JPWO2015107933A1 - Aqueous surface treatment agent and article using the same - Google Patents

Abstract

The present invention provides an aqueous surface treatment agent comprising an aqueous polyurethane (A) having a 100% modulus of 10 to 20 MPa and a carbodiimide-based crosslinking agent (B), and an article using the same. The aqueous surface treating agent of the present invention does not substantially contain an organic solvent, can impart excellent wear resistance to the surface of various articles such as synthetic leather and polyvinyl chloride (PVC) leather, and bends such as synthetic leather. Will not be damaged. Moreover, when giving a mat feeling to the surface of articles | goods, such as a synthetic leather, and setting it as a high-grade design, it can be set as the aqueous surface treating agent which contains a filler (C) further.

Description

  The present invention is an aqueous surface that does not substantially contain an organic solvent, can impart excellent wear resistance to the surface of various articles such as synthetic leather and polyvinyl chloride (PVC) leather, and does not impair the flexibility of synthetic leather and the like. The present invention relates to a treatment agent and an article using the same.

  In the production process of synthetic leather, polyvinyl chloride (PVC) leather, etc., finishing with a surface treatment agent is performed for the purpose of improving the wear resistance of the surface. Resin compositions used in conventional surface treatment agents were mainly solvent type containing organic solvents, but due to the recent increase in environmental regulations, development of aqueous surface treatment agents that are substantially free of organic solvents has been promoted. It has been. Particularly in automobile interior applications, there is a strong demand for the surface treatment agent to be water-based, since the effects of residual organic solvents on the human body are feared.

  However, when the surface treatment agent is made water-based, there is a problem that the high abrasion resistance of the conventional solvent-type surface treatment agent is lowered. There is a need for materials with comparable high wear resistance.

  As the aqueous surface treating agent, one using aqueous polyurethane has been proposed (see, for example, Patent Documents 1 and 2). When these aqueous surface treatment agents are used for leather, they are excellent in design properties such as the texture of the leather surface and mat feeling, but the wear resistance is not sufficient.

  On the other hand, what contains aqueous polyurethane and a polyisocyanate type crosslinking agent is proposed as what improved abrasion resistance with the aqueous surface treating agent (for example, refer patent document 3). Although this aqueous surface treatment agent has high abrasion resistance, the coating film is hard, and when applied to leather, there is a problem that the flexibility of the leather is impaired.

  Therefore, an aqueous surface treatment agent that does not substantially contain an organic solvent, can impart excellent wear resistance to the surface of various articles such as synthetic leather and polyvinyl chloride (PVC) leather, and does not impair the flexibility of synthetic leather and the like. There has been a need for an aqueous surface treating agent.

JP 2007-262248 A JP 2004-161945 A JP 2007-314919 A

  The problem to be solved by the present invention is that it is substantially free of organic solvents, can impart excellent wear resistance to the surface of various articles such as synthetic leather and polyvinyl chloride (PVC) leather, and bends such as synthetic leather. An aqueous surface treating agent that does not impair the properties and an article using the same.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are substantially free of an organic solvent due to a combination of an aqueous polyurethane having a 100% modulus of a certain value or more and a carbodiimide-based crosslinking agent. The present inventors have found that excellent wear resistance can be imparted to the surfaces of various articles such as synthetic leather and polyvinyl chloride (PVC) leather, and that the flexibility of synthetic leather and the like is not impaired.

  That is, the present invention relates to an aqueous surface treatment agent comprising an aqueous polyurethane (A) having a 100% modulus in the range of 10 to 20 MPa and a carbodiimide-based crosslinking agent (B), and an article using the same.

  The aqueous surface treating agent of the present invention does not substantially contain an organic solvent, and can impart excellent wear resistance to the surface of various articles such as synthetic leather and polyvinyl chloride (PVC) leather. Since it is not damaged, it can be used as an environmentally friendly material, and can be optimally used for leather used in applications such as vehicle seats, sports shoes, clothing, furniture and the like that are strongly required to have no residual organic solvent.

  The aqueous surface treating agent of the present invention contains an aqueous polyurethane (A) having a 100% modulus of the coating film in the range of 10 to 20 MPa and a carbodiimide-based crosslinking agent (B).

  The aqueous polyurethane (A) has a 100% modulus in the range of 10 to 20 MPa, has an active hydrogen group capable of crosslinking with a carbodiimide-based crosslinking agent (B) described later, and is in an aqueous medium. Those having a hydrophilic group capable of being dissolved or dispersed are preferred. Examples of such an aqueous polyurethane (A) include polycarbonate-based, polyether-based, and polyester-based ones. Also, polycarbonate is preferred for uses such as vehicle seats and furniture that require high wear resistance, and polyether is preferred for uses such as sports shoes where soft texture is important. Furthermore, what modified | denatured with the silicone compound can also be used as aqueous | water-based polyurethane (A).

  The 100% modulus of the aqueous polyurethane (A) is a value obtained by preparing a film of the aqueous polyurethane (A) and measuring with a tensile tester. As the tensile tester, for example, “Autograph AG-I” manufactured by Shimadzu Corporation can be used. Moreover, as a method for producing the film of the aqueous polyurethane (A), for example, a coating liquid containing the aqueous polyurethane (A) is applied onto a release paper using a gravure coater, knife coater, comma coater, air knife coater, or the like. Examples thereof include a method of peeling from a release paper after drying, a method of extruding the aqueous polyurethane (A) itself using a T die or the like and processing it into a film.

  The aqueous polyurethane (A) comprises a compound (a-1) having an active hydrogen group, a compound (a-2) having at least one active hydrogen group and a hydrophilic group, and a compound (a-3) having an isocyanate group. It is obtained by reacting. The active hydrogen group capable of crosslinking with the carbodiimide-based crosslinking agent (B) is obtained by leaving or introducing an active hydrogen group after the reaction of these compounds, and is dissolved or dispersed in an aqueous medium. The hydrophilic groups that can be obtained are likewise obtained by leaving or introducing hydrophilic groups after the reaction of these compounds.

  As an active hydrogen group which the said compound (a-1) has, a hydroxyl group, a phenolic hydroxyl group, an amino group, a mercapto group etc. are mentioned, for example. Among these, a hydroxyl group, a carboxyl group, and an amino group are preferable. The compound (a-1) preferably has two or more of these active hydrogen groups in one molecule.

  Examples of the compound (a-1) include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedi Methanol, bisphenol A, hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts, glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentae Relatively low molecular weight polyols such Suritoru like.

  Moreover, as said compound (a-1) other than the above, polyester polyol, polyether polyol, polycarbonate polyol, polyacetal polyol, polyacrylate polyol, polyesteramide polyol, polythioether polyol, polyolefin polyol, polyamine etc. are mentioned, for example. . These compounds (a-1) can be used alone or in combination of two or more.

  The polyester polyol is obtained by copolymerizing a polyester obtained by a dehydration condensation reaction such as a diol compound, a dicarboxylic acid compound, or a hydroxycarboxylic acid compound, a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone, and these reactions. can get. Examples of the diol compound used as a raw material for the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5-pentane. Diol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1 , 4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone, and alkylene oxide adducts thereof.

  Examples of the dicarboxylic acid compound used as a raw material for the polyester polyol include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2- And bis (phenoxy) ethane-p, p′-dicarboxylic acid.

  Furthermore, examples of the hydroxycarboxylic acid compound used as a raw material for the polyester polyol include p-hydroxybenzoic acid and p- (2-hydroxyethoxy) benzoic acid.

  Examples of the polyether polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, Glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, aconite sugar, femellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2,3-propane Ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydride are added to compounds having two or more active hydrogen groups such as trithiol. , Tetrahydrofuran, obtained by addition polymerization of cyclic ether compounds such as cycloalkyl Fe xylene, or the cyclic ether compound cationic catalyst, protonic acids include those of Lewis acid to ring-opening polymerization as a catalyst.

  The polycarbonate polyol can be obtained by reacting a diol compound such as 1,4-butanediol, 1,6-hexanediol, diethylene glycol and the like with diphenyl carbonate and phosgene.

  Examples of the polyamine include ethylenediamine, 1,6-hexamethylenediamine, piperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-dimethyl-4,4′-dicyclohexylmethanediamine. 1,4-cyclohexanediamine, 1,2-propanediamine, diethylenetriamine, triethylenetetramine, hydrazine and the like.

  The compound (a-2) is a compound having at least one active hydrogen group and a hydrophilic group, and has at least one active hydrogen group as described above. Examples of the hydrophilic group include a carboxyl group and a sulfonic acid group. And a compound having a salt thereof, a nonionic hydrophilic group having a repeating unit of an alkylene oxide, and the like. These compounds (a-2) can be used alone or in combination of two or more.

  Examples of the compound having a carboxyl group as the hydrophilic group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, and 2,6-dioxy. A carboxyl group such as benzoic acid, 3,4-diaminobenzoic acid, succinic acid, adipic acid, maleic acid, phthalic acid, alanine, aminobutyric acid, aminocaproic acid, glycine, glutamic acid, aspartic acid, histidine and the like, a hydroxyl group or an amino group Or a dicarboxylic acid compound.

  Examples of the compound having a sulfonic acid group as the hydrophilic group include 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3- Examples thereof include a compound having a sulfonic acid group such as phenylenediamine-4,6-disulfonic acid and 2,4-diaminotoluene-5-sulfonic acid and a hydroxyl group, a carboxyl group or an amino group, or a disulfonic acid compound.

  Furthermore, examples of the compound having a nonionic hydrophilic group as the hydrophilic group include polyethylene glycol, polypropylene glycol, a copolymer of ethylene oxide and propylene oxide, a copolymer of ethylene oxide and polybutylene oxide, and ethylene. Examples thereof include a copolymer of oxide and other alkylene oxide.

  Examples of the compound (a-3) having an isocyanate group include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4-diphenylmethane diisocyanate, 2 , 4′-diphenylmethane diisocyanate, 2,2-diphenylmethane diisocyanate, 3,3-dimethyl-4,4-biphenylene diisocyanate, 3,3-dimethoxy-4,4′-biphenylene diisocyanate, 3,3′-dichloro-4, 4-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexanemethylene diisocyanate, dodecamethylene Diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclophenylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4 -Polyisocyanates such as dicyclohexylmethane diisocyanate and 3,3-dimethyl-4,4-dicyclohexylmethane diisocyanate. These compounds containing an isocyanate group can be used alone or in combination of two or more.

  Among the compounds having the isocyanate group (a-3), 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate are preferable because the raw material cost can be reduced, and 1,6-hexamethylene is preferable. Diisocyanate, isophorone diisocyanate, and 4,4-dicyclohexylmethane diisocyanate are preferable because light resistance and heat resistance can be improved.

  In order to set the 100% modulus of the aqueous polyurethane (A) in the range of 10 to 20 MPa, the ratio of the compound (a-1) having an active hydrogen group and the compound (a-3) having an isocyanate group is adjusted. Is possible. For example, increasing the proportion of the compound (a-1) having an active hydrogen group decreases the 100% modulus, and increasing the proportion of the compound (a-3) having an isocyanate group increases the 100% modulus.

  The carbodiimide-based crosslinking agent (B) is preferably a polycarbodiimide compound having two or more carbodiimide groups. Examples of such a carbodiimide crosslinking agent (B) include poly (4,4′-diphenylmethanecarbodiimide) and poly (p-phenylenecarbodiimide). , Aromatic polycarbodiimides such as poly (m-phenylenecarbodiimide), poly (diisopropylphenylcarbodiimide), poly (triisopropylphenylcarbodiimide); alicyclic polycarbodiimides such as poly (dicyclohexylmethanecarbodiimide), poly (diisopropylcarbodiimide), etc. And aliphatic polycarbodiimide.

  Further, as the carbodiimide-based crosslinking agent (B), the aqueous surface treatment agent of the present invention is obtained by dispersing the aqueous polyurethane (A) in an aqueous medium, so that it is water-soluble or water-dispersible (emulsion type). There are preferred.

  Commercial products that can be used as the carbodiimide-based crosslinking agent (B) include “Carbodilite SV-02”, “Carbodilite V-02”, “Carbodilite V-02-L2”, and “Carbodilite V” manufactured by Nisshinbo Chemical Co., Ltd. -04 "," Carbodilite E-01 "," Carbodilite E-02 "and the like.

  As the usage-amount of the said carbodiimide type crosslinking agent (B), since it does not impair the texture at the time of using for leather, improving abrasion resistance more, it is 1-per 100 mass parts of said water-based polyurethane (A). The range of 50 parts by mass is preferable, the range of 2 to 25 parts by mass is more preferable, and the range of 3 to 20 parts by mass is more preferable.

  In the aqueous surface treating agent of the present invention, a filler (C) may be blended as necessary in order to impart a matte feeling to the coating film. Examples of the filler (C) include silica particles, organic beads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, alumina silicate, and the like. Can be mentioned. These fillers (C) can be used alone or in combination of two or more.

  Examples of the silica particles include dry silica and wet silica. Among these, dry silica is preferred because of its high scattering effect and wide gloss value adjustment range. The average particle diameter of these silica particles is preferably in the range of 2 to 14 μm, more preferably in the range of 3 to 12 μm.

  Examples of the organic beads include acrylic beads, urethane beads, silicon beads, and olefin beads.

  The filler (C) may be used in an appropriate amount depending on the mat feeling to be imparted, but is usually preferably in the range of 1 to 150 parts by mass with respect to 100 parts by mass of the aqueous polyurethane (A). The range of parts by mass is more preferable, and the range of 7 to 100 parts by mass is more preferable.

  In addition to the aqueous polyurethane (A), carbodiimide-based crosslinking agent (B), and filler (C), the aqueous surface treatment agent of the present invention includes various surfactants, antifoaming agents, leveling agents, thickeners, viscosity agents. Elasticity modifier, antifoaming agent, wetting agent, dispersing agent, preservative, film forming agent, plasticizer, penetrating agent, fragrance, bactericidal agent, acaricide, antifungal agent, UV absorber, antioxidant, antistatic Additives such as additives, flame retardants, dyes, pigments (eg, titanium white, bengara, phthalocyanine, carbon black, permanent yellow, etc.) may be blended.

  As a base material to which the aqueous surface treating agent of the present invention is applied, synthetic leather and polyvinyl chloride (PVC) leather are preferable. Moreover, the article of the present invention has a coating film of the aqueous surface treating agent of the present invention. Specific examples of the article of the present invention include synthetic leather, artificial leather, natural leather, vehicle seats using polyvinyl chloride (PVC) leather, sports shoes, clothing, furniture, and the like.

  Hereinafter, the present invention will be described specifically by way of examples.

(Production Example 1: Production of aqueous polyurethane PUD-1)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 500 parts by mass of 1,6-hexanediol-based polycarbonate diol (weight average molecular weight: 1,000) under a nitrogen stream, 34 parts by mass of methylolpropionic acid and 355 parts by mass of methyl ethyl ketone were added and mixed uniformly. Next, after adding 295 parts by weight of dicyclohexylmethane diisocyanate, 0.1 part by weight of dibutyltin dilaurate is added and reacted at 70 ° C. for about 4 hours, whereby a urethane prepolymer having an isocyanate group at the molecular end (in terms of solid content). Of NCO%: 3.8% by mass) was obtained.

  After adding 25 parts by mass of triethylamine to the methyl ethyl ketone solution of the urethane prepolymer obtained above and neutralizing the carboxyl group in the urethane prepolymer, 1,555 parts by mass of ion-exchanged water was added. Next, 23 parts by mass of ethylenediamine was added and reacted. After completion of the reaction, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous polyurethane PUD-1 (nonvolatile content: 35% by mass, 100% modulus: 15 MPa).

(Production Example 2: Production of aqueous polyurethane PUD-2)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 500 parts by mass of 1,6-hexanediol-based polycarbonate diol (weight average molecular weight: 1,000) under a nitrogen stream, 34 parts by mass of methylolpropionic acid and 330 parts by mass of methyl ethyl ketone were added and mixed uniformly. Next, after adding 236 parts by weight of dicyclohexylmethane diisocyanate, 0.1 part by weight of dibutyltin dilaurate was added and reacted at 70 ° C. for about 4 hours, thereby making a urethane prepolymer having an isocyanate group at the molecular terminal (in terms of solid content). Of NCO%: 1.6% by mass) was obtained.

  After adding 25 parts by mass of triethylamine to the methyl ethyl ketone solution of the urethane prepolymer obtained above and neutralizing the carboxyl group in the urethane prepolymer, 1,420 parts by mass of ion-exchanged water was added. Next, 9 parts by mass of ethylenediamine was added and reacted. After completion of the reaction, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous polyurethane PUD-2 (nonvolatile content: 35% by mass, 100% modulus: 7 MPa).

(Production Example 3: Production of aqueous polyurethane PUD-3)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 500 parts by mass of 1,6-hexanediol-based polycarbonate diol (weight average molecular weight: 1,000) under a nitrogen stream, 34 parts by mass of methylolpropionic acid and 397 parts by mass of methyl ethyl ketone were added and mixed uniformly. Next, after adding 393 parts by weight of dicyclohexylmethane diisocyanate, 0.1 part by weight of dibutyltin dilaurate was added and reacted at 70 ° C. for about 4 hours, whereby a urethane prepolymer having an isocyanate group at the molecular end (in terms of solid content). Of NCO%: 6.8% by mass) was obtained.

  After adding 25 parts by mass of triethylamine to the methyl ethyl ketone solution of the urethane prepolymer obtained above and neutralizing the carboxyl group in the urethane prepolymer, 1,779 parts by mass of ion-exchanged water was added. Next, 45 parts by mass of ethylenediamine was added and reacted. After completion of the reaction, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous polyurethane PUD-3 (nonvolatile content: 35 mass%, 100% modulus: 26 MPa).

  The 100% modulus of the aqueous polyurethane obtained in Production Examples 1 to 3 is a value measured by a tensile tester according to the following method.

  First, aqueous polyurethane was applied onto a release paper and dried to prepare a film having a thickness of 100 μm. The obtained film was cut into a length of 100 mm and a width of 5 mm to obtain a test piece. Both ends of this test piece are sandwiched between chucks, and using a tensile tester “Autograph AG-I” (manufactured by Shimadzu Corporation), in an atmosphere at a temperature of 23 ° C. and a humidity of 60%, a crosshead speed of 300 mm / min And 100% modulus (MPa) of the test piece was measured. At this time, the distance between the marked lines was 20 mm, and the initial distance between the chucks was 20 mm.

Example 1
286 parts by mass (100 parts by mass as an aqueous polyurethane) of the aqueous polyurethane PUD-1 (non-yellowing type polycarbonate-based aqueous polyurethane, non-volatile content: 35% by mass, 100% modulus: 15 MPa) obtained in Production Example 1, carbodiimide-based crosslinking agent (“Carbodilite V-02-L2” manufactured by Nisshinbo Chemical Co., Ltd., nonvolatile content: 40% by mass) 28.6 parts by mass (11.4 parts by mass as a carbodiimide-based crosslinking agent), filler (“ACEMATT TS 100 manufactured by Evonik Degussa) ”, 8.6 parts by mass of silica particles produced by a dry process, average particle size: 10 μm), associative thickener (“ Hydran Assister T10 ”manufactured by DIC Corporation, nonvolatile content: 30% by mass) 8.6 A mass part (2.6 parts by mass as an associative thickener) and 629 parts by mass of ion-exchanged water are mixed uniformly. To give an aqueous surface treatment agent (1). Using the aqueous surface treating agent (1) thus obtained, the following storage stability, abrasion resistance and flexibility were evaluated.

[Evaluation of storage stability]
The aqueous surface treatment agent (1) obtained above was allowed to stand at 25 ° C. for 24 hours, and then the appearance was visually observed to confirm the presence or absence of separation and aggregate formation. Also, the viscosity of the BM type viscometer ("TVB-22LT" manufactured by Toki Sangyo Co., Ltd., # 3 rotor, 60 rpm) immediately after preparation of the aqueous surface treatment agent (1) obtained above and after standing for 24 hours at 25 ° C. Measured with

[Evaluation of wear resistance]
The aqueous surface treatment agent was applied onto PVC leather using a 50 μm bar coater and dried in a gear oven at 120 ° C. for 2 minutes to obtain a sample for evaluation. Next, the obtained evaluation sample was tested using a Taber abrasion tester ("Taber abrasion tester 5150ABRASER" manufactured by NORTH TONAWADA) under the conditions of wear wheel: CS-10, 2000 times, and evaluation after the test. The sample was visually checked for changes in appearance and evaluated for wear resistance.

[Evaluation of flexibility]
The evaluation sample obtained above was tested under a 1 kg load and 2000 conditions using a Scott Stag tester ("IT-SCA-W" manufactured by Intec). The flexibility was evaluated by visual inspection.

(Comparative Example 1)
The aqueous polyurethane PUD-1 used in Example 1 was replaced with 286 parts by mass (100 parts by mass as an aqueous polyurethane) of the aqueous polyurethane PUD-2 (nonvolatile content: 35% by mass, 100% modulus: 7 MPa) obtained in Production Example 2. The carbodiimide-based crosslinking agent was changed to 11.4 parts by mass of an isocyanate-based crosslinking agent (“Hydran Assist C2” manufactured by DIC Corporation, nonvolatile content: 100% by mass). A treating agent (R1) was obtained.

(Comparative Example 2)
The aqueous polyurethane PUD-1 used in Example 1 was replaced with 286 parts by mass (100 parts by mass as an aqueous polyurethane) of the aqueous polyurethane PUD-2 (nonvolatile content: 35% by mass, 100% modulus: 7 MPa) obtained in Production Example 2. Except having changed, it carried out similarly to Example 1 and obtained the aqueous surface treating agent (R2).

(Comparative Example 3)
The aqueous polyurethane PUD-1 used in Example 1 was replaced with 286 parts by mass (100 parts by mass as an aqueous polyurethane) of the aqueous polyurethane PUD-3 (nonvolatile content: 35% by mass, 100% modulus: 26 MPa) obtained in Production Example 3. Except having changed, it carried out similarly to Example 1 and obtained the aqueous surface treating agent (R3).

  About aqueous | water-based surface treating agent (R1)-(R3) obtained by said Comparative Examples 1-3, the storage stability, abrasion resistance, and flexibility were evaluated similarly to Example 1. FIG.

  Table 1 shows the composition of the aqueous surface treatment agents (1) and (R1) to (R3) obtained in Example 1 and Comparative Examples 1 to 3, the storage stability, the wear resistance, and the evaluation results of the sag test. Shown in In addition, the compounding composition shown in Table 1 is described in a non-volatile content.

  From the results shown in Table 1, it is confirmed that the aqueous surface treating agent (1) of Example 1 which is the aqueous surface treating agent of the present invention has all good evaluations of storage stability, abrasion resistance and flexibility. did it.

  Comparative Example 1 is an example of an aqueous surface treatment agent using an isocyanate type crosslinking agent that is not a carbodiimide type, and it was confirmed that the aqueous surface treatment agent has insufficient storage stability.

  Comparative Example 2 is an example of an aqueous surface treatment using a 7 MPa aqueous polyurethane that is less than 10 MPa, which is the lower limit of the 100% modulus range of the aqueous polyurethane used in the present invention. It was confirmed that the property was insufficient.

  Comparative Example 3 is an example of an aqueous surface treatment agent using 26 MPa aqueous polyurethane exceeding 20 MPa, which is the upper limit of the 100% modulus range of the aqueous polyurethane used in the present invention. This aqueous surface treatment agent has flexibility. It was confirmed that it was insufficient.

Claims (3)

  An aqueous surface treating agent comprising an aqueous polyurethane (A) having a 100% modulus in the range of 10 to 20 MPa and a carbodiimide-based crosslinking agent (B).   Furthermore, the aqueous surface treating agent of Claim 1 containing a filler (C).   An article having a coating film of the aqueous surface treating agent according to claim 1 or 2.