wiper device

Abstract

To provide a wiper device capable of exhibiting greater wiping property than before.SOLUTION: A wiper device for a windshield comprises a wiper arm, and a wiper blade fitted to the wiper arm. The wiper blade comprises a blade rubber and a blade stay for supporting the blade rubber. The blade rubber has; a base part being a fitting part to the blade stay of the blade rubber; a lip part; and a neck part for oscillatably coupling the lip part to the base part. At least a part of a tip of the lip part forms a contact part with the windshield, the wiper arm is brought into contact with a glass flat plate and is moved. In a state of stopping the wiper arm, a width of the contact part of the blade rubber and the glass flat plate is 1.0 μm or more and 20.0 μm or less, and an angle θ formed by a specific position of the lip part and the glass flat plate is 20° or more and 80° or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a wiper device that wipes the surface of a windshield of a vehicle or the like. [Background technology]

[0002] 2. Description of the Related Art Automobiles, trains, ships, aircraft, and the like are equipped with cleaning members to wipe away water droplets and dirt adhering to glass surfaces such as windshields and rear windows to ensure visibility for the driver. Among these cleaning members, wiper blades, which have a wiper blade rubber attached to the portion that comes into contact with the glass surface, are well known. This wiper blade rubber moves in close contact with the glass surface, thereby wiping away water droplets and other debris adhering to the glass surface. From the perspective of ensuring good visibility for the driver, wiper blades with excellent wiping properties are desired, capable of thoroughly wiping away water droplets and dirt from the glass surface.

[0003] Patent Document 1 discloses a wiper device that has a wiper blade composed of a base, a neck, and a lip, where the lip has a certain gap from the surface of the base and a certain width in the wiping direction, and has a lip tip that slides on the surface of the windshield panel, and is provided with a means for setting the angle θ between the windshield panel and the lip to 30 degrees≦θ≦55 degrees during wiping movement. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 07-246916 Summary of the Invention [Problem to be solved by the invention]

[0005] As disclosed in the above Patent Document 1, even when the contact angle between the lip of the wiper blade and the surface of the member to be cleaned is controlled to 30 to 50 degrees, the thickness of the water film after wiping may not be stable, or uneven wiping may occur. One aspect of the present disclosure is to provide a wiper device that can exhibit even higher wiping performance than conventional wipers. [Means for solving the problem]

[0006] One aspect of the present disclosure is a windshield wiper device, comprising: The wiper device includes a wiper arm and a wiper blade attached to the wiper arm, The wiper blade has a blade rubber and a blade stay that supports the blade rubber, The blade rubber has a base portion that is an attachment portion of the blade rubber to the blade stay, a lip portion, and a neck portion that pivotally connects the lip portion to the base portion, At least a part of the tip of the lip portion forms a contact portion with the windshield, With the arm pressing force of the wiper arm set to 18 N / m, the lip portion of the wiper blade was brought into contact with the first surface of the flat glass plate, and the wiper blade was moved at a speed of 1.65 m / s in direction A from a first point P1 to a second point P2 on the first surface of the flat glass plate, for 50 cm in a direction perpendicular to the longitudinal direction of the blade rubber, and then stopped. The contact portion between the lip portion and the glass plate is observed from the second surface side of the glass plate opposite to the first surface, and the width of the contact portion in the direction perpendicular to the longitudinal direction of the blade rubber is measured. When the width is A, the corresponding contact width A is 1.0 μm or more and 20.0 μm or less, and When the blade rubber was observed from the side in the longitudinal direction of the blade rubber using an optical microscope at a magnification of 200 times, The point of contact between the lip portion and the glass flat plate that is farthest from P1 is designated as point Q1, a perpendicular line is drawn to the first surface of the glass flat plate at a position 200 μm from point Q1 in direction A, and the first intersection of the perpendicular line with the lip portion is designated as point Q2. This is intended for a wiper device in which the angle θ formed by the line connecting point Q1 and point Q2 and the first surface of the glass flat plate is 20° or more and 80° or less. [Effects of the Invention]

[0007] According to one aspect of the present disclosure, it is possible to provide a wiper device that can exhibit even higher wiping performance than conventional wipers. [Brief explanation of the drawings]

[0008] [Figure 1] Conventional example of contact between wiper blade and object to be cleaned [Figure 2] Schematic diagram of a wiper device [Figure 3] Schematic diagram of a wiper blade cross section [Figure 4] Figures 4(a) and (b) are explanatory diagrams showing the state of the blade rubber during the cleaning process. [Figure 5] Diagram explaining the contact and movement test of the wiper device [Figure 6] Diagram explaining the angle of the blade rubber tip [Figure 7] Enlarged view of the first edge [Figure 8] Enlarged view of the first line segment [Figure 9] Enlarged view of the observation area 12 and its vicinity with P0 as the center of gravity [Figure 10] Schematic diagram of the testing machine [Figure 11] Illustrative diagram of wiping performance test [Figure 12] Schematic diagram of the wiper blade and the vicinity of the contact point with the member to be cleaned [Figure 13] 10 is an explanatory diagram of a contact width A and a contact width B in the present disclosure. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0009] In the present disclosure, unless otherwise specified, the expressions "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way.

[0010] The present inventors conducted a more detailed observation of the state of wiping of the windshield surface by the wiper blade according to Patent Document 1. In particular, they conducted a microscopic observation of the contact area between the lip of the wiper blade and the windshield. As a result, the very tip of the lip of the wiper blade was curved due to friction with the surface of the glass 101 (hereinafter also referred to as the "glass surface"). As shown in Figure 1, when the wiper blade was moved in the traveling direction P, the contact angle θp of the lip tip with the glass was smaller than the angle specified in Patent Document 1. In addition, the lip tip was stretched due to friction with the glass surface, and the width of the contact area between the lip tip and the glass surface (nip width) also increased.

[0011] Therefore, it is believed that the pressure (see arrow A) pressing the wiper blade against the glass surface is not as high as intended. In addition, because the contact angle of the tip of the lip is small, as shown in Figure 1, water accumulated between the tip and the glass surface applies force to the tip in direction B, which lifts the wiper blade from the glass surface. As a result, it is believed that the contact pressure of the wiper blade is weaker. These phenomena are thought to be the cause of uneven wiping with this wiper blade. can be obtained. From these findings, we have come to the realization that in order to further improve wiping performance, it is necessary to control the contact state between the very tip of the blade and the surface of the material to be cleaned, something that has not been discussed until now.

[0012] <Configuration of vehicle wiper blades> A wiper device according to one aspect of the present disclosure can be used in vehicles such as automobiles, transportation equipment such as airplanes and ships, and industrial machinery and equipment such as construction machinery. These transportation equipment and industrial machinery and equipment are collectively referred to as vehicles. The present disclosure relates to a wiper device for a vehicle windshield. The windshield is not limited to a front window, but also includes side windows and rear windows.

[0013] 2, the wiper device includes a wiper arm 300 and a wiper blade 200 attached to the wiper arm 300. The wiper blade 200 includes a blade rubber 100 and a blade stay 210 that supports the blade rubber 100.

[0014] 3, the blade rubber 100 includes a base 1, which is an attachment portion of the blade rubber 100 to the blade stay 210, and a lip portion 3 that is swingably connected to the base 1 via a neck portion 2. The wiper blade is formed with a substantially uniform cross-sectional shape in the longitudinal direction. In a cross section perpendicular to the longitudinal direction of the wiper blade, the lip portion 3 has a shoulder portion 31 at the end of the lip portion 3 on the neck portion side that extends laterally beyond the neck portion. Furthermore, to stabilize the contact posture of the wiper blade, the lip portion 3 may have a tapered portion 4 whose width gradually decreases from the side closer to the base portion 1 toward the direction away from the base portion 1. The degree of decrease in the width of the tapered portion 4 may also vary in stages. For example, the lip portion 3 may have a lip tip portion where the degree of decrease in the tapered portion's width becomes smaller on the side closer to the tip, away from the base portion 1 of the lip portion. The lip tip portion may also have a portion whose width is uniform or approximately uniform from the side closer to the base portion 1 toward the tip. The wiper blade shown in FIG. 3 has a plate-shaped portion connected to the tapered portion 4 on the tip side of the lip portion 3.

[0015] The wiper device cleans the surface of the member to be cleaned, typically a glass surface, such as a windshield, by bringing at least a portion of the tip of the lip portion 3 into contact with the surface. As a result, at least a portion of the tip of the lip portion 3 forms a contact portion with the windshield. For example, in a cross section perpendicular to the longitudinal direction of the wiper blade, the neck portion 2 may be narrower than the base portion 1 and the lip portion 3. As a result, as shown in Figures 4(a) and 4(b), the lip portion 3 is inclined in the wiping direction, and one surface of the lip portion 3 that is connected to the tapered portion, i.e., at least a part of the tip of the side surface 5 or 6, comes into contact with the surface of the member to be cleaned.

[0016] 4(a) and 4(b) are explanatory diagrams showing the state of the wiper blade during cleaning. In Figure 4(a), the lip portion 3 of the wiper blade has the tapered portion 4. The lip portion 3 also has a first side surface 5 continuing from the tapered portion 4, a second side surface 6 opposite to the first side surface 5, and a tip surface 7 which, together with the first side surface 5 and the second side surface 6, constitute a first edge 8 and a second edge 9 on the side farthest from the base portion 1 of the lip portion 3 (see Figures 3 and 7 for the first edge, second edge, and tip surface). In FIG. 4(b), the lip portion 3 of the wiper blade has a second side surface 6 continuing from the tapered portion 4 that abuts against the member to be cleaned 10, a first side surface 5 opposite to the second side surface 6, and the first side surface 5. The lip portion 3 has a first side surface 5 and a second side surface 6, and a tip surface 7 that constitutes a first edge 8 and a second edge 9 on the side (tip side) furthest from the base 1 of the lip portion 3 (see Figures 3 and 7 for the first edge, second edge, and tip surface). The arrow R indicates the cleaning direction of the wiper blade. When the cleaning direction is reversed from the direction of arrow R in Fig. 4(a) to the direction of arrow R in Fig. 4(b), the side of the lip portion 3 that comes into contact with the object to be cleaned switches from the tip on the first side surface 5 side to the tip on the second side surface 6 side.

[0017] In this disclosure, the contact state between the member to be cleaned and the wiper device is observed under the following conditions. An overview is shown in Figure 5. First, the wiper arm pressing force is set to 18 N / m, and the lip portion of the wiper blade is brought into contact with the first surface of a flat glass plate. Then, the wiper blade is moved 50 cm at a speed of 1.65 m / s in direction A from a first point P1 to a second point P2 on the first surface of the flat glass plate, in a direction perpendicular to the longitudinal direction of the blade rubber, and then stopped and observed. The arm pressing force of 18 N / m is the highest pressing force per blade length under the test conditions specified in JIS D 5710:1998. Therefore, the lip portion is pressed particularly hard during wiping, which tends to reduce the contact angle and increase the contact width. Furthermore, the speed of 1.65 m / s corresponds to the middle speed measured at the center of the wiper blade (M zone in JIS D 5710:1998) on actual automobiles sold in Japan.

[0018] When the contact area between the lip portion and the glass plate is observed from the second surface side opposite the first surface of the glass plate, and the width of the contact area in a direction perpendicular to the longitudinal direction of the blade rubber is defined as contact width A, contact width A is 1.0 μm or more and 20.0 μm or less (see Figure 13). By setting the contact width A within the above range, the wiper blade according to the present disclosure can have excellent wiping performance for the surface to be cleaned. That is, by setting the contact width A to 1.0 μm or more, the contact of the tip of the lip portion 3 with the surface to be cleaned can be more stabilized. Furthermore, by setting the contact width A to 20.0 μm or less, the contact pressure per unit area of ​​the contact portion can be maintained high, preventing uneven wiping, provided that the angle θ formed between a specific position of the lip portion and the surface to be cleaned, which will be described later, is within a specific range. On the other hand, if the contact width A exceeds 20.0 μm, the contact pressure per unit area of ​​the contact portion decreases, making the blade more susceptible to the force of water lifting the blade. As a result, water is more likely to be scraped away downstream in the wiping direction. The contact width A is preferably 1.1 μm or more and 15.0 μm or less, more preferably 1.2 μm or more and 10.0 μm or less, even more preferably 1.2 μm or more and 6.5 μm or less, and even more preferably 1.2 μm or more and 5.0 μm or less.

[0019] The standard deviation of the contact width A is preferably 6.00 μm or less, more preferably 4.00 μm or less, even more preferably 2.00 μm or less, still more preferably 1.00 μm or less, and particularly preferably 0.80 μm or less. The smaller the standard deviation of the contact width A, the better, and although there is no particular lower limit, it is preferably 0.00 μm or more, or 0.10 μm or more.

[0020] The contact width B, defined as follows, is preferably 1.0 μm to 20.0 μm, more preferably 1.0 μm to 15.0 μm, and even more preferably 1.0 μm to 10.0 μm. That is, the wiper arm pressing force is set to 10 N / m, and the lip portion of the wiper blade is brought into contact with the first surface of the flat glass plate. Then, the wiper blade is moved at a speed of 1.65 m / s in a direction A from a first point P1 to a second point P2 on the first surface of the flat glass plate, for 50 cm in a direction perpendicular to the longitudinal direction of the blade rubber, and then stopped. In the stopped state, the contact portion between the lip portion and the flat glass plate is brought into contact with the first surface of the glass plate. When observed from the second surface side opposite to the first surface side, the width of the contact portion in the direction perpendicular to the longitudinal direction of the blade rubber is defined as the contact width B.

[0021] From the contact width A and the contact width B, the load dependency of the contact width can be calculated by the following formula (A). Load dependency of contact width (μm / (N / m)) =(Contact width A(μm)-Contact width B(μm)) / (Load 18(N / m)-Load 10(N / m))...(A)

[0022] The load dependency of the contact width calculated by the above formula (A) is preferably smaller, and there is no particular lower limit, but it is preferably 0.01 μm to 0.60 μm, more preferably 0.01 μm to 0.50 μm, even more preferably 0.02 μm to 0.30 μm, and even more preferably 0.02 μm to 0.10 μm. The state of contact between the wiper blade and the surface to be cleaned may vary depending on the shape of the surface to be cleaned and the state of the force transmitted from the wiper arm to the tip lip of the blade rubber. By keeping the load dependency of the contact width within the above range, it is possible to achieve stable wiping performance along the length. The load dependency of the contact width is due to deformation of the micro region in response to the load, and can be controlled by controlling the elastic modulus of the micro region as described below.

[0023] The load dependency of the contact width A and the contact width is dominated by the influence of deformation in the microscopic region near the contact point with the object to be cleaned. By suppressing deformation of the lip tip against the pressing force transmitted from the wiper arm 300 to the base 1 and wiping with a narrow contact width, high wiping performance is achieved. One effective means for keeping the contact width A and the load dependency of the contact width within the above range is, for example, to increase the elastic modulus of the blade rubber, particularly in the micro region of the lip portion 3. Increasing the elastic modulus of the blade rubber in the micro region can suppress deformation of the lip portion 3 tip due to the contact force. It can also suppress stretching of the lip portion tip due to friction with the surface to be cleaned. As a result, it is possible to suppress expansion of the contact width of the lip portion with the surface to be cleaned during the wiping process. On the other hand, if the micro elastic modulus of the blade rubber is low, the contact width may suddenly expand due to deformation caused by the pressing force and expansion of the lip portion tip due to friction with the surface to be cleaned during wiping.

[0024] The elastic modulus of the micro region can be measured using a scanning probe microscope (hereinafter referred to as SPM) (hereinafter simply referred to as "elastic modulus"). In order to control the contact width A within an appropriate range, it is preferable that the elastic modulus of the micro region be in the range of 15.0 to 470.0 MPa. The elastic modulus of the micro region measured using SPM will be described in detail later. Examples of ways to increase the elastic modulus include increasing the crosslink density and adding a reinforcing additive. In particular, when a urethane resin is used as the constituent material of the blade rubber, the elastic modulus of the micro region can be controlled within the above range by using a polyfunctional isocyanate or polyfunctional polyol or by selecting a catalyst to take advantage of the properties of a block copolymer consisting of hard segments and soft segments, as described below, and designing the crosslinked structure. As a result, the contact width can be controlled within an appropriate range, which is preferable.

[0025] It is also preferable to make the contact width uniform in the longitudinal direction of the blade rubber and to set the standard deviation of the contact width A within the above range. High uniformity of the contact width A enables wiping without leaks. If the contact width A is non-uniform, streaky leaks may occur starting from that area. The effect of uniformity is particularly noticeable when wiping dirt, such as oil film, which has strong adhesive properties to the object being cleaned. As an index that affects the standard deviation of the contact width, for example, the elastic modulus of the micro region shown above The coefficient of variation can be cited as an example. By keeping the coefficient of variation of the elastic modulus of the micro region small and increasing the uniformity of the elastic modulus of the micro region, it is possible to further reduce the variation in the contact width A in the longitudinal direction. By keeping the coefficient of variation of the elastic modulus of the micro region small, it is possible to suppress unevenness in the contact width A, which is preferable for achieving uniform wiping performance. Specifically, it is preferable to keep the coefficient of variation of the elastic modulus by SPM at 17.6% or less. This will be described in detail later. To suppress the coefficient of variation of the microscopic elastic modulus, it is preferable to use a urethane resin, since the structure can be controlled at the molecular level, or nanoscale, compared to the method of adding a reinforcing additive as described above. Furthermore, it is preferable to utilize the properties of a urethane resin and a block copolymer consisting of hard segments and soft segments, as described below, to finely disperse the hard segments and thereby increase the uniformity of the elastic modulus.

[0026] Furthermore, in the wiper blade according to the present disclosure, the angle θ formed between a specific position on the lip portion and the glass flat plate, as observed by the following method, is 20° or more and 80° or less. With the wiper arm pressing force set to 18 N / m, the lip portion of the wiper blade was brought into contact with the first surface of the glass plate. The wiper blade was then moved at a speed of 1.65 m / s in a direction A from a first point P1 to a second point P2 on the first surface of the glass plate, a distance perpendicular to the longitudinal direction of the blade rubber, for 50 cm, and then stopped. In this state, the blade rubber was observed from the longitudinal side using an optical microscope at 200x magnification. Point Q1 was designated as the point of contact (abutment) between the lip portion and the glass plate, and a perpendicular line was drawn 200 μm from point Q1 in the direction A to the first surface of the glass plate. The first intersection of the perpendicular line with the lip portion was designated point Q2. The angle between the line connecting points Q1 and Q2 and the first surface of the glass plate was designated θ.

[0027] The angle θ within the above range means that the lip contacts the surface of the workpiece at an angle even at the very tip of the lip, in the microscopic region, making it less likely to receive a force perpendicular to the workpiece caused by the wiped water or dirt, and the blade rubber is less likely to lift up, allowing the blade rubber to adequately scrape off water and other debris from the workpiece. If the angle θ is less than 20°, the wiped water is more likely to exert a vertical force on the member to be cleaned, which makes the blade rubber more likely to lift, resulting in uneven wiping and leakage.

[0028] On the other hand, when the angle θ is large, using a material that deforms significantly upon contact can cause the contact state to become unstable, resulting in uneven wiping in the longitudinal direction of the blade rubber and blade chatter. When using conventional materials, it was difficult to set the angle θ. By designing the angle θ in conjunction with the contact width, stable wiping becomes possible even when the angle is increased within the above range. However, even in this design, if the angle θ is too large, the contact state becomes unstable, resulting in uneven wiping in the longitudinal direction of the blade rubber and blade chatter.

[0029] The angle θ is preferably 40° or more and 78° or less, and more preferably 60° or more and 75° or less. For example, three factors can be considered to affect the angle θ. Each factor is shown in Figure 6(a), Figure 6(b), and Figure 6(c). The first factor that affects the angle θ is the deformation of the neck, which affects the macro tilt of the blade rubber (Figure 6(a)). The wiper blade contacts the object to be cleaned in a tilted state due to the deformation of the neck. The deformation of the neck and the contact of the shoulder with the base suppresses changes in the contact position, allowing for stable wiping. One way to control the macro tilt of the blade rubber is to adjust the length of the neck and shoulder.

[0030] Figure 6(d) shows the length of each part. In Figure 6(d), NL is the length of the blade rubber. NT is the length of the neck in a cross section perpendicular to the longitudinal direction of the blade rubber, which can correspond to the distance between the base and the lip. NT is the thickness of the neck, i.e., the length of the neck in the direction perpendicular to the longitudinal direction of the blade rubber and along the surface of the object to be cleaned (windshield) when the lip tip of the blade rubber is brought into vertical contact with the object to be cleaned (windshield). SL is the length from the tip of the shoulder to the neck in a cross section perpendicular to the longitudinal direction of the blade rubber; in other words, when the lip tip of the blade rubber is brought into vertical contact with the object to be cleaned (windshield), it is the length from the shoulder to the neck in a direction (width direction) perpendicular to the longitudinal direction of the blade rubber and along the surface of the object to be cleaned. Furthermore, LL is the length of the lip portion, i.e., the length of the lip portion in a direction perpendicular to the longitudinal direction of the blade rubber and perpendicular to the object to be cleaned (windshield) (hereinafter also referred to as the "height direction"). LM is the length of the lip tip portion. LT is the thickness of the tip surface 7 of the lip portion, i.e., the length of the lip tip portion in the width direction of the blade rubber. In the blade rubber shown in Figure 3, LT corresponds to the width of the plate-shaped portion continuing to the tapered portion 4, and LM corresponds to the length (in the height direction) of the plate-shaped portion continuing to the tapered portion 4.

[0031] Specifically, it is preferable to increase the ratio of the length of the shoulder portion to the length of the neck portion. Specifically, by shortening the length of the neck portion and lengthening the length of the shoulder portion, the macro tilt of the blade rubber can be increased. However, if the length of the neck portion is short, deformation in the macro tilt direction may not be possible, and the desired macro tilt may not be achieved. Therefore, the neck length NL is preferably 200 μm to 1500 μm, and more preferably 250 μm to 1200 μm.

[0032] Increasing the macroscopic tilt angle acts to increase the angle θ in the microscopic region. To keep the angle θ within the above range, the ratio of the shoulder length SL to the neck length NL (SL / NL) in a cross section perpendicular to the longitudinal direction of the blade rubber is preferably set to a range of 0.37 to 9.00. It is more preferably 1.00 to 6.00, even more preferably 2.00 to 5.00, and even more preferably 2.50 to 4.00.

[0033] The second factor that affects the angle θ is the deformation of the blade rubber from the neck to the tip of the lip (Figure 6(b)). In addition to the tilt caused by the deformation of the neck as explained above, the lip is deflected by the pressing force applied from the base. The deflection of the lip 3 reduces the angle θ at the tip. The elongation of the neck, which has a small longitudinal length, and the deflection (deformation) of the lip have a particularly large effect. Methods for controlling the deflection of the lip include, for example, designing the shape of the neck and lip, which are subject to large deformation, and designing a material with increased tensile strength.

[0034] Specific examples of shape-based measures include increasing the thickness of the neck and lip portions. Increasing the neck thickness NT can suppress deformation caused by the pressing force stretching the blade rubber toward the tip, making it easier to control the macro tilt angle. However, if the neck thickness NT is too thick, deformation in the macro tilt direction may be hindered, and the desired macro tilt may not be achieved. Therefore, the neck thickness NT is preferably 500 μm or less. It is more preferably 150 μm to 500 μm, even more preferably 180 μm to 400 μm, and even more preferably 200 μm to 350 μm.

[0035] Furthermore, by increasing the thickness of the lip portion and shortening its length, it is possible to suppress the flexural deformation of the lip portion. As a result, it is possible to prevent the formed angle θ and the formed angle θ', which will be described later, from becoming too small. Specifically, the thickness LT of the tip of the lip portion is, for example, preferably 200 μm to 1000 μm, more preferably 400 μm to 750 μm, and even more preferably 500 μm to 650 μm. By setting the thickness LT within the above range, the lip portion does not become excessively rigid. This makes it possible to prevent a decrease in the ability of the wiper blade to follow the member to be cleaned in the longitudinal direction.

[0036] The length LL of the lip portion is preferably 3000 μm to 5000 μm, more preferably 3600 μm to 4500 μm. The length LM of the lip tip portion is preferably 800 μm to 2000 μm, more preferably 1000 μm to 1600 μm.

[0037] It is preferable to increase the tensile strength of the material. Specifically, the tensile stress at 50% elongation of the tip of the lip portion measured with a tensile tester (hereinafter referred to as the 50% modulus) is preferably 1.8 MPa to 20.0 MPa, more preferably 2.0 MPa to 15.0 MPa, even more preferably 3.0 MPa to 14.0 MPa, and even more preferably 3.5 MPa to 13.5 MPa. In order to achieve the tensile strength within the above range, for example, the crosslink density can be increased or a reinforcing additive can be added. However, it is difficult to achieve both the above-mentioned elastic modulus range and tensile strength. To achieve this, it is preferable to use a urethane resin, and by using a polyfunctional isocyanate or a polyfunctional polyol or by selecting a catalyst, the crosslinking state can be controlled, as described above, to control the elastic modulus and increase the tensile strength. Specifically, as described below, a method can be used that utilizes the properties of a block copolymer consisting of a hard segment and a soft segment.

[0038] The third factor affecting the angle θ is the deformation of the micro-region at the lip tip that comes into contact with the workpiece. Deformation of the contact area with the workpiece due to the pressing force and elongation of the lip due to the friction between the lip and the workpiece have a particularly large effect on the value of the angle θ. Therefore, to keep the angle θ within the above range, it is necessary to suppress deformation and elongation in the micro-region at the very tip of the lip.

[0039] As described above, the micro-region at the extreme tip of the lip portion of the wiper blade has a significant effect on wiping performance, so it is important to control the deformation of the third micro-region in addition to the three factors listed above. As mentioned above, increasing the elastic modulus in the micro region is an effective means of suppressing deformation and elongation in the micro region. Increasing the elastic modulus in the micro region suppresses deformation due to contact force and elongation due to frictional force, and can prevent the angle θ from becoming too small. Specifically, the elastic modulus of the blade rubber, particularly the tip of the lip portion, is preferably set to a range of 15.0 MPa or more and 470.0 MPa or less according to the SPM mentioned above.

[0040] Examples of methods for increasing the modulus of elasticity include increasing the crosslink density and adding a reinforcing additive. In particular, when a urethane resin is used, it is preferable to use a polyfunctional isocyanate or polyfunctional polyol or to select a catalyst to control the crosslinking state, thereby controlling the contact width A. One method for increasing the modulus of elasticity is to utilize the properties of a block copolymer consisting of a hard segment and a soft segment, which will be described later.

[0041] The angle θ′ measured under the following conditions is preferably 20° to 85°, more preferably 30° to 80°, and even more preferably 40° to 78°. Specifically, the wiper arm pressing force was set to 18 N / m, and the lip of the wiper blade was brought into contact with the first surface of the flat glass plate. The wiper blade was then moved at a speed of 0.60 m / s in direction A from a first point P1 to a second point P2 on the first surface of the flat glass plate for 50 cm in a direction perpendicular to the longitudinal direction of the blade rubber, and then stopped. The wiper blade rubber is moved under the above conditions and then stopped. The blade rubber is observed from the longitudinal side of the blade rubber using an optical microscope at a magnification of 200x. The point of contact between the lip and the glass plate that is furthest from P1 is designated as point Q1, and the point from point Q1 in the direction A is A perpendicular line is drawn to the first surface of the glass plate at a position 200 μm away, and the first intersection of the perpendicular line with the lip portion is designated as point Q2. At this time, the angle formed by the line connecting points Q1 and Q2 and the first surface of the glass plate is designated as θ'.

[0042] The angle θ' is an angle when the wiping speed is slower than the angle θ, so even if the angle is large, the contact state is relatively unlikely to become unstable. Further, from the formed angles θ and θ', the wiping speed dependency of the formed angle θ is calculated by the following formula (B). Dependence of angle θ on wiping speed (%) = (Angle θ´ - Angle θ) / Angle θ×100 (B)

[0043] The wiping speed dependency of the angle θ is preferably 0.2% to 18.5%, more preferably 0.2% to 15.0%, even more preferably 0.2% to 10.0%, and even more preferably 0.2% to 5.0%. Many wiper blades wipe with a circular motion, in which case the wiping speed often varies along the length. By keeping the wiping speed dependency of the angle θ within the above range, the wiper blade can exhibit stable wiping performance throughout the entire length. The dependence of the angle θ on the wiping speed can be controlled by controlling the change in the angle θ due to macroscopic deformation with the 50% modulus, and by controlling the change in the angle θ due to microscopic deformation with the elastic modulus in the microscopic region.

[0044] Even when a conventional wiper blade, such as the wiper blade disclosed in Patent Document 1, is used to increase the angle between the lip portion and the object being cleaned macroscopically using a method such as the shape described above, the microscopic observation conditions of the present disclosure reveal that the very tip of the lip portion curves due to friction with the glass surface, resulting in a small contact angle. Specifically, when the angle θ was measured using a conventional wiper blade, the angle θ was approximately 15° to 18°. Furthermore, the lip portion of a conventional wiper blade has a large contact width due to rubber elongation. Therefore, even when the shape or settings of a conventional wiper blade are changed, it is difficult to achieve both the contact width A and the angle θ of the present invention. As a result, the average contact pressure of the blade rubber is low, making it more susceptible to vertical force from water on the object being cleaned, which can easily cause the blade rubber to lift. Therefore, the concept behind conventional wiper blades is to spread a very thin film of water to ensure visibility on the windshield.

[0045] On the other hand, satisfying the above contact width A and angle θ means that the average contact pressure of the blade rubber is high and the extreme tip of the lip is in an upright position when in contact with the object to be cleaned. Therefore, a wiper device that satisfies the above contact width A and angle θ can wipe away almost all of the water film on the windshield, thereby achieving even better wiping performance than conventional wipers.

[0046] Oily pollutants floating in the air can form an oil film on the windshield of a vehicle. These pollutants can spread across the entire windshield as the wiper blades wipe, forming a widespread oil film. Because oil films do not mix well with water, conventional wiper blades, which aim to keep the water film extremely thin, tend to break down into droplets, causing glare and other diffuse reflections that impair visibility. In contrast, the wiper device of the present disclosure, which satisfies the above-mentioned contact width A and angle θ, can wipe away almost all of the water film, and even wipe away not only the water film but also the oil film. This allows for even better wiping performance than conventional wipers, ensuring clearer visibility regardless of the windshield's condition.

[0047] Next, a preferred embodiment of the blade rubber in the wiper device will be described. Figure 7 is an enlarged view of the first edge 8 and its vicinity. As shown in Figure 7, assume that a first line segment 11 is drawn on the first side surface 5 at the tip of the blade rubber that contacts the member to be cleaned, parallel to the first edge 8 and 10 μm away from the first edge 8. The length of the first line segment is L1. 8 is an enlarged view of the vicinity of the first line segment 11. As shown in Fig. 8, points (1 / 8)L1, (1 / 2)L1, and (7 / 8)L1 from one end side on the first line segment 11 are designated as P0, P1, and P2, respectively. At this time, three rectangular observation areas 12 are set on the first side surface 5, with the centers of gravity being points P0, P1, and P2 on the first line segment 11, one side being 70 μm long and parallel to the first line segment, and one side being 10 μm long and perpendicular to the first line segment.

[0048] FIG. 9 shows an enlarged view of the vicinity of the observation area 12 with P0 as the center of gravity. As with P0 in Figure 9, including P1 and P2, the elastic modulus of the first side surface is measured at 70,000 points at a pitch (interval) of 0.1 μm for each of the three observation areas using a scanning probe microscope (hereinafter referred to as SPM). From the viewpoint of appropriately controlling the contact width A and the angle θ, it is preferable that the average value of the obtained elastic modulus values ​​of 210,000 pieces is 15.0 MPa to 470.0 MPa. Furthermore, from the viewpoint of the wiping uniformity mentioned above, it is preferable that the coefficient of variation of the elastic modulus is 17.6% or less.

[0049] Similar to the measurement on the first side surface, a second line segment is assumed to be drawn on the second side surface 6 at the tip of the blade rubber that contacts the member to be cleaned, parallel to the second edge 9 and 10 μm away from the second edge 9. The length of the second line segment is defined as L2. The points (1 / 8)L2, (1 / 2)L2, and (7 / 8)L2 from one end side on the second line segment are designated as P3, P4, and P5, respectively. At this time, three rectangular observation areas are set on the second side surface 6, with the centers of gravity being points P3, P4, and P5 on the second line segment, one side being 70 μm long and parallel to the second line segment, and one side being 10 μm long and perpendicular to the second line segment. The elastic modulus of the second side surface is measured at 70,000 points at a pitch (interval) of 0.1 μm in each of the three observation regions using an SPM. For the same reasons as above, the average value of the elastic modulus obtained from a total of 210,000 samples is preferably 15.0 MPa or more and 470.0 MPa or less, and the coefficient of variation of the elastic modulus is preferably 17.6% or less.

[0050] The behavior of the reciprocating wiper blade during cleaning was observed in detail. As a result, it was confirmed that the wiper blade contacts the object to be cleaned in an area on the first and second sides, including a position approximately 10 μm from the first edge and the second edge, respectively. Furthermore, the wiper device according to the present disclosure can further improve wiping performance by satisfying a predetermined standard for the average value of the elastic modulus and its coefficient of variation in the longitudinal direction of the area that can form the contact portion with the object to be cleaned. Furthermore, by satisfying this standard, the contact width A and the angle θ become uniform, making it easier to stably satisfy the contact width A and the angle θ.

[0051] In a wiper device according to one aspect of the present disclosure, the average value of the elastic modulus measured at a position 10 μm from the first edge and the second edge of each of the first and second side surfaces, which may constitute a contact portion that comes into contact with a member to be cleaned, at a predetermined position in the longitudinal direction in a region in the vicinity thereof is preferably 15.0 MPa or more and 470.0 MPa or less. In addition, in the measurement of the elastic modulus of each of the first and second side surfaces, the coefficient of variation of the elastic modulus is preferably 17.6% or less. In measuring the elastic modulus of the first side and the second side, the average value of the elastic modulus was 32. The elastic modulus of the first and second side surfaces is preferably 0 MPa or more and 62.0 MPa or less, more preferably 42.0 MPa or more and 61.0 MPa or less, and even more preferably 45.0 MPa or more and 60.0 MPa or less. In measuring the elastic modulus of the first and second side surfaces, the coefficient of variation of the elastic modulus is more preferably 6.0% or less, even more preferably 5.0% or less, and even more preferably 4.0% or less. The smaller the coefficient of variation of the elastic modulus, the better, so there is no particular lower limit, but it is preferably, for example, 0.1% or more.

[0052] When the average value of the elastic modulus is within the above range, a portion of the side surface can be brought into contact with the object to be cleaned over a narrow contact width at an angle θ along the longitudinal direction of the wiper blade during cleaning. In other words, the contact area can be made to approach line contact, and the pressing force is concentrated at the contact area, ensuring that the deposits are scraped off reliably rather than simply wiped or spread off the object to be cleaned. As a result, the wiper blade can exhibit significantly higher wiping performance than conventional wiper blades. Furthermore, a coefficient of variation in the elastic modulus of 17.6% or less means that the elastic modulus of the contact portion of the side surface is more uniform or more homogeneous in the longitudinal direction. This allows the wiper blade to stably contact the object to be cleaned with a narrow contact width along its longitudinal direction. As a result, the cleaning surface of the wiper blade does not undulate or become disordered along the longitudinal direction during cleaning, suppressing chattering and other disturbances, allowing for uniform tracking and contact with the object to be cleaned. As a result, the wiper blade can stably wipe away highly adhesive dirt, such as dust and oil film, without leaving any residue or uneven wiping across the entire longitudinal direction of the wiper blade.

[0053] The coefficient of variation of the elastic modulus is calculated by the following formula (1). Formula (1): Coefficient of variation (%) = standard deviation / average value of elastic modulus × 100

[0054] FIG. 12 is a schematic diagram showing the vicinity of the contact point between the wiper blade and the member to be cleaned. As shown in Figure 12(a), it was confirmed that conventional wiper blades that do not satisfy the above-mentioned contact width A, angle θ, average value of elastic modulus, and coefficient of variation thereof contact the cleaning target with their sides in a belly contact state (surface contact). On the other hand, as shown in Figure 12(b), the blade rubber in the wiper device of the present disclosure contacts the cleaning target with its sides in an edge-to-edge manner, with its sides in near-line contact. It is believed that this difference in contact state leads to a significant difference in wiping performance.

[0055] The material for forming the lip portion including the tapered portion is not particularly limited as long as it satisfies the above-mentioned requirements for the contact width A and the angle θ. Specifically, for example, the lip portion preferably contains polyurethane, which has excellent mechanical properties and makes it easy to achieve the above-mentioned contact width A and the angle θ. In addition, polyurethane also makes it easy to achieve the requirements for the average value and coefficient of variation of the elastic modulus.

[0056] The polyurethane is preferably a polyurethane elastomer. Polyurethane elastomers are obtained mainly from raw materials such as polyols, chain extenders, polyisocyanates, catalysts, and other additives. The polyurethane elastomer is a block copolymer consisting of hard segments and soft segments. The hard segments are generally composed of polyisocyanates and chain extenders containing short-chain diols. On the other hand, the soft segments are generally composed of long-chain polyols such as polyester polyols, polyether polyols, and polycarbonate polyols and polyisocyanates.

[0057] In order to achieve the above-mentioned specifications regarding the contact width A and the formed angle θ, as well as the average value of the elastic modulus and the coefficient of variation of the elastic modulus, for example, One of the advantages of this method is that it utilizes the properties of block copolymers. Conventional polyurethanes have hard segments formed by further aggregation of urethane bond interactions. The aggregated urethane bond segments further aggregate to form relatively large hard segments. Therefore, according to the inventors' investigations, wiper blades manufactured using such polyurethanes do not satisfy the contact width A and angle θ, or at least one of the average value of the elastic modulus and the coefficient of variation of the elastic modulus, as required by the present disclosure. In other words, because conventional polyurethanes have relatively large hard segments, it is difficult to achieve the coefficient of variation of the elastic modulus of 17.6% or less at 210,000 locations measured using a scanning probe microscope, as required by the present disclosure. In the case of polyurethanes with a small amount of hard segments, further aggregation of the aggregated portions of urethane bonds is suppressed, and it is thought that the coefficient of variation can be kept small. However, in such cases, it is difficult to achieve an average elastic modulus of 15.0 MPa or more, and it becomes difficult to satisfy the above-mentioned contact width A and angle θ.

[0058] A lip portion satisfying the physical properties according to the present disclosure can be formed, for example, by using polyurethane in which hard segments are finely and uniformly dispersed. Such polyurethanes are described below. That is, by using a diisocyanate or a polyfunctional isocyanate having three or more functional groups and a diol or a polyfunctional alcohol having three or more functional groups in an appropriate concentration range as urethane raw materials, aggregation of hard segments is suppressed, and a polyurethane in which the hard segments are finely and uniformly dispersed can be obtained.

[0059] Specifically, for example, it is preferable to use at least one of an alcohol containing a tri- or higher functional polyfunctional alcohol and an isocyanate compound containing a tri- or higher functional polyfunctional isocyanate as the urethane raw material. It is also preferable to use, as urethane raw materials, an alcohol containing at least one selected from diols and tri- or higher functional alcohols, and an isocyanate compound containing tri- or higher functional isocyanate. It is also preferable to use, as urethane raw materials, an alcohol containing a tri- or higher functional polyfunctional alcohol and an isocyanate compound containing a diisocyanate and a tri- or higher functional polyfunctional isocyanate. In particular, it is preferable to use a tri- or higher functional polyfunctional isocyanate and a tri- or higher functional polyfunctional alcohol as the urethane raw material.

[0060] Polyurethanes obtained by reacting tri- or higher functional isocyanates with tri- or higher functional alcohols have steric hindrance that suppresses molecular orientation and more reliably suppresses aggregation of hard segments, making them suitable for achieving the contact width A and angle θ, as well as the elastic modulus and coefficient of variation of the present disclosure. Furthermore, when the soft segment portion has, for example, a linear alkylene structure, the soft segments stack together, increasing crystallinity. As a result, the hard segments also become difficult to disperse. Therefore, introducing an alkylene structure with a side chain into the soft segment portion is also effective in suppressing the aggregation of the hard segments. Specifically, for example, introducing a partial structure such as that shown in the following structural formulas (i) to (iv) into the soft segment portion between two urethane bonds is effective in miniaturizing the hard segments. -CH2-CH(CH3)-CH2-CH2-O- (i) -CH2-CH2-CH(CH3)-CH2-O- (ii) -CH2-CH(CH3)-O- (iii) -CH(CH3)-CH2-O- (iv)

[0061] The structures of structural formulas (i) and (ii) are capable of ring-opening polymerization of 3-methyltetrahydrofuran. These structures are essentially the same. Furthermore, the structures of structural formulas (iii) and (iv) are essentially the same, being structures obtained by ring-opening polymerization of 1,2-propylene oxide. Urethane resins having these structures between two adjacent urethane bonds can be obtained by reacting a polyether polyol or polyester polyol having these structures with an isocyanate. When a bifunctional alcohol (diol) and a bifunctional isocyanate (diisocyanate) are used as urethane raw materials, it is usually difficult to finely disperse the hard segments. However, by introducing the above partial structure into the soft segment portion, it is possible to finely disperse the hard segments, even when a diol and a diisocyanate are used as urethane raw materials. As a result, a polyurethane can be obtained that provides a wiper blade that satisfies the parameters of the present disclosure.

[0062] In addition to introducing side chains into the soft segments, another method for suppressing crystallization due to stacking of soft segments and preventing aggregation of hard segments is to use two or more alcohols with different carbon numbers in the linear chain portion as the urethane raw material. Polyurethanes obtained using two or more alcohols with different carbon numbers in the linear chain portion can suppress crystallization due to stacking of soft segments, even if the soft segments have a linear alkylene structure, due to the different carbon numbers. Furthermore, the different carbon numbers in the soft segments suppress aggregation of urethane bonds, thereby preventing aggregation of hard segments. Therefore, even when diols and diisocyanates having a linear alkylene structure in their molecules are used as urethane raw materials, using multiple diols with different carbon numbers in the linear alkylene structure as the diols can achieve finer hard segments. As a result, polyurethanes that provide wiper blades that satisfy the parameters described herein can be obtained. An example of multiple diols is the combined use of polybutylene adipate polyester polyol and polyhexylene adipate polyester polyol.

[0063] Examples of the alcohol include the following: Polyester polyols such as polyethylene adipate polyester polyol, polybutylene adipate polyester polyol, polyhexylene adipate polyester polyol, (polyethylene / polypropylene) adipate polyester polyol, (polyethylene / polybutylene) adipate polyester polyol, and (polyethylene / polyneopentylene) adipate polyester polyol; polycaprolactone-based polyols obtained by ring-opening polymerization of caprolactone; polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol; and polycarbonate diols. These can be used alone or in combination of two or more.

[0064] As mentioned above, it is preferable to use two or more polyols with different numbers of carbon atoms in the linear portion (alkylene chain) as the alcohol, because this suppresses crystallization of the soft segment and allows for the production of a urethane in which aggregation of the hard segment is suppressed. In this case, it is preferable to use at least two selected from the group consisting of polyester polyols such as polyethylene adipate polyester polyol, polybutylene adipate polyester polyol, polyhexylene adipate polyester polyol, (polyethylene / polypropylene) adipate polyester polyol, (polyethylene / polybutylene) adipate polyester polyol, and (polyethylene / polyneopentylene) adipate polyester polyol.

[0065] As the chain extender, diols capable of extending the polyurethane elastomer chain and polyfunctional alcohols having three or more functional groups can also be used. Examples of diols include the following: Ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (PG), dipropylene glycol (DPG), 1,4-butanediol (1,4-BD), 1,6-hexanediol (1,6-HD), 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, xylylene glycol (terephthalyl alcohol), triethylene glycol. These can be used alone or in combination of two or more.

[0066] Examples of trifunctional or higher polyfunctional alcohols include trimethylolpropane (TMP), glycerin, pentaerythritol (PEN), and sorbitol, which can be used alone or in combination of two or more.

[0067] One method for improving the elastic modulus of polyurethane elastomers is to introduce a crosslinked structure. A preferred method for introducing crosslinks is to use a trifunctional or higher polyfunctional alcohol as the chain extender. Furthermore, the introduction of a branched structure into polyurethane using a trifunctional or higher polyfunctional alcohol can suppress the crystallization of polyurethane and further suppress the aggregation of hard segments. Here, a trifunctional alcohol is preferably used as the polyfunctional alcohol in order to suppress an excessive increase in hardness due to an excessive degree of crosslinking of the polyurethane. Among these, triols, which have a methylene skeleton next to a hydroxyl group and can form a flexible crosslinked structure in terms of molecular structure, are preferred because they have an even greater effect of suppressing the crystallinity of hard segments. Examples of such triols include trimethylolpropane (TMP) and glycerin.

[0068] Examples of the isocyanate compound include the following: 4,4'-Diphenylmethane Diisocyanate (4,4'-MDI), Polymeric MDI, 2,4-Tolylene Diisocyanate (2,4-TDI), 2,6-Tolylene Diisocyanate (2,6-TDI), Xylene Diisocyanate (XDI), 1,5-Naphthylene Diisocyanate (1,5-NDI), p-Phenylene Diisocyanate (PPDI), Hexamethylene Diisocyanate (HDI), Isophorone Diisocyanate (IPDI), 4,4'-Dicyclohexylmethane Diisocyanate (Hydrogenated MDI), Tetramethylxylene Diisocyanate (TMXDI), Carbodiimide-Modified MDI, Triphenylmethane-4,4',4''-Triisocyanate (TTI), Tris(phenylisocyanate)thiophosphate (TPTI).

[0069] Among these, 4,4'-MDI is preferred because the two isocyanate groups have equal reactivity and provide high mechanical properties. It is also preferable to use a tri- or higher functional polyfunctional isocyanate in combination. The use of a tri- or higher functional polyfunctional isocyanate allows for the introduction of a branched structure into the polyurethane, which is effective in further suppressing aggregation of hard segments. Furthermore, a denser crosslinked structure can be introduced into the polyurethane, which can more stably contact the lip portion with the object to be cleaned. As a result, incomplete wiping and uneven wiping of the object to be cleaned can be more effectively suppressed.

[0070] The trifunctional or higher polyfunctional isocyanate may be at least one selected from the group consisting of triphenylmethane-4,4',4''-triisocyanate (TTI), tris(phenylisocyanate)thiophosphate (TPTI), and polymeric MDI. Among these, tris(phenylisocyanate)thiophosphate (TPTI) and polymeric MDI are more preferably used. These isocyanates have methylene groups or ether groups between multiple NCO groups, allowing the distance between multiple urethane bonds to be appropriately maintained. This is therefore advantageous in suppressing aggregation of hard segments.

[0071] Here, polymeric MDI is represented by the following chemical formula (1) and chemical formula (1)'. In chemical formula (1)', n is preferably 1 or more and 4 or less. Chemical formula (1) is the case where n is 1 in chemical formula (1)'. [ka]

[0072] When the lip portion according to the present disclosure contains polyurethane, which is a reaction product of a raw material composition containing an isocyanate compound including a diisocyanate and a tri- or higher functional isocyanate, and an alcohol including a tri- or higher functional alcohol, the lip portion preferably has the following physical properties:

[0073] That is, suppose that a line segment is drawn on the first and second side surfaces of the lip portion, parallel to the first and second edges, with a distance of 0.5 mm from the first and second edges. The length of the line segment is L', and the points 1 / 8L', 1 / 2L', and 7 / 8L' from one end of the line segment are P0', P1', and P2', respectively. The sample sampled at each of P0', P1', and P2' in the first and second aspects is heated and vaporized in an ionization chamber, and heated to 1000°C at a heating rate of 10°C / s using a direct sample introduction mass spectrometer that ionizes the sample molecules. The resulting detected amount of all ions is designated M1, and the integrated intensity of the peak in the extracted ion thermogram corresponding to the range of m / z values ​​derived from the tri- or higher functional isocyanate is designated M2. In this case, in the first and / or second aspects, M2 / M1 is preferably 0.0010 to 0.0150, and particularly preferably 0.0030 to 0.0150.

[0074] Furthermore, when M3 is the integrated intensity of the peak in an extracted ion thermogram corresponding to the range of m / z values ​​derived from the diisocyanate, M3 / M1 in the first and / or second aspects is preferably 0.0200 to 0.1100, and more preferably 0.0380 to 0.0760. By having M2 / M1 and M3 / M1 within the above ranges, the polyurethane contains an appropriate amount of a structure derived from a trifunctional or higher functional isocyanate with low crystallinity, thereby suppressing aggregation of hard segments and allowing the hard segments to be more finely and uniformly dispersed. Furthermore, excessive development of crosslinked structures in the polyurethane is suppressed, making it easier to control the contact width A and the angle θ. Furthermore, the average elastic modulus can be more easily adjusted within a range of 15.0 MPa or more and 470.0 MPa.

[0075] Furthermore, it is preferable that M2 / M3 is 0.0130 or more and 0.3000 or less. M2 / M3 is the ratio of the diisocyanate-derived isocyanate in the isocyanate-derived structure of the polyurethane. This is a parameter that represents the ratio of the structural portion derived from the isocyanate having a functionality of 3 or more to the structural portion derived from the trifunctional or higher polyfunctional isocyanate. By setting M2 / M3 within the above range, an excessive increase in the elastic modulus can be suppressed and a polyurethane can be obtained in which aggregation of hard segments is further suppressed.

[0076] Here, when the polyurethane is a polyurethane produced using polymeric MDI represented by the above chemical formula (1)' as a tri- or higher functional polyfunctional isocyanate, M2 may be the sum of the integrated intensities of peaks in the extracted ion thermogram obtained by the above mass spectrometry, where the m / z value due to n=1 in the structure represented by chemical formula (1)' is in the range of 380.5 to 381.5, the m / z value due to n=2 is in the range of 511.5 to 512.5, the m / z value due to n=3 is in the range of 642.5 to 643.5, and the m / z value due to n=4 is in the range of 773.5 to 774.5.

[0077] Furthermore, when the polyurethane is one in which 4,4'-MDI represented by chemical formula (2) is used as one of the raw materials as a diisocyanate, M3 may be defined as the integrated intensity of a peak corresponding to an m / z value in the range of 249.5 to 250.5 derived from the structure represented by chemical formula (2) in the ion thermogram obtained by the above-described mass spectrometry. [ka]

[0078] Furthermore, when the lip portion of a wiper device according to one embodiment of the present disclosure includes polyurethane, which is a reaction product of a raw material composition including an isocyanate compound containing a trifunctional or higher polyfunctional isocyanate and an alcohol containing a trifunctional or higher polyfunctional alcohol, the lip portion preferably has the following physical properties: Assuming that a line segment is drawn on a first side surface and a second side surface of the lip portion parallel to the first edge and the second edge, respectively, and 0.5 mm away from the first edge and the second edge, the length of the line segment is L', and points 1 / 8L', 1 / 2L', and 7 / 8L' from one end of the line segment are designated P0', P1', and P2', respectively. Samples taken at P0', P1', and P2' on the first side surface and the second side surface are measured by pyrolysis GC / MS (gas chromatography and mass spectrometry). The concentration of the component derived from a trifunctional or higher polyfunctional alcohol in the polyurethane is preferably 0.04 mmol / g to 0.39 mmol / g, more preferably 0.14 mmol / g to 0.39 mmol / g, and even more preferably 0.22 mmol / g to 0.39 mmol / g.

[0079] When the concentration of the tri- or higher polyfunctional alcohol-derived component is 0.04 mmol / g or higher, the polyurethane can be one in which aggregation of hard segments is more reliably suppressed. Furthermore, when the concentration of the tri- or higher polyfunctional alcohol-derived component is 0.39 mmol / g or lower, excessive development of crosslinked structures in the polyurethane can be suppressed, preventing the modulus of elasticity from becoming too high. Therefore, a tapered portion having the above physical properties can more easily satisfy the requirements for the contact width, angle θ, average value of modulus of elasticity, and coefficient of variation of modulus of elasticity. The concentration of the tri- or higher polyfunctional alcohol in the polyurethane can be calculated using the following formula (2):

[0080] Equation (2): Concentration of trifunctional or higher polyfunctional alcohol (mmol / g) = [Amount of trifunctional or higher polyfunctional alcohol (g) / Molecular weight of trifunctional or higher polyfunctional alcohol x 10 00) / [Polyurethane mass (g)]

[0081] The urethane raw material may contain a catalyst for accelerating the reaction between the isocyanate compound and the alcohol. As the catalyst, a catalyst commonly used for curing polyurethane elastomers may be used, such as a tertiary amine catalyst or a tertiary amino alcohol. Specific examples include the following: Amino alcohols such as dimethylethanolamine, N,N,N'-trimethylaminopropylethanolamine, and N,N'-dimethylhexanolamine; trialkylamines such as triethylamine; tetraalkyldiamines such as N,N,N'N'-tetramethyl-1,3-butanediamine; triethylenediamine, piperazine-based compounds, and triazine-based compounds.

[0082] Examples of tertiary amino alcohols include 2-(dimethylamino)ethanol, 3-(dimethylamino)propanol, 2-(dimethylamino)-1-methylpropanol, 2-{2-(dimethylamino)ethoxy}ethanol, 2-{2-(diethylamino)ethoxy}ethanol, and 2-[{2-(dimethylamino)ethyl}methylamino]ethanol. In addition, organic acid salts of metals such as potassium acetate and potassium alkali octylate can also be used. Furthermore, metal catalysts typically used in urethanization, such as dibutyltin dilaurate, can also be used. These can be used alone or in combination of two or more.

[0083] Among these, temperature-sensitive catalysts such as 2-{2-(diethylamino)ethoxy}ethanol and 2-[{2-(dimethylamino)ethyl}methylamino]ethanol can react the above-mentioned polyfunctional isocyanate with polyol with extremely high efficiency, and can effectively form a highly crosslinked structure in the polyurethane.

[0084] The raw materials constituting the blade rubber may contain additives such as pigments, plasticizers, waterproofing agents, antioxidants, UV absorbers, light stabilizers, and hydrolysis inhibitors, as needed, as long as they do not affect the contact width A and the angle θ.

[0085] <Surface treatment> The lip portion of the blade rubber, including at least the tapered portion, may be surface-treated by electron beam irradiation, ultraviolet irradiation, surface layer coating, surface hardening treatment, etc. Preferred surface treatment methods in the present disclosure include, for example, (i) a method including a step of irradiating the workpiece with ultraviolet rays, and (ii) a method including a step of applying a material for forming a hardened region to the workpiece and hardening the material. However, as described above, deformations in the macro to micro regions contribute to performance, so by carrying out the design before surface treatment as described above and then carrying out the surface treatment, the effect will be more effective.

[0086] (i) The conditions for irradiating ultraviolet light are not particularly limited. The ultraviolet light may have a wavelength of 400 nm or less, but preferably 200 nm or more. A wavelength of 200 nm or more can effectively increase the elastic modulus. The wavelength of the maximum emission peak of the light emitted by the light source is preferably 200 nm or more and 400 nm or less. It is particularly preferable that the wavelength of the maximum emission peak be near 254 nm, for example, in the range of 254±1 nm. This is because ultraviolet light in the above wavelength range or with the above wavelength can efficiently generate active oxygen that modifies the surface of the tapered portion of the wiper blade. When there are multiple ultraviolet light emission peaks, it is preferable that one of them be near 254 nm.

[0087] The intensity of light emitted from the light source is not particularly limited, and values ​​measured using a spectroradiometer (trade name: USR-40V / D, manufactured by Ushio Inc.), an ultraviolet integrating actinometer (trade name: UIT-150-A, UVD-S254, VUV-S172, VUV-S365, manufactured by Ushio Inc.), or the like can be used. The integrated amount of ultraviolet light irradiated onto the lip portion in the surface treatment step may be appropriately selected depending on the desired effect of the surface treatment. This can be determined by adjusting the irradiation time of light from the light source, the output of the light source, the distance from the light source, and the like, and may be, for example, 10,000 mJ / cm. 2 It is sufficient to determine the amount of light so as to obtain the desired cumulative amount of light.

[0088] The cumulative amount of ultraviolet light irradiated onto the lip portion can be calculated by the following method. UV cumulative light intensity (mJ / cm 2 ) = UV intensity (mW / cm 2 ) x irradiation time (sec)

[0089] As a light source that emits ultraviolet light, for example, a high-pressure mercury lamp or a low-pressure mercury lamp can be suitably used. These light sources are preferred because they can stably emit ultraviolet light of a suitable wavelength that is little attenuated over the irradiation distance and can uniformly irradiate the entire surface.

[0090] (ii) The conditions for applying and curing the hardened region-forming material are not particularly limited. The hardened region on the lip portion can be formed by applying and curing the hardened region-forming material. This process can effectively increase the elastic modulus of the hardened portion. It is preferable that the hardened region be formed on at least both the first and second side surfaces of the lip portion that come into contact with the cleaning object.

[0091] The material for forming the cured region is diluted with a diluent solvent as needed and can be applied by known means such as dipping, spraying, using a dispenser, brushing, or roller coating. Furthermore, after applying the material for forming the cured region, a further treatment such as heat treatment may be performed. The material for forming the cured region may be impregnated into the polyurethane contained in the lip portion. Since impregnation is promoted by making the material for forming the cured region high-concentration and low-viscosity, the material for forming the cured region may be heated and impregnated without dilution. The degree of curing may be adjusted by the temperature of the material for forming the cured region, the impregnation or immersion time, the temperature and time of heat treatment after impregnation or immersion, and the subsequent standing time.

[0092] The temperature of the material for forming the cured region should be about 60°C to 90°C. The impregnation or immersion time is preferably about 10 to 180 seconds, although this cannot be generalized. After applying the material for forming the cured region to the cured region, a heat treatment may be carried out. The heat treatment reduces the viscosity of the material for forming the cured region present on the surface of the polyurethane, facilitating its penetration and diffusion into the polyurethane.

[0093] The heating method includes, but is not limited to, passing the material through a heating furnace, blowing heated air onto the material, etc. For example, the heating furnace may be a radiation heating furnace or a circulating air heating furnace, and the device for generating heated air may be a hot air blower or a far-infrared heater. The cured region can be widened by using a higher temperature and / or a longer heating time. As for the heating conditions, the surface temperature of the treated surface is preferably set to, for example, 90° C. to 110° C. Furthermore, the heating time is preferably set to, for example, 10 minutes to 60 minutes.

[0094] Furthermore, the amount of residual isocyanate during polyurethane molding tends to gradually decrease over time after molding. Therefore, the formation of the cured region should be carried out promptly after polyurethane molding, but is not particularly limited. For example, it is recommended to carry out the formation within 3 hours. The amount of residual isocyanate can also be adjusted by the mixing ratio of the composition used during polyurethane formation.

[0095] The material for forming the hardened region is not particularly limited as long as it is capable of hardening polyurethane or forming a hardened region on the surface of polyurethane. Examples of the material include an isocyanate compound and an acrylic compound. The material for forming the cured region may be diluted with a solvent or the like. The solvent used for dilution is not particularly limited as long as it dissolves the material used, and examples thereof include toluene, xylene, butyl acetate, methyl isobutyl ketone, and methyl ethyl ketone.

[0096] When the lip of the wiper blade is made of polyurethane, it is preferable to use an isocyanate compound, which is a polyurethane constituent material, as the material for forming the cured region, taking into consideration compatibility with the lip material and impregnation. The isocyanate compound can be one having one or more isocyanate groups in the molecule.

[0097] As the isocyanate compound having one isocyanate group in the molecule, an aliphatic monoisocyanate such as octadecyl isocyanate (ODI), an aromatic monoisocyanate such as phenyl isocyanate (PHI), or the like can be used. As the isocyanate compound having two isocyanate groups in the molecule, those typically used in the production of polyurethane resins can be used, and specific examples include the following: 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (MDI), m-phenylene diisocyanate (MPDI), tetramethylene diisocyanate (TMDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), etc.

[0098] Furthermore, examples of isocyanate compounds having three or more isocyanate groups in the molecule include 4,4',4"-triphenylmethane triisocyanate, 2,4,4'-biphenyl triisocyanate, and 2,4,4'-diphenylmethane triisocyanate. In addition, modified derivatives and polymers of isocyanate compounds having two or more isocyanate groups can also be used. To efficiently increase the elastic modulus of the cured region, MDI with high crystallinity, i.e., MDI with a symmetric structure, is preferred. Furthermore, MDI containing modified compounds is liquid at room temperature, making it easy to work with.

[0099] <Blade rubber manufacturing method> The method for producing the blade rubber is not particularly limited and can be selected from known methods. For example, a lip portion having a tapered portion can be obtained by injecting, for example, a polyurethane elastomer raw material composition into a cavity in a mold for the blade rubber and heating and curing it. The tip of the tapered portion may be cut to form a shape. This is preferable because it allows the first edge and the second edge to be molded with high smoothness. Alternatively, a wiper blade may be produced by producing a pair of tandem-shaped molded bodies formed with tapered portions abutting each other and cutting them longitudinally. The base and neck may be produced using conventionally known materials and production methods.

[0100] <Wiper device> The wiper device includes, for example, a wiper arm connected to a drive motor (not shown) and a wiper blade attached to the wiper arm. The wiper device is not particularly limited and may have a known configuration. For example, various types of wiper devices, such as a tandem type and an opposing wiping type, may be used. The structure of the wiper blade is not particularly limited, and a known structure can be used. The wiper blade has a blade rubber and a blade stay that supports the blade rubber. Various types of blade stays, such as a flat type and a tournament type, can be used. In a bat blade, the blade stay is a support having, for example, spring elasticity, that holds the blade rubber over its entire length. To ensure uniform longitudinal contact, a backing blade may be attached to the blade rubber and used. [Example]

[0101] The present disclosure will be described below with reference to Production Examples, Examples, and Comparative Examples, but the present disclosure is not limited to these Examples. Reagents or industrial chemicals were used as raw materials other than those indicated in the Examples and Comparative Examples. Note that "parts" in the Examples and Comparative Examples are all by mass unless otherwise specified.

[0102] In the examples and comparative examples, wiper blades were manufactured and evaluated. The formulations and evaluation results of the examples and comparative examples are shown in Tables 3 to 9.

[0103] Example 1 <Preparation of raw materials for wiper blades> 191.1 g of 4,4'-diphenylmethane diisocyanate (trade name: Millionate MT, manufactured by Tosoh Corporation) (hereinafter referred to as 4,4'-MDI, and simply referred to as "MDI" in the table), 210.0 g of polymeric MDI (trade name: Millionate MR-200, manufactured by Tosoh Corporation) (hereinafter referred to as MR200) ​​as a trifunctional or higher polyfunctional isocyanate, 598.9 g of polybutylene adipate polyester polyol (trade name: Nipporan 3027, manufactured by Tosoh Corporation) (hereinafter referred to as PBA2500) having a number average molecular weight of 2500 was reacted at 80° C. for 3 hours to obtain a prepolymer having an NCO content of 10.2 mass %.

[0104] Next, the components in Table 1 below were mixed to prepare a curing agent. [Table 1]

[0105] This curing agent was added to the prepolymer and mixed to obtain a raw material composition. This raw material composition was poured into a mold for forming a wiper blade and cured at 130°C for 2 minutes. The mold was then demolded to obtain a polyurethane molded product. The inside of the mold for forming a wiper blade had been coated with release agent A in advance. Release agent A was a mixture of the materials listed in Table 2 below. [Table 2]

[0106] The lip tip end of the obtained polyurethane molded article was cut to obtain a wiper blade according to this example. The longitudinal length of the wiper blade was 700 mm. As shown in FIG. 3, the cross-sectional shape of the wiper blade had a plate-like portion connected to the tapered portion 4 at the tip end of the lip portion 3. The length NL and thickness NT of the neck portion, the length SL of the shoulder portion, and the lengths LM, LL, and thickness LT of the lip portions are shown in Table 3. The obtained wiper blade was evaluated by the following methods.

[0107] [Method for measuring 50% modulus of lip] The tip of the lip portion (if the lip portion has a tapered lip tip, the lip tip itself) was cut out (approximately 100 mm in the longitudinal direction) from the wiper blade, and the thickness and width of the cut piece were measured. The cut piece was measured using a tensile tester (product name: RTG-1225, manufactured by A&D Co., Ltd.) in accordance with JIS K6254-1993. The measurement conditions were a tensile speed of 500 mm / min, a gauge length of 20 mm, a test temperature of 25°C, and three measurements. The average of the three measurement results was taken as the 50% modulus. The results are shown in Table 3.

[0108] [Method for measuring contact width A and angle θ] (Contact and movement test against a glass plate) The lip portion of the blade rubber attached to the arm was brought into contact with the first surface of the glass plate. The blade rubber to be attached was prepared by cutting the blade rubber prepared above and adjusting the longitudinal length to 15 mm to prepare a blade rubber test piece. The blade rubber test piece was gripped by pinching the base of the blade rubber test piece to form a shape that resembled the grip portion of a vehicle wiper. The blade rubber test piece was moved in a direction perpendicular to the longitudinal direction of the blade rubber, and the lip portion wiped the glass plate and then stopped. The blade rubber was observed in the stopped state to evaluate the contact posture of the wiper blade during wiping.

[0109] Figure 10 shows a schematic diagram of the testing machine used for the evaluation. The testing machine has a mechanism that can control the pressure applied to the blade rubber test piece, allowing it to be stably brought into contact with the glass plate and wipe at a specified speed. The testing machine uses a balance system, and the pressure can be controlled by changing the load applied by the weight. 10 and 5, the pressing force on the blade rubber test piece was 18 N / m (longitudinal length), the lip portion of the blade rubber test piece was brought into contact with the first surface of a flat glass plate, and the wiper blade was moved at a speed of 1.65 m / s in direction A from a first point P1 to a second point P2 on the first surface of the flat glass plate for 50 cm in a direction perpendicular to the longitudinal direction of the blade rubber, and then stopped. The stopped state was observed to evaluate the contact posture when wiping the flat glass plate under the following fixed conditions.

[0110] The blade rubber to be evaluated is divided into 10 equal parts in the longitudinal direction, and test pieces are sampled from each part to obtain 10 test pieces evenly spaced from the blade rubber, and evaluation is performed. [Wipe-off conditions] Arm pressure: 18N / m (18N per 1m of length) Wiper blade test piece length: 15 mm Glass plate moving speed: 1.65 m / sec Sweeping distance: 50cm

[0111] (Measurement of contact width) In the contact and movement test against the glass plate, the lip portion was wiped away and then stopped, and the contact area between the lip portion and the glass plate was observed from the second surface of the glass plate opposite the first surface using a microscope (a confocal microscope (product name: OPTELICS HYBRID, manufactured by Lasertec Corporation)). Observation conditions were a 20x objective lens and 1024 x 1024 pixels. Observations were made at 1 mm intervals from the edge in the longitudinal direction of the contact area between the blade rubber test piece and the glass plate. For 10 test pieces, the contact width, which is the distance between the most upstream and most downstream points perpendicular to the direction of movement in contact with the glass surface, was measured at 10 points in the longitudinal direction from the observation image of the field of view at each observation point. The average of the values ​​from all 100 points was calculated. This average value was designated as the contact width A. In addition, the standard deviation of the measured values ​​at 100 points was calculated and used as the standard deviation of the contact width A, which indicates the unevenness of the contact width.

[0112] In addition, contact width B was measured in the same manner as above, except that the arm pressing force was changed to 10 N / m, and this was taken as contact width B. The ratio of the change in contact width to the change in arm pressing force was calculated. This value is shown in Table 3 as the load dependency of contact width.

[0113] (Measurement of the angle θ) In the contact and movement test against the glass plate, the blade rubber was stopped after being brushed away, and a still image was observed from the longitudinal side of the blade rubber using an optical microscope (a camera unit (product name: High-Speed ​​Color Camera Unit VW-600C, manufactured by Keyence Corporation), a high-speed microscope (product name: High-Speed ​​Microscope VW-9000, manufactured by Keyence Corporation), and a zoom lens (product name: Long-Distance, High-Performance Zoom Lens VH-Z50L, manufactured by Keyence Corporation)) at an observation magnification of 200x. As shown in Figure 5, the point farthest from P1 in the contact area between the lip and the glass plate was designated as point Q1, and a perpendicular line was drawn to the first surface of the glass plate at a position 200 μm from point Q1 in direction A. The first intersection of this perpendicular line with the lip was designated as point Q2, and the angle θ formed by the line connecting points Q1 and Q2 and the first surface of the glass plate was evaluated. Ten test pieces were evaluated in the same manner, and the average value was defined as the angle θ.

[0114] The angle θ' was measured in the same manner as above, except that the glass plate moving speed was changed to 0.60 m / sec as a wiping condition. The ratio (%) of the difference between the angle θ when the glass plate moving speed was 1.65 m / sec and the angle θ' when the glass plate moving speed was 0.60 m / sec to the angle θ when the glass plate moving speed was 1.65 m / sec was calculated. This value is shown in Table 3 as the dependency of the angle θ on the wiping speed.

[0115] [Method for measuring polyfunctional alcohol species and concentration] Polyfunctional alcohols were detected by pyrolysis GC / MS (gas chromatography and mass spectrometry) under the following measurement conditions: Sampling position: Lines on the first and second sides of the lip, parallel to the first and second edges, respectively, at a distance of 0.5 mm from the first and second edges. Assuming that a line segment is drawn, the length of the line segment is L', and the points 1 / 8L', 1 / 2L', and 7 / 8L' from one end of the line segment are designated as P0', P1', and P2', respectively. The samples taken at P0', P1' and P2' of the first and second sides were measured by the following method. For sampling, a member such as polyurethane was cut out with a biocutter. Device: Thermal decomposition equipment: Product name: EGA / PY-3030D, manufactured by Frontier Labs Gas chromatography equipment: TRACE1310 gas chromatograph, Thermo Fisher Scientific Mass spectrometer: ISQLT, manufactured by Thermo Fisher Scientific ·Thermal decomposition temperature: 500℃ GC column: 0.25mm inner diameter x 30m stainless steel capillary column Stationary phase: 5% phenylpolydimethylsiloxane Heating conditions: Hold at 50°C for 3 minutes, then heat to 300°C at 8°C / min. ·MS conditions: Mass number range m / z10~650 Scan speed: 1 second / scan

[0116] The polyfunctional alcohol species were characterized by GC / MS. A calibration curve was created by GC analysis of known concentrations of the characterized polyfunctional alcohol species, and quantification was performed from the GC peak area ratio. The arithmetic mean values ​​of the values ​​obtained from each of the samples P0', P1', and P2' of the first and second aspects were used as the polyfunctional alcohol concentrations of the first and second aspects, respectively.

[0117] [Measurement of M1, M2 and M3] Measurements of M1 to M3 were carried out using the direct sample introduction method (DI method), in which the sample was introduced directly into the ion source without passing through a gas chromatograph (GC). The equipment used was an ion trap GC / MS (trade name: POLARIS Q, Thermof A direct exposure probe (DEP) was used as the direct introduction probe. Assuming that a line segment is drawn on the first side and the second side of the lip portion, parallel to the first edge and the second edge, respectively, with a distance of 0.5 mm from the first edge and the second edge, the length of the line segment is L', and the points 1 / 8L', 1 / 2L', and 7 / 8L' from one end side on the line segment are designated as P0', P1', and P2', respectively. The samples taken at P0', P1' and P2' of the first and second sides were measured by the following method. For sampling, a member such as polyurethane was cut out with a biocutter. Approximately 0.1 μg of the sample sampled at each of the P0′, P1′, and P2′ on the first and second sides was fixed to a filament located at the tip of the probe and directly inserted into the ionization chamber, which was then rapidly heated from room temperature to 1000°C at a constant temperature increase rate (approximately 10°C / s), and the vaporized gas was detected by a mass spectrometer.

[0118] The detected amount M1 of all ions is the sum of the integrated intensities of all peaks in the obtained total ion current thermogram, When the sum of the integrated intensities of the peaks in the extracted ion thermogram of m / z values ​​derived from the tri- or higher functional isocyanate is defined as M2, (M2 / M1) is calculated using the values ​​of M1 and M2. When the sum of the integrated intensities of the peaks in the extracted ion thermogram of m / z values ​​derived from the diisocyanate is defined as M3, (M3 / M1) is calculated using the values ​​of M1 and M3. Then, the arithmetic mean values ​​of the numerical values ​​obtained from each of the samples P0', P1', and P2' of the first and second aspects, respectively, are calculated as M2 / M3. The values ​​of (M2 / M1) and (M3 / M1) were used.

[0119] In this example, TTI used as the trifunctional or higher polyfunctional isocyanate has a structure represented by the following chemical formula (3). In the extracted ion thermogram obtained in this evaluation, a peak derived from the cationized product of TTI was detected, with a peak top at m / z 366.5 to 367.5. Therefore, in this example, the integrated intensity of this peak was designated M2. [ka]

[0120] In other examples described later, for an elastic portion made of polyurethane synthesized using polymeric MDI as a tri- or higher functional isocyanate, peaks derived from cationized polymeric MDI were detected in the extracted ion thermogram obtained in this evaluation, with peaks having peak tops at m / z values ​​in the range of 380.5 to 381.5 indicating n = 1 in the structure represented by chemical formula (1)', m / z values ​​in the range of 511.5 to 512.5 indicating n = 2, m / z values ​​in the range of 642.5 to 643.5 indicating n = 3, and m / z values ​​in the range of 773.5 to 774.5 indicating n = 4. Therefore, in these examples, the sum of the integrated intensities of these peaks was defined as M2.

[0121] Similarly, in the examples described below, tris(phenylisocyanate)thiophosphate (TPTI) used as a trifunctional or higher polyfunctional isocyanate has a structure represented by chemical formula (4). In the extracted ion thermogram obtained in this evaluation, a peak derived from the cationized product of TPTI was detected, with a peak top at m / z 464.5 to 465.5. Therefore, in these examples, the integrated intensity of this peak was designated M2. [ka]

[0122] On the other hand, in the case of the diisocyanate 4,4'-MDI, the structure represented by the above chemical formula (2) derived from 4,4'-MDI was detected as a cationized structure in the m / z range of 249.5 to 250.5. The extracted ions corresponding to this structure were The integrated intensity of the peak in the thermogram was taken as (M3).

[0123] [Method for measuring elastic modulus] The elastic modulus was measured by SPM using a scanning probe microscope (SPM) (trade name: MFP-3D-Origin, manufactured by Oxford Instruments) using the following method. First, samples were prepared as follows. For the obtained wiper blade, a first edge formed by the first side surface and the tip surface was set as shown in FIG. 7. A first line segment with a length L1 was drawn parallel to the first edge, with a distance of 10 μm from the first edge. Three 2 mm square measurement samples with one side parallel to the first line segment were cut out, with the centers of gravity set at points P0, P1, and P2, respectively, at 1 / 8L, 1 / 2L, and 7 / 8L from one end of the line segment. Next, a 100 μm square, 1 μm thick polyurethane slice with one side parallel to the first line segment and centers of gravity set at P0, P1, and P2 was cut out from each measurement sample at -50°C using a cryomicrotome (UC-6 (product name), manufactured by Leica Microsystems). At this temperature, three measurement samples were prepared. Each of the obtained measurement samples was placed on a smooth silicon wafer and left to stand for 24 hours in an environment at room temperature of 25°C and humidity of 50%.

[0124] Next, the silicon wafer with the measurement sample mounted on it was set on the SPM stage and observed using the SPM. The spring constant and proportionality constant of the silicon cantilever (product name: OMCL-AC160, manufactured by Olympus, tip curvature radius: 8 nm) were previously confirmed to be as follows using the thermal noise method installed in this SPM device: spring constant: 30.22 nN / nm, proportionality constant: 82.59 nm / V. The cantilever was tuned in advance to determine its resonance frequency (285 KHz (first order) and 1.60 MHz (higher order)). The SPM measurement mode was AM-FM mode, the cantilever free amplitude was 3 V, the set point amplitude was 2 V (first order) and 25 mV (higher order), and the field of view was 70 μm × 70 μm. The scan speed was 1 Hz, and the number of scan points was 256 vertically and 256 horizontally to obtain phase images. The field of view was selected so that P0, P1, and P2 of each measurement sample were located in the center of the field of view and one side was parallel to the first line segment. From the obtained phase image, the locations on the measurement sample where the elastic modulus was measured by force curve measurement were specified. Specifically, as shown in Figures 8 and 9, in the 70 μm × 70 μm phase image, the measurement locations were specified as 70,000 positions corresponding to 70,000 points at a pitch (interval) of 0.1 μm in the vertical and horizontal directions in a rectangular region having the centers of gravity at points P0, P1, and P2, one side of which is 70 μm long and parallel to the first line segment, and the other side of which is 10 μm long and perpendicular to the first line segment.

[0125] Force curves were then measured once in contact mode at each point. The force curves were acquired under the following conditions: The piezoelectric element driving the cantilever was controlled so that it would bend when the tip of the cantilever contacted the sample surface and reached a certain deflection. This turning point, called the trigger value, represents the voltage increase required from the deflection voltage at the start of the force curve to cause the cantilever to bend. In this measurement, the trigger value was set to 0.2 V. Other force curve measurement conditions included a 500 nm distance from the cantilever tip in its standby state to the point where the cantilever bends at the trigger value, and a 1 Hz scan rate (the speed at which the probe makes one reciprocating motion). Each of the force curves was then fitted based on Hertzian theory to calculate the elastic modulus. The elastic modulus (Young's modulus) according to Hertzian theory is calculated using the following formula (*1).

[0126] Calculation formula (*1) F=(4 / 3)E * R 1 / 2 d 3 / 2 where F is the force exerted by the cantilever on the sample at the point where the cantilever turns back, E * is the composite elastic modulus, R is the radius of curvature of the tip of the cantilever (8 nm), and d is the deformation of the sample at the point where the cantilever turns back.

[0127] Then, d was calculated using the following formula (*2). Calculation formula (*2) Calculated as d=Δz-D. Δz is the displacement of the piezoelectric element from when the tip of the cantilever contacts the sample until it bends back, and D is the amount of warping of the cantilever at the point where it bends back. D was calculated using the following formula (*3).

[0128] Calculation formula (*3) D=α·ΔVdeflection In the calculation formula (*3), α is the proportionality constant (Invols constant) of the cantilever, and ΔVdeflection represents the change in deflection voltage from when the cantilever starts to contact the sample to when it turns back.

[0129] Furthermore, F was calculated using the following formula (*4). Calculation formula (*4) F=κ·D κ is the spring constant of the cantilever. Since ΔVdeflection and Δz are actual measured values, E in formula (*1) can be calculated from formulas (*1) to (*4). * Furthermore, the elastic modulus (Young's modulus) Es was calculated using the following formula (*5).

[0130] Calculation formula (*5) 1 / E * =[(1-Vs 2 ) / Es]-[(1-Vi 2 ) / Ei] Vs: Poisson's ratio of the sample (fixed at 0.33 in this example); Vi: Poisson's ratio of the cantilever tip (in this example, the value for silicon is used); Ei: Young's modulus of the cantilever tip (in this example, the value for silicon is used).

[0131] The elastic modulus was measured at 70,000 points at a pitch (interval) of 0.1 μm in both the vertical and horizontal directions in a rectangular observation area (three 10 μm × 70 μm observation areas) with each of P0, P1, and P2 as the center of gravity, one side of which was 70 μm long and parallel to the first line segment, and the other side of which was 10 μm long and perpendicular to the first line segment. The average value of the elastic modulus values ​​calculated from the force curves at a total of 210,000 points was taken as the elastic modulus of the first side surface. The standard deviation was calculated from the elastic modulus at a total of 210,000 points. The coefficient of variation of the elastic modulus of the first side surface was calculated from the average value and standard deviation of the elastic modulus values ​​using the following formula 1. Formula (1): Coefficient of variation (%) = standard deviation / average value of elastic modulus × 100

[0132] The average value of the elastic modulus of the second side surface and the coefficient of variation of the elastic modulus of the second side surface were calculated in the same manner as above. The results are shown in Table 3.

[0133] <Evaluation of water wiping performance> The wiping performance of the wiper blade was evaluated using the testing equipment for the wiping performance test described in Japanese Industrial Standards (JIS) D5710:1998 (Automotive parts - Wiper arms and wiper blades). In this test, the wiper blade was attached with the backing blade attached to it, and water droplets were sprayed onto the entire surface to be wiped using a spray bottle, and cleaning was performed under the following conditions. The remaining part of the glass surface after the wiper blade was wiped once on the forward path (the direction in which the first side wipes the glass surface) was checked by contacting a water-sensitive test paper (product name: Water-sensitive Test Paper 20301) with the wiping surface. The water-sensitive test paper used had a long side length of 76 mm and a short side length of 52 mm. The test paper was contacted at the center of the wiping direction in the wiping area, with the long side of the water-sensitive test paper aligned with the longitudinal direction of the wiper blade when the longitudinal center of the wiper blade 200 was brought into contact with the glass surface 220 (A in Figure 11(a)).

[0134] The water-sensitive test paper in contact with the wiping surface was observed at 50x magnification using a video microscope (product name: DIGITAL MICROSCOPE VHX-5000, manufactured by Keyence Corporation) and a zoom lens (product name: Swing Head Zoom Lens VH-ZST, manufactured by Keyence Corporation). As shown in Figure 11(b), 24 observation points were observed: 8 points on the long side and 3 points on the short side of the water-sensitive test paper. From the observed image, the percentage of the area of ​​the portion not discolored by water ((area not discolored by water) / area of ​​the observation area at 50x magnification) × 100) was calculated, and the average value of the 24 observation points (hereinafter referred to as the water film removal area percentage (%)) was calculated.

[0135] Similarly, the remaining area on the glass surface after one wipe on the return path (the direction in which the second side wipes the glass surface) was checked by contacting a water-sensitive test paper with the wiping surface. The wiping performance was evaluated based on the calculated water film removal area ratio according to the following evaluation criteria. The results were taken as the initial wiping performance. The results of the initial evaluation are shown in Table 3 as the wiping performance of the wiper blade.

[0136] Similarly, for both the forward and backward wiper blades, the water-sensitive test paper 230 was placed in contact with the wiper blade at five points evenly spaced from the inside to the outside edge in the longitudinal direction, as shown in Figure 11(a), at the center of the wiping area in the wiping direction, and the water film removal area ratio was calculated in the same manner. The difference between the maximum and minimum water film removal area ratios was calculated from the five points on each of the forward and backward wiper blades, for a total of 10 points, and the percentage (%) of this difference relative to the average value was evaluated as the variation in wiping performance, and the wiping performance unevenness was evaluated according to the following evaluation criteria.

[0137] [Wipe-off conditions] Wiping environment: Temperature 20±5℃, humidity 70% or more Judgment time: Within 3 seconds after wiping Wiper blade length: 700mm Wiper blade load: 18N / m Wiper blade wiping reciprocating speed: 55 times / minute (1.65 m / s in M ​​zone) Water application: Water droplets are sprayed onto the entire glass surface in a mist

[0138] [Water wiping performance evaluation criteria] Rank A: Water film removal area rate is 95% or more Rank B: Water film removal area rate is 90% or more but less than 95% Rank C: Water film removal area rate is 85% or more but less than 90% Rank D: Water film removal area rate is 80% or more but less than 85% Rank E: Water film removal area rate is less than 50%

[0139] [Evaluation criteria for unevenness in water wiping performance] Rank A: Variation in wiping performance is less than 3% Rank B: Variation in wiping performance is 3% or more but less than 10% Rank C: Variation in wiping performance is 10% or more but less than 20% Rank D: Variation in wiping performance is 20% or more but less than 40% Rank E: Variation in wiping performance is 40% or more

[0140] <Evaluation of oil film wiping performance> The wiping performance of wiper blades was evaluated using the testing equipment for wiping performance tests described in Japanese Industrial Standards (JIS) D5710:1998 (Automotive parts - Wiper arms and wiper blades). In this test, a wiper blade was attached, and silicone oil (trade name: KF-96-50cs, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to the entire surface to be wiped to simulate an oil film on the glass surface to be cleaned, and cleaning was performed under the following conditions. After one reciprocal wipe of the wiper blade, the remaining part of the glass surface was observed from the back side of the cleaned surface, and the unevenness of gloss and the influence on visibility were visually confirmed. The results were calculated as the ratio of the area of ​​the part where the silicone oil film was removed to the area of ​​the surface wiped by the wiper blade (hereinafter referred to as the silicone oil film removal area rate (%)). The wiping performance was evaluated based on the calculated oil film removal area rate according to the following criteria. The results are taken as the initial wiping performance. The results are shown in Table 3 as the wiper blade's oil film wiping performance.

[0141] [Wipe-off conditions] Wiper blade load: 18N / m Wiper blade wiping reciprocating speed: 55 times / minute (1.65 m / s in M ​​zone) [Evaluation criteria] Rank A: Silicone oil film removal area rate is 95% or more Rank B: Silicone oil film removal area rate is 90% or more but less than 95% Rank C: Silicone oil film removal area rate is 85% or more but less than 90% Rank D: Silicone oil film removal area rate is 80% or more but less than 85% Rank E: Silicone oil film removal area rate is 70% or more but less than 80% Rank F: Silicone oil film removal area rate is less than 50%

[0142] Examples 2 to 19 Wiper blades were produced and evaluated in the same manner as in Example 1, except that the types and amounts of various materials for the prepolymer, the types and amounts of various materials for the curing agent, and the wiper shape were as shown in Tables 3 and 4.

[0143] The materials used are as follows: MDI: 4,4'-diphenylmethane diisocyanate (trade name: Millionate MT, manufactured by Tosoh Corporation) (hereinafter also referred to as 4,4'-MDI, and simply referred to as "MDI" in the table) TTI: Triphenylmethane-4,4',4''-triisocyanate (trade name: Ultite Super CA, manufactured by Toho Chemical Industry Co., Ltd.) TPTI: Tris(phenyl isocyanate) thiophosphate (trade name: Ultite Super CAII, manufactured by Toho Chemical Industry Co., Ltd.) Glycerin: (Tokyo Chemical Industry Co., Ltd.) TMP: Trimethylolpropane (Tokyo Chemical Industry Co., Ltd.) PEN: Pentaerythritol (Tokyo Chemical Industry Co., Ltd.) MR200: Polymeric MDI (product name: Millionate MR-200, manufactured by Tosoh Corporation) MR400: Polymeric MDI (product name: Millionate MR-400, manufactured by Tosoh Corporation) M-200: Polymeric MDI (product name: Cosmonate M-200, manufactured by Mitsui Chemicals, Inc.) PBA2500: Polybutylene adipate polyester polyol with a number average molecular weight of 2500 (trade name: Nipporan 3027, manufactured by Tosoh Corporation) PBA1000: Polybutylene adipate polyester polyol (trade name: Nipporan 4009, manufactured by Tosoh Corporation) PBA2000: Polybutylene adipate polyester polyol with a number average molecular weight of 2000 (trade name: Nipporan 4010, manufactured by Tosoh Corporation) PHA1000: Polyhexylene adipate polyester polyol (trade name: Nipporan 164, manufactured by Tosoh Corporation, number average molecular weight 1000) PHA2600: Polyhexylene adipate polyester polyol with a number average molecular weight of 2600 (trade name: Nipporan 136, manufactured by Tosoh Corporation) PTG-2000SN: Polytetramethylene ether glycol with a number average molecular weight of 2000 (trade name: PTG-2000SN, manufactured by Hodogaya Chemical Co., Ltd.) PTG1000SN: Polytetramethylene ether glycol with a number average molecular weight of 1000 (trade name: PTG-1000SN, manufactured by Hodogaya Chemical Co., Ltd.) 1,4-BD: 1,4-butanediol (Tokyo Chemical Industry Co., Ltd.) Polycat46: (product name, manufactured by Air Products Japan) No. 25: N,N'-dimethylhexanolamine (product name: Kao Raiser No. 25, manufactured by Kao Corporation) RX5: 2-[{2-(dimethylamino)ethyl}methylamino]ethanol (trade name: TOYOCAT-RX5, manufactured by Tosoh Corporation)

[0144] Example 20 A 2 mm portion of the lip tip of a wiper blade fabricated in the same manner as in Example 14 was immersed in 4,4'-MDI dissolved at 80°C for 90 seconds. The 4,4'-MDI adhering to the surface of the immersed portion of the wiper blade was then wiped off using a sponge soaked in butyl acetate, and the wiper blade was then heated at 100°C for 30 minutes. The wiper blade was then aged for 24 hours in an environment at 23°C and 50% relative humidity to form a hardened region at the lip tip. This resulted in the production of a wiper blade according to this example. This wiper blade was evaluated in the same manner as in Example 1.

[0145] Example 21 A hardened region was formed at the tip of the lip of a wiper blade produced in the same manner as in Example 19, in the same manner as in Example 20. In this way, a wiper blade according to this example was produced. This wiper blade was evaluated in the same manner as in Example 1.

[0146] Example 22 A 2 mm portion of the lip tip of a wiper blade prepared in the same manner as in Example 18 was immersed in 4,4'-MDI dissolved at 80°C for 90 seconds. A sponge soaked in butyl acetate was then used to wipe off the 4,4'-MDI adhering to the surface of the immersed portion of the wiper blade. The wiper blade was then aged for 24 hours in an environment at 23°C and 50% relative humidity to form a hardened region at the lip tip. This resulted in the production of a wiper blade according to this example. This wiper blade was evaluated in the same manner as in Example 1.

[0147] Example 23 A wiper blade was produced in the same manner as in Example 19. Then, an ultraviolet integrated light dose of 492 mJ / cm 2 was applied to the lip portion of this wiper blade. 2 The wiper blade according to this example was obtained by irradiating the wiper blade with ultraviolet light so that the maximum emission wavelength peak was at 254 nm. The ultraviolet light source used was a low-pressure mercury ozone-free lamp (manufactured by Toshiba Lighting & Technology Corporation). This wiper blade was evaluated in the same manner as in Example 1.

[0148] Example 24 A wiper blade was produced in the same manner as in Example 13. Then, an ultraviolet integrated light dose of 1968 mJ / cm 2 was applied to the lip portion of this wiper blade. 2 The wiper blade according to this example was obtained by irradiating the wiper blade with ultraviolet light so that the maximum emission wavelength peak was at 254 nm. The ultraviolet light source used was a low-pressure mercury ozone-free lamp (manufactured by Toshiba Lighting & Technology Corporation). This wiper blade was evaluated in the same manner as in Example 1.

[0149] Example 25 A wiper blade was produced in the same manner as in Example 18. Then, an ultraviolet integrated light dose of 3936 mJ / cm 2 was applied to the lip portion of this wiper blade. 2 The wiper blade according to this example was obtained by irradiating the wiper blade with ultraviolet light so that the maximum emission wavelength peak was at 254 nm. The ultraviolet light source used was a low-pressure mercury ozone-free lamp (manufactured by Toshiba Lighting & Technology Corporation). This wiper blade was evaluated in the same manner as in Example 1.

[0150] Example 26 To 100 parts by mass of acrylonitrile butadiene rubber (hereinafter referred to as NBR) (trade name: JSR NBR N220S, manufactured by JSR Corporation), 75.0 parts by mass of carbon black (trade name: Toka Black #7360SB, manufactured by Tokai Carbon Co., Ltd.), 5.0 parts by mass of zinc oxide (trade name: Zinc oxide type 2, manufactured by Sakai Chemical Industry Co., Ltd.), and 1.0 part by mass of zinc stearate (trade name: SZ-2000, manufactured by Sakai Chemical Industry Co., Ltd.) were added, and the mixture was kneaded for 15 minutes in an internal mixer adjusted to 50°C. To this, 2.6 parts by mass of sulfur and 4.5 parts by mass of tetrabenzyl thiuram sulfide (TBzTD) (trade name: Percasit TBzTD, manufactured by Frekins) were added as vulcanizing agents. The mixture was then kneaded for 10 minutes in a two-roll mill cooled to a temperature of 25°C to obtain a rubber composition. The obtained rubber composition was placed in a mold for forming a wiper blade and vulcanized by heating at a temperature of 170°C for 20 minutes. The composition was then demolded to obtain a wiper blade according to this example. The obtained wiper blade was evaluated in the same manner as in Example 1.

[0151] Comparative Example 1 To 100 parts by mass of natural rubber, 50.0 parts by mass of carbon black (trade name: Toka Black #7360SB, manufactured by Tokai Carbon Co., Ltd.), 5.0 parts by mass of zinc oxide (trade name: Zinc oxide type 2, manufactured by Sakai Chemical Industry Co., Ltd.), 1.0 part by mass of zinc stearate (trade name: SZ-2000, manufactured by Sakai Chemical Industry Co., Ltd.), and 25 parts by mass of calcium carbonate (trade name: Nanox #30, manufactured by Maruo Calcium Co., Ltd.) were added, and the mixture was kneaded for 15 minutes in an internal mixer adjusted to 50°C. To this, 1.2 parts by mass of sulfur and 4.5 parts by mass of tetrabenzyl thiuram sulfide (TBzTD) (trade name: Percasit TBzTD, manufactured by Frekins) were added as vulcanizing agents. The mixture was then kneaded for 10 minutes in a two-roll mill cooled to a temperature of 25°C to obtain a rubber composition. The obtained rubber composition was placed in a mold for forming a wiper blade and heated at a temperature of 170°C for 20 minutes to be vulcanized. The composition was then demolded to obtain a wiper blade according to this comparative example. The obtained wiper blade was evaluated in the same manner as in Example 1.

[0152] Comparative Example 2 A wiper blade was produced in the same manner as in Comparative Example 1 except that the rubber composition obtained in the same manner as in Comparative Example 1 was used and the wiper shape was as shown in Table 6, and then evaluated. Compared to Comparative Example 1, although the macroscopic contact posture was upright, deformation in the microscopic region was large, the contact width increased, and the angle θ also became smaller. As a result, no improvement in performance was observed.

[0153] Comparative Examples 3 and 4 A wiper blade was produced in the same manner as in Comparative Example 1 except that the rubber composition obtained in the same manner as in Example 26 was used and the wiper shape was as shown in Table 6, and then evaluated. In Comparative Example 3, chattering was observed during wiping, and along with this, leakage of water and oil films in the form of waves was observed. In Comparative Example 4, floating occurred due to the water or oil film during wiping, and leakage was confirmed as a result.

[0154] Tables 3 to 6 show the evaluation results of the wiper blades according to the examples and comparative examples. [Table 3] In Tables 3 to 6, "outgoing contact posture" is an evaluation of the first side surface side, and "returning contact posture" is an evaluation of the second side surface side.

[0155] [Table 4]

[0156] [Table 5]

[0157] [Table 6] [Explanation of symbols]

[0158] 1: blade support portion, 2: neck, 3: lip portion, 4: tapered portion, 5: first side surface, 6: second side surface, 7: tip surface, 8: first edge, 9: second edge, 10: member to be cleaned, 11: first line segment, 12: observation area

Claims

1. A windshield wiper device, comprising: The wiper device includes a wiper arm and a wiper blade attached to the wiper arm, The wiper blade has a blade rubber and a blade stay that supports the blade rubber, The blade rubber has a base portion that is an attachment portion of the blade rubber to the blade stay, a lip portion, and a neck portion that pivotally connects the lip portion to the base portion, At least a part of the tip of the lip portion forms a contact portion with the windshield, With the arm pressing force of the wiper arm set to 18 N / m, the lip portion of the wiper blade was brought into contact with the first surface of the flat glass plate, and the wiper blade was moved at a speed of 1.65 m / sec in direction A from a first point P1 to a second point P2 on the first surface of the flat glass plate for 50 cm in a direction perpendicular to the longitudinal direction of the blade rubber, and then stopped. When the contact portion between the lip portion and the glass plate is observed from the second surface side opposite to the first surface of the glass plate, and the width of the contact portion in the direction perpendicular to the longitudinal direction of the blade rubber is defined as a contact width A, the contact width A is 1.0 μm or more and 20.0 μm or less, and When the blade rubber was observed from the side in the longitudinal direction of the blade rubber using an optical microscope at a magnification of 200 times, a wiper device characterized in that, when a point Q1 is defined as the point of contact between the lip portion and the glass flat plate that is farthest from P1, a perpendicular line is drawn to the first surface of the glass flat plate at a position 200 μm from point Q1 in direction A, and the first intersection of the perpendicular line with the lip portion is defined as point Q2, an angle θ formed by a straight line connecting point Q1 and point Q2 and the first surface of the glass flat plate is 20° or more and 80° or less.

2. The wiper device according to claim 1, wherein the standard deviation of the contact width A is 6.00 μm or less.

3. With the arm pressing force of the wiper arm set to 10 N / m, the lip portion of the wiper blade was brought into contact with the first surface of the glass flat plate, and the wiper blade was moved at a speed of 1.65 m / sec in a direction A from a first point P1 toward a second point P2 on the first surface of the glass flat plate for 50 cm in a direction perpendicular to the longitudinal direction of the blade rubber, and then stopped. When the contact portion between the lip portion and the glass plate is observed from the second surface side opposite to the first surface of the glass plate, and the width of the contact portion in a direction perpendicular to the longitudinal direction of the blade rubber is defined as a contact width B, 3. The wiper device according to claim 1, wherein the load dependency of the contact width calculated from the contact width A and the corresponding contact width B using the following formula (A) is 0.01 μm to 0.60 μm. Load dependency of contact width (μm / (N / m)) = (Contact width A (μm) - Contact width B (μm)) / (Load 18 (N / m) - Load 10 (N / m)) ... (A)

4. With the arm pressing force of the wiper arm set to 18 N / m, the lip portion of the wiper blade was brought into contact with the first surface of the glass flat plate, and the wiper blade was moved at a speed of 0.60 m / sec in a direction A from a first point P1 toward a second point P2 on the first surface of the glass flat plate for 50 cm in a direction perpendicular to the longitudinal direction of the blade rubber, and then stopped. When the blade rubber is observed from the side in the longitudinal direction of the blade rubber using an optical microscope at a magnification of 200 times, The point farthest from P1 among the contact points between the lip portion and the glass plate is defined as point Q1. A perpendicular line is drawn to the first surface of the glass plate at a position 200 μm from point Q1 in the direction A, and the first intersection of the perpendicular line with the lip portion is designated as point Q2. The angle θ' is the angle formed by the line connecting points Q1 and Q2 and the first surface of the glass plate. The wiper device according to any one of claims 1 to 3, wherein the wiping speed dependency of the angle θ calculated from the angle θ and the angle θ' using the following formula (B) is 0.2% to 18.5%: Dependence of angle θ on wiping speed (%) = (formed angle θ' - formed angle θ) / formed angle θ × 100 (B)

5. The lip portion has a shoulder portion at an end of the lip portion on the neck portion side, the shoulder portion extending laterally beyond the neck portion.

5. The wiper device according to claim 1, wherein a ratio (SL / NL) of a length SL of the shoulder portion to a length NL of the neck portion in a cross section perpendicular to the longitudinal direction of the blade rubber is 0.37 to 9.

00.

6. The wiper device according to any one of claims 1 to 5, wherein a tensile stress at a tip end of the lip portion when elongated by 50% using a tensile tester is 1.8 MPa to 20.0 MPa.

7. The lip portion has a tapered portion in which a cross section in a direction perpendicular to the longitudinal direction of the blade rubber gradually decreases in width from a side closer to the base portion toward a side farther from the base portion, The lip portion is a first side surface and a second side surface continuing from the tapered portion; a tip surface that, together with the first side surface and the second side surface, constitutes a first edge and a second edge of the lip portion on a side farthest from the base portion, Assuming that a first line segment is drawn on the first side surface parallel to the first edge and at a distance of 10 μm from the first edge, The length of the first line segment is L1, The points (1 / 8)L1, (1 / 2)L1, and (7 / 8)L1 from one end side on the first line segment are designated as P0, P1, and P2, respectively; the elastic modulus of the first side surface is measured at 70,000 points at a pitch of 0.1 μm using a scanning probe microscope for each of three rectangular observation regions on the first side surface, the observation regions having centers of gravity at each of the points P0, P1, and P2, one side of which is 70 μm in length parallel to the first line segment and one side of which is 10 μm in length perpendicular to the first line segment, and the average value of a total of 210,000 values ​​of the elastic modulus obtained is 15.0 MPa to 470.0 MPa; When it is assumed that a second line segment is drawn on the second side surface parallel to the second edge and at a distance of 10 μm from the second edge, The length of the second line segment is L2, The points (1 / 8)L2, (1 / 2)L2, and (7 / 8)L2 from one end side on the second line segment are designated as P3, P4, and P5, respectively; The elastic modulus of the second side surface is measured at 70,000 points at a pitch of 0.1 μm for each of three rectangular observation regions of the second side surface, each of which has a center of gravity at each of the points P3, P4, and P5, and which has one side parallel to the second line segment and a length of 70 μm and one side perpendicular to the second line segment and a length of 10 μm, using a scanning probe microscope, and the average value of the elastic modulus of the second side surface is 15.0 MPa to 470.0 MPa. The wiper device according to any one of claims 1 to 6.

8. In measuring the elastic modulus of the first side surface, The average value of the elastic modulus is 32.0 MPa or more and 62.0 MPa or less, In measuring the elastic modulus of the second side, 8. The method according to claim 7, wherein the average value of the elastic modulus is 32.0 MPa or more and 62.0 MPa or less. The wiper device described above.

9. In measuring the elastic modulus of the first side surface, The coefficient of variation of the elastic modulus is 17.6% or less, In measuring the elastic modulus of the second side, 9. The wiper device according to claim 7, wherein the coefficient of variation of the elastic modulus is 17.6% or less.

10. In measuring the elastic modulus of the first side surface, The coefficient of variation of the elastic modulus is 6.0% or less, In measuring the elastic modulus of the second side, The wiper device according to any one of claims 7 to 9, wherein the coefficient of variation of the elastic modulus is 6.0% or less.

11. The lip portion contains polyurethane, The wiper device according to any one of claims 1 to 9, wherein the polyurethane comprises a reaction product of a raw material composition including at least one of an alcohol including a tri- or higher functional polyfunctional alcohol and an isocyanate compound including a tri- or higher functional polyfunctional isocyanate.

12. The wiper device according to claim 11, wherein the alcohol further comprises a diol.

13. The wiper device according to claim 11 or 12, wherein the isocyanate compound further comprises a diisocyanate.

14. The lip portion has a tapered portion in which a cross section in a direction perpendicular to the longitudinal direction of the blade rubber gradually decreases in width from a side closer to the base portion toward a side farther from the base portion, The lip portion is a first side surface and a second side surface that form the tapered portion; a tip surface that, together with the first side surface and the second side surface, constitutes a first edge and a second edge of the lip portion on a side farthest from the base portion, Assuming that a line segment is drawn on the first side surface and the second side surface of the lip portion, parallel to the first edge and the second edge, with a distance of 0.5 mm between the first edge and the second edge, the length of the line segment is L', and points 1 / 8L', 1 / 2L', and 7 / 8L' from one end side on the line segment are P0', P1', and P2', respectively; a sample sampled at each of the P0', P1', and P2' points of the first and second aspects is heated and vaporized in an ionization chamber, and heated to 1000°C at a heating rate of 10°C / s using a direct sample introduction mass spectrometer that ionizes sample molecules; The detected amount of all ions is M1, M2 is the integrated intensity of a peak in the extracted ion thermogram corresponding to the m / z value range derived from the tri- or higher functional isocyanate; When the integrated intensity of the peak in the extracted ion thermogram corresponding to the range of m / z values ​​derived from the diisocyanate is M3, In the first aspect, M2 / M1 is 0.0010 to 0.0150, and M3 / M1 is 0.0200 to 0.1100; 14. The wiper device according to claim 13, wherein in the second aspect, M2 / M1 is 0.0010 to 0.0150, and M3 / M1 is 0.0200 to 0.1100.

15. The lip portion has a tapered portion in which a cross section in a direction perpendicular to the longitudinal direction of the blade rubber gradually decreases in width from a side closer to the base portion toward a side farther from the base portion, The lip portion is a first side surface and a second side surface that form the tapered portion; a tip surface that, together with the first side surface and the second side surface, constitutes a first edge and a second edge of the lip portion on a side farthest from the base portion, Assuming that a line segment is drawn on the first side surface and the second side surface of the lip portion, parallel to the first edge and the second edge, with a distance of 0.5 mm from the first edge and the second edge, the length of the line segment is L', and points 1 / 8L', 1 / 2L', and 7 / 8L' from one end side on the line segment are P0', P1', and P2', respectively; When samples sampled at each of the P0′, P1′, and P2′ in the first and second aspects are measured by pyrolysis GC / MS, In the first aspect, the concentration of the tri- or higher functional alcohol in the polyurethane is 0.04 mmol / g to 0.39 mmol / g; 15. The wiper device according to claim 11, wherein the concentration of the tri- or higher functional alcohol in the polyurethane is 0.04 mmol / g to 0.39 mmol / g.

16. The wiper device according to any one of claims 11 to 15, wherein the tri- or higher functional alcohol includes at least one selected from the group consisting of pentaerythritol, trimethylolpropane, and glycerin.

17. The wiper device according to any one of claims 11 to 16, wherein the trifunctional or higher polyfunctional isocyanate is at least one selected from the group consisting of triphenylmethane-4,4',4''-triisocyanate (TTI), tris(phenylisocyanate) thiophosphate (TPTI), and polymeric MDI.

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