Cleaning wiper blade

Abstract

A cleaning wiper blade is provided that achieves excellent wiping performance against a surface being cleaned, even under weak pressure. The cleaning wiper blade includes a gripping portion for gripping by hand and an elastic portion for pressing against the surface being cleaned, the elastic portion being supported by the gripping portion. The elastic portion has a main surface on its front end that faces the member being cleaned and a front end surface that, together with the main surface, forms a front end edge. Within a specific observation area of the front end surface and the main surface, the average value of the elastic modulus, measured at 0.1 μm intervals, ranges from 15 MPa to 470 MPa, and the coefficient of variation of the elastic modulus is 17.6% or less.

Description

Technical Field

[0001] The present disclosure relates to a wiper blade for cleaning a surface of a component to be cleaned. Background Art

[0002] As a cleaning tool for a surface to be cleaned such as a glass surface, there is a cleaning tool having a cleaning portion and a grip portion that can be gripped by a cleaning worker (PTL 1).

[0003] Citation List

[0004] Patent Literature

[0005] [PTL 1] Japanese Patent Application Publication No. 2019-115471 Summary of the Invention

[0006] Problems to be solved by the invention

[0007] Conventional wiper blades tend to rub unevenly when the pressure on the surface being cleaned is weak. However, when the surface being cleaned is pressed strongly, the contact portion with the cleaned member tends to be disrupted. In some cases, this can cause so-called vibration, which can lead to uneven wiping.

[0008] In particular, for window glass in buildings and showrooms, such as those facing the street, stains with strong adhesion, such as fine particles contained in automobile exhaust, dust, or asphalt oil film, etc., are deposited on the glass surface and cannot be easily wiped off. As a result, wiping unevenness may become unusual.

[0009] One aspect of the present disclosure is to provide a cleaning wiper blade that exhibits excellent wiping performance that is less likely to cause uneven wiping, for example, even when the pressing force against the cleaned surface is not strengthened.

[0010] Solutions for solving problems

[0011] The inventors have found that in order to achieve excellent wiping performance with a cleaning wiper blade even under weak pressing force, it is effective to control the elastic modulus and its coefficient of variation of a specific portion of the elastic portion of the cleaning wiper blade that contacts the member to be cleaned so as to fall within a specific range.

[0012] According to one aspect of the present disclosure, there is provided a cleaning wiper blade comprising:

[0013] A grip portion for grasping by hand; and

[0014] an elastic portion supported by the gripping portion and pressed against the surface to be cleaned;

[0015] making a portion of the elastic portion contact the surface of the member to be cleaned, thereby cleaning the surface of the member to be cleaned,

[0016] When the side of the elastic portion most distant from the gripping portion is defined as the front end side of the wiper blade,

[0017] The elastic portion has, on the front end side, a main surface facing the member to be cleaned and a front end surface forming a front end side edge together with the main surface;

[0018] Assuming that a first line segment is drawn on the front end surface in parallel with the front end side edge at a distance of 10 μm from the front end side edge,

[0019] The length of the first line segment is defined as L1;

[0020] points at (1 / 8) L1, (1 / 2) L1, and (7 / 8) L1 from one end side on the first line segment are defined as P0, P1, and P2, respectively; and

[0021] When the elastic modulus at 70,000 points at 0.1 μm intervals in each of three rectangular observation areas on the front end surface is measured using a scanning probe microscope, each of the rectangular observation areas having respective centers of gravity at P0, P1, and P2 and having a 70 μm-long side parallel to the first line segment and a 10 μm-long side perpendicular to the first line segment,

[0022] The average value of the 210,000 obtained elastic modulus values is 15 MPa to 470 MPa, and the coefficient of variation of the elastic modulus is 17.6% or less; and

[0023] Assuming that a second line segment is drawn on the main surface in parallel with the front end side edge at a distance of 10 μm from the front end side edge,

[0024] The length of the second line segment is defined as L2;

[0025] points at (1 / 8) L2, (1 / 2) L2, and (7 / 8) L2 from one end side on the second line segment are defined as P3, P4, and P5, respectively; and

[0026] When it is assumed that measurement is performed at 70,000 points at 0.1 μm pitch in each of three rectangular observation areas on the main surface using a scanning probe microscope, each of the rectangular observation areas has a center of gravity at P3, P4, and P5 and has a 70 μm long side parallel to the second line segment and a 10 μm long side perpendicular to the second line segment,

[0027] The average value of the elastic modulus values obtained from 210,000 samples was 15 MPa to 470 MPa, and the coefficient of variation of the elastic modulus was 17.6% or less.

[0028] Effects of the Invention

[0029] According to one aspect of the present disclosure, it is possible to provide a cleaning wiper blade capable of exhibiting excellent wiping performance even when the pressing force against a surface to be cleaned is weak. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] [ Figure 1 ] Figure 1 (a), (b), (c) and (d) are examples of schematic diagrams of wiper blades.

[0031] [ Figure 2 ] Figure 2 (a) and (b) are explanatory diagrams illustrating the state during the cleaning process of the wiper blade.

[0032] [ Figure 3 ] An enlarged schematic diagram of the contact portion between the elastic portion of the wiper blade and the component to be cleaned.

[0033] [ Figure 4 ]Enlarged view near the front side edge.

[0034] [ Figure 5 ]Enlarged view near the first line segment.

[0035] [ Figure 6 ]Enlarged view near the observation area 12 with the center of gravity at P0.

[0036] [ Figure 7 ] Figure 7 (a) and (b) are schematic diagrams showing the vicinity of the contact portion of the wiper blade with the member to be cleaned.

[0037] [ Figure 8 ] Schematic diagram of a tester for evaluating the wiping performance of a wiper blade.

[0038] [ Figure 9 ] An enlarged view of the contact portion between the elastic portion of the wiper blade and the glass surface. DETAILED DESCRIPTION

[0039] In the present disclosure, the description “from XX to YY” or “XX to YY” expressing a numerical range means that the numerical range includes the lower limit and the upper limit endpoints unless otherwise specified.

[0040] When numerical ranges are described in sections, the upper and lower limits of each numerical range can be arbitrarily combined.

[0041] <Construction of Wiper Blade>

[0042] A cleaning wiper blade (hereinafter also referred to as a wiper blade) according to one aspect of the present disclosure includes a gripping portion 1 gripped by a hand and an elastic portion 2 supported by the gripping portion and pressed against a surface to be cleaned. Figure 1 The wiper blade comes into contact with the surface of the member to be cleaned at a portion of its elastic portion and cleans the surface of the member to be cleaned.

[0043] Figure 1 An example of a schematic diagram of a wiper blade is shown. Figure 1 (a) shows a structure including a gripping portion 1 and an elastic portion 2. However, as shown in (b), a supporting portion 3 for supporting the elastic portion 1 may be included between the gripping portion 1 and the elastic portion 2.

[0044] Alternatively, for example, Figure 1 As shown in (c), a support gripping portion 4 may be included that integrally includes a support portion and a gripping portion.

[0045] like Figure 1 As shown in (d), the elastic portion and the gripping portion may be integrated with each other.

[0046] The gripping portion 1 , the supporting portion 3 and the elastic portion 2 may be detachable or integrated with each other.

[0047] Figure 2 1 is an explanatory diagram showing a state in which the elastic portion 2 of the wiper blade contacts and slides against the member to be cleaned 5 for cleaning. Figure 2 As shown, the wiper blade can be used in a push direction C, so as to move from the gripping portion 1 towards the elastic portion 2 , and in a pull direction W.

[0048] Figure 3 2 is an enlarged schematic diagram of the contact portion between the elastic portion 2 and the member to be cleaned 5. The front end side of the wiper blade is defined as the side of the elastic portion that is farthest from the gripping portion. Figure 3 As shown, the elastic portion 2 has a main surface 6 on the front end side opposite to the member to be cleaned 5, and a front end surface 8 that forms a front end side edge 9 together with the main surface 6. The front end side edge 9 extending along the length direction of the elastic portion 2 is formed on the elastic portion 2 by the main surface 6 and the front end surface 8.

[0049] Figure 4 9 is an enlarged view of the front end side edge 9. Figure 4 As shown, it is assumed that a first line segment 10 is drawn on the front end surface 8 in parallel with the front end side edge 9 at a distance of 10 μm from the front end side edge 9. Here, L1 represents the length of the first line segment 10. Figure 5 is an enlarged view near the first line segment. Figure 5 As shown, P0, P1, and P2 represent points at (1 / 8) L1, (1 / 2) L1, and (7 / 8) L1, respectively, from one end side on the first line segment 10. Here, three rectangular observation areas are provided on the front end surface 8, each having a 70 μm long side parallel to the first line segment 10 and a 10 μm long side perpendicular to the first line segment, and having respective centers of gravity at P0, P1, and P2 on the first line segment.

[0050] Figure 6 An enlarged view of the vicinity of the observation area 12 with P0 as its center of gravity is shown. Figure 6 Similar to P0 in FIG, the elastic modulus of the front end surface was measured using a scanning probe microscope (hereinafter referred to as SPM) at 70,000 points (including P1 and P2) at a pitch (interval) of 0.1 μm in each of three observation areas, including both P1 and P2. The average value of the total 210,000 elastic modulus values obtained was 15 MPa to 470 MPa, and the coefficient of variation of the elastic modulus was 17.6% or less.

[0051] Similar to the measurement at the front surface, assuming that Figure 4 As shown, a second line segment 11 is drawn on the main surface 6 parallel to the front edge 9 at a distance of 10 μm from the front edge 9. Here, L2 represents the length of the second line segment 11. In addition, P3, P4, and P5 represent points at (1 / 8) L2, (1 / 2) L2, and (7 / 8) L2 from one end of the second line segment 11, respectively.

[0052] Here, three rectangular observation areas were provided on main surface 6. These areas had 70 μm-long sides parallel to second line segment 11 and 10 μm-long sides perpendicular to the second line segment, with their respective centers of gravity at P3, P4, and P5 on the second line segment. Using SPM, the elastic modulus of the main surface was measured at 70,000 points with 0.1 μm spacing (intervals) for each of the three observation areas. The average value of the 210,000 elastic modulus values obtained was between 15 MPa and 470 MPa, and the coefficient of variation of the elastic modulus was 17.6% or less.

[0053] The behavior of the wiper blade during cleaning was observed in detail. It was found that when the wiper blade moved in the direction C from the gripping portion toward the spring portion, the wiper blade contacted the member being cleaned in an area including a position approximately 10 μm from the front end side edge 9 on the front end surface 8. When the wiper blade moved in the pulling direction W, the wiper blade was found to contact the member being cleaned in an area including a position approximately 10 μm from the front end side edge 9 on the main surface 6.

[0054] A wiper blade according to one aspect of the present disclosure prevents wiping streaks and uneven wiping from occurring at the wiping portion of the member to be cleaned due to the fact that the average value of the elastic modulus in the length direction of each area that can constitute the above contact portion with the member to be cleaned and the coefficient of variation of the elastic modulus meet predetermined regulations.

[0055] In a wiper blade according to one aspect of the present disclosure, the average value of the elastic modulus values measured at a position 10 μm away from the front end surface and the front end side edge on the main surface of the contact portion that can constitute the contact portion with the cleaned member, and at a position in the longitudinal direction of the area near the 10 μm position, is 15 MPa to 470 MPa, and the coefficient of variation of the elastic modulus is 17.6% or less. The average value of the elastic modulus values is preferably 32 MPa to 62 MPa. The coefficient of variation of the elastic modulus is preferably 6.0% or less. The coefficient of variation of the elastic modulus is preferably as small as possible, so the lower limit is not particularly limited, but is, for example, 0.10% or more.

[0056] When the average elastic modulus value falls within the above range, a portion of the wiper blade's elastic portion can contact the component being cleaned within a narrow width across the entire length of the wiper blade during cleaning. This allows the contact portion to approximate line contact, concentrating the pressing force there. This allows deposits to be reliably scraped off the component being cleaned, rather than simply being wiped off or scattered. This results in significantly higher wiping performance compared to conventional wiper blades.

[0057] The feature in which the coefficient of variation of the elastic modulus is 17.6% or less means that the elastic modulus of the elastic portion at the contact portion is more uniform or more homogeneous in the length direction of the elastic portion. As a result, the pressing force from the wiper blade to the component to be cleaned can be applied evenly over the entire length direction of the wiper blade. As a result, this allows for stable tracking and contact with the cleaned portion of the component to be cleaned, while suppressing the occurrence of vibrations, etc., and there are no ripples on the cleaned surface in the length direction of the wiper blade during cleaning. Therefore, the wiper blade according to one aspect of the present disclosure can stably provide excellent wiping performance without wiping streaks or uneven wiping, and this is also true for highly viscous stains such as oil films that adhere to the component to be cleaned.

[0058] The coefficient of variation of the elastic modulus was calculated according to the following formula (1).

[0059] Formula (1): Coefficient of variation (%) = (standard deviation of elastic modulus value / average value) × 100

[0060] For example, when the wiper blade is pressed against the member being cleaned under a load of 16.7 N / m, in the case of a conventional wiper blade used for cleaning, the contact angle near the contact portion is about 25°, the gap width is 20-30 μm, and the maximum contact pressure is 1.5 MPa. In contrast, the wiper blade of the present disclosure produced measured values including a contact angle of about 55°, a gap width of 5-6 μm, and a contact pressure of 6.0 MPa.

[0061] Figure 7 Schematic diagram showing the vicinity of the contact portion between the wiper blade and the member to be cleaned. Figure 7 As shown in (a), the conventional wiper blade has a relatively wide surface in contact with the component to be cleaned. Figure 7 As shown in (b) , the wiper blade according to one aspect of the present disclosure is in contact with the member to be cleaned in a state of approximately line contact.

[0062] The material constituting the elastic portion 2 is not particularly limited, provided that it is a material capable of forming a contact portion with the member to be cleaned and that the average value of the elastic modulus and the coefficient of variation of the elastic modulus at and near a position 10 μm from the front end surface and the front end side edge of the main surface meet the above-mentioned specifications. Specifically, for example, the elastic portion preferably comprises polyurethane, which exhibits excellent mechanical properties and whose properties are relatively easy to adjust.

[0063] In addition, the above-mentioned polyurethane is preferably a polyurethane elastomer. Polyurethane elastomer is mainly obtained from raw materials such as polyols, chain extenders, polyisocyanates, catalysts and other additives. The above-mentioned polyurethane elastomer is a block copolymer composed of hard segments and soft segments. The hard segments are usually composed of chain extenders such as polyisocyanates and short-chain diols. The soft segments are usually composed of polyisocyanates and long-chain polyols such as polyester polyols, polyether polyols or polycarbonate polyols.

[0064] In order to achieve the average value of the elastic modulus according to the present disclosure, and to adjust the coefficient of variation of the elastic modulus according to the present disclosure, for example, the characteristics of the block copolymer composed of the hard segment and the soft segment may be utilized.

[0065] In conventional polyurethanes, the aggregated portion of the carbamate bond portion resulting from the aggregation generated by the interaction of carbamate bonds has relatively large hard segments, which in turn are generated by further aggregation. As a result, the inventors' research has revealed that wiper blades produced using conventional polyurethanes do not meet at least one of the average value of the elastic modulus value and the coefficient of variation of the elastic modulus according to the present disclosure. That is, conventional polyurethanes have relatively large hard segments, and therefore, in a scanning probe microscope, it is difficult to make the coefficient of variation of the elastic modulus of 210,000 sites less than 17.6% as in the present disclosure. It is believed that in the case of polyurethanes having a small amount of hard segments themselves, the further aggregation of the aggregated portion of the carbamate bond can be suppressed, and the coefficient of variation can be kept small. However, in this case, it is difficult to set the average value of the elastic modulus value to more than 15MPa.

[0066] The elastic portion according to one aspect of the present disclosure may be formed of, for example, polyurethane in which hard segments are finely and uniformly dispersed.

[0067] Various examples of polyurethane in which hard segments are finely and uniformly dispersed will be further explained below. However, the constituent material of the elastic part according to the present disclosure is not limited to such polyurethane.

[0068] By using polyurethane raw materials in the form of diisocyanate or trifunctional or higher polyfunctional isocyanate and diol or trifunctional or higher polyfunctional alcohol within an appropriate concentration range, a polyurethane having fine and uniform dispersion of hard segments while suppressing aggregation of hard segments can be obtained.

[0069] Specifically, for example, an alcohol including at least one of trifunctional or higher polyfunctional alcohols and an isocyanate compound including trifunctional or higher polyfunctional isocyanate are preferably used as the polyurethane raw material.

[0070] It is also preferred to use an alcohol including at least one selected from diols and trifunctional or higher polyfunctional alcohols, and an isocyanate compound including trifunctional or higher polyfunctional isocyanate as the polyurethane raw materials.

[0071] It is also preferred to use alcohols including trifunctional or higher polyfunctional alcohols and isocyanate compounds including diisocyanates and trifunctional or higher polyfunctional isocyanates as polyurethane raw materials.

[0072] Particularly preferably, trifunctional or higher polyfunctional isocyanates and trifunctional or higher polyfunctional alcohols are used as polyurethane raw materials.

[0073] Due to steric hindrance, the polyurethane obtained as the reaction product of a trifunctional or higher polyfunctional isocyanate and a trifunctional or higher polyfunctional alcohol exhibits suppressed molecular orientation, which further reliably suppresses hard segment aggregation. As a result, the polyurethane is suitable for achieving the elastic modulus and coefficient of variation according to the present disclosure.

[0074] In addition, when the soft segment portion has, for example, a linear alkylene structure, the crystallinity is improved by stacking the soft segments. As a result, the hard segments are not easily dispersed. Therefore, introducing an alkylene structure having a side chain portion into the soft segment portion is also effective in suppressing the aggregation of the hard segments. Specifically, for example, introducing a substructure into the soft segment portion between two urethane bonds, such as the substructure represented by the following structural formulas (i) to (iv), is effective in making the hard segments smaller.

[0075] -CH2-CH(CH3)-CH2-CH2-O- (i)

[0076] -CH2-CH2-CH(CH3)-CH2-O- (ii)

[0077] -CH2-CH(CH3)-O- (iii)

[0078] -CH(CH3)-CH2-O- (iv)

[0079] The structures of substantially the same structural formula (i) and (ii) are obtained by the ring-opening polymerization of 3-methyltetrahydrofuran. The structures of substantially the same structural formula (iii) and (iv) are obtained by the ring-opening polymerization of 1,2-propylene oxide. Here, by reacting a polyether polyol or polyester polyol having these structures with an isocyanate, a polyurethane resin having these structures between two adjacent urethane bonds can be obtained. When difunctional alcohols (diols) and difunctional isocyanates (diisocyanates) are used as polyurethane raw materials, it is generally difficult to achieve fine dispersion of the hard segments. However, even when diols and diisocyanates are used, the hard segments can also be finely dispersed by introducing the above-mentioned substructures into the soft segment portion. As a result, a polyurethane for a wiper blade that meets the parameters according to the present disclosure can be obtained.

[0080] In addition to introducing side chains into the soft chain portion as described above, methods for suppressing crystallization from soft segment stacking and preventing hard segment aggregation also include, for example, methods involving the use of two or more alcohols having linear moieties with different numbers of carbon atoms as the alcohol in the polyurethane raw material. In polyurethanes obtained by using two or more linear moieties having different numbers of carbon atoms, crystallization from soft segment stacking can also be suppressed due to the different carbon numbers, and also when the soft segment portion has a linear alkylene structure. Taking into account the different carbon number of the soft segment portion, the aggregation of the urethane bond portion is suppressed, which allows the hard segment to be prevented from aggregating. Therefore, when using diisocyanates and diols having linear alkylene structures in the molecule as polyurethane raw materials, by using multiple diols having different numbers of carbon atoms in the linear alkylene structure as the above diols, the hard segment can also be made smaller. As a result, a polyurethane for a wiper blade that meets the parameters of the present disclosure can be obtained. Examples of multiple types of diols include, for example, the simultaneous use of polytetramethylene glycol adipate polyester polyol and polyhexamethylene glycol adipate polyester polyol.

[0081] Examples of the above-mentioned alcohols include the following.

[0082] Polyester polyols, such as polyethylene glycol adipate polyester polyol, polybutylene glycol adipate polyester polyol, polyhexylene glycol adipate polyester polyol, (polyethylene glycol / polypropylene glycol) adipate polyester polyol, (polyethylene glycol / polybutylene glycol) adipate polyester polyol, and (polyethylene glycol / polyneopentyl glycol) 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. The foregoing can be used alone or in combination of two or more.

[0083] As described above, it is preferable to use two or more polyols having linear moieties (alkylene chains) having different numbers of carbon atoms, because in this case, a polyurethane in which soft segments are suppressed from crystallizing and hard segments are suppressed from aggregating is obtained. In this case, it is preferable to use, for example, at least two selected from the group consisting of polyester polyols such as polyethylene glycol adipate polyester polyol, polybutylene glycol adipate polyester polyol, polyhexylene glycol adipate polyester polyol, (polyethylene glycol / polypropylene glycol) adipate polyester polyol, (polyethylene glycol / polybutylene glycol) adipate polyester polyol, and (polyethylene glycol / polyneopentyl glycol) adipate polyester polyol.

[0084] As the chain extender, a diol or a trifunctional or higher-functional alcohol capable of extending the polyurethane elastomer chain can be used.

[0085] Examples of the diols include the following.

[0086] 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, xylene glycol (p-phenylenediol), and triethylene glycol. The foregoing can be used alone or in combination of two or more.

[0087] Examples of trifunctional or higher polyfunctional alcohols include trimethylolpropane (TMP), glycerol, pentaerythritol, and sorbitol. The foregoing may be used alone or in combination of two or more.

[0088] A method of increasing the elastic modulus of a polyurethane elastomer may involve, for example, introducing a cross-linked structure. A preferred method of introducing a cross-linked structure involves, for example, using a trifunctional or higher polyfunctional alcohol as the above-mentioned chain extender. By using a trifunctional or higher polyfunctional alcohol, a branched structure is introduced into the polyurethane so as to suppress polyurethane crystallization and further suppress hard segment aggregation. From the viewpoint of suppressing the excessive increase in hardness caused by the excessively high degree of cross-linking of the polyurethane, preferably, a trifunctional alcohol is used as the polyfunctional alcohol. Preferred among the aforementioned are triols, because these have a methylene skeleton adjacent to a hydroxyl group, can produce a flexible cross-linked structure in the molecular structure, and induce an effect of further suppressing the crystallinity of the hard segment. Examples of such triols include, for example, trimethylolpropane (TMP) and glycerol.

[0089] Examples of the above-mentioned isocyanate compound include the following.

[0090] 4,4'-diphenylmethane diisocyanate (4,4'-MDI), polymeric MDI, 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), xylene diisocyanate (XDI), 1,5-naphthalene 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), and triphenylphosphorothioate (TPTI).

[0091] Among the aforementioned, 4,4'-MDI is preferred because its two isocyanate groups are quite reactive and the compound provides high mechanical properties. Preferably, a trifunctional or higher polyfunctional isocyanate is used simultaneously. The use of a trifunctional or higher polyfunctional isocyanate allows the introduction of a branched structure into the polyurethane and is effective in further suppressing the aggregation of hard segments. In addition, a denser cross-linked structure can be introduced into the polyurethane, thereby making the contact of the elastic portion to the component being cleaned more stable. As a result, wiping streaks and uneven wiping in the component being cleaned can be effectively suppressed.

[0092] Examples of trifunctional or higher polyfunctional isocyanates include at least one selected from the group consisting of triphenylmethane-4,4',4"-triisocyanate (TTI), triphenylphosphorothioate (TPTI) and polymeric MDI. Among the aforementioned, triphenylphosphorothioate (TPTI) and polymeric MDI can be more suitably used. These isocyanates have a methylene group or an ether group between multiple NCO groups, thereby being able to appropriately maintain the distance between multiple urethane bonds. Therefore, these isocyanates are advantageous in suppressing the aggregation of hard segments.

[0093] Polymeric MDI is represented by the following chemical formula (1) and chemical formula (1)'. In chemical formula (1)', n is preferably 1 to 4. Chemical formula (1) is an example in which n is 1 in chemical formula (1)'.

[0094] [C1]

[0095]

[0096] Preferably, when the elastic portion according to the present disclosure comprises the following polyurethane, the elastic portion has the following physical properties: it is a cured product of a composition comprising an isocyanate compound including a diisocyanate and a trifunctional or higher polyfunctional isocyanate, and an alcohol including a trifunctional or higher polyfunctional alcohol. Specifically, assume that line segments are drawn on the front end surface and main surface of the elastic portion, parallel to the front end side edge and at a distance of 0.5 mm from the front end side edge. With L' being the length of each line segment, P0', P1', and P2' represent points at 1 / 8 L', 1 / 2 L', and 7 / 8 L', respectively, from one end of the line segment.

[0097] Using a mass spectrometer with direct sample introduction, in which the sample is heated and vaporized in an ionization chamber to ionize the sample molecules, each sample taken at the aforementioned points P0', P1', and P2' on the tip surface and main surface is heated to 1000°C at a heating rate of 10°C / s. Here, M1 represents the amount of all ions detected as a result, and M2 represents the peak integrated intensity in the extracted ion thermogram corresponding to the m / z value range derived from trifunctional or higher polyfunctional isocyanates. In this case, the ratio M2 / M1 on the tip surface and / or main surface is preferably in the range of 0.0010 to 0.0150, and particularly preferably in the range of 0.0030 to 0.0150.

[0098] Taking M3 as the peak integrated intensity in the extracted ion thermogram corresponding to the m / z value range derived from diisocyanate, M3 / M1 on the front surface and / or main surface is preferably in the range of 0.0200 to 0.1100, and more preferably in the range of 0.0380 to 0.0760.

[0099] Due to the fact that M2 / M1 and M3 / M1 are within the above ranges, an appropriate amount of low-crystalline structures derived from trifunctional or higher-functional isocyanates are introduced into the polyurethane; as a result, aggregation of the hard segments can be suppressed, and the hard segments can be dispersed more finely and uniformly. In addition, the development of crosslinked structures in the polyurethane can be prevented from becoming excessive, and the average elastic modulus can be easily adjusted to within the range of 15 MPa to 470 MPa.

[0100] Preferably, M2 / M3 is set within the range of 0.0130 to 0.3000. Here, M2 / M3 is a parameter representing the ratio of diisocyanate-derived moieties to tri- or higher-functional isocyanate-derived moieties within the isocyanate-derived structure in the polyurethane. Setting M2 / M3 within this range can suppress excessive increases in the elastic modulus of the polyurethane and further inhibit aggregation of hard segments within the polyurethane.

[0101] In the case where the polyurethane according to one aspect of the present disclosure is a polyurethane produced using polymeric MDI represented by chemical formula (1)', as a trifunctional or higher polyfunctional isocyanate, in the extracted ion thermogram obtained by the above-mentioned mass spectrometry, M2 can be set to the sum of the peak integrated intensities corresponding to the m / z values in the range of 380.5 to 381.5 derived from n=1, the m / z values in the range of 511.5 to 512.5 derived from n=2, the m / z values in the range of 642.5 to 643.5 derived from n=3, and the m / z values in the range of 773.5 to 774.5 derived from n=4 in the structure represented by chemical formula (1)'.

[0102] In the case where the polyurethane according to one aspect of the present disclosure is a polyurethane produced using 4,4'-MDI represented by the following chemical formula (2) as a difunctional isocyanate (diisocyanate) as one of the raw materials, in the extracted ion thermogram obtained by the above-mentioned mass spectrometry, M3 can be set to the peak integrated intensity corresponding to the m / z value in the range of 249.5 to 250.5 derived from the structure represented by chemical formula (2).

[0103] [C2]

[0104]

[0105] Preferably, in the case where the elastic portion of the wiper blade according to one aspect of the present disclosure includes the following polyurethane, the elastic portion has the following physical properties, the polyurethane being a reaction product of a raw material composition including an alcohol containing a trifunctional or higher polyfunctional alcohol. Specifically, in each line segment drawn on the front end surface and main surface of the elastic portion in parallel with the front end side edge, at a distance of 0.5 mm from the front end side edge, and with L' as the length of each line segment, P0', P1' and P2' respectively represent points at 1 / 8L', 1 / 2L' and 7 / 8L' from one end side on the line segment. Samples sampled at each of the above-mentioned P0', P1' and P2' on the front end surface and main surface were measured by pyrolysis GC / MS (gas chromatography and mass spectrometry). In this case, the concentration of the trifunctional or higher polyfunctional alcohol in the polyurethane at the front end surface and the main surface 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. In the case where the concentration of the trifunctional or higher polyfunctional alcohol is 0.04 mmol / g or more, the aggregation of the hard segments can be more reliably suppressed. In addition, due to the fact that the concentration of the trifunctional or higher polyfunctional alcohol is 0.39 mmol / g or less, the excessive development of the cross-linked structure in the polyurethane can be suppressed, and the elastic modulus can be prevented from becoming too high. Therefore, the elastic portion having the above-mentioned physical properties can more easily meet the above-mentioned regulations related to the average value of the elastic modulus value (15 to 470 MPa) and the coefficient of variation of the elastic modulus (17.6% or less).

[0106] The concentration of trifunctional or higher polyfunctional alcohol in the polyurethane was calculated according to the following formula (2).

[0107] Formula (2): Concentration of trifunctional or higher polyfunctional alcohol (mmol / g) =

[0108] [Amount of trifunctional or higher polyfunctional alcohol (g) / molecular weight of trifunctional or higher polyfunctional alcohol × 1000] / [mass of polyurethane (g)]

[0109] In the case where the elastic portion of the wiper blade according to the present disclosure comprises polyurethane, the raw material composition of the polyurethane may contain a catalyst for promoting the reaction of the isocyanate compound and the alcohol. Such a catalyst may be, for example, a tertiary amine catalyst, in particular the amines exemplified below. 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; as well as triethylenediamine, piperazine-based compounds, and triazine-based compounds. Alkali metal organic acid salts such as potassium acetate and potassium octoate may also be used. Metal catalysts commonly used for carbamate formation may also be used, such as dibutyltin dilaurate. The aforementioned may be used alone or in combination of two or more.

[0110] The raw material constituting the elastic part of the wiper blade may be formulated with pigments, plasticizers, water repellents, antioxidants, ultraviolet absorbers, and light stabilizers as needed within a range that does not affect the elastic modulus or coefficient of variation of the elastic part.

[0111] Surface treatment

[0112] The elastic portion of the wiper blade may be surface treated. Preferred surface treatment methods in the present disclosure include, for example, (i) a method comprising projecting ultraviolet rays onto the object to be treated, and (ii) a method comprising impregnating the object to be treated by coating it with a material for forming a cured region and then curing the material for forming a cured region.

[0113] (i) Surface treatment method including ultraviolet irradiation step

[0114] There is no particular restriction on the conditions for irradiating the object to be treated (wiper blade) with ultraviolet rays. The wavelength of the ultraviolet rays may be 400 nm or less, but is preferably 200 nm or more. If the wavelength of the ultraviolet rays is 200 nm or more, the elastic modulus can be effectively increased. Preferably, the wavelength of the maximum emission peak of the light emitted by the light source is 200 nm to 400 nm. Particularly preferably, the wavelength of the maximum emission peak is around 254 nm, for example, within the range of 254 ± 1 nm. This is because ultraviolet rays within the above-mentioned wavelength range or at the above-mentioned wavelength can effectively generate active oxygen, which changes the surface of the elastic portion of the wiper blade. In the case where there are multiple emission peaks of ultraviolet rays, preferably, one of the peaks exists near 254 nm.

[0115] The intensity of light emitted from the light source is not particularly limited, and for example, a value measured using a spectroradiometer (trade name: USR-40V / D, Ushio Inc.) or an integrated UV meter (trade name: UIT-150-A, UVD-S254, VUV-S172 or VUV-S365, Ushio Inc.) can be adopted.

[0116] The cumulative light intensity of the ultraviolet rays projected onto the elastic portion of the wiper blade in the surface treatment step can be appropriately selected depending on the surface treatment effect to be obtained. For example, the irradiation with light from the light source can be performed according to the irradiation duration, the output of the light source, and the distance to the light source, and, for example, a desired cumulative light intensity of, for example, 10,000 mJ / cm can be obtained. 2 .

[0117] The integrated light intensity of ultraviolet rays projected onto the elastic portion of the wiper blade can be calculated according to the following method.

[0118] Cumulative UV light intensity (mJ / cm 2 ) = UV intensity (mW / cm 2 )×irradiation duration (seconds)

[0119] For example, a high-pressure mercury lamp or a low-pressure mercury lamp can be suitably used as a light source for emitting ultraviolet rays. These light sources are preferred because they can stably emit ultraviolet rays having a suitable wavelength, have little attenuation due to irradiation distance, and allow uniform full-surface irradiation.

[0120] (ii) A surface treatment method comprising the steps of impregnating the object to be treated by coating the object with a cured region forming material and curing the material

[0121] To form a cured region on the front end surface and main surface of the elastic portion of a wiper blade, a cured region-forming material is applied to the front end and main surfaces, impregnating the object to a certain depth from the front end and main surfaces. The object impregnated with the material is then cured. This effectively increases the elastic modulus measured at the front end and main surfaces.

[0122] The cured region forming material may be used after being diluted with a diluting solvent as needed, and may be applied by means such as dipping, spraying, dispenser coating, brushing, roller coating, etc. Application of the cured region forming material may be followed by a heat treatment.

[0123] Preferably, the cured region-forming material is impregnated into the polyurethane contained in the elastic member. Impregnation is facilitated by increasing the concentration and decreasing the viscosity of the cured region-forming material, thereby allowing the cured region-forming material to be heated and impregnated without being diluted. The degree of curing can be adjusted, for example, based on the duration of the immersion or dipping process, the temperature and duration of the subsequent heat treatment, and / or the subsequent resting time.

[0124] The temperature of the curing region-forming material can be set within a range of approximately 60°C to 90°C. The immersion or immersion time cannot be specified, but is preferably within a range of approximately 10 seconds to 180 seconds. After the curing region-forming material is applied to the curing region, a heat treatment may be performed. As a result of the heat treatment, the viscosity of the curing region-forming material present on the polyurethane surface decreases; this, in turn, facilitates the penetration and diffusion of the material into the polyurethane.

[0125] The heating method is not particularly limited and may be a method involving passing through a heating furnace or a method involving blowing a hot air flow. The heating furnace includes, for example, a radiation heating furnace and a circulating air heating furnace, and the device for forming the hot air flow includes a hot air blower and a far-infrared heater.

[0126] By setting the heating conditions to high temperatures and / or long durations, the cured area becomes wider, which translates into higher elasticity. In preferred heating conditions, the surface temperature of the treated surface is set within a range of, for example, 90°C to 110°C. Preferably, the heating time is set within a range of, for example, 10 minutes to 60 minutes.

[0127] Furthermore, the amount of isocyanate remaining during polyurethane formation tends to decrease gradually over time after formation. Therefore, although not limited thereto, the cured region can be formed immediately after the polyurethane is formed. For example, the cured region can be formed within 3 hours after the polyurethane is formed. The amount of residual isocyanate can also be adjusted based on the mixing ratio of the composition used during polyurethane formation.

[0128] When the elastic portion is made of polyurethane, the material for forming the cured region is not particularly limited, as long as it is a material capable of forming a cured region upon curing in polyurethane and capable of forming a cured region on the surface of the polyurethane. Examples of such materials include isocyanate compounds and acrylic resins. The cured region-forming material can be used after being 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 include toluene, xylene, butyl acetate, methyl isobutyl ketone, and methyl ethyl ketone.

[0129] When an isocyanate compound is used as the material for forming the cured region, an isocyanate compound having one or more isocyanate groups in the molecule can be suitably used. Aliphatic monoisocyanates such as octadecyl isocyanate (ODI) or aromatic monoisocyanates such as phenyl isocyanate (PHI) can be used as the isocyanate compound having one isocyanate group in the molecule.

[0130] As the isocyanate compound having two isocyanate groups in the molecule, a compound commonly used in the production of polyurethane resins can be used. Specific examples thereof include the following. 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (MDI), metaphenylene diisocyanate (MPDI), tetramethylene diisocyanate (TMDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI). Examples of isocyanate compounds having three or more isocyanate groups in the molecule include the following. 4,4',4"-triphenylmethane triisocyanate, 2,4,4'-biphenyl triisocyanate and 2,4,4'-diphenylmethane triisocyanate.

[0131] Isocyanate compounds having two or more isocyanate groups may also be used in the form of modified derivatives or polymers thereof. Here, MDI exhibiting high crystallinity (i.e., a symmetrical structure) is preferred in order to effectively increase the hardness of the cured region; in terms of workability, MDI including modified products is more preferred because MDI is, after all, liquid at room temperature.

[0132] Method for manufacturing elastic portion of wiper blade

[0133] The manufacturing method of the elastic portion of the wiper blade is not particularly limited and can be selected from known methods. For example, a raw material composition of polyurethane can be injected into the mold cavity of a forming mold for the elastic portion of the wiper blade, and then the composition is cured by heating, followed by demoulding to obtain a formed product. The formed product can be used as a wiper blade as it is. Alternatively, the formed product can be appropriately formed, for example by cutting, and then used as a wiper blade. In this case, the front end surface and the main surface are preferably formed by cutting the elastic portion, because in this case, the smoothness of the front end side edge can be increased. As another forming method, a pair of serial-shaped formed products can be produced in such a form that the front end surfaces of the elastic portion are in contact while facing each other, and then the formed product is cut in the length direction to produce each wiper blade.

[0134] The composition of the cleaning wiper blade

[0135] The wiper blade includes a gripping portion 1 and an elastic portion 2 supported by the gripping portion 1 and pressed against the surface to be cleaned. The wiper blade may have a supporting portion 3, which is a portion located between the elastic portion 2 and the gripping portion 1 and supports the elastic portion 2. The gripping portion 1 is a portion that can be gripped by a cleaning work subject, such as a human hand or a robot hand. Figure 1 As shown in (a) and (b), the gripping portion 1 is connected to the elastic portion directly or via the supporting portion 3. The gripping portion 1 may be connectable / detachable to the elastic portion 2 and / or the supporting portion 3, or may be integrated with the elastic portion 2 and / or the supporting portion 3. The gripping portion 1 extends in a direction intersecting with the extending direction of the elastic portion 2. There is no particular restriction on the shape of the gripping portion 1 as long as it can be gripped or held by the cleaning work subject. A clamp for cleaning assistance may be connected to the gripping portion. Examples of the clamp include a clamp that extends the gripping portion for cleaning high places. There is no particular restriction on the material of the gripping portion 1, and the gripping portion 1 may be made of resin or metal.

[0136] like Figure 1 As shown in (b), the support portion 3 is a portion located between the elastic portion 2 and the grip portion 1 and supports the elastic portion 2. Figure 1 As shown in (a), the wiper blade may lack the supporting portion 3, and then the elastic portion 2 is directly connected to the gripping portion 1. However, in order to cause the elastic portion to be in stable contact with the component to be cleaned, it is preferred to have a supporting portion. The supporting portion 3 is connected to the elastic portion 2 in a direction perpendicular to the extension direction of the elastic portion 2. The elastic portion 2 may be connectable / detachable to the supporting portion 3, or integrated with the supporting portion 3. The shape of the supporting portion 3 is not limited as long as it can support the elastic portion 2. For example, the supporting portion 3 may have a shape that clamps a portion of the elastic portion 2. The material of the supporting portion 3 is not particularly limited, and the supporting portion 3 is made of resin or metal.

[0137] How to use the wiper blade

[0138] Next, the method of using the wiper blade will be explained.

[0139] The cleaning agent holds the grip 1 or the support grip 4 and moves the wiper blade in a direction intersecting the extending direction of the elastic portion 2 while pressing the elastic portion 2 against the surface of the member to be cleaned, thereby removing dirt. Figure 2 An explanatory diagram showing a state of a cleaning process in which a wiper blade contacts and slides on a member to be cleaned during cleaning.

[0140] The direction in which the wiper blade moves is, for example, a direction intersecting the direction in which the elastic portion 2 extends; Figure 2 (a) shows the direction of push C and Figure 2 The pulling direction W shown in (b) is used for movement.

[0141] Stains can be pre-moistened with liquid detergent, water, etc. and removed together with the liquid detergent, water, etc.

[0142] Shape of wiper blade

[0143] In the wiper blade, the shapes and mounting methods of the elastic part 2, the supporting part 3 and the gripping part 1 or the supporting gripping part 4 are not limited. The mounting method of the supporting part 3 to the elastic part 2 and the mounting method of the gripping part 1 or the supporting gripping part 4 to the supporting part 3 are not limited.

[0144] Example

[0145] The present disclosure will be explained below by manufacturing examples, working examples and comparative examples, but the present disclosure is not limited by these examples in any way. Except those listed in the examples and comparative examples, reagents or industrial chemicals are also used as raw materials. Unless otherwise stated, the term "part" in the examples and comparative examples refers to a mass basis throughout.

[0146] Example 1

[0147] Preparation of starting materials for the elastic portion

[0148] The materials given in Table 1 were mixed and reacted at a temperature of 80° C. for 3 hours to prepare a prepolymer having an NCO content of 10.0% by mass.

[0149] Table 1

[0150]

[0151] The curing agent was prepared by mixing the materials given in Table 2.

[0152] Table 2

[0153]

[0154] A polyurethane raw material composition was prepared by mixing the aforementioned prepolymer and curing agent. This raw material composition was injected into a mold for forming the elastic portion of a wiper blade and then cured at 130°C for 2 minutes. The mold was then demolded to produce a polyurethane molded product. Release agent A was previously applied to the interior of the mold. Release agent A was a mixture of the materials listed in Table 3.

[0155] Table 3

[0156]

[0157] The front end side of the polyurethane molded product was cut to produce an elastic portion having a main surface and a front end surface that, together with the main surface, constitutes the front end side edge. The lengths in the thickness, transverse, and longitudinal directions were set to 1.8 mm, 20 mm, and 300 mm, respectively. The resulting elastic portion was evaluated as follows.

[0158] Evaluation 1: Measurement of concentration of polyfunctional alcohol species

[0159] The polyfunctional alcohol was detected by pyrolysis GC / MS (gas chromatography and mass spectrometry). The measurement conditions were set as follows.

[0160] Sampling Locations: On the front end and main surface of the elastic portion, along lines drawn parallel to the front end edge at a distance of 0.5 mm from the front end edge, with L' being the length of each line segment, P0', P1', and P2' were set at 1 / 8 L', 1 / 2 L', and 7 / 8 L', respectively, from one end of the line segment. Samples taken from these P0', P1', and P2' points on the front end and main surface were measured using the following method. For these samplings, a biocutter was used to cut polyurethane components, etc.

[0161] Device:

[0162] - Pyrolyzer: Trade name: EGA / PY-3030D, Frontier Laboratories Ltd.,

[0163] -Gas chromatography apparatus: Trade name: TRACE 1310 gas chromatograph, Thermo Fisher Scientific Inc.,

[0164] -Mass spectrometer: Trade name: ISQLT, Thermo Fisher Scientific Inc.

[0165] -Pyrolysis temperature: 500℃

[0166] -GC column: stainless steel capillary column, inner diameter 0.25mm×30m

[0167] -Stationary phase: 5% phenyl polydimethylsiloxane

[0168] - Heating conditions: maintain at 50°C for 3 minutes and heat to 300°C at 8°C / min

[0169] -MS conditions: mass range m / z 10 to 650

[0170] - Scanning speed: 1 second / scan

[0171] Characterize the polyfunctional alcohol species by GC / MS. A calibration curve is prepared by GC analysis of a qualitatively characterized polyfunctional alcohol species of known concentration, and the species is quantified based on the GC peak area ratio. The arithmetic mean of the values obtained for each sample at points P0′, P1′, and P2′ on the front end surface and main surface is taken as the polyfunctional alcohol concentration on the front end surface and main surface.

[0172] Evaluation 2: Measurement of M1 to M3

[0173] Here, M1 to M3 are measured relying on a direct sample introduction method (DI method), in which a sample is introduced directly into an ion source bypassing a gas chromatograph (GC).

[0174] The apparatus used was an ion trap GC / MS (trade name: POLARIS Q, Thermo Fisher Scientific Inc.) using a direct exposure probe (DEP) as a direct introduction probe.

[0175] On the front end surface and main surface of the elastic part, in each line segment drawn parallel to the front end side edge, at a distance of 0.5 mm from the front end side edge, and with L' as the length of each line segment, P0', P1' and P2' are respectively set at 1 / 8L', 1 / 2L' and 7 / 8L' from one end side on the line segment.

[0176] The samples taken at the above-mentioned points P0', P1' and P2' on the front end surface and the main surface, respectively, were measured according to the following method: When taking the samples, a polyurethane member or the like was cut using a biocutter.

[0177] Approximately 0.1 μg of each sample, taken at points P0', P1', and P2' on the front and main surfaces, was attached to a filament at the tip of the probe, and the entire probe was directly inserted into an ionization chamber. The sample was then rapidly heated from room temperature to 1000°C at a constant heating rate (approximately 10°C / s), and the resulting vaporized gas was detected using a mass spectrometer.

[0178] The sum of the integrated intensities of all peaks in the obtained total ion current thermogram is taken as the detected amount M1 of all ions.

[0179] Furthermore, (M2 / M1) was calculated using the above values of M1 and M2, where M2 is the sum of the peak integrated intensities in the extracted ion thermogram derived from the m / z values of trifunctional or higher polyfunctional isocyanates. Furthermore, (M3 / M1) was calculated using the values of M1 and M3, where M3 is the sum of the peak integrated intensities in the extracted ion thermogram derived from the m / z values of diisocyanates. The arithmetic mean of the values obtained for each sample at P0′, P1′, and P2′ on the front end surface and the main surface was taken as the respective values of (M2 / M1) and (M3 / M1) on the front end surface and the main surface.

[0180] In this example, TTI, used as a trifunctional or higher-functional isocyanate, has a structure represented by the following chemical formula (3). In the extracted ion thermogram obtained in this evaluation, a peak of a cationic product derived from TTI was detected, with a peak top at an m / z position of 366.5 to 367.5. Therefore, in this example, the integrated intensity of this peak was taken as M2.

[0181] [C3]

[0182]

[0183] In another example described below, in the extracted ion thermogram obtained in this evaluation, for the elastic portion made of polyurethane synthesized using polymeric MDI as a trifunctional or higher polyfunctional isocyanate, a peak derived from a cationic product of polymeric MDI having a structure represented by chemical formula (1)' was detected, and this peak had peak tops at positions where the m / z value representing n = 1 was in the range of 380.5 to 381.5, the m / z value representing n = 2 was in the range of 511.5 to 512.5, the m / z value representing n = 3 was in the range of 642.5 to 643.5, and the m / z value representing n = 4 was in the range of 773.5 to 774.5. Therefore, in the above example, the sum of the peak integrated intensities was taken as M2.

[0184] Similarly, triphenylphosphothioate (TPTI), used as a trifunctional or higher polyfunctional isocyanate in the following examples, has a structure represented by chemical formula (4). In the extracted ion thermogram obtained in this evaluation, a peak of a cationic product derived from TPTI was detected, with a peak top at an m / z position of 464.5 to 465.5. Therefore, in the above examples, the sum of the peak integrated intensities was taken as M2.

[0185] [C4]

[0186]

[0187] In the extracted ion thermogram obtained in this evaluation, a peak derived from the cationic product of 4,4′-MDI (a diisocyanate) represented by chemical formula (2) was detected, with the peak having a peak top at m / z positions of 249.5 to 250.5. Therefore, the integrated intensity of this peak was designated as M3.

[0188] Evaluation 3: Measurement of elastic modulus

[0189] The elastic modulus of the SPM was measured using a scanning probe microscope (SPM) (trade name: MFP-3D Origin, Oxford Instruments plc) according to the following method.

[0190] First, the sample was prepared as follows. Assume that a first line segment of length L was drawn on the front end surface of the elastic portion in parallel with the front end side edge and at a distance of 10 μm from the front end side edge, and three 2 mm 2 A square measurement sample was prepared, one side of which was parallel to the first line segment and had its center of gravity at points P0, P1, and P2 at 1 / 8L, 1 / 2L, and 7 / 8L from one end of the first line segment. A cryostat (UC-6 (trade name, Leica Microsystems GmbH) was used to cut out individual 100 μm squares from the measurement sample. 2 A polyurethane sheet with a thickness of 1 μm, maintained at -50°C, having one side parallel to the first line segment and having its center of gravity set at P0, P1, and P2, was prepared. Each of the obtained measurement samples was placed on a smooth silicon wafer and left in an environment at 25°C and 50% humidity for 24 hours.

[0191] Next, the silicon wafer with the measurement sample placed on it was placed on the SPM stage and observed using the SPM. The spring constant and proportionality constant of the silicon cantilever (trade name: OMCL-AC160, Olympus Corporation, tip curvature radius: 8 nm) were previously determined using the SPM apparatus using the thermal noise method as follows: spring constant: 30.22 nN / nm, proportionality constant: 82.59 nm / V.

[0192] The cantilever was pre-tuned and the resonant frequencies of the cantilever were determined (285 KHz (1st order) and 1.60 MHz (higher orders)).

[0193] The SPM measurement mode was AM-FM mode, with the cantilever's free amplitude set to 3 V (1st order) and 25 mV (higher orders), and the setpoint amplitude set to 2 V (1st order). Phase maps were acquired at a scan rate of 1 Hz and 256 vertical and 256 horizontal scan points over a 70 μm × 70 μm square field of view. The position of the field of view was selected so that P0, P1, and P2 of each measured sample were located in the center of the field of view, and one side of the field of view was parallel to the first line segment.

[0194] Based on the phase map obtained, as a result of the force curve measurement, the position of each measurement sample to be measured for the elastic modulus is specified. Specifically, as Figure 5 and Figure 6 As shown, within a 70 μm×70 μm phase diagram, in a rectangular area having respective centers of gravity located at P0, P1, and P2 and having 70 μm long sides parallel to a first line segment and 10 μm long sides perpendicularly intersecting the first line segment, measurement positions are specified in the form of positions corresponding to 70,000 points at a pitch (interval) of 0.1 μm, both horizontally and vertically.

[0195] After that, for all points, a force curve measurement in contact mode is performed at each point. In the force curve measurement, the piezoelectric element serving as the driving source of the cantilever is controlled so that once the deflection resulting from contact with the sample surface presents a constant value, the front end of the cantilever folds back. The folding point at this time is called the trigger value, which indicates the specific degree of voltage increase from the deflection voltage at the beginning of the force curve at which the cantilever folds back. In this measurement, the force curve is measured with the trigger value set to 0.2V. As other force curve measurement conditions, the distance from the cantilever front end position in the standby state to the cantilever folding back under the trigger value is set to 500nm, and the scanning speed (the speed at which the probe reciprocates once) is set to 1Hz. Thereafter, fitting based on Hertz theory is applied to the obtained force curves one by one to calculate the elastic modulus. The elastic modulus (Young's modulus) according to Hertz theory is calculated according to the following formula (*1).

[0196] Formula (*1)

[0197] F=(4 / 3)E*R 1 / 2 d 3 / 2

[0198] In formula (*1), F represents the force applied by the cantilever to the sample at the time the cantilever folds back, E* is the composite elastic modulus, R is the radius of curvature of the cantilever tip (8 nm), and d is the degree of deformation of the sample at the time the cantilever folds back.

[0199] In addition, d is calculated by the following formula (*2).

[0200] Formula (*2)

[0201] d=ΔZ-D

[0202] In equation (*2), Δz is the displacement of the piezoelectric element from the moment the cantilever tip contacts the sample until the tip folds back, and D is the amount of cantilever deflection at the moment the cantilever folds back. Furthermore, D is calculated using equation (*3) below.

[0203] Formula (*3)

[0204] D=α·ΔV 偏转

[0205] In formula (*3), α is the proportional constant of the cantilever, ΔV 偏转 It is the change in deflection voltage from the time the cantilever starts to touch the sample until the time the cantilever returns.

[0206] Furthermore, F is calculated based on the following formula (*4).

[0207] Formula (*4)

[0208] F=κ·D

[0209] In formula (*4), κ is the spring constant of the cantilever. Here, ΔV 偏转 Since Δz and Δz are actually measured values, E* in formula (*1) is calculated based on formulas (*1) to (*4). The elastic modulus (Young's modulus) E to be obtained is calculated based on the following formula (*5).

[0210] Formula (*5)

[0211] 1 / E*=[(1-Vs 2 ) / Es]-[(1-Vi 2 ) / Ei]

[0212] Vs: Poisson's ratio of the sample (fixed at 0.33 in this example);

[0213] Vi: Poisson's ratio of the cantilever tip (the value of silicon is used in this embodiment);

[0214] Ei: Young's modulus of the cantilever tip (in this embodiment, the value of silicon is used).

[0215] The elastic modulus was measured at 70,000 points in the horizontal and vertical directions at 0.1 μm intervals (spacing) in a rectangular observation area (three 10 μm × 70 μm observation areas) with each center of gravity at P0, P1, and P2 and having a 70 μm long side parallel to the first line segment and a 10 μm long side 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 then taken as the elastic modulus of the front end surface.

[0216] The standard deviation was calculated from the elastic moduli of a total of 210,000 points. From the average value and the standard deviation of the elastic modulus values, the coefficient of variation of the elastic modulus of the first front end surface was calculated based on the following formula 1.

[0217] Formula (1): Coefficient of variation (%) = (standard deviation of elastic modulus value / average value) × 100

[0218] The average value of the elastic modulus values of the main surfaces and the coefficient of variation of the elastic modulus were calculated in the same manner as described above.

[0219] Evaluation 4: Evaluation of wiping performance

[0220] The elastic portion 13 is clamped in the longitudinal direction of the elastic portion 13 over its total length. Figure 8 The following test evaluated the performance of the wiper blade in removing stains from a glass surface using the gripping portion 801 of the evaluation device shown. The elastic portion 13 was gripped by the gripping portion to a position of 10 mm from the mounting side on the main surface side, and to a position of 15 mm from the mounting side on the side opposite the main surface. Silicone oil (trade name: KF-96-50cs, Shin-Etsu Chemical Co., Ltd.) was applied to the entire surface of the glass plate 14, serving as the member to be cleaned, in a state simulating an oil film. The elastic portion 13 was then brought into contact with the surface of the glass plate 14 to which the silicone oil had been applied (hereinafter also referred to as the "cleaned surface"). Figure 9 An enlarged view of the contact portion between the elastic portion of the wiper blade and the surface to be cleaned is shown. Figure 9 As shown, the elastic portion 13 is brought into contact so that the angle θ formed by the main surface 6 and the cleaned surface 14 - 01 is 45 degrees.

[0221] The glass plate 14 was moved along the vertical axis at a speed of 10 mm / sec using an electric cylinder 15 (trade name: RCP4-SA5C, IAI Corporation). Figure 9 The wiper blade 13 moves back and forth in the directions of arrows W and C. The camera is then used to visually capture the state of silicone oil being wiped on the surface 14-01 being cleaned, from the surface of the glass plate 14 on the opposite side of the surface 14-01 being cleaned. The ratio of the surface area of the portion from which silicone oil has been removed relative to the contact surface area of the wiper blade 13 and the surface 14-01 being cleaned (hereinafter also referred to as the "silicone oil removal area rate (%)") is calculated and evaluated according to the following criteria. The pressing force applied to the glass surface by the elastic portion per 1m of length in the longitudinal direction is set to two levels, namely 7 N / m and 15 N / m, and the silicone oil removal area rate is calculated for each level.

[0222] Evaluation Criteria

[0223] Grade A: Silicone oil film removal area rate is more than 95%

[0224] Grade B: Silicone oil film removal area rate is 90% to less than 95%

[0225] Grade C: Silicone oil film removal area rate is 85% to less than 90%

[0226] Grade D: Silicone oil film removal area rate is 80% to less than 85%

[0227] Grade E: Silicone oil film removal area rate is less than 50%

[0228] Examples 2 to 32

[0229] Tables 4 to 7 illustrate the types and amounts of various materials used for the prepolymer, and the types and amounts of various materials used for the curing agent. Each elastic portion was produced and evaluated in the same manner as in Example 1 except for the following notes.

[0230] In Example 3, triphenylphosphorothioate (trade name: Ultite Super CAII, Toho Kasei Kogyo Co. Ltd.) (TPTI) was used as a tri- or higher-functional isocyanate.

[0231] In Example 5, polymeric MDI (trade name: Millionate MR-400, Tosoh Corporation) (hereinafter referred to as MR400) was used as trifunctional or higher polyfunctional isocyanate. The NCO% in Example 5 was 10.2% by mass.

[0232] In Example 6, glycerin (Tokyo Chemical Industry Co., Ltd.) was used as a polyfunctional alcohol of the curing agent.

[0233] In Example 13, trimethylolpropane (Tokyo Chemical Industry Co., Ltd.) (hereinafter also referred to as "TMP") was used as a trifunctional or higher functional alcohol for a curing agent.

[0234] In Example 14, polymeric MDI (trade name: Millionate MR-200, Tosoh Corporation) (hereinafter also referred to as MR200) was used as a trifunctional or higher polyfunctional isocyanate for the prepolymer.

[0235] In Example 18, polytetramethylene glycol adipate polyester polyol (trade name: Nippollan 4009, Tosoh Corporation) (hereinafter also referred to as PBA1000) having a number average molecular weight of 1000 was used as a polyol for a curing agent.

[0236] In Example 19, polytetramethylene glycol adipate polyester polyol (trade name: Nippollan 136, Tosoh Corporation) having a number average molecular weight of 2600 (hereinafter also referred to as PHA2600) was used as the polyol for the prepolymer.

[0237] In Example 29, polymeric MDI (trade name: Cosmonate M-200, Mitsui Chemicals, Inc.) (hereinafter referred to as "M200") was used as the trifunctional or higher-functional isocyanate for the prepolymer. Polytetramethylene ether glycol (trade name: PTG-2000SN, Hodogaya Chemical Co., Ltd.) (hereinafter referred to as "PTG2000SN") having a number average molecular weight of 2000 was used as the polyol for the prepolymer. The prepolymer of Example 29 had an NCO content of 7.9% by mass. Polytetramethylene ether glycol (trade name: PTG-1000SN, Hodogaya Chemical Co., Ltd.) (hereinafter referred to as "PTG1000SN") having a number average molecular weight of 1000 was used as the polyol for the curing agent. The curing time was set to 6 minutes.

[0238] In Examples 30 to 32, the curing time of the raw material composition was also set to 6 minutes.

[0239] Example 33

[0240] A prepolymer having an NCO content of 9.0% by mass was obtained using the prepolymer materials listed in Table 7. PBA2000 is a polytetramethylene glycol adipate polyester polyol (trade name: Nippollan 4010, Tosoh Corporation) with a number-average molecular weight of 2000. A curing agent was prepared using the curing agent materials listed in Table 7. Similar to Example 1, a raw material composition prepared by mixing the prepolymer and curing agent was injected into a mold for forming the elastic portion of a wiper blade. This composition was cured at 130°C for 10 minutes. Subsequently, the composition was demolded and post-cured at 130°C for 60 minutes to obtain the elastic portion of this example.

[0241] Example 34

[0242] A wiper blade elastic portion was produced and evaluated in the same manner as in Example 1, except that the types and amounts of the various materials used for the prepolymer and the types and amounts of the various materials used for the curing agent were as shown in Table 7. Next, a wiper blade elastic portion according to this embodiment was obtained on the main surface and the front end surface of the wiper blade elastic portion. A low-pressure mercury ozone-free lamp (Toshiba Lighting & Technology Corporation) having a maximum emission wavelength peak at a wavelength of 254 nm was used as a light source for ultraviolet light. The wiper blade elastic portion was evaluated in the same manner as in Example 1.

[0243] Examples 35 and 36

[0244] Wiper blades were produced and evaluated in the same manner as in Example 1, except that the types and amounts of the various materials used for the prepolymer and the types and amounts of the various materials used for the curing agent were as shown in Table 7. Then, wiper blade elastic portions according to Examples 35 and 36 were obtained by irradiating the obtained wiper blades with ultraviolet rays in the same manner as in Example 34, except that the integrated light intensity was modified to the values shown in Table 7. These wiper blade elastic portions were evaluated in the same manner as in Example 1.

[0245] Example 37

[0246] A prepolymer having an NCO content of 7.0% by mass was obtained using the materials for the prepolymer listed in Table 7. Curing agents were prepared using the various materials for the curing agent listed in Table 7. The raw material composition obtained by mixing the prepolymer and curing agent was injected into a mold for forming the elastic portion of a wiper blade and cured at 130°C for 10 minutes in the same manner as in Example 1. The composition was then demolded and post-cured at 130°C for 60 minutes to obtain the elastic portion of a wiper blade.

[0247] Similar to Example 34, the main surface and the front end surface of the elastic portion of the obtained wiper blade were irradiated with ultraviolet rays so that the cumulative light intensity was 1968 mJ / cm 2 The wiper blade elastic portion according to the present embodiment is thus obtained.

[0248] Example 38

[0249] A wiper blade elastic portion was produced and evaluated in the same manner as in Example 1, except that the kinds and amounts of various materials used for the prepolymer and the kinds and amounts of various materials used for the curing agent were as given in Table 7.

[0250] Examples 39 and 40

[0251] Wiper blades were produced and evaluated in the same manner as in Example 1, except that the types and amounts of the various materials used for the prepolymer and the types and amounts of the various materials used for the curing agent were as shown in Table 7. Then, wiper blade elastic portions according to Examples 39 and 40 were obtained by irradiating the obtained wiper blades with ultraviolet rays in the same manner as in Example 34, except that the integrated light intensity was modified to the values shown in Table 7. These wiper blade elastic portions were evaluated in the same manner as in Example 1.

[0252] Example 41

[0253] A prepolymer having an NCO content of 9.0% by mass was obtained using the materials for the prepolymer listed in Table 8. The curing agent was prepared using the various materials for the curing agent listed in Table 8. The raw material composition obtained by mixing the prepolymer and curing agent was injected into a mold for forming the elastic portion of a wiper blade and cured at 130°C for 10 minutes in the same manner as in Example 1. The mold was then demolded and post-cured at 130°C for 60 minutes to obtain a polyurethane molded product. The obtained polyurethane molded product was processed in the same manner as in Example 1 to obtain the elastic portion of a wiper blade according to this embodiment.

[0254] Examples 42 to 44

[0255] Prepolymers were prepared in the same manner as in Example 41, except that the types and amounts of the various materials used in the prepolymers were as given in Table 7. The NCO content of the prepolymer of Example 42 was 8.2% by mass, the NCO content of the prepolymer of Example 43 was 15.0% by mass, and the NCO content of the prepolymer of Example 44 was 18.0% by mass.

[0256] The curing agent was prepared in the same manner as in Example 41, except that the various materials and amounts used for the curing agent were as shown in Table 7. The elastic portions of the wiper blades according to Examples 42 to 44 were produced and evaluated in the same manner as in Example 41, except that these prepolymers and curing agents were used.

[0257] Examples 45 and 46

[0258] The wiper blade elastic portion obtained in Example 44 was irradiated with ultraviolet rays in the same manner as in Example 34, except that the integrated light intensity was set to the value given in Table 7, thereby obtaining wiper blade elastic portions according to Examples 45 and 46. The obtained wiper blade elastic portions were evaluated in the same manner as in Example 1.

[0259] Examples 47 to 50

[0260] Prepolymers were prepared in the same manner as in Example 41, except that the kinds and amounts of the various materials used for the prepolymers were as shown in Table 7. The NCO content of the prepolymer according to Example 47 was 10.0% by mass, the NCO content of the prepolymer according to Example 48 was 9.6% by mass, the NCO content of the prepolymer according to Example 49 was 9.3% by mass, and the NCO content of the prepolymer according to Example 50 was 9.2% by mass.

[0261] A curing agent was prepared in the same manner as in Example 41, except that the various materials and amounts used for the curing agent were as shown in Table 7. Elastic portions of wiper blades according to Examples 47 to 50 were produced in the same manner as in Example 41, except that the above-mentioned prepolymer and curing agent were used, and the produced wiper blades were evaluated.

[0262] Example 51

[0263] Here, a wiper blade elastic portion obtained in the same manner as in Example 37 was immersed in 4,4'-MDI dissolved at 80°C for one minute on its main and front end surfaces, extending 2 mm from the front end edge. The 4,4'-MDI adhering to the impregnated surface of the wiper blade elastic portion was then wiped off using a sponge soaked in butyl acetate. The wiper blade elastic portion was then aged for 24 hours in an environment at 23°C and 50% relative humidity, resulting in a wiper blade elastic portion according to this example, in which a cured region formed near the front end edge of the main and front end surfaces. The wiper blade elastic portion was evaluated in the same manner as in Example 1.

[0264] Example 52

[0265] The wiper blade elastic portion according to this example was produced in the same manner as in Example 51, except that the 4,4′-MDI adhering to the surface of the impregnated portion of the wiper blade elastic portion was heated at 100° C. for 30 minutes after wiping off the 4,4′-MDI adhering to the surface of the impregnated portion of the wiper blade elastic portion; the wiper blade elastic portion was evaluated in the same manner as in Example 1.

[0266] Example 53

[0267] The wiper blade elastic portion according to this example was obtained by subjecting the wiper blade elastic portion produced in the same manner as in Example 4 to the same surface treatment as in Example 51, except that the immersion time in 4,4'-MDI was set to 3 minutes. The wiper blade elastic portion was evaluated in the same manner as in Example 1.

[0268] Example 54

[0269] The wiper blade elastic portion according to this example was produced in the same manner as in Example 53, except that the 4,4′-MDI adhering to the surface of the impregnated portion of the wiper blade elastic portion was heated at 100° C. for 30 minutes after wiping off the 4,4′-MDI adhering to the surface of the impregnated portion of the wiper blade elastic portion; the wiper blade elastic portion was evaluated in the same manner as in Example 1.

[0270] Comparative Example 1

[0271] A prepolymer having an NCO content of 14.0% by mass was prepared using the various materials for the prepolymer given in Table 10. A curing agent was prepared using the various materials for the curing agent given in Table 10. The raw material composition obtained by mixing the above prepolymer and the curing agent was injected into a forming mold for the elastic portion of the wiper blade and cured at a temperature of 130°C for 10 minutes in the same manner as in Example 1. Subsequently, demolding was performed and secondary curing was performed at a temperature of 130°C for 60 minutes to obtain a polyurethane molded product. The obtained polyurethane molded product was processed in the same manner as in Example 1 to produce the wiper blade elastic portion according to this embodiment. The obtained wiper blade was evaluated in the same manner as in Example 1.

[0272] Comparative Example 2

[0273] A prepolymer having an NCO content of 9.0% by mass was obtained using the materials for the prepolymer listed in Table 10. Curing agents were prepared using the various materials for the curing agent listed in Table 10. A wiper blade elastic portion was produced and evaluated in the same manner as in Comparative Example 1, except that the above-mentioned prepolymer and curing agent were used.

[0274] Comparative Example 3

[0275] A prepolymer having an NCO content of 9.0% by mass was obtained using the materials for the prepolymer listed in Table 10. A curing agent was prepared using the various materials for the curing agent listed in Table 10. A wiper blade elastic portion was produced in the same manner as in Comparative Example 1, except that the above-mentioned prepolymer and curing agent were used. Except that the integrated light intensity was set to 8200 mJ / cm 2 The wiper blade elastic portion according to this comparative example was obtained by irradiating the obtained wiper blade elastic portion with ultraviolet rays in the same manner as in Example 34. The obtained wiper blade elastic portion was evaluated in the same manner as in Example 1.

[0276] Comparative Example 4

[0277] To 100 parts by mass of natural rubber were added 48.0 parts by mass of carbon black (trade name: Toka Black #7360SB, Tokai Carbon Co., Ltd.), 5.0 parts by mass of zinc oxide (trade name: Zinc White 2, Sakai Chemical Industry Co., Ltd.), 1.0 part by mass of zinc stearate (trade name: SZ-2000, Sakai Chemical Industry Co., Ltd.), and 20 parts by mass of calcium carbonate (trade name: Nanox #30, Maruo Calcium Co., Ltd.), and the whole was kneaded in a sealed mixer adjusted to a temperature of 50° C. for 15 minutes.

[0278] To the obtained kneaded product, 1.2 parts by mass of sulfur and 4.5 parts by mass of tetrabenzylthiuram sulfide (TBzTD) (trade name: Perkacit TBzTD, FlexSys, Inc.) were further added as a vulcanizing agent. The obtained product was kneaded for 10 minutes using a two-roll machine cooled to a temperature of 25°C to obtain a rubber composition. The obtained rubber composition was placed in a forming mold for the wiper blade elastic portion and compression-vulcanized at 170°C for 20 minutes to obtain the wiper blade elastic portion. The obtained wiper blade elastic portion was evaluated in the same manner as in Example 1.

[0279] Tables 4 to 10 show the evaluation results of the respective Examples and Comparative Examples.

[0280] [Table 4] Table 4

[0281]

[0282] [Table 5] Table 5

[0283]

[0284] [Table 6] Table 6

[0285]

[0286] [Table 7] Table 7

[0287]

[0288] [Table 8] Table 8

[0289]

[0290] [Table 9] Table 9

[0291]

[0292] [Table 10]

[0293] Table 10

[0294]

[0295] The present disclosure is not limited to the above embodiments, and various changes and modifications can be adapted without departing from the spirit and scope of the present disclosure. Therefore, in order to disclose the scope of the present disclosure, the following claims are attached.

[0296] This application claims priority based on Japanese Patent Application No. 2020-130823 filed on July 31, 2020, Japanese Patent Application No. 2021-077324 filed on April 30, 2021, and Japanese Patent Application No. 2021-106520 filed on June 28, 2021, the entire contents of which are incorporated herein.

[0297] Description of Reference Numerals

[0298] 1 Grip

[0299] 2 Elastic part

[0300] 3 Support part

[0301] 4 Support grip

[0302] 5. Components to be cleaned

[0303] 6 Main surface

[0304] 8Front end surface

[0305] 9 front side edge

[0306] 10The first line segment

[0307] 11 The second line segment

[0308] 12 Observation Area

[0309] 13 Wiper blade elastic part

[0310] 14 Glass Pane

[0311] 15 Electric Cylinder

Claims

1. A cleaning wiper blade, characterized in that: It includes: A grip portion for grasping by hand; as well as an elastic portion supported by the gripping portion and pressed against the surface to be cleaned; making a portion of the elastic portion contact the surface of the member to be cleaned, thereby cleaning the surface of the member to be cleaned, When the side of the elastic portion most distant from the gripping portion is defined as the front end side of the wiper blade, The elastic portion has, on the front end side, a main surface facing the member to be cleaned and a front end surface forming a front end side edge together with the main surface; Assuming that a first line segment is drawn on the front end surface in parallel with the front end side edge at a distance of 10 μm from the front end side edge, The length of the first line segment is defined as L1; points at (1 / 8) L1, (1 / 2) L1, and (7 / 8) L1 from one end side on the first line segment are defined as P0, P1, and P2, respectively; and When the elastic modulus is measured at 70,000 points at 0.1 μm intervals in each of three rectangular observation areas on the front end surface using a scanning probe microscope, each of the rectangular observation areas having a respective center of gravity at P0, P1, and P2 and having a 70 μm-long side parallel to the first line segment and a 10 μm-long side perpendicular to the first line segment, The average value of the 210,000 obtained elastic modulus values is 15 MPa to 470 MPa, and the coefficient of variation of the elastic modulus is 17.6% or less; and Assuming that a second line segment is drawn on the main surface in parallel with the front end side edge at a distance of 10 μm from the front end side edge, The length of the second line segment is defined as L2; Points at (1 / 8) L2, (1 / 2) L2, and (7 / 8) L2 from one end side on the second line segment are defined as P3, P4, and P5, respectively; and When measured at 70,000 points at 0.1 μm pitch in each of three rectangular observation areas on the main surface using a scanning probe microscope, each of the rectangular observation areas has a center of gravity at P3, P4, and P5 and has a 70 μm-long side parallel to the second line segment and a 10 μm-long side perpendicular to the second line segment, The average value of the elastic modulus values obtained from 210,000 samples is 15 MPa to 470 MPa, and the coefficient of variation of the elastic modulus is 17.6% or less. It is assumed that On the front end surface and the main surface of the elastic portion, respective line segments are drawn parallel to the front end side edge and at a distance of 0.5 mm from the front end side edge. The length of each line segment is defined as L', points at 1 / 8L', 1 / 2L', and 7 / 8L' from one end side on each line segment are defined as P0', P1', and P2', respectively; and When the samples sampled at P0′, P1′, and P2′ on the front end surface and the main surface are heated to 1000° C. at a heating rate of 10° C. / s by a mass spectrometer using a direct sample introduction method in which each sample is heated and vaporized in an ionization chamber and molecules of each sample are ionized, the obtained The detected amount of all ions is defined as M1, The integrated intensity of the peak in the extracted ion thermogram corresponding to the m / z value range derived from trifunctional or higher polyfunctional isocyanate is defined as M2; and The integrated intensity of the peak in the extracted ion thermogram corresponding to the m / z value range derived from diisocyanate is defined as M3; On the front end surface, M2 / M1 is 0.0010 to 0.0150, and M3 / M1 is 0.0200 to 0.1100; and On the main surface, M2 / M1 is 0.0010 to 0.0150, and M3 / M1 is 0.0200 to 0.1100.

2. The cleaning wiper blade according to claim 1, wherein the elastic portion comprises polyurethane; and The polyurethane comprises the reaction product of a composition comprising at least one of: Alcohols including trifunctional or higher polyfunctional alcohols; and Isocyanate compounds including trifunctional or higher polyfunctional isocyanates.

3. The cleaning wiper blade according to claim 1, wherein the elastic portion comprises polyurethane; and The polyurethane is a reaction product of a composition comprising an isocyanate compound and an alcohol. The isocyanate compound includes a diisocyanate and a trifunctional or higher polyfunctional isocyanate, and the alcohol includes a trifunctional or higher polyfunctional alcohol.

4. The cleaning wiper blade according to any one of claims 1 to 3, It is assumed that respective line segments are drawn on the front end surface and the main surface of the elastic portion in parallel with the front end side edge at a distance of 0.5 mm from the front end side edge. Let the length of each line segment be L', and Points located 1 / 8L', 1 / 2L', and 7 / 8L' from one end side of each line segment are defined as P0', P1', and P2', respectively; and When samples taken at P0′, P1′, and P2′ on the front end surface and the main surface are measured by pyrolysis GC / MS, The concentration of trifunctional or higher polyfunctional alcohol in the polyurethane on the front end surface is 0.04 mmol / g to 0.39 mmol / g; and The concentration of the trifunctional or higher polyfunctional alcohol in the polyurethane on the main surface is 0.04 mmol / g to 0.39 mmol / g. 5 . The cleaning wiper blade according to claim 2 , wherein the trifunctional or higher polyfunctional alcohol comprises at least one selected from the group consisting of trimethylolpropane and glycerin. The cleaning wiper blade according to any one of claims 1 to 3, wherein the trifunctional or higher polyfunctional isocyanate is at least one selected from the group consisting of triphenylmethane-4,4',4"-triisocyanate (TTI), triphenylphosphothioate (TPTI) and polymeric MDI.

7. The cleaning wiper blade according to any one of claims 1 to 3, wherein in the measurement of the elastic modulus on the front end surface, The average value of the elastic modulus is 32 MPa to 62 MPa; and In the measurement of the elastic modulus on the main surface, The average value of the elastic modulus is 32 MPa to 62 MPa.

8. The cleaning wiper blade according to any one of claims 1 to 3, wherein in the measurement of the elastic modulus on the front end surface, The coefficient of variation of the elastic modulus is 6.0% or less; and In the measurement of the elastic modulus on the main surface, The coefficient of variation of the elastic modulus is 6.0% or less.

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