Cleaning wiper blade

Abstract

A cleaning wiper blade is provided that exhibits excellent wiping properties even when pressed against a surface to be cleaned by a weak pressure. The cleaning wiper blade is used to abut a portion of an elastic portion to clean the surface of a component to be cleaned, wherein the polyurethane of the elastic portion comprises a reactant 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), the diisocyanate having an aromatic ring in the molecule, and when M1 is the detected amount of all ions, M2 is a trifunctional or higher polyfunctional isocyanate, and M3 is a diisocyanate, M2 / M1 is 0.001 to 0.028, M3 / M1 is 0.020 to 0.110, and M2 / M3 is 0.013 to 0.300, and the concentration of the trifunctional or higher polyfunctional alcohol in the polyurethane is 0.12 mmol / g to 0.65 mmol / g.

Description

Technical Field

[0001] The present disclosure relates to a cleaning wiper blade for cleaning the surface of a member 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, for example, a cleaning wiper blade that is less likely to cause uneven wiping and exhibits excellent wiping performance even when pressure against a cleaned surface is not strengthened.

[0010] Solutions for solving problems

[0011] According to one aspect of the present disclosure, there is provided:

[0012] A cleaning wiper blade comprising:

[0013] A grip portion to be grasped by hand; and

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

[0015] A portion of the elastic portion contacts the surface of the member to be cleaned, thereby cleaning the surface of the member to be cleaned, wherein

[0016] The elastic portion comprises polyurethane,

[0017] The polyurethane comprises a reactant comprising an isocyanate compound containing a diisocyanate and a trifunctional or higher polyfunctional isocyanate and an alcohol containing a trifunctional or higher polyfunctional alcohol.

[0018] The diisocyanate has an aromatic ring in the molecule, and

[0019] When the polyurethane is heated to 1000° C. at a heating rate of 10° C. / s using a mass spectrometer with a direct sample injection system in which a sample is heated and vaporized in an ionization chamber and molecules of the sample are ionized, the detected amount of all ions obtained is defined as M1, the integrated intensity of the peak of 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 of the extracted ion thermogram corresponding to the m / z value range derived from diisocyanate is defined as M3,

[0020] M2 / M1 is 0.001~0.028,

[0021] M3 / M1 is 0.020~0.110,

[0022] M2 / M3 is 0.013 to 0.300, and

[0023] The concentration of the trifunctional or higher polyfunctional alcohol in the polyurethane is 0.12 mmol / g to 0.65 mmol / g.

[0024] Effects of the Invention

[0025] 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

[0026] [ Figure 1 ] Figure 1 (a), (b), (c) and (d) are each an example of a schematic diagram of a wiper blade.

[0027] [ Figure 2 ] Figure 2 (a) and (b) are each an explanatory diagram showing a state during a cleaning process of a wiper blade.

[0028] [ Figure 3 ] An enlarged schematic diagram of the contact portion between the elastic portion of the wiper blade and the member to be cleaned.

[0029] [ Figure 4 ]Enlarged view near the front side.

[0030] [ Figure 5 ]Enlarged view near the first line segment.

[0031] [ Figure 6 ] Schematic diagram of the test equipment used to evaluate the wiping performance of a wiper blade.

[0032] [ Figure 7 ] An enlarged view of the portion where the elastic portion of the wiper blade and the glass surface are in contact with each other.

[0033] [ Figure 8 ] Figure 8 (a) and (b) are the binarized images of Example 1 and Comparative Example 1. DETAILED DESCRIPTION

[0034] 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.

[0035] When numerical ranges are described in sections, the upper and lower limits of each numerical range can be arbitrarily combined.

[0036] The present inventors consider that, with conventional wiper blades made of polyurethane, a difference occurs between hard segments and soft segments in polyurethane in how force is transmitted to the member being cleaned, resulting in the appearance of, for example, streaky unwiped portions.

[0037] Further research based on this understanding has led to the discovery that including a specific polyurethane in the elastic portion of a wiper blade is effective in further improving wiping performance. This specific polyurethane inhibits the aggregation of hard segments. As a result, it is conceivable that the force transmitted to the cleaned surface becomes uniform across the length (width) of the wiper blade, effectively suppressing the occurrence of streaky, unwiped areas.

[0038] <Construction of Wiper Blade>

[0039] 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.

[0040] Figure 1 An example of a schematic diagram of a wiper blade is shown. Figure 1 (a) shows a gripping portion 1 and an elastic portion 2. However, as Figure 1 As shown in (b), a support portion 3 for supporting the elastic portion 1 may be included between the grip portion 1 and the elastic portion 2.

[0041] Alternatively, for example, Figure 1 As shown in (c), it can have a support and gripping portion 4 in which the support portion and the gripping portion are integrated.

[0042] like Figure 1 As shown in (d), the elastic portion and the gripping portion may be integrated with each other.

[0043] The gripping portion 1 , the supporting portion 3 and the elastic portion 2 may be detachable or integrated with each other.

[0044] 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.

[0045] Figure 3 It is an enlarged schematic diagram of the contact portion between the elastic portion 2 and the member to be cleaned 5 .

[0046] like Figure 3 As shown, when the side of the elastic portion farthest from the grip portion is defined as the front end side of the wiper blade, the elastic portion 2 has a main surface 6 opposite to the member to be cleaned 5 and a front end surface 8 forming a front end side 9 with the main surface 6 on the front end side.

[0047] With the main surface 6 and the front end surface 8 , a front end side 9 extending in the length direction is formed for the elastic portion 2 .

[0048] As described above, it is considered that with a conventional wiper blade made of polyurethane, a difference occurs between the hard segment and the soft segment in the polyurethane when force is transmitted to the member being cleaned, resulting in the appearance of streaky unwiped portions.

[0049] The reason for this is speculated as follows. It is thought that in polyurethanes used in conventional wiper blades, hard segment aggregation progresses, resulting in agglomeration. As a result, at the microscopic polymer level, a significant difference in hardness occurs between the hard and soft segments, creating a state of uneven hardness.

[0050] It is considered that when the wiper blade contacts the member to be cleaned in this state, strong contact force portions and weak contact force portions appear irregularly; therefore, during cleaning (wiping operation), streak-like unwiped portions appear.

[0051] Therefore, it is believed that finely and evenly dispersing the hard segments in the polyurethane can solve the problem of uneven hardness. Based on this consideration, the composition of the polyurethane is set to specific conditions. This allows the hard segments to be finely and evenly dispersed in the polyurethane. As a result, the wiping performance of the component being cleaned can be further improved.

[0052] The elastic portion of the present disclosure comprises polyurethane,

[0053] The polyurethane comprises a reactant comprising an isocyanate compound including a diisocyanate and a trifunctional or higher polyfunctional isocyanate, and an alcohol including a trifunctional or higher polyfunctional alcohol, wherein the diisocyanate has an aromatic ring in the molecule. Furthermore, when the polyurethane is heated to 1000° C. at a heating rate of 10° C. / s using a mass spectrometer with a direct sample injection system in which a sample is heated and vaporized in an ionization chamber and molecules of the sample are ionized, the amount of all ions detected is defined as M1.

[0054] The integrated intensity of the peak of the extracted ion thermogram corresponding to the m / z value range derived from trifunctional or higher polyfunctional isocyanate is defined as M2, and

[0055] When the integrated intensity of the peak of the extracted ion thermogram corresponding to the m / z value range derived from diisocyanate is defined as M3,

[0056] M2 / M1 is 0.001~0.028,

[0057] M3 / M1 is 0.020~0.110,

[0058] M2 / M3 is 0.013~0.300, and

[0059] The concentration of the trifunctional or higher polyfunctional alcohol in the polyurethane is 0.12 mmol / g to 0.65 mmol / g.

[0060] A detailed description will be given below.

[0061] Hard segments are primarily formed by interactions between urethane bonds or between the aromatic rings of diisocyanates. When hard segments can overlap regularly, they tend to become larger. Therefore, by disrupting this regularity, hard segment miniaturization can be achieved.

[0062] Therefore, as described above, by obtaining a composition comprising trifunctional or higher polyfunctional isocyanates and trifunctional or higher polyfunctional alcohols at an appropriate concentration ratio, orientation is suppressed by steric hindrance. As a result, hard segments are less likely to aggregate. As a result, the hard segments are miniaturized and uniformly dispersed.

[0063] As a result, the contact force of the contact area with the component being cleaned is uniform across the entire length of the elastic portion. Therefore, the contact portion can be uniformly moved across the surface of the component being cleaned. Consequently, the wiper blade exhibits excellent wiping performance without causing uneven wiping across the entire length of the blade.

[0064] When M2 / M1 is 0.001 or more, a structure derived from a trifunctional or higher functional isocyanate having low crystallinity is introduced into the polyisocyanate forming the hard segment, which can suppress aggregation of the hard segment and thus disperse the hard segment finely and uniformly.

[0065] When M2 / M1 is 0.028 or less, aggregation between low molecular weight polyfunctional components can be suppressed, which can suppress aggregation of hard segments. However, when it is 0.015 or less, aggregation can be suppressed at a higher level.

[0066] When M3 / M1 is 0.020 or more, a higher molecular weight tends to be obtained during the curing reaction, thereby improving wear resistance. A ratio of 0.040 or more is preferred.

[0067] Since the higher the concentration of diisocyanate, the more the hard segment aggregation progresses, M3 / M1 is set to 0.110 or less. By setting M3 / M1 to 0.110 or less, the aggregation of the hard segment can be further suppressed. In addition, 0.100 or less is preferred.

[0068] When M2 / M3 is 0.013 or more, sufficient trifunctional or higher-functional isocyanate exists for diisocyanate, thereby suppressing the crystallization of diisocyanate, which can suppress the aggregation of hard segments.

[0069] On the other hand, when M2 / M3 is 0.300 or less, aggregation between low molecular weight polyfunctional components can be suppressed, which can suppress aggregation of hard segments. However, when it is 0.150 or less, aggregation can be suppressed at a higher level.

[0070] In addition, it is preferred that

[0071] M2 / M1 is 0.001~0.015,

[0072] M3 / M1 is 0.040~0.100,

[0073] M2 / M3 is 0.013~0.150, and

[0074] The concentration of the trifunctional or higher polyfunctional alcohol in the polyurethane is 0.22 mmol / g to 0.39 mmol / g.

[0075] The concentration of the trifunctional or higher polyfunctional alcohol in the polyurethane is calculated by the following equation (1). When the concentration of the trifunctional or higher polyfunctional alcohol falls within the aforementioned range, the hard segment aggregation inhibition effect is high. That is, the concentration of the trifunctional or higher polyfunctional alcohol in the polyurethane is 0.12 mmol / g to 0.65 mmol / g, and preferably 0.22 mmol / g to 0.39 mmol / g.

[0076] Equation (1): Concentration of trifunctional or higher polyfunctional alcohol (mmol / g) =

[0077] [Amount of trifunctional or higher polyfunctional alcohol (g) / molecular weight of trifunctional or higher polyfunctional alcohol × 1000] / [mass of polyurethane (g)]

[0078] The polyurethane is preferably a polyurethane elastomer.

[0079] Polyurethane elastomers can be obtained from raw materials mainly including polyols, chain extenders, polyisocyanates, catalysts, and other additives.

[0080] Polyurethane elastomers are block copolymers containing hard segments and soft segments. The hard segments typically include polyisocyanates and chain extenders containing short-chain diols. On the other hand, the soft segments typically include long-chain polyols such as polyester polyols, polyether polyols, polycarbonate polyols, and polyisocyanates.

[0081] As the polyisocyanate, a diisocyanate and a trifunctional or higher functional isocyanate are used in combination.

[0082] Examples of the diisocyanate may include the following.

[0083] 4,4'-diphenylmethane diisocyanate (4,4'-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), tetramethylxylene diisocyanate (TMXDI) and carbodiimide-modified MDI.

[0084] As diisocyanate, diisocyanate having an aromatic ring in the molecule is used. Use of diisocyanate containing an aromatic ring can provide favorable mechanical properties and high reactivity.

[0085] The diisocyanate preferably has a structure in which NCO is directly bonded to an aromatic ring. As a result, aggregation of the hard segments can be better suppressed, and even finer dispersion thereof is possible.

[0086] Examples of the trifunctional or higher polyfunctional isocyanate may include the following.

[0087] Polymeric MDI, triphenylmethane-4,4',4"-triisocyanate (TTI), tris(phenylisocyanate)phosphorothioate (TPTI), 4-isocyanatemethyl-1,8-octamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylbenzene triisocyanate, diphenylmethane-2,4-4'-triisocyanate.

[0088] The trifunctional or higher polyfunctional isocyanate is more preferably at least one selected from the group consisting of polymeric MDI, triphenylmethane-4,4′,4″-triisocyanate, and tris(phenylisocyanate)phosphorothioate.

[0089] The polyfunctional isocyanate having three or more functions is preferably selected from at least one of the group consisting of polymeric MDI and tris(phenyl isocyanate)phosphorothioate. The isocyanate has a methylene group or an ether group between the NCO groups. For this reason, the distance between the urethane bonds can be appropriately maintained. For this reason, this is preferred for suppressing the aggregation of the hard segments.

[0090] Polymeric MDI is represented by the following chemical formula (1) and chemical formula (1)'.

[0091] In the chemical formula (1)', n is preferably 1-4.

[0092] Chemical formula (1) represents the case where n is 1 in Chemical formula (1)'.

[0093] [C1]

[0094]

[0095] The branched chains of trifunctional or higher polyfunctional alcohols can suppress crystallization and aggregation of hard segments.

[0096] On the other hand, when there are too many branches, the density of urethane bonds around the trifunctional or higher polyfunctional alcohol increases, making the hard segments tend to aggregate more easily. Therefore, among the trifunctional or higher polyfunctional alcohols, trifunctional alcohols are preferably used.

[0097] Among them, alcohols represented by the following formula (a) or (b) are preferable because they have a methylene group adjacent to a hydroxyl group, which allows the distance between urethane bonds to be appropriately maintained.

[0098] Specific examples of trifunctional or higher polyfunctional alcohols may include trimethylolethane (one in which R1 is CH3 in the following formula (a)), trimethylolpropane (TMP: one in which R1 is C2H5 in the following formula (a)), glycerol, pentaerythritol and sorbitol.

[0099] The trifunctional or higher polyfunctional alcohol is preferably at least one selected from the group consisting of alcohols represented by the following formulae (a) and (b), glycerol, and pentaerythritol.

[0100] Trifunctional or higher polyfunctional alcohols may be used alone or in combination of two or more thereof.

[0101] [C2]

[0102]

[0103] In formulae (a) and (b), R1 and R2 each independently represent H, CH3 or C2H5.

[0104] Examples of the polyol may include the following.

[0105] 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-type polyols obtained by ring-opening polymerization of caprolactone; polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; and polycarbonate diols. These can be used alone or in combination of two or more.

[0106] Among the polyols, polyester polyol using adipate is preferable because a polyurethane elastomer excellent in mechanical properties can be obtained.

[0107] In particular, a polyol having an alkylene group with 4 or more carbon atoms, such as polybutylene glycol adipate polyester polyol or polyhexylene glycol adipate polyester polyol, is preferred. Furthermore, polyols having alkylene groups with different carbon numbers, such as polybutylene glycol adipate polyester polyol and polyhexylene glycol adipate polyester polyol, are preferably used in combination. Using different types of polyols can also improve the crystallization suppression of the soft segment, making it less likely for the soft segment to aggregate. As a result, the dispersibility of the hard segment can be further improved.

[0108] As the chain extender, diols and trifunctional or higher-functional alcohols capable of extending the polyurethane elastomer chain can be used.

[0109] Examples of the diol may include the following.

[0110] 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. These can be used alone or in combination of two or more.

[0111] As the catalyst, a general-purpose polyurethane elastomer curing catalyst can be used. Examples thereof include tertiary amine catalysts. Specific examples include 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; and triethylenediamine, piperazine compounds, and triazine compounds. In addition, organic acid salts of alkali metals, such as potassium acetate or potassium octoate, can also be used.

[0112] In addition, metal catalysts commonly used in urethanization, such as dibutyltin dilaurate, are also usable. These can be used alone or in combination of two or more.

[0113] To the raw material forming the elastic portion, additives such as a pigment, a plasticizer, a water-repellent agent, an antioxidant, an ultraviolet absorber, and a light stabilizer may be mixed, if necessary.

[0114] <Manufacturing Method of Wiper Blade>

[0115] The method for manufacturing the wiper blade is not particularly limited and can be selected from known methods.

[0116] For example, in a mold for a wiper blade, for example, a polyurethane elastomer raw material composition is injected into a mold cavity, and heated and cured. As a result, an elastic portion can be obtained.

[0117] Optionally, the front end portion of the elastic portion may be cut to form a shape. By doing so, a front end edge having high smoothness may be formed.

[0118] Still alternatively, it is also acceptable to manufacture a cleaning wiper blade by manufacturing a pair of molded bodies in a tandem shape formed in contact with each other so that the front end surfaces of the elastic portions face each other, and cutting in the length direction.

[0119] <Cleaning Wiper Blade Structure>

[0120] 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 located between the elastic portion 2 and the gripping portion 1 and used to support the elastic portion 2.

[0121] The grip portion 1 is a portion that can be gripped or held by a cleaning operator, typically a hand.

[0122] like Figure 1 As shown in (a) or (b), the gripping portion 1 is directly connected to the elastic portion, or is connected via the supporting portion 3. In addition, the gripping portion 1 may be detachable from the elastic portion 2 or the supporting portion 3, or may be integrated with the elastic portion 2 or the supporting portion 3.

[0123] Furthermore, the gripping portion 1 can be detachable from the elastic portion 2 or the supporting portion 3. The gripping portion 1 extends in a direction intersecting the direction in which the elastic portion 2 extends. Furthermore, the gripping portion 1 is not particularly limited in shape, as long as it can be grasped or held by the cleaning agent. A clamp used as a cleaning aid can be connected to the gripping portion.

[0124] For example, there can be mentioned a jig for extending the grip to clean a high place, etc. Furthermore, the material for the grip 1 is not particularly limited, and may be made of resin, or may be made of metal.

[0125] 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 for supporting the elastic portion 2.

[0126] like Figure 1 As shown in (a), the wiper blade has no supporting portion 3, and the elastic portion 2 can be directly coupled to the gripping portion 1. However, the wiper blade preferably has a supporting portion in order to stabilize the elastic portion and to bring the elastic portion into contact with the member to be cleaned.

[0127] The support portion 3 is connected to the elastic portion 2 in a direction perpendicular to the extending direction of the elastic portion 2. In addition, the elastic portion 2 may be detachable from the support portion 3 or may be integrated with the support portion 3. In addition, the shape of the support portion 3 is not particularly limited as long as it can support the elastic portion 2.

[0128] For example, the support portion 3 may be in a shape that sandwiches a portion of the elastic portion 2. The material of the support portion 3 is not particularly limited, and may be made of resin, or may be made of metal.

[0129] <How to use the wiper blade>

[0130] A method of using the wiper blade will be described.

[0131] The cleaning working body holds the supporting grip portion 4 and, while pressing the elastic portion 2 against the surface of the member to be cleaned, moves the wiper blade in a direction intersecting the extending direction of the elastic portion 2 , thereby removing dirt.

[0132] Figure 2 An explanatory diagram showing a state of a process in which, for cleaning, a wiper blade comes into contact with a member to be cleaned and slides for cleaning.

[0133] The moving direction of the wiper blade is a direction that intersects with the extending direction of the elastic portion 2. Figure 2 (a) shows the pushing direction C and Figure 2 The wiper blade is used by moving in the pulling direction W shown in (b).

[0134] Furthermore, the stains may be moistened in advance with a liquid detergent, water, or the like so as to be removed together with the liquid detergent, water, or the like.

[0135] <Shape of Wiper Blade>

[0136] For the wiper blade, there is no limitation on the respective shapes and mounting methods of the elastic portion 2, the supporting portion 3, and the supporting gripping portion 4.

[0137] Furthermore, the method for mounting the support portion 3 relative to the elastic portion 2 and the method for mounting the support grip portion 4 relative to the support portion 3 are also not limited.

[0138] [Example]

[0139] Below, the present disclosure will be described by manufacturing examples, embodiments, and comparative examples. However, the present disclosure is not limited to the embodiments, etc. For materials other than those shown in the embodiments and comparative examples, reagents or industrial chemicals were used. In addition, unless otherwise specified, all expressions "parts" in the embodiments and comparative examples are based on mass.

[0140] [Example 1]

[0141] <Preparation of Raw Materials for Elastic Part>

[0142] The materials in Table 1 below were mixed and reacted with each other at a temperature of 80° C. for 3 hours, thereby preparing a prepolymer having an NCO content of 10.6% by mass.

[0143] [Table 1]

[0144]

[0145] The materials described in Table 2 below were mixed to prepare a curing agent.

[0146] [Table 2]

[0147]

[0148] The prepolymer and curing agent were mixed to prepare a polyurethane raw material composition. The raw material composition was injected into the mold cavity of a mold for forming the elastic portion of a wiper blade and cured at 130°C for 2 minutes. The mold was then demolded to obtain a polyurethane molded body.

[0149] Furthermore, before the raw material composition was injected, a mold release agent A was applied to the mold cavity of the forming mold. The mold release agent A was a mixture of materials shown in Table 3 below.

[0150] [Table 3]

[0151]

[0152] The front end of the obtained polyurethane molded article was cut to produce an elastic portion having a main surface and a front end surface that formed a front end side edge with the main surface. The thickness and longitudinal lengths of the elastic portion were set to 1.8 mm and 300 mm, respectively. The obtained elastic portion was evaluated as follows.

[0153] [Evaluation 1: Measurement of Hard Segment Size]

[0154] The size of the hard segments was measured using a scanning probe microscope (SPM) in the following manner.

[0155] For the scanning probe microscope (SPM), MFP-3D-Origin (Oxford Instruments Co., Ltd.) was used.

[0156] The sample preparation method is as follows.

[0157] Here, as a result of observing the behavior of the wiper blade in detail, when the wiper blade moves in the pushing direction C in the direction from the gripping portion toward the elastic portion (see Figure 2 (a)), the wiper blade contacts the cleaned surface in an area centered at a position about 10 μm from the front side edge 9 at the front end surface 8 (see Figure 4 ).

[0158] Furthermore, when the wiper blade moves in the pulling direction W (see Figure 2 (b)), the wiper blade contacts the surface to be cleaned in an area centered at a position approximately 10 μm from the front end side edge 9 at the main surface 6 opposite to the surface to be cleaned (see Figure 4 ).

[0159] Therefore, if Figure 4 ( Figure 4 is an enlarged view of the front side 9 and Figure 5 ( Figure 5As shown in the figure (which is an enlarged view near the first line segment 10), when the distance between the first line segment 10 (the second line segment 11 for the main surface) and the front end side 9 is 10 μm, and assuming that a length L1 is drawn parallel to the front end side 9 at the front end surface 8 of the elastic portion of the resulting wiper blade, three 2 mm square measurement samples were cut from one end side of the first line segment, with one side of each being parallel to the first line segment. The centers of gravity were at points P0, P1, and P2 at (1 / 8) L1, (1 / 2) L1, and (7 / 8) L1, respectively. Then, from each measurement sample, using a cryo-microscope (UC-6 (trade name), manufactured by Leica Microsystems Co.), a polyurethane sheet was cut at -50°C, with the center of gravity at P0, P1, or P2. Each sheet was 100 μm square, one side was parallel to the first line segment, and the thickness of each sheet was 1 μm. In this way, three measurement samples were prepared. Each of the obtained measurement samples was placed on a smooth silicon wafer and allowed to stand under an environment of room temperature 25° C. and humidity 50% for 24 hours.

[0160] Then, the silicon wafer on which the measurement sample was placed was set on the SPM stage and subjected to SPM observation. Furthermore, the spring constant and proportionality constant of the silicon cantilever (trade name: OMCL-AC160, manufactured by Olympus Corporation, tip curvature radius: 8 nm) mounted on this SPM apparatus were previously confirmed using the thermal noise method as follows (spring constant: 30.22 nN / nm, proportionality constant: 82.59 nm / V).

[0161] Furthermore, previously, tuning of the cantilever was performed to determine the resonant frequencies of the cantilever (285 KHz (1st order) and 1.60 MHz higher orders)).

[0162] The SPM measurement mode was set to 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). Scanning was performed at a scan rate of 1 Hz within a 1 μm × 1 μm square field of view, with 256 points scanned vertically and 256 points scanned horizontally, to obtain a three-phase image (256 grayscale levels). Furthermore, the field of view was selected so that P0, P1, and P2 of each measurement sample appeared in the center of the field of view, with each side parallel to the first line segment.

[0163] Each phase image obtained was binarized using an image processing analysis system (trade name: Luzex-AP, manufactured by NIRECO Corporation). Specifically, the phase image was binarized using the binarization setting function of the image processing analysis system. In addition, the threshold of the binarization setting function was set to 85 (the 85th on the 256 grayscales). This operation provided a binarized image in which the soft segment was displayed in black and the hard segment was displayed in white. As an example, Figure 8 (a) shows the binarized image of Example 1, Figure 8 (b) shows the binarized image of Comparative Example 1.

[0164] The size of the hard segments in the resulting binary images was measured using an image processing and analysis system. The size of the hard segments was measured using the "equivalent circle diameter" parameter.

[0165] Furthermore, also for the main surface, three binarized images were formed in the same manner as described above, and the size of the hard segment in each binarized image was measured.

[0166] The arithmetic mean of the sizes of all the hard segments measured from a total of six binarized images thus obtained is shown in Table 4 or Table 5 as the size of the hard segment in the present disclosure.

[0167] [Evaluation 2: Measurement of M1 to M3]

[0168] The measurement of M1 to M3 was performed using a direct sample introduction method (DI method) in which a sample is introduced directly into an ion source without passing through a gas chromatograph (GC). As an apparatus, an ion trap type GC / MS (trade name: POLARIS Q, manufactured by ThermoFisher Scientific Co.) was used. As a direct introduction probe, a direct exposure probe (DEP) was used.

[0169] 0.1 μg of sample sampled at P0, P1 and P2 of the front surface and the main surface (P0, P1 and P2 are also set on the main surface as with the front surface) is fixed on the filament located at the front end of the probe and directly introduced into the ionization chamber. Subsequently, the sample is rapidly heated from room temperature to 1000°C at a constant heating rate (about 10°C / s), and the evaporated gas is detected by a mass spectrometer. When it is assumed that the total ion detection amount M1 is the sum of the integrated intensities of all peaks on the obtained total ion current thermogram, and it is assumed that the sum of the integrated intensities of the peaks of the extracted ion thermogram of the m / z values ​​derived from trifunctional or higher polyfunctional isocyanates is M2, the values ​​of M1 and M2 are used to calculate (M2 / M1). In addition, when it is assumed that the sum of the integrated intensities of the peaks of the extracted ion thermogram of the m / z values ​​derived from diisocyanates is M3, the values ​​of M1 and M3 are used to calculate (M3 / M1). Then, the arithmetic mean of the values ​​obtained from each sample of each P0', P1' and P2' of the front end surface and the main surface is referred to as the respective values ​​of (M2 / M1) and (M3 / M1) of the front end surface and the main surface.

[0170] Here, in this embodiment, for the elastic portion comprising a polyurethane synthesized using polymeric MDI as a trifunctional or higher polyfunctional isocyanate, in the extracted ion thermogram obtained by the aforementioned analysis, peaks derived from a cationized product of polymeric MDI were detected, with peak tops at respective positions where the m / z value indicating n=1 of the structure represented by Chemical Formula (1)' falls within the range of 380.5 to 381.5; the m / z value indicating n=2 falls within the range of 511.5 to 512.5; the m / z value indicating n=3 falls within the range of 642.5 to 643.5; and the m / z value indicating n=4 falls within the range of 773.5 to 774.5. Therefore, in this embodiment, the sum of the integrated intensities of the respective peaks is referred to as M2.

[0171] In other examples described later, TTI used as a trifunctional or higher-functional isocyanate has a structure represented by the following chemical formula (2). In the extracted ion thermogram obtained by analysis of the elastic portion comprising a polyurethane synthesized using TTI, a peak derived from a cationized product of TTI was detected, with a peak top at an m / z range of 366.5 to 367.5. Therefore, in this example, the integrated intensity of the peak is referred to as M2.

[0172] [C3]

[0173]

[0174] Similarly, in the examples described later, TPTI used as a trifunctional or higher polyfunctional isocyanate has a structure represented by the following chemical formula (3). Then, for the elastic portion comprising a polyurethane synthesized using TPTI, in the extracted ion thermogram obtained by analysis, a peak derived from a cationized product of TPTI was detected, having a peak top at a position within the m / z range of 464.5 to 465.5. Therefore, in this example, the integrated intensity of the peak is referred to as M2.

[0175] [C4]

[0176]

[0177] On the other hand, 4,4'-MDI, used as the diisocyanate in this example, has a structure represented by the following chemical formula (7). In the extracted ion thermogram obtained by analysis of the elastic portion comprising the polyurethane synthesized using 4,4'-MDI, a peak derived from a cationized product of 4,4'-MDI was detected, with a peak top at an m / z of 249.5 to 250.5. Therefore, the integrated intensity of the peak is referred to as M3.

[0178] [C5]

[0179]

[0180] Toluene diisocyanate (TDI) used as the diisocyanate in other examples has structures represented by the following chemical formulas (4a) and (4b).

[0181] In the extracted ion thermogram obtained by analysis of the elastic portion comprising polyurethane synthesized using TDI, a peak derived from a cationized product of TDI was detected, with a peak top located in the m / z range of 173.5 to 174.5. Therefore, the integrated intensity of the peak is referred to as M3.

[0182] [C6]

[0183]

[0184] Meta-xylene diisocyanate (XDI) of the diisocyanate has a structure represented by the following chemical formula (5). In the extracted ion thermogram obtained by analysis of the elastic portion comprising the polyurethane synthesized using XDI, a peak derived from a cationized product of XDI was detected, having a peak top at a position within the m / z range of 187.5 to 188.5.

[0185] Therefore, the integrated value of the peak is called M3.

[0186] [C7]

[0187]

[0188] Furthermore, 1,5-naphthalene diisocyanate (NDI) as a diisocyanate has a structure represented by the following chemical formula (6). In the extracted ion thermogram obtained by analysis of the elastic portion comprising polyurethane synthesized using NDI, a peak derived from a cationized product of NDI was detected, with a peak top at an m / z range of 209.5 to 210.5. Therefore, the integrated intensity of the peak is referred to as M3.

[0189] [C8]

[0190]

[0191] [Evaluation 3: Polyfunctional alcohol types and concentration measurement]

[0192] The detection of polyfunctional alcohols was performed by pyrolysis GC / MS (gas chromatography and mass spectrometry). The measurement conditions are as follows.

[0193] Sampling position: The sample to be sampled is measured at each of P0, P1, and P2 of the front end surface and the main surface in the following manner (as with the front end surface, P0, P1, and P2 are also set for the main surface). In addition, for sampling, a polyurethane member or the like is cut by a biocutter.

[0194] Device:

[0195] Pyrolysis device: Trade name: EGA / PY-3030D, manufactured by Frontier Laboratories Ltd.

[0196] Gas chromatography apparatus: TRACE1310 gas chromatograph, manufactured by Thermo Fisher Scientific Co.

[0197] Mass spectrometer: ISQLT, manufactured by Thermo Fisher Scientific Co.

[0198] Pyrolysis temperature: 500℃

[0199] GC column: 0.25mm inner diameter × 30m long stainless steel capillary column

[0200] Stationary phase: 5% phenyl polydimethylsiloxane

[0201] Heating conditions: Keep at 50°C for 3 minutes, then increase the temperature to 300°C at a heating rate of 8°C / min

[0202] MS conditions: mass range m / z 10-650

[0203] Scan rate: 1 second / scan

[0204] Polyfunctional alcohol species were quantified using GC / MS. A calibration curve was created for GC analysis of known concentrations of the quantified polyfunctional alcohol species, and quantification was performed based on GC peak area ratios. In this disclosure, the arithmetic mean of all measured values ​​obtained for each sample at locations P0, P1, and P2 on the front end surface and main surface was defined as the polyfunctional alcohol concentration. The results are shown in Tables 4 and 5.

[0205] <Evaluation 4: Wiping Performance Test>

[0206] The elastic portion of the wiper blade was brought into contact with the top of the glass surface and slidably contacted with the top of the glass surface through a reciprocating stroke including a pull-back movement, thereby observing the state of wiping the stains on the glass surface. As a result, the wiping performance of the wiper blade was evaluated. A schematic diagram of the tester used for the evaluation is shown in FIG. Figure 6 .

[0207] Using this test, Figure 6 The elastic portion 13 of the wiper blade is shown mounted. Water droplets are sprayed in the form of mist on the entire surface of the glass plate 14 of the member to be cleaned. Therefore, cleaning is performed under the following conditions.

[0208] The elastic portion 13 of the wiper blade is formed over the entire length thereof in the longitudinal direction. Figure 6 The gripping portion 601-1 of the evaluation device 601 shown is gripped. Thus, a test of the wiping performance of the wiper blade on the dirt on the surface of the glass 14 is conducted. One surface of the glass plate 14 is entirely wetted with water. Then, the elastic portion is brought into contact with the water-wetted surface of the glass plate 14 (hereinafter also referred to as the "cleaned surface"). Here, Figure 7 FIG. 1 shows an enlarged view of a portion where the elastic portion of the wiper blade and the cleaned surface 14-01 of the glass plate 14 contact each other. Figure 7 As shown in FIG. 1 , the elastic portion 13 of the wiper blade is brought into contact with the wiper blade so that the angle θ formed between the main surface 6 of the elastic portion and the surface to be cleaned 14-01 becomes 45 degrees. Then, an electric cylinder (trade name: RCP4-SA5C, manufactured by IAI Co., Ltd.) 15 is used to move the glass plate 14 along the surface at a speed of 10 mm / sec. Figure 7 The elastic portion reciprocated in the W and C directions indicated by the arrows. Furthermore, the force applied to the glass surface per meter along the longitudinal direction of the elastic portion was set to 10 N / m. The state of water removed from the cleaned surface immediately after wiping was visually observed and evaluated according to the following criteria.

[0209] [Evaluation criteria]

[0210] Grade A: 1 or less hairline (unwiped portion of very fine streaks with a width of 0.5 mm or less), 0 thicker lines (unwiped portion of fine streaks with a width of 1 mm or less), and wide lines (unwiped portion in the form of a band with a width of up to about 1 to 20 mm, including a collection of several hairlines and thicker lines, and film-like unwiped portions)

[0211] Grade B: 2 hair lines, 0 thicker and wider lines,

[0212] Level C: 2 hair lines, 1 thick line, and 0 wide lines

[0213] Level D: 3 hairlines, 1 thicker line, and 0 wide lines

[0214] Grade E: 4 or more hair lines, or 2 or more thick hair lines, or 1 or more wide hair lines

[0215] [Examples 2 to 48, Comparative Examples 1 to 6]

[0216] A prepolymer and a curing agent were obtained in the same manner as in Example 1, except that the materials and the mixing amounts were changed as shown in Table 4 or Table 5. The obtained wiper blade was evaluated in the same manner as in Example 1.

[0217] In addition to the materials shown in Example 1, the details of the materials used are shown below.

[0218] Polytetramethylene glycol adipate polyester polyol having a number average molecular weight of 1000 (trade name: NIPPOLAN 4009, manufactured by TOSOH CORPORATION Ltd.) (hereinafter described as PBA1000)

[0219] Polyhexamethylene glycol adipate polyester polyol having a number average molecular weight of 1000 (trade name: NIPPOLAN 164, manufactured by TOSOH CORPORATION Ltd.) (hereinafter described as PHA1000)

[0220] Polyhexamethylene glycol adipate polyester polyol having a number average molecular weight of 2600 (trade name: NIPPOLAN 136, manufactured by TOSOH CORPORATION Ltd.) (hereinafter described as PHA2600)

[0221] Polyhexamethylene glycol adipate polyester polyol having a number average molecular weight of 4500 (trade name: HS2H-451A, manufactured by HOKOKU Corporation) (hereinafter described as PHA 4500)

[0222] Polytetramethylene ether glycol having a number average molecular weight of 1000 (trade name: PTG-1000SN, manufactured by Hodogaya Chemical Co., Ltd.) (hereinafter described as PTMG 1000)

[0223] Polytetramethylene ether glycol having a number average molecular weight of 2000 (trade name: PTG-2000SN, manufactured by Hodogaya Chemical Co., Ltd. (hereinafter described as PTMG 2000)

[0224] Glycerin (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0225] Pentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0226] Toluene diisocyanate (trade name: CORONATE T-80, manufactured by TOSOH CORPORATION Ltd.) (hereinafter referred to as TDI)

[0227] m-Xylene diisocyanate (product code: D0127, manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter described as XDI)

[0228] 1,5-Naphthalene diisocyanate (Product code: N0168, manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter described as NDI)

[0229] Triphenylmethane-4,4',4"-triisocyanate (trade name: ULTIGHT SUPER CA, manufactured by Toho Kasei Kogyo Co., Ltd.) as a trifunctional or higher polyfunctional isocyanate (hereinafter referred to as TTI)

[0230] Tris(phenylisocyanate) thiophosphate as a trifunctional or higher polyfunctional isocyanate (trade name: ULTIGHT SUPER CAII ULTIGHT SUPER CAII, manufactured by Toho Kasei Kogyo Co., Ltd.) (hereinafter described as TPTI)

[0231] The evaluation results of Examples 1 to 48 and Comparative Examples 1 to 6 are shown in Tables 4 and 5.

[0232] [Table 4]

[0233]

[0234] [Table 5]

[0235]

[0236] The present disclosure is not limited to the embodiments, and various changes and modifications can be made 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.

[0237] This application claims priority based on Japanese Patent Application No. 2020-130703 filed on July 31, 2020, and Japanese Patent Application No. 2021-112662 filed on July 7, 2021, the entire contents of which are incorporated herein by reference.

[0238] Description of Reference Numerals

[0239] 1 Grip

[0240] 2 Elastic part

[0241] 3 Support part

[0242] 4 Support grip

[0243] 5. Components to be cleaned

[0244] 6 Main surface

[0245] 8Front end surface

[0246] 9 front side

[0247] 10The first line segment

[0248] 11 The second line segment

[0249] 13 Wiper blade elastic part

[0250] 14 Glass Pane

[0251] 15 Electric Cylinder

Claims

1. A cleaning wiper blade, characterized in that: It includes: A grip portion for grasping by hand; and an elastic portion, which is supported by the gripping portion and pressed against the surface to be cleaned, A portion of the elastic portion contacts the surface of the member to be cleaned, thereby cleaning the surface of the member to be cleaned, wherein The elastic portion comprises polyurethane, The polyurethane comprises a reactant of a composition comprising an isocyanate compound and an alcohol, wherein the isocyanate compound comprises a diisocyanate and a trifunctional or higher polyfunctional isocyanate, and the alcohol comprises a trifunctional or higher polyfunctional alcohol. The diisocyanate has an aromatic ring in the molecule, and When the polyurethane is heated to 1000° C. at a heating rate of 10° C. / s using a mass spectrometer of a direct sample injection system in which a sample is heated and vaporized in an ionization chamber and molecules of the sample are ionized, the obtained The detected amount of all ions is defined as M1, The integrated intensity of the peak of the extracted ion thermogram corresponding to the m / z value range derived from trifunctional or higher polyfunctional isocyanate is defined as M2, and When the integrated intensity of the peak of the extracted ion thermogram corresponding to the m / z value range derived from diisocyanate is defined as M3, M2 / M1 is 0.001~0.028, M3 / M1 is 0.020~0.110, M2 / M3 is 0.013~0.300, and The concentration of the trifunctional or higher polyfunctional alcohol in the polyurethane is 0.12 mmol / g to 0.65 mmol / g.

2. The cleaning wiper blade according to claim 1, wherein The M2 / M1 is 0.001~0.015, The M3 / M1 is 0.040~0.100, The M2 / M3 is 0.013~0.150, and The concentration of the trifunctional or higher polyfunctional alcohol in the polyurethane is 0.22 mmol / g to 0.39 mmol / g.

3. The cleaning wiper blade according to claim 1 or 2, The diisocyanate has a structure in which NCO is directly bonded to an aromatic ring.

4. The cleaning wiper blade according to claim 1 or 2, The trifunctional or higher polyfunctional isocyanate is at least one selected from the group consisting of polymeric MDI, triphenylmethane-4,4',4''-triisocyanate and tris(phenylisocyanate)phosphorothioate.

5. The cleaning wiper blade according to claim 1 or 2, The trifunctional or higher polyfunctional alcohol is at least one selected from the group consisting of an alcohol represented by the following formula (a), an alcohol represented by the following formula (b), and pentaerythritol: [C1] ， Wherein in the formulae (a) and (b), R1 and R2 each independently represent H, CH3 or C2H5.

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