matrix fresh from the molding step into a fluorine type solvent obtained by dispersing fluorine gas in perfluorohexane, for example, may be used.
To promote the fluorination, the treatment by either of the methods described above may be carried out with irradiation of ultraviolet light or some other radiant ray. Otherwise, the treatment may be performed in combination with a treatment using plasma.
The wiper blade of this invention which is obtained as described above has the surface layer portion thereof fluorinated substantially completely.-Next, examples served to compare the wiper blade of the present invention with the conventional wiper blade in various properties will be illustrated below.
Example 1 ]
Wiper blade matrices for an automobile were molded severally of EM and EPDM as raw materials and fluorinated in a mixed gas of 90% try volume) of nitrogen and 10% of fluorine at 40C for 40 minutes to obtain wiper blades according to this invention. Separately, a wiper blade matrix was molded of natural rubber and chlorinated to obtain a conventional wiper blade.
With regard to the wiper blades of the present invention and the conventional wiper blade so prepared wiping durability test was carried out and the coefficient of friction was measured. The results are shown in Table 1.
~2330~0 The specification of the wiping durability test is as follows:
a sample wiper blade lOOrDrn in length was reciprocated on a flat sheet glass at 45 strokes per minute under the conditions Or 155 g of arm pressure and 150 morn of stroke length, at one cycle of Srninutes consisting of water sprinting for 4 minutes and no water sprinkling for 1 minutes. The friction coefficient (~) was measured on the sample in a dry state. In Table 1, A
represents the conventional wiper blade involving chlorination of natural rubber, B the wiper blade involving fluorination of END and C the wiper blade involving fluorination of EM, respectively.
[Table 1 Friction coefficient l Number of blade A B
reciprocations 0 0.750.44 0.45 10,000 1.540.44 owe 50,000 1.960.45 owe 100,000 owe 0.50 300,000 2.010.65 0.72 500,000 2.040.91 1.01 It us noted from Table 1 that the wiper blades according to this invention shows extremely small friction coefficients us at all the indicated steps between 0 and 500,000 times of respire-cation strokes of the durability test as compared with the conventional wiper blade. The result indicates that they possess durability several tens of times higher than the durability of the conventional wiper blade.
~233(~
[Example 2]
Similarly to Example 1, wiper blades according to the present invention were prepared by using EM and EPDM as raw materials and performing fluorination and a conventional wiper blade by using natural rubber as a raw material and performing chlorination. These wiper blades were tested with a cut body for durability rated by amount of abrasion (mm3) per unit length (1 cm). The results are summarized in Table 2.
In the cut-body wiping durability test, a sample wiper blade 450 mm in length was reciprocated at 45 strokes per minute under the condition of 700 g of arm pressure, at one cycle of 5 minutes consisting of a spray with water for 4 minutes, no spray with water for 0.5 minutes and no driving for 0.5 minutes.
In Table 2, A through C have the same meanings as described above.
[Table 2 Amount of abrasion (mm3/cm)]
Length of' durability A C
_ 50 h 0.110 oily 0.053 t 100 h 0.217 0.082 0.090 150 h 0.302 0.107 0.115 t 200 h 0.406 0.164 0.180 It is noted from Table 2 that the amounts of abrasion of the wiper blades according to this invention after 200 hours of test were substantially equal to the amount of abrasion ox the conventional wiper blade after 50 hours of test. The results show that the wiper blades of this invention involving fluorination are superior to the conventional ~L2330~
wiper blade involving chlorination m terms of abrasion resistance.
[Example 3]
Similarly to Example 1, wiper blades according to this invention were prepared by molding wiser blade matrices severally of EM and EPDM and fluoridating these wiper blade matrices and a conventional wiper blade was prepared by molding a wiper blade matrix of natural rubber and chlorinating the wiper blade. These wiper blades were tested for weather-ability with Sun shining Weather-meter~and then tested for wiping durability. The results are shown in Table 3.
In the weather test with the Sun shining Wé~ther-~eter, a sample wiper blade was left standing at a black panel-temper-azure of 63 1 3C for 48 hours, with irradiation for 120 minutes and a spray for 18 minutes in each cycle, by following the method of JIG B7753 (Sunshine carbon-arc type weather test) with necessary modifications. In Table 3, A through C have the same meanings as indicated above.
table 3 Friction coefficient after weather test l Number of blade _ I _ C
reciprocations A I B
0 1.10 0.45 0.45 10,000 1.75 0.45 owe 50,000 2.05 0.45 owe 100,000 2.07 owe 0.50 300,000 2.07 owe 0.69 ~00,000 owe 0.90 1.01 It is noted from Table 3 that even after the weather test, the wiper blades obtained by using saturated organic high
The wiser blade used for vehicles is intended to wipe water drops, snow, etc. away the windshield surface by sliding on the windshield surface.
It is, therefore, required to give even wiping to the windshield by being pressed uniformly against the windshield and to operate smoothly an-d avoid emitting objectionable noise by offering low frictional resistance.
t has been customary, therefore, to form the wiper blade with natural rubber, synthetic rubber such as chloroprene rubber, resin such as polye~len thereby to confer us thermoplastic elastomers such as urethane type e].astomer, ox synthetic /
the wiper blade the elasticity high enough for the wiper blade j to slide evenly on the shield surface and, at the same time, ¦ subject the surface of the wiper blade to a treatment of ¦ chlorination or bromination thereby to cause bonding of chlorine atoms or bromide atoms to the carbon atoms in the main chain of the rubber or elastomers and induce degradation of frictional resistance.
The treatment of chlorination or bromination, however, is incapable of amply lowering the frictional resistance.
Particularly, the Cal bond or Cur bond is chemically instable , - 1~33(~
and is readily unbounded by heat, water, ultraviolet light, ozone, oxygen, or chemicals to remove Of or Bra The conventional wiper blade, therefore, is deficient in resistance to the conditions of nature and looses the performance as a wiper blade within a short time.
When the treatment of chlorination, for example, is carried out to a high degree for the purpose of lowering the friction resistance and enhancing the durability, adversely, cracks are produced easily on the surface thereof, the permanent set resistance is reduced and the striped trace remains on the surface thereof after wiping, whereby the wiping properties are lowered.
It is known that the ethylene-propylene copolymer (hereinafter refried to as EM) and the ethylene-propylene-dine copolymer (hereinafter referred to as EPDM) obtained by adding a small amount of a dine compound to EM for enhancing its valcanizability have a remarkable quality in resistance to aging, ozone, chemicals, water and permanent set. The above-mentioned problems, therefore, can be solved, if EM or EPDM may be used as a material for the wiper blade.
Since EM and EPDM are saturated organic high molecular compounds possessing no double bond in the main chains thereof, however, they form neither Cal bond nor Cur bond even if they are subjected to the treatment of chlorination or bromination.
~:3;~0~C~
The present invention is accomplished by studying the fact that fluorine is extremely active and substitutes for the hydrogen atom of the C-F bond to form a C-F bond.
SUMMARY OF THE INVENTION
According to this invention, it is provided that a wiper blade produced by molding a wiper blade matrix of ethylene-propylene copolymer (EM) or ethylene-propylene-diene copolymer (EPDM) and fluoridating the wiper blade matrix thereby causing fluorine atoms to be bonded to the carbon atoms of the aforementioned copolymer in the surface layer of the wiper blade matrix.
- An object of this invention, therefore, is to provide a wiper blade possessing a low friction coefficient and is excellent in resistance to aging, ozone, chemicals, abrasion, and permanent set.
The other and further objects and characteristic features of this invention will become apparent to those skilled in the art from the further disclosure of this invention to be made in the following detailed description of a preferred embodiment and described in the appended claims and various advantages not referred to herein will become obvious to those of ordinary skill in the art through employment of the invention in practice.
Now a preferred embodiment of the invention will be described below in conjunction with concrete experiments.
~;~330~C~
retailed Description of Preferred Embodiments:
A method for the manufacture of a wiper blade according to the present invention will be described. First, a lopper blade matrix Or a prescribed shape is molded of EM or EPDM
as the material. Then the wiper blade matrix so produced is fluorinated to have fluorine atoms bonded to the carbon atoms forming the main chain of the saturated organic high molecular compound (EM or EPDM) in the surface layer of the wiper blade matrix.
In the EM so used, the ethylene content falls in the range of 75 to 50% by weight and the propylene content in the range of 25 to 50% by weight. In the EPDM, the ethylene and propylene contents are in the ranges mentioned above and the dine content is in a minute proportion. Here, the fluorination may be effected in the form of a gaseous-phase reaction or a liquid-phase reaction. The gaseous-phase reaction can be carried our by a method of directly exposing the wiper blade matrix fresh from the molding step to an atmosphere solely Or fluorine gas, an atmosphere formed of fluorine gas mixed with a small amount Or oxygen gas, or an atmosphere prepared by diluting fluorine gas or a mixture of fluorine gas and a small amount of oxygen was with an inert gas such as helium, Argo nor nitrogen. The reaction of this method is ~errormed at a fluorine concentration of 5 to 100%, preferably about 10%, at a temperature in the range of 0 to 100C. An excessively high fluorine concentration is undesirable because cracks occur easily on the surface of the ,., 33(~
wiper blade. As means of effecting the liquid-phase treatment, the method which comprises immersing a wiper blade matrix fresh from the molding step into a fluorine type solvent obtained by dispersing fluorine gas in perfluorohexane, for example, may be used.
To promote the fluorination, the treatment by either of the methods described above may be carried out with irradiation of ultraviolet light or some other radiant ray. Otherwise, the treatment may be performed in combination with a treatment using plasma.
The wiper blade of this invention which is obtained as described above has the surface layer portion thereof fluorinated substantially completely.-Next, examples served to compare the wiper blade of the present invention with the conventional wiper blade in various properties will be illustrated below.
Example 1 ]
Wiper blade matrices for an automobile were molded severally of EM and EPDM as raw materials and fluorinated in a mixed gas of 90% try volume) of nitrogen and 10% of fluorine at 40C for 40 minutes to obtain wiper blades according to this invention. Separately, a wiper blade matrix was molded of natural rubber and chlorinated to obtain a conventional wiper blade.
With regard to the wiper blades of the present invention and the conventional wiper blade so prepared wiping durability test was carried out and the coefficient of friction was measured. The results are shown in Table 1.
~2330~0 The specification of the wiping durability test is as follows:
a sample wiper blade lOOrDrn in length was reciprocated on a flat sheet glass at 45 strokes per minute under the conditions Or 155 g of arm pressure and 150 morn of stroke length, at one cycle of Srninutes consisting of water sprinting for 4 minutes and no water sprinkling for 1 minutes. The friction coefficient (~) was measured on the sample in a dry state. In Table 1, A
represents the conventional wiper blade involving chlorination of natural rubber, B the wiper blade involving fluorination of END and C the wiper blade involving fluorination of EM, respectively.
[Table 1 Friction coefficient l Number of blade A B
reciprocations 0 0.750.44 0.45 10,000 1.540.44 owe 50,000 1.960.45 owe 100,000 owe 0.50 300,000 2.010.65 0.72 500,000 2.040.91 1.01 It us noted from Table 1 that the wiper blades according to this invention shows extremely small friction coefficients us at all the indicated steps between 0 and 500,000 times of respire-cation strokes of the durability test as compared with the conventional wiper blade. The result indicates that they possess durability several tens of times higher than the durability of the conventional wiper blade.
~233(~
[Example 2]
Similarly to Example 1, wiper blades according to the present invention were prepared by using EM and EPDM as raw materials and performing fluorination and a conventional wiper blade by using natural rubber as a raw material and performing chlorination. These wiper blades were tested with a cut body for durability rated by amount of abrasion (mm3) per unit length (1 cm). The results are summarized in Table 2.
In the cut-body wiping durability test, a sample wiper blade 450 mm in length was reciprocated at 45 strokes per minute under the condition of 700 g of arm pressure, at one cycle of 5 minutes consisting of a spray with water for 4 minutes, no spray with water for 0.5 minutes and no driving for 0.5 minutes.
In Table 2, A through C have the same meanings as described above.
[Table 2 Amount of abrasion (mm3/cm)]
Length of' durability A C
_ 50 h 0.110 oily 0.053 t 100 h 0.217 0.082 0.090 150 h 0.302 0.107 0.115 t 200 h 0.406 0.164 0.180 It is noted from Table 2 that the amounts of abrasion of the wiper blades according to this invention after 200 hours of test were substantially equal to the amount of abrasion ox the conventional wiper blade after 50 hours of test. The results show that the wiper blades of this invention involving fluorination are superior to the conventional ~L2330~
wiper blade involving chlorination m terms of abrasion resistance.
[Example 3]
Similarly to Example 1, wiper blades according to this invention were prepared by molding wiser blade matrices severally of EM and EPDM and fluoridating these wiper blade matrices and a conventional wiper blade was prepared by molding a wiper blade matrix of natural rubber and chlorinating the wiper blade. These wiper blades were tested for weather-ability with Sun shining Weather-meter~and then tested for wiping durability. The results are shown in Table 3.
In the weather test with the Sun shining Wé~ther-~eter, a sample wiper blade was left standing at a black panel-temper-azure of 63 1 3C for 48 hours, with irradiation for 120 minutes and a spray for 18 minutes in each cycle, by following the method of JIG B7753 (Sunshine carbon-arc type weather test) with necessary modifications. In Table 3, A through C have the same meanings as indicated above.
table 3 Friction coefficient after weather test l Number of blade _ I _ C
reciprocations A I B
0 1.10 0.45 0.45 10,000 1.75 0.45 owe 50,000 2.05 0.45 owe 100,000 2.07 owe 0.50 300,000 2.07 owe 0.69 ~00,000 owe 0.90 1.01 It is noted from Table 3 that even after the weather test, the wiper blades obtained by using saturated organic high
3~30~0 molecular compounds and performing fluorination show substantially the same friction coefficients as before the test. The results indicate that the wiper blades of this invention are superior to the conventional wiper blade in weather ability.
example 4]
Similarly to Example l, wiper blades according to the present invention were prepared by using EM and EPDM
severally as raw materials and performing fluorination and a conventional wiper blade was prepared by using natural rubber and performing chlorination. These wiper blades were left standing as stretched to 120% of the original length in an atmosphere kept at 40C with an ozone concentration of 50 ppm.
After the standing, they were visually examined for occurrence of cracks. The results are shown in Table 4. In Table 4, A through C have the same meanings as indicated above.
[Table 4 Occurrence of cracks]
wiper blade _ __ _ _ _ . . ___ Occurrence Large crack No crack No crack of cracks occurred even occurred even occurred even crier 96 hours asker 2000 hours after 2000 hours _ __ of' standing of standing of standing It is noted from Table 4 that the wiper blades obtained by using Err and EPDM and performing fluorination are superior to the conventional wiper blade in terms of resistance to ozone.
[Example 5]
Similarly to Example l, wiper blades according to the present invention were prepared by using EM and EPDM separately -` ~2330~) as raw materials and performing fluorination, and a conventional wiper blade was prepped by using natural rubber and performing chlorination. With respect to these wiper blades, a permanent set test was conducted by compressing the wiper blades with a load of 15.5 Kg/cm at 100c for 72 hours. The results are shown in Table 5. In Table 5, A through C have the same meanings as indicated above.
[Table 5 an angle of a permanent set]
wiper blade A B C
and, angle , of deformation 52 22 11 Jo -It it noted from Table 5 that the wiper blades of this invention are extremely excellent in a permanent set resistance as compared with the conventional wiper blade.
- As described above, the present invention produces a wiper blade by molding a wiper blade matrix of EM or EPDM
and flurorinatin~ the wiper blade matrix thereby causing fluorine atoms to be bonded through substitution to the carbon atoms forming the main chain of EM or END The wiper blade so produced, therefore, shows a notably small friction coefficient and is excellent in resistance to aging, abrasion, ozone, and permanent set, and in weatherabilit~ as compared with the conventional wiper blade.
Plainly many modifications and variations of the present ~L2~3~
invention are possible in light of the preceding teachings.
It is, therefore, to be understood that within the scope of the appended claims, the present invention may be practiced otherwise than as specifically described herein.
example 4]
Similarly to Example l, wiper blades according to the present invention were prepared by using EM and EPDM
severally as raw materials and performing fluorination and a conventional wiper blade was prepared by using natural rubber and performing chlorination. These wiper blades were left standing as stretched to 120% of the original length in an atmosphere kept at 40C with an ozone concentration of 50 ppm.
After the standing, they were visually examined for occurrence of cracks. The results are shown in Table 4. In Table 4, A through C have the same meanings as indicated above.
[Table 4 Occurrence of cracks]
wiper blade _ __ _ _ _ . . ___ Occurrence Large crack No crack No crack of cracks occurred even occurred even occurred even crier 96 hours asker 2000 hours after 2000 hours _ __ of' standing of standing of standing It is noted from Table 4 that the wiper blades obtained by using Err and EPDM and performing fluorination are superior to the conventional wiper blade in terms of resistance to ozone.
[Example 5]
Similarly to Example l, wiper blades according to the present invention were prepared by using EM and EPDM separately -` ~2330~) as raw materials and performing fluorination, and a conventional wiper blade was prepped by using natural rubber and performing chlorination. With respect to these wiper blades, a permanent set test was conducted by compressing the wiper blades with a load of 15.5 Kg/cm at 100c for 72 hours. The results are shown in Table 5. In Table 5, A through C have the same meanings as indicated above.
[Table 5 an angle of a permanent set]
wiper blade A B C
and, angle , of deformation 52 22 11 Jo -It it noted from Table 5 that the wiper blades of this invention are extremely excellent in a permanent set resistance as compared with the conventional wiper blade.
- As described above, the present invention produces a wiper blade by molding a wiper blade matrix of EM or EPDM
and flurorinatin~ the wiper blade matrix thereby causing fluorine atoms to be bonded through substitution to the carbon atoms forming the main chain of EM or END The wiper blade so produced, therefore, shows a notably small friction coefficient and is excellent in resistance to aging, abrasion, ozone, and permanent set, and in weatherabilit~ as compared with the conventional wiper blade.
Plainly many modifications and variations of the present ~L2~3~
invention are possible in light of the preceding teachings.
It is, therefore, to be understood that within the scope of the appended claims, the present invention may be practiced otherwise than as specifically described herein.
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A wiper blade, produced by molding a wiper blade matrix of ethylene-propylene copolymer (EPM) or ethylene-propylene-diene copolymer (EPDM) and fluorinating said wiper blade matrix thereby causing fluorine atoms to be bonded to the carbon atoms of said copolymer in the surface layer of said wiper blade matrix, said wiper blade having improved performance characteristics and improved stability to resist the natural conditions.
2. A wiper blade according to Claim 1, wherein said fluorination is carried out in a fluorine gas-containing atmosphere.
3. A wiper blade according to Claim 2, wherein said fluorine gas-containing atmosphere is an atmosphere formed solely of fluorine gas, an atmosphere of fluorine gas mixed with a small amount of oxygen gas, or an atmosphere obtained by diluting either of the two atmospheres mentioned above with an inert gas.
4. A wiper blade according to Claim 1, wherein said fluorination is carried out at a fluorine concentration in the range of 5 to 100%.
5. A wiper blade according to Claim 4, wherein said fluorine concentration is about 10%.
6. A wiper blade according to Claim 1, wherein said fluorination is carried out at a temperature in the range of 0° to 100°C.
7. A wiper blade according to Claim 6, wherein said temperature is about 40°C.
8. A wiper blade according to Claim 1, wherein said fluorination is carried out in a fluorine type solvent prepared by dispersing fluorine gas in a solvent.
9. A wiper blade according to Claim 8, wherein said solvent is perfluorohexane.
10. A wiper blade according to Claim 1, wherein said ethylene-propylene copolymer has an ethylene content in the range of 75 to 50% by weight, and a propylene content in the range of 25 to 50% by weight.
11. A wiper blade as claimed in Claim 1, 2 or 10, wherein the wiper blade is fluorinated essentially immediately after the wiper blade is molded.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59040190A JPS60184531A (en) | 1984-03-02 | 1984-03-02 | Wiper blade |
| JP59-40190 | 1984-03-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1233010A true CA1233010A (en) | 1988-02-23 |
Family
ID=12573852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000475197A Expired CA1233010A (en) | 1984-03-02 | 1985-02-26 | Wiper blade |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS60184531A (en) |
| CA (1) | CA1233010A (en) |
| DE (1) | DE3506766A1 (en) |
| FR (1) | FR2560602B1 (en) |
| GB (1) | GB2154864B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6393650A (en) * | 1986-10-09 | 1988-04-23 | Nippon Waipabureede Kk | Rubber for wiper blade |
| AT389315B (en) * | 1987-06-09 | 1989-11-27 | Air Prod & Chem | Processes for the surface modification of polymers and their use |
| BE1002383A3 (en) * | 1988-08-25 | 1991-01-22 | Helvoet Pharma | METHOD FOR TREATING VULLCANIZED PHARMACEUTICAL RUBBER PRODUCTS AND TREATED VULLCANIZED PHARMACEUTICAL RUBBER PRODUCTS |
| DE3904152A1 (en) * | 1989-02-11 | 1990-08-16 | Swf Auto Electric Gmbh | Rubber-elastic component and method for manufacturing it |
| GB2363318A (en) * | 2000-06-15 | 2001-12-19 | Federal Mogul Technology Ltd | Windscreen wiper blade with reduced friction |
| DE102006013710A1 (en) * | 2006-03-24 | 2007-09-27 | Air Liquide Deutschland Gmbh | Wiper blade for windscreen wiper has underside of wiping lip formed opposite connecting part and at least wiping lip has at least partly fluorized surface |
| DE102008040209A1 (en) * | 2008-07-07 | 2010-01-14 | Robert Bosch Gmbh | Method for modifying the surface of a wiper blade for wipers under the action of ozone |
| JP5479339B2 (en) | 2008-07-22 | 2014-04-23 | 株式会社ミツバ | Blade rubber manufacturing method and wiper blade |
| DE102009001365A1 (en) * | 2009-03-06 | 2010-09-09 | Robert Bosch Gmbh | Wiper blade for motor vehicle, has wiping cloth attachment connected with wiping cloth tip, and powder-coating region partially connected with another region and including hydrogen atom and/or ethylene-unit with fluoro- and/or choro-polymer |
| DE102013203194A1 (en) * | 2013-02-27 | 2014-08-28 | Robert Bosch Gmbh | Dispersion-coated squeegee |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1160611B (en) * | 1961-12-06 | 1964-01-02 | Kalle Ag | Process for increasing the affinity for printing inks in films made of ethylene-propylene low-pressure copolymers |
| US3997935A (en) * | 1975-05-29 | 1976-12-21 | Acushnet Company | Windshield wiper blade treatment |
| US4296151A (en) * | 1978-12-12 | 1981-10-20 | Phillips Petroleum Company | Fluorinated polymeric surfaces |
| JPS5757641A (en) * | 1980-09-25 | 1982-04-06 | Nok Corp | Surface treatment of formed rubber material |
| US4508781A (en) * | 1982-06-07 | 1985-04-02 | The United States Of America As Represented By The Secretary Of Agriculture | Fluorination by inorganic fluorides in glow discharge |
-
1984
- 1984-03-02 JP JP59040190A patent/JPS60184531A/en active Pending
-
1985
- 1985-02-26 DE DE19853506766 patent/DE3506766A1/en active Granted
- 1985-02-26 CA CA000475197A patent/CA1233010A/en not_active Expired
- 1985-02-28 GB GB08505132A patent/GB2154864B/en not_active Expired
- 1985-03-01 FR FR8503041A patent/FR2560602B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2560602B1 (en) | 1988-05-20 |
| DE3506766A1 (en) | 1985-09-12 |
| GB2154864B (en) | 1987-07-15 |
| GB8505132D0 (en) | 1985-04-03 |
| GB2154864A (en) | 1985-09-18 |
| JPS60184531A (en) | 1985-09-20 |
| DE3506766C2 (en) | 1988-09-15 |
| FR2560602A1 (en) | 1985-09-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |