Moisture-curable composition for shoes and method for repairing shoes

Abstract

Provided is a moisture-curable composition for shoes, wherein the cured product of said composition is excellent in wear resistance, exhibits minimized generation of air bubbles, and has superior transparency. Also provided is method for repairing shoes using the moisture-curable composition for shoes, wherein the cured product of said composition is excellent in wear resistance, exhibits minimized generation of air bubbles, and has superior transparency. More specifically, provided is a moisture-curable composition for shoes, containing: (A) a cross-linkable silyl group-containing polyether and / or a cross-linkable silyl group-containing polyurethane, (B) a cross-linkable silyl group-containing vinyl-based organic polymer, and (C) a diluent and / or a plasticizer.

Description

Moisture-curing shoe composition and shoe repair method

[0001] The present invention relates to a moisture-curable shoe composition and a shoe repair method, and more particularly to a moisture-curable shoe composition that exhibits excellent surface abrasion resistance after curing, suppresses the generation of bubbles inside the cured product, and provides excellent transparency after curing, and a shoe repair method using the same.

[0002] In recent years, shoe compositions have become known for repairing shoes with worn soles, etc. When repairing a shoe sole using a shoe composition, the damaged part of the shoe sole can be repaired by applying the shoe composition to the repaired part of the shoe sole, or by pouring the shoe composition into a casting mold formed with a formwork and leaving it at room temperature to dry and harden.

[0003] Patent Document 1 discloses a shoe sole repair agent containing rubber, a reinforcing agent such as carbon black, and a hydrocarbon solvent, with the hydrocarbon solvent content being 35 to 65 wt %, preferably 40 to 60 wt %. This shoe sole repair agent is said to be easy to use, allowing for easy repair regardless of the shape of the sole by simply building up the surface of the worn-out sole. After curing, it becomes a rubber-like elastic body, achieving a finish comparable to that of a normal sole, and is a one-component repair agent that is easy to handle, eliminating the need for mixing components. Patent Document 2 discloses a shoe sole repair agent characterized by a one-component thermosetting composition primarily composed of a urethane prepolymer and / or a polyisocyanate compound containing terminal isocyanate groups and a latent curing agent. This shoe sole repair agent is intended for repairing shoe soles and heels, and is said to be free from the problem of solvent evaporation, cure quickly, experience little deformation or shrinkage due to curing, and be able to repair to the desired shape in a single repair operation.

[0004] JP 2002-60552 A JP 2006-34882 A

[0005] The shoe sole repair agent described in Patent Document 1 is a solvent-based sole repair agent, and the solvent evaporates during drying and curing, causing problems with odor, working environment, and safety and health. Furthermore, drying and curing takes a long time, and the repaired area may shrink as the repair agent dries and cures, making it impossible to achieve the desired shape in one repair operation, necessitating repeated repairs. The shoe sole repair agent described in Patent Document 2 is said to be free of the problem of solvent evaporation, cure in a short time, cause almost no deformation or shrinkage associated with curing, and achieve the desired shape in one repair operation. However, because it is a urethane-based sole repair agent, it contains bubbles generated during the reaction within the cured product. Wear on the surface of the cured product at the repaired area causes problems with the appearance of the repaired area, and further accelerates wear of the repaired area. Furthermore, both the shoe sole repair agents described in Patent Documents 1 and 2 have problems with the transparency of the cured product.

[0006] The problem to be solved by the present invention is to provide a moisture-curable shoe composition that provides a cured product with excellent abrasion resistance, suppressed bubble formation within the cured product, and excellent transparency.The problem to be solved by the present invention is to provide a shoe repair method using a moisture-curable shoe composition that provides a cured product with excellent abrasion resistance, suppressed bubble formation within the cured product, and excellent transparency.

[0007] The present inventors conducted extensive research to solve the above-mentioned problems, and discovered that the above-mentioned problems can be solved by a moisture-curing shoe composition having a specific composition and a shoe repair method using the moisture-curing shoe composition, thereby completing the present invention. Specifically, the present invention is as follows: [Item 1] A moisture-curing shoe composition containing (A) a crosslinkable silyl group-containing polyether and / or a crosslinkable silyl group-containing polyurethane, (B) a crosslinkable silyl group-containing vinyl organic polymer, and (C) a diluent and / or plasticizer. [Item 2] The moisture-curing shoe composition according to Item 1, which exhibits an abrasive mass of 130 mg or less in a taper abrasion test according to JIS K 6264 (abrasive wheel material H22, applied force 9.8 N, test rotation speed 1,000 rpm). [Item 3] The moisture-curing shoe composition according to Item 1 or 2, wherein the diluent and / or plasticizer (C) has a boiling point of 150°C or higher. [Item 4] The moisture-curable shoe composition according to any one of Items 1 to 3, wherein the (C) diluent and / or plasticizer includes a plasticizer having a number average molecular weight of 3,000 or less. [Item 5] The moisture-curable shoe composition according to any one of Items 1 to 4, further comprising (D) silica powder. [Item 6] The moisture-curable shoe composition according to any one of Items 1 to 5, further comprising (E) a curing catalyst. [Item 7] A shoe repair method using the moisture-curable shoe composition according to any one of Items 1 to 6.

[0008] The present invention provides a moisture-curable shoe composition that exhibits excellent surface abrasion resistance, suppresses bubble formation within the cured product, and produces a cured product with excellent transparency. The present invention also provides a shoe repair method using a moisture-curable shoe composition that exhibits excellent surface abrasion resistance, suppresses bubble formation within the cured product, and produces a cured product with excellent transparency. The moisture-curable shoe composition of the present invention does not suffer from odor, working environment, and safety and health issues caused by solvents that volatilize during drying and curing, as occurs with conventional solvent-based shoe sole repair agents. Furthermore, the short time required for drying and curing eliminates the shrinkage associated with drying and curing, allowing for repair to the desired shape in a single repair operation. Furthermore, the excellent transparency of the cured product makes it possible to make the repaired area less noticeable without color-matching the moisture-curable shoe composition, and it can also be colored to any color tone as needed. Furthermore, suppressing bubble formation within the cured product allows for maintaining abrasion resistance even within the cured product, thereby extending the time until the repaired area needs to be re-repaired.

[0009] The moisture-curable shoe composition and shoe repair method of the present invention will be described in detail below. These are shown by way of example, and it goes without saying that various modifications are possible without departing from the technical concept of the present invention.

[0010] {Moisture-Curable Shoe Composition} The moisture-curable shoe composition of the present invention is a moisture-curable shoe composition containing (A) a crosslinkable silyl group-containing polyether and / or a crosslinkable silyl group-containing polyurethane, (B) a crosslinkable silyl group-containing vinyl organic polymer, and (C) a diluent and / or a plasticizer. The moisture-curable shoe composition of the present invention may further contain (D) silica powder. The moisture-curable shoe composition of the present invention may further contain (E) a curing catalyst. The moisture-curable shoe composition of the present invention may have a cured product with an abrasive mass of 130 mg or less in a taper abrasion test according to JIS K 6264 (abrasive wheel material H22, applied force 9.8 N, test rotation speed 1,000 rpm)

[0011] [Component (A)] Component (A) constituting the moisture-curable shoe composition of the present invention is a crosslinkable silyl group-containing polyether and / or a crosslinkable silyl group-containing polyurethane. Component (A) may consist of a crosslinkable silyl group-containing polyether, a crosslinkable silyl group-containing polyurethane, or a crosslinkable silyl group-containing polyether and a crosslinkable silyl group-containing polyurethane.

[0012] <Crosslinkable silyl group-containing polyether> The crosslinkable silyl group-containing polyether is a compound having a crosslinkable silyl group and a polyether skeleton in the molecule. The crosslinkable silyl group is located on a side chain and / or at the end of the molecule, preferably at the end of the molecule. The crosslinkable silyl group-containing polyether may be used alone or in combination of two or more.

[0013] (Crosslinkable Silyl Group) The crosslinkable silyl group constituting the crosslinkable silyl group-containing polyether has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and is a group that can crosslink by forming a siloxane bond. As the crosslinkable silyl group, for example, a group represented by structural formula (1) is preferable. -Si(R １１ ) ３－ａ１ X １１ ａ１ ...(1) In structural formula (1), R １１ represents a hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, R １１ ３ SiO-(R １１ is the same as above), or a triorganosiloxy group represented by the formula -CH ２ OR １１ Group (R １１ is the same as above). １１ is a group in which at least one hydrogen atom on the 1st to 3rd carbon atoms is a halogen, -OR １２ , -NR １３ R １４ , -N=R １５ , -SR １６ (R １２ , R １３ , R１４ , R １６ are each a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; R １５ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may or may not have a substituent. ), a perfluoroalkyl group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a cyano group. １１ is preferably a methyl group. １１ When there are two or more R １１ may be the same or different. １１ represents a hydroxyl group or a hydrolyzable group, and X １１ If there are two or more X １１ may be the same or different, and a1 is an integer of 0, 1, 2, or 3. In consideration of curability, in order to obtain a moisture-curable shoe composition having a sufficient curing rate, it is preferable that a1 in structural formula (1) be 2 or more.

[0014] One to three hydrolyzable groups or hydroxyl groups can be bonded to one silicon atom. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming the crosslinkable silyl group may be one or two or more.

[0015] X １１The hydrolyzable group represented by the formula (I) is not particularly limited as long as it is other than a fluorine atom. Examples include a hydrogen atom, a halogen atom (chlorine atom, bromine atom, iodine atom), an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferred, and an alkoxy group, a halogen atom, an amide group, and an aminooxy group are more preferred. From the viewpoint of mild hydrolysis and easy handling, an alkoxy group is particularly preferred. The number of carbon atoms in the alkoxy group is not particularly limited, but is 1 or more carbon atoms, for example, 12 or less, preferably 6 or less, for example, 1 to 12 carbon atoms, for example, 1 to 6 carbon atoms. The fewer the carbon atoms in the alkoxy group, the higher the reactivity, and the greater the carbon number, in the order of methoxy group > ethoxy group > propoxy group, the lower the reactivity. The group can be selected depending on the purpose and application, but methoxy groups and ethoxy groups are usually used.

[0016] Specific examples of the crosslinkable silyl group include trialkoxysilyl groups such as trimethoxysilyl and triethoxysilyl groups [—Si(OR) ３ ], dialkoxysilyl groups such as methyldimethoxysilyl group and methyldiethoxysilyl group [—SiR １ (OR) ２ ]. When increasing reactivity, a trimethoxysilyl group is preferred, and when suppressing reactivity, a dialkoxysilyl group is preferred. Here, R may be the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. From the viewpoint of the adhesion, weather resistance, mechanical properties (elongation), and abrasion resistance of the resulting moisture-curable shoe composition and / or its cured product, the crosslinkable silyl group is preferably a trimethoxysilyl group. One type of crosslinkable silyl group may be used alone, or two or more types may be used in combination.

[0017] The crosslinkable silyl group may be present at the end of the main chain and / or the end of the side chain of the polyether molecular chain. In particular, it is preferable that the crosslinkable silyl group is present only at the end of the main chain of the polyether molecular chain. In this case, the effective network length of the polyether molecular chain contained in the finally formed cured product is increased, thereby exhibiting excellent properties in terms of adhesion, weather resistance, mechanical strength, etc. Furthermore, multiple crosslinkable silyl groups represented by structural formula (1) may be linked to each other.

[0018] In the moisture-curable shoe composition of the present invention, the number of crosslinkable silyl groups contained in one molecule of the crosslinkable silyl group-containing polyether (A), component (A), is not particularly limited. It can be, for example, an average of 0.5 or more, preferably an average of 1.0 or more, and for example, an average of 5.0 or less, preferably an average of 4.5 or less, more preferably an average of 4.0 or less, for example, an average of 0.5 or more and an average of 5.0 or less, for example, an average of 0.5 or more and an average of 4.5 or less, for example, an average of 0.5 or more and an average of 4.0 or less, for example, an average of 1.0 or more and an average of 5.0 or less, for example, an average of 1.0 or more and an average of 4.5 or less, for example, an average of 1.0 or more and an average of 4.0 or less. If the number of crosslinkable silyl groups contained in one molecule is less than 0.5 on average, the curability will be insufficient, and problems may arise in terms of adhesion and curability. If the number of crosslinkable silyl groups contained in one molecule is more than 5.0 on average, production will be difficult, and the curability will be too high, which may result in reduced storage stability and handleability, or the cured coating may become hard and brittle.

[0019] (Polyether Skeleton) Examples of the polyether skeleton constituting the crosslinkable silyl group-containing polyether include those represented by the structural formula (2): -O-R ２１ A skeleton having a repeating unit represented by the following structural formula (2) is preferred. The polyether skeleton may consist of only one type of repeating unit, or may consist of two or more types of repeating units. ２１ is a divalent organic group. ２１can be, for example, a linear or branched alkylene group having 1 to 14 carbon atoms, and preferably a linear or branched alkylene group having 2 to 4 carbon atoms. A specific example of the repeating unit represented by structural formula (2) is preferably a polyoxyalkylene repeating unit. Examples of polyoxyalkylene repeating units include, for example, -CH ２ O-, -CH ２ CH ２ O-, -CH ２ CH (CH ３ ) O—, —CH ２ CH(C ２ H ５ ) O—, —CH ２ C(CH ３ ) ２ O-, -CH ２ CH ２ CH ２ O-, -CH ２ CH ２ CH ２ CH ２ O-, -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ In the present invention, in the crosslinkable silyl group-containing polyether, the polyether skeleton is preferably constituted by a polyoxyalkylene polymer comprising polyoxyalkylene repeating units, and more preferably constituted by a polyoxypropylene polymer.

[0020] In the crosslinkable silyl group-containing polyether, the method for synthesizing the polyoxyalkylene polymer constituting the polyether skeleton is not particularly limited. Examples include polymerization of alkylene oxide using an alkali catalyst such as KOH, and polymerization of alkylene oxide using a double metal cyanide complex catalyst. Polymerization using a double metal cyanide complex catalyst can produce a polyoxyalkylene polymer with a number average molecular weight of 20,000 or more and a Mw / Mn ratio of 1.6 or less, and a narrow molecular weight distribution.

[0021] (Method for Producing Crosslinkable Silyl Group-Containing Polyether) The method for producing the crosslinkable silyl group-containing polyether is not particularly limited. For example, a crosslinkable silyl group-containing polyether (crosslinkable silyl group-containing polyoxyalkylene polymer) can be obtained by a "polymer reaction method" in which a functional group such as an unsaturated group, a hydroxyl group, an epoxy group, or an isocyanate group is introduced into the molecule of the polyoxyalkylene polymer as needed, and a compound having a crosslinkable silyl group and a functional group reactive with the functional group possessed by the polyoxyalkylene polymer is reacted.

[0022] A specific example of the polymer reaction method is a method in which an unsaturated group-containing polyoxyalkylene polymer is subjected to hydrosilylation or mercapto conversion with a hydrosilane having a crosslinkable silyl group or a mercapto compound having a crosslinkable silyl group to obtain a polyoxyalkylene polymer having a crosslinkable silyl group. The unsaturated group-containing polyoxyalkylene polymer can be obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that is reactive with the functional group. Other specific examples of the polymer reaction method include a method in which a polyoxyalkylene polymer having a terminal hydroxyl group is reacted with a compound having an isocyanate group and a crosslinkable silyl group, and a method in which a polyoxyalkylene polymer having a terminal isocyanate group is reacted with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silyl group. The use of an isocyanate compound makes it easy to obtain a polyoxyalkylene polymer having a crosslinkable silyl group.

[0023] (Number Average Molecular Weight) The crosslinkable silyl group-containing polyether (A), component (A) in the moisture-curable shoe composition, may be either a linear or branched polymer. The number average molecular weight of the crosslinkable silyl group-containing polyether (A), component (A) of the moisture-curable shoe composition of the present invention, is not particularly limited. In terms of polystyrene equivalent in GPC, it may be, for example, 1,000 or more, preferably 2,000 or more, and may be, for example, 100,000 or less, preferably 50,000 or less, more preferably 40,000 or less. For example, it may be 1,000 to 100,000, for example, 1,000 to 50,000, for example, 1,000 to 40,000, for example, 2,000 to 100,000, for example, 2,000 to 50,000, or for example, 2,000 to 40,000. If the number average molecular weight is less than 1,000, the adhesiveness will decrease, and if the number average molecular weight exceeds 100,000, the viscosity will be high, which may cause problems in terms of workability when repairing shoes.

[0024] <Crosslinkable silyl group-containing polyurethane> The crosslinkable silyl group-containing polyurethane is a compound having a crosslinkable silyl group and a polyurethane skeleton in the molecule. The crosslinkable silyl group is located on a side chain and / or at the end of the molecule, preferably at the end of the molecule. The crosslinkable silyl group-containing polyurethane may be used alone or in combination of two or more.

[0025] (Crosslinkable silyl group) The crosslinkable silyl group constituting the crosslinkable silyl group-containing polyurethane has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and is a group that can crosslink by forming a siloxane bond. Examples of the crosslinkable silyl group include the same groups as the crosslinkable silyl groups described in (Crosslinkable silyl group) in the above <Crosslinkable silyl group-containing polyether>. The crosslinkable silyl group of the crosslinkable silyl group-containing polyether and the crosslinkable silyl group of the crosslinkable silyl group-containing polyurethane may be the same or different.

[0026] The crosslinkable silyl group may be present at the end of the main chain and / or the end of the side chain of the polyurethane molecular chain. In particular, it is preferable that the crosslinkable silyl group is present only at the end of the main chain of the polyurethane molecular chain. In this case, the effective network length of the polyurethane molecular chain contained in the finally formed cured product is increased, thereby exhibiting excellent properties in terms of adhesion, weather resistance, mechanical strength, etc. Furthermore, multiple crosslinkable silyl groups represented by structural formula (1) may be linked to each other.

[0027] In the moisture-curable shoe composition of the present invention, the number of crosslinkable silyl groups contained in one molecule of the crosslinkable silyl group-containing polyurethane (A), component (A), is not particularly limited. The number of crosslinkable silyl groups contained in one molecule of the crosslinkable silyl group-containing polyurethane may be, for example, an average of 0.5 or more, preferably an average of 1.0 or more, and may be, for example, an average of 5.0 or less, preferably an average of 4.5 or less, more preferably an average of 4.0 or less. For example, an average of 0.5 or more and an average of 5.0 or less, for example, an average of 0.5 or more and an average of 4.5 or less, for example, an average of 0.5 or more and an average of 4.0 or less, for example, an average of 1.0 or more and an average of 5.0 or less, for example, an average of 1.0 or more and an average of 4.5 or less, for example, an average of 1.0 or more and an average of 4.0 or less. If the number of crosslinkable silyl groups contained in one molecule is less than 0.5 on average, curability may be insufficient, resulting in problems with adhesion and curability. If the number of crosslinkable silyl groups contained in one molecule exceeds 5.0 on average, production may be difficult, and the curability may be too high, resulting in reduced storage stability and handleability.

[0028] (Polyurethane Skeleton) Examples of the polyurethane skeleton constituting the crosslinkable silyl group-containing polyurethane include those represented by the structural formula (3): —O—R ３１ -OC(=O)-NH-R ３２ A skeleton having a repeating unit represented by the formula: —NH—C(═O)— (3) is preferred. The polyurethane skeleton may consist of only one type of repeating unit, or may consist of two or more types of repeating units. In the structural formula (3), R ３１ is a polyol residue, R ３２is a polyisocyanate residue. The polyol residue is a group derived from a polyol described below, and the polyisocyanate residue is a group derived from a polyisocyanate described below.

[0029] In the crosslinkable silyl group-containing polyurethane, the polyurethane polymer constituting the polyurethane skeleton may be synthesized by any method. For example, the polyurethane may be obtained by reacting a polyol compound having two or more hydroxyl groups per molecule, a polyisocyanate compound having two or more isocyanate groups per molecule, and an optional chain extender. A known urethane catalyst or organic solvent may also be used in synthesizing the polyurethane polymer.

[0030] Polyol Compound The polyol compound used in synthesizing the polyurethane polymer is not particularly limited as long as it is a compound having two or more hydroxyl groups. In the present invention, a polymer polyol having a number average molecular weight of 500 or more is preferred. Examples of polymer polyols include polyester polyols, polyether polyols, polycarbonate polyols, polybutadiene polyols, polyisoprene polyols, polyolefin polyols, and poly(meth)acrylic acid ester polyols. One type of polyol compound may be used alone, or two or more types may be used in combination.

[0031] Polyisocyanate Compound The polyisocyanate compound used in synthesizing the polyurethane polymer is not particularly limited as long as it has two or more isocyanate groups. For example, aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, etc. are preferably used. Examples of aromatic polyisocyanate compounds include diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, polymeric MDI, tolylene diisocyanate, xylylene diisocyanate, naphthalene-1,5-diisocyanate, p-phenylene diisocyanate, and m-phenylene diisocyanate. Examples of aliphatic polyisocyanate compounds include ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, lysine diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, etc. Examples of alicyclic polyisocyanate compounds include norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexylene diisocyanate, bis(isocyanatemethyl)cyclohexane, dicyclohexylmethane diisocyanate, etc. One type of polyisocyanate compound may be used alone, or two or more types may be used in combination.

[0032] Chain extender The chain extender used as needed in synthesizing the polyurethane polymer is not particularly limited as long as it is a compound having two or more groups reactive with an isocyanate group. Examples include low-molecular-weight polyols having a molecular weight of 500 or less, such as ethylene glycol, propylene glycol, 1,4-butanediol, and trimethylolpropane, and polyamine compounds such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine. One type of chain extender may be used alone, or two or more types may be used in combination.

[0033] (Method for Producing Crosslinkable Silyl Group-Containing Polyurethane) The method for producing the crosslinkable silyl group-containing polyurethane is not particularly limited. For example, a functional group such as an unsaturated group, a hydroxyl group, an epoxy group, or an isocyanate group may be introduced into the polyurethane polymer molecule as needed, and a compound having a crosslinkable silyl group and a functional group reactive with the functional group possessed by the polyurethane polymer may be reacted to produce the crosslinkable silyl group-containing polyurethane.

[0034] In particular, either of the following methods is preferred: (i) a method in which a hydroxyl group-containing polyurethane polymer is obtained by reacting a polyol compound having two or more hydroxyl groups per molecule, a polyisocyanate compound having two or more isocyanate groups per molecule, and an optional chain extender so that the hydroxyl groups are in excess, and the resulting polymer is reacted with a compound having a functional group reactive with hydroxyl groups and a crosslinkable silyl group; or (ii) a method in which a polyol compound having two or more hydroxyl groups per molecule, a polyisocyanate compound having two or more isocyanate groups per molecule, and an optional chain extender so that the isocyanate groups are in excess, and the resulting polymer is reacted with a compound having a functional group reactive with isocyanate groups and a crosslinkable silyl group.

[0035] Examples of compounds having a crosslinkable silyl group and a functional group reactive with the functional group of a polyurethane polymer include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. The compound having a crosslinkable silyl group and a functional group reactive with the functional group of the polyurethane polymer may be used alone or in combination of two or more.

[0036] (Number Average Molecular Weight) The crosslinkable silyl group-containing polyurethane (A), component (A) of the moisture-curable shoe composition of the present invention, may be either a linear or branched polymer. The number average molecular weight of the crosslinkable silyl group-containing polyurethane (A), component (A) of the moisture-curable shoe composition of the present invention, is not particularly limited. In terms of polystyrene equivalent in GPC, it may be, for example, 1,000 or more, preferably 2,000 or more, and may be, for example, 100,000 or less, preferably 75,000 or less, and more preferably 50,000 or less. For example, it may be 1,000 to 100,000, for example, 1,000 to 75,000, for example, 1,000 to 50,000, for example, 2,000 to 100,000, for example, 2,000 to 75,000, or for example, 2,000 to 50,000. If the number average molecular weight is less than 1,000, the adhesiveness will decrease, and if the number average molecular weight exceeds 100,000, the viscosity will be high, which may cause problems in terms of workability when repairing shoes.

[0037] <Content of Component (A)> The content of the (A) “crosslinkable silyl group-containing polyether and / or crosslinkable silyl group-containing polyurethane” in the moisture-curable shoe composition is not particularly limited. Taking the total amount of the moisture-curable shoe composition as 100% by mass, the content can be, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. It can be, for example, 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less. For example, 5% by mass or more to 90% by mass or less, for example, 5% by mass or more to 85% by mass or less, for example, 5% by mass or more to 80% by mass or less, for example, 10% by mass or more to 90% by mass or less, for example, 10% by mass or more to 85% by mass or less, for example, 10% by mass or more to 80% by mass or less, for example, 15% by mass or more to 90% by mass or less, for example, 15% by mass or more to 85% by mass or less, for example, 15% by mass or more to 80% by mass or less.

[0038] [Component (B)] Component (B) constituting the moisture-curable shoe composition of the present invention is a crosslinkable silyl group-containing vinyl organic polymer. The crosslinkable silyl group-containing vinyl organic polymer is a compound having a crosslinkable silyl group and a vinyl organic polymer skeleton in the molecule. The crosslinkable silyl group is located on the side chain and / or terminal of the molecule, preferably on the side chain and terminal of the molecule. The crosslinkable silyl group-containing vinyl organic polymer may be used alone or in combination of two or more types.

[0039] <Crosslinkable silyl group> The crosslinkable silyl group of the crosslinkable silyl group-containing vinyl organic polymer is the same as the crosslinkable silyl group described in (Crosslinkable silyl group) of the above-mentioned [Component (A)] <Crosslinkable silyl group-containing polyether>. As the crosslinkable silyl group of the crosslinkable silyl group-containing vinyl organic polymer, an alkyltrialkoxysilyl group is preferred, and a trimethoxysilyl group is more preferred. The crosslinkable silyl group of component (A) and the crosslinkable silyl group of component (B) may be the same or different.

[0040] In the moisture-curable shoe composition of the present invention, the average number of crosslinkable silyl groups contained in one molecule of the crosslinkable silyl group-containing vinyl organic polymer (B), component (B), is not particularly limited. For example, it can be an average of 0.5 or more, preferably an average of 1.0 or more, more preferably an average of 1.5 or more, and for example, an average of 5.0 or less, preferably an average of 4.5 or less, more preferably an average of 4.0 or less, for example, an average of 0.5 or more and an average of 5.0 or less, for example, an average of 0.5 or more and an average of 4.5 or less, for example, an average of 0.5 or more and an average of 4.0 or less, for example, an average of 1.0 or more and an average of 5.0 or less, for example, an average of 1.0 or more and an average of 4.5 or less, for example, an average of 1.0 or more and an average of 4.0 or less, for example, an average of 1.5 or more and an average of 5.0 or less, for example, an average of 1.5 or more and an average of 4.5 or less, for example, an average of 1.5 or more and an average of 4.0 or less. The crosslinkable silyl group-containing vinyl organic polymer of component (B) can include, for example, one having an average of 0 to 4.0 crosslinkable silyl groups at the molecular terminals and an average of 0 to 4.0 crosslinkable silyl groups at the molecular side chains. In the moisture-curable shoe composition of the present invention, the crosslinkable silyl group-containing vinyl organic polymer of component (B) preferably includes, for example, one having an average of 1.0 to 2.0 crosslinkable silyl groups at the molecular terminals and an average of 1.0 to 2.0 crosslinkable silyl groups at the molecular side chains.

[0041] <Main Chain> The vinyl organic polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer is not particularly limited, as long as it is a vinyl organic polymer that is an addition polymer of a vinyl monomer containing a carbon-carbon unsaturated bond. Examples of vinyl organic polymers include (meth)acrylate polymers; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene polymers, isobutylene-isoprene copolymers, polychloroprene polymers, polyisoprene polymers, isoprene and / or butadiene-acrylonitrile and / or styrene copolymers, polybutadiene polymers, and hydrogenated polymers of diene polymers; diallyl phthalate polymers; and the like. The vinyl organic polymers constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer may be used alone or in combination of two or more. Among these, the vinyl organic polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer preferably contains a (meth)acrylate polymer and / or a hydrocarbon polymer, and more preferably contains a (meth)acrylate polymer.

[0042] ((Meth)acrylate Polymer) The (meth)acrylate polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer is not particularly limited as long as it is a (meth)acrylate polymer formed by polymerizing a monomer component containing a (meth)acrylate monomer. The (meth)acrylate monomer is not particularly limited as long as it is a monomer having a (meth)acryloyl group. Examples include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, and lauryl (meth)acrylate; alicyclic (meth)acrylates; aromatic (meth)acrylates; oxygen-containing (meth)acrylates such as 2-methoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate, and glycidyl (meth)acrylate; silyl group-containing (meth)acrylates such as γ-(methacryloyloxypropyl)trimethoxysilane and γ-(methacryloyloxypropyl)dimethoxymethylsilane; (meth)acrylic acid; and fluorine-containing (meth)acrylates. One type of (meth)acrylate monomer may be used alone, or two or more types may be used in combination. Examples of monomers other than (meth)acrylate-based monomers that may be contained in the monomer component containing a (meth)acrylate-based monomer include styrene, maleic anhydride, vinyl acetate, etc. The monomers other than (meth)acrylate-based monomers may be used alone or in combination of two or more.

[0043] In the present invention, the (meth)acrylate polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer includes (i) a (meth)acrylate polymer composed of a (meth)acrylate monomer, (ii) a (meth)acrylate polymer containing one or more alkyl (meth)acrylate monomers, and optionally a (meth)acrylate monomer other than the alkyl (meth)acrylate monomer.By using a silyl group-containing (meth)acrylate monomer in combination as the (meth)acrylate monomer, the number of silicon groups in the (meth)acrylate polymer can be controlled.In addition, in this specification, (meth)acrylate means acrylate and / or methacrylate.

[0044] (Hydrocarbon Polymer) The hydrocarbon polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer is not particularly limited as long as it is a hydrocarbon polymer formed by polymerizing a monomer component containing a hydrocarbon monomer. As the hydrocarbon polymer, saturated hydrocarbon polymers are preferred. Examples of hydrocarbon monomers include olefin monomers having 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, and isobutylene; diene monomers, such as butadiene and isoprene; and the like. One type of hydrocarbon monomer may be used alone, or two or more types may be used in combination. Among these, isobutylene polymers and hydrogenated polybutadiene polymers are preferred, with isobutylene polymers being particularly preferred, in terms of ease of introducing functional groups to the terminals, ease of controlling the molecular weight, and ease of increasing the number of terminal functional groups.

[0045] <Method for producing a crosslinkable silyl group-containing vinyl organic polymer> The method for producing a crosslinkable silyl group-containing vinyl organic polymer is not particularly limited. As a method for synthesizing a crosslinkable silyl group-containing (meth)acrylate polymer, for example, a radical polymerization method using a radical polymerization reaction can be used. Examples of the radical polymerization method include a radical polymerization method (free radical polymerization method) in which a predetermined monomer is copolymerized using a polymerization initiator, and a controlled radical polymerization method in which a crosslinkable silyl group is introduced at a controlled position such as a terminal.

[0046] Various living polymerization methods can be used to synthesize crosslinkable silyl group-containing saturated hydrocarbon polymers. For example, when the saturated hydrocarbon polymer is an isobutylene polymer, the inifer polymerization discovered by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed., 1997, Vol. 15, p. 2843) can be used. This polymerization method can produce polymers with molecular weights of approximately 500 to 100,000 with a molecular weight distribution of 1.5 or less, and can introduce various functional groups to the molecular ends. Another example is cationic polymerization, which uses a combination of an organic halogen compound that generates stable carbocations and a Friedel-Crafts acid catalyst as a polymerization initiator.

[0047] The free radical polymerization method used to synthesize crosslinkable silyl group-containing (meth)acrylate polymers is a method in which a vinyl monomer and a crosslinkable silyl group-containing vinyl monomer are copolymerized using a polymerization initiator. Examples of the polymerization initiator include azo compound polymerization initiators and peroxide polymerization initiators, with azo compound polymerization initiators being preferred. By copolymerizing the crosslinkable silyl group-containing vinyl monomer, a crosslinkable silyl group can be introduced into the side chain. The free radical polymerization method has a relatively wide molecular weight distribution, moderate fluidity, and excellent workability. Since the polymer does not contain any metal components derived from the catalyst, it is possible to improve problems such as crosslinking reaction inhibition and coloration, and it is possible to impart a suitable pot life.

[0048] Examples of the azo compound polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, ... Examples of the polymerization initiator include 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis(N,N'-dimethyleneisobutylamidine), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(isobutylamido) dihydrate, 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2-cyanopropanol), dimethyl-2,2'-azobis(2-methylpropionate), and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]. Examples of the peroxide polymerization initiator include benzoyl peroxide and laurium peroxide. These polymerization initiators may be used alone or in combination of two or more. When using the polymerization initiator, the entire amount may be added, or it may be added successively in multiple installments. In the present invention, it is preferable to use a method in which a crosslinkable silyl group is introduced into the molecular side chain by a free radical polymerization method using an azo compound, peroxide, or the like as a polymerization initiator, and then a crosslinkable silyl group is introduced into the molecular terminal.

[0049] Controlled radical polymerization methods used to synthesize crosslinkable silyl group-containing (meth)acrylate polymers include free radical polymerization and living radical polymerization methods in which vinyl monomers are polymerized using a chain transfer agent having a specific functional group, with living radical polymerization methods such as reversible addition-fragmentation chain transfer (RAFT) polymerization and radical polymerization using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) being more preferred. Also suitable are reactions using a thiol compound having a crosslinkable silyl group and reactions using a thiol compound and a metallocene compound having a crosslinkable silyl group.

[0050] A method for producing a crosslinkable silyl group-containing vinyl organic polymer using a reaction of a thiol compound having a crosslinkable silyl group and a metallocene compound includes, for example, using a compound of the structural formula (4): and a crosslinkable silyl group-containing thiol compound, and in the presence of this catalyst, a (meth)acrylate monomer having a polymerizable unsaturated bond is polymerized.

[0051] In structural formula (4), M is a metal selected from the group consisting of metals of groups 4, 5, and 14 of the periodic table, chromium, ruthenium, and palladium. Examples of M include titanium, zirconium, chromium, ruthenium, vanadium, palladium, and tin. In structural formula (4), R ４１ and R ４２ are each independently at least one group selected from the group consisting of an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a silicon-containing group which may have a substituent, or a hydrogen atom or a single bond. ３１ and R ３２may combine to bond two 5-membered rings in the compound represented by structural formula (3). In structural formula (4), b1 and b2 each independently represent an integer of 1 to 4, X represents a hydrocarbon group in which at least a portion of the hydrogen atoms may be substituted with halogen atoms or a halogen atom, and n represents an integer of 0 or the valence of the metal M minus 2.

[0052] Examples of the metallocene compound represented by structural formula (4) include dicyclopentadiene-Ti-dichloride, dicyclopentadiene-Ti-bisphenyl, dicyclopentadiene-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadiene-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadiene-Ti-bis-2,5,6-trifluorophenyl-1-yl, and dicyclopentadiene-Ti-bis-2,6-difluorophenyl. -1-yl, dicyclopentadiene-Ti-bis-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluoro-3-(pyr-1-yl)-phenyl-1- titanocene compounds such as dicyclopentadienyl-Zr-dichloride, dicyclopentadiene-Zr-bisphenyl, dicyclopentadiene-Zr-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadiene-Zr-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadiene-Zr-bis-2,5,6-trifluorophenyl-1-yl, dicyclopentadiene-Zr-bis-2,6-di ... zirconocene compounds such as ene-Zr-bis-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-Zr-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Zr-bis-2,3,5,6-tetrafluorophenyl-1-yl, dimethylcyclopentadienyl-Zr-bis-2,6-difluorophenyl-1-yl, and dimethylcyclopentadienyl-Zr-bis-2,6-difluoro-3-(pyr-1-yl)-phenyl-1-yl;Examples of the metallocene compounds include dicyclopentadienyl V-chloride, bismethylcyclopentadienyl V-chloride, bispentamethylcyclopentadienyl V-chloride, dicyclopentadienyl Ru-chloride, and dicyclopentadienyl Cr-chloride. One metallocene compound may be used alone, or two or more metallocene compounds may be used in combination.

[0053] The metallocene compound can be used in a normal catalytic amount, and can be, for example, 0.001 part by mass or more, preferably 0.005 part by mass or more, and for example, 1.0 part by mass or less, preferably 0.01 part by mass or less, for example, 0.001 part by mass or more and 1.0 part by mass or less, for example, 0.001 part by mass or more and 0.01 part by mass or less, for example, 0.005 part by mass or more and 1.0 part by mass or less, for example, 0.005 part by mass or more and 0.01 ... relative to 100 parts by mass of the (meth)acrylate monomer to be polymerized.

[0054] Examples of the crosslinkable silyl group-containing thiol compound used together with the metallocene compound represented by the structural formula (4) include compounds represented by the structural formula (5): HS-R ５１ In the structural formula (5), R ５１ is a group having a crosslinkable silyl group. Examples of the crosslinkable silyl group include the same crosslinkable silyl groups as described in [Component (A)]. In particular, at least one crosslinkable silyl group selected from the group consisting of a hydroxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a chlorosilyl group, and a bromosilyl group is preferred.

[0055] Examples of the compound represented by structural formula (4) include 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxysilane, 3-mercaptopropyl-monomethyldimethoxysilane, 3-mercaptopropyl-monophenyldimethoxysilane, 3-mercaptopropyl-dimethylmonomethoxysilane, 3-mercaptopropyl-monomethyldiethoxysilane, 4-mercaptobutyl-trimethoxysilane, 3-mercaptobutyl-trimethoxysilane, etc. The crosslinkable silyl group-containing thiol compounds may be used alone or in combination of two or more.

[0056] The amount of the crosslinkable silyl group-containing thiol compound used can be appropriately set in consideration of the properties of the polymer to be obtained. Increasing the amount of the crosslinkable silyl group-containing thiol compound used in the reaction system increases the polymerization rate per unit time and the ultimate polymerization rate. On the other hand, increasing the amount of the metallocene compound used increases the polymerization rate per unit time, but does not have a significant effect on the ultimate polymerization rate.

[0057] The amount of metallocene compound used has almost no effect on the molecular weight of the resulting polymer, but the reaction does not proceed effectively without the use of a metallocene compound. Increasing the amount of thiol compound used increases the polymerization rate. From these trends, it is believed that in the catalyst used to produce component (B) of the present invention, the metallocene compound acts as an activating catalyst throughout the reaction, while the thiol compound exerts a polymerization initiation effect (acts as a polymerization initiation species). It is believed that the amount of crosslinkable silyl group-containing thiol compound used in the catalyst used to prepare component (B) of the present invention is a limiting factor for the molecular weight and polymerization rate.

[0058] The amount of the crosslinkable silyl group-containing thiol compound used can be appropriately set in consideration of the molecular weight of the polymer to be obtained, the polymerization rate, etc. In order to smoothly proceed with the reaction and prevent the reaction from going out of control, the metallocene compound and the crosslinkable silyl group-containing thiol compound can be used in a molar ratio (metallocene compound:crosslinkable silyl group-containing thiol compound) ranging from 100:1 to 1.0:50,000, preferably from 10:1 to 1:10,000.

[0059] The crosslinkable silyl group-containing thiol compound can be used by (i) adding the entire amount at the start of the reaction, (ii) adding the crosslinkable silyl group-containing thiol compound first and reacting for a desired time, and then additionally adding the crosslinkable silyl group-containing thiol compound, or (iii) additionally adding both the crosslinkable silyl group-containing thiol compound and the (meth)acrylate monomer, etc. In this way, the additional addition of the crosslinkable silyl group-containing thiol compound, or the additional addition of the crosslinkable silyl group-containing thiol compound and the (meth)acrylate monomer, can improve the polymerization rate.

[0060] A crosslinkable silyl group-containing vinyl organic polymer obtained by polymerizing a (meth)acrylate monomer having a polymerizable unsaturated bond in the presence of a metallocene compound represented by structural formula (4) and a crosslinkable silyl group-containing thiol compound represented by structural formula (5) as a polymerization catalyst has at least one terminal thereof a residue (-S-R) in which a hydrogen atom is eliminated from the crosslinkable silyl group-containing thiol compound used as a catalyst. ５１ ) is bonded. ５１ is a group having a crosslinkable silyl group.

[0061] In the present invention, a metallocene compound represented by structural formula (4) and a crosslinkable silyl group-containing thiol compound represented by structural formula (5) are used as polymerization catalysts, and when a (meth)acrylate monomer having a polymerizable unsaturated bond is polymerized in the presence of this catalyst, in addition to the crosslinkable silyl group-containing thiol compound, it is also possible to use in combination: alkyl thiol compounds having no functional groups other than thiol groups, such as ethyl mercaptan, butyl mercaptan, hexyl mercaptan, tertiary dodecyl mercaptan, normal dodecyl mercaptan, and octyl mercaptan; aromatic thiol compounds having no functional groups other than thiol groups, such as phenyl mercaptan and benzyl mercaptan; thiol compounds having functional groups other than thiol groups, such as β-mercaptopropionic acid, mercaptoethanol, and thiophenol; polyfunctional thiol compounds esterified with trithioglycerin, pentaerythritol, and β-mercaptopropionic acid; and polymeric thiols having active thiol groups, such as polysulfide polymers.

[0062] In the present invention, in addition to the metallocene compound and the crosslinkable silyl group-containing thiol compound, sulfide compounds such as disulfide compounds, trisulfide compounds, and tetrasulfide compounds can be used for the purpose of adjusting the polymerization rate and degree of polymerization. Examples of disulfide compounds, trisulfide compounds, and tetrasulfide compounds that can be used as polymerization modifiers include diethyl trisulfide, dibutyl tetrasulfide, diphenyl disulfide, bis(2-hydroxyethyl) disulfide, bis(4-hydroxybutyl) tetrasulfide, bis(3-hydroxypropyl) trisulfide, bis(3-carboxypropyl) trisulfide, bis(3-carboxypropyl) tetrasulfide, bis(3-propyltrimethoxysilane) disulfide, and bis(3-propyltriethoxysilane) tetrasulfide. One type of sulfide compound may be used alone, or two or more types may be used in combination. Such a sulfide compound can be used in the polymerization of the present invention to an extent that it does not deactivate the polymerization. Specifically, it can be used in an amount of, for example, 50 parts by mass or less, preferably 20 parts by mass or less, per 100 parts by mass of the (meth)acrylate monomer to be polymerized.

[0063] <Examples of Component (B)> Examples of the crosslinkable silyl group-containing vinyl organic polymer that is component (B) include a crosslinkable silyl group-containing (meth)acrylate polymer. Examples of the crosslinkable silyl group-containing (meth)acrylate polymer include a polymer having a crosslinkable silyl group and a main chain represented by the structural formula (6): -CH ２ -C(R ６１ ) (COOR ６２ )-...(6) (wherein, R ６１ is a hydrogen atom or a methyl group, R ６２ represents an alkyl group having 1 to 5 carbon atoms), and a (meth)acrylate monomer unit represented by structural formula (7): —CH ２ -C(R ７１ ) (COOR ７２ )-...(7) (wherein, R ７１ is the R ６１ is the same as R７２ In structural formula (6), R represents an alkyl group having 6 or more carbon atoms. ６２ Examples of R include alkyl groups having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and a t-butyl group. ６２ may be the same or different. ７２ Examples of R include long-chain alkyl groups having 6 or more carbon atoms, typically 7 to 30 carbon atoms, and preferably 8 to 20 carbon atoms, such as 2-ethylhexyl, lauryl, and stearyl groups. ７２ may be the same or different from each other.

[0064] <Weight-Average Molecular Weight> In the moisture-curable shoe composition of the present invention, the crosslinkable silyl group-containing vinyl organic polymer (B), component (B), may be linear or branched, and its weight-average molecular weight is not particularly limited. The weight-average molecular weight, as calculated in polystyrene equivalent by GPC, can be, for example, 500 or more, preferably 1,000 or more, and for example, 1,000,000 or less, preferably 300,000 or less, for example, 500 or more to 1,000,000 or less, for example, 500 or more to 300,000 or less, for example, 1,000 or more to 1,000,000 or less, for example, 1,000 or more to 300,000 or less. The molecular weight distribution of the crosslinkable silyl group-containing vinyl organic polymer (B), component (B), is not particularly limited. For example, it can be 9.0 or less, preferably 3.0 or less, for example, 1.02 or more, preferably 1.2 or more, for example, 1.02 or more and 9.0 or less, for example, 1.02 or more and 3.0 or less, for example, 1.2 or more and 9.0 or less, for example, 1.2 or more and 3.0 or less.

[0065] <Content of Component (B)> The content of the (B) “crosslinkable silyl group-containing vinyl organic polymer” in the moisture-curable shoe composition is not particularly limited. It can be, for example, 25 parts by mass or more, preferably 40 parts by mass or more, and for example, 400 parts by mass or less, preferably 250 parts by mass or less, for example, 25 parts by mass or more and 400 parts by mass or less, for example, 25 parts by mass or more and 250 parts by mass or less, for example, 40 parts by mass or more and 400 parts by mass or less, for example, 40 parts by mass or more and 250 parts by mass or less, relative to 100 parts by mass of the (A) crosslinkable silyl group-containing polyether.

[0066] [Component (C)] Component (C) constituting the moisture-curable shoe composition of the present invention is a diluent and / or plasticizer. The diluent and / or plasticizer preferably has a boiling point of 150°C or higher. The diluent and / or plasticizer having a boiling point of 150°C or higher improves the storage stability of the moisture-curable shoe composition and maintains good workability during coating film formation. The diluent and / or plasticizer may contain a plasticizer with a number-average molecular weight of 3,000 or less. The inclusion of a plasticizer with a number-average molecular weight of 3,000 or less maintains good workability during coating film formation and improves thread breakage resistance when forming uneven shapes such as anti-slip structures during shoe repair, particularly during shoe sole repair.

[0067] <Diluent> The diluent is not particularly limited as long as it is a compound that can adjust the physical properties such as viscosity of the moisture-curable shoe composition. Examples include alcohol-based compounds, aliphatic hydrocarbon-based compounds, aromatic hydrocarbon-based compounds, ester-based compounds, and ketone-based compounds. One type of diluent may be used alone, or two or more types may be used in combination.

[0068] Examples of alcohol compounds include monoalcohol compounds such as ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, and diacetone alcohol; polyhydric alcohol compounds such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 3-methyl-1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin; and polyhydric alcohol compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, and ethylene glycol monomethyl ether. Examples of glycol ether compounds include phenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and 3-methyl-3-methoxybutanol. Of these, glycol ether compounds are preferred. The alcohol compounds may be used alone or in combination of two or more.

[0069] Examples of the aliphatic hydrocarbon compound include saturated hydrocarbon compounds such as normal paraffin and isoparaffin, and α-olefin derivatives such as Linearene Dimer (trade name, manufactured by Idemitsu Kosan Co., Ltd.) The aliphatic hydrocarbon compound may be used alone or in combination of two or more types.

[0070] Examples of aromatic hydrocarbon compounds include toluene, xylene, etc. The aromatic hydrocarbon compounds may be used alone or in combination of two or more.

[0071] Examples of ester compounds include ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, acetyltriethyl citrate, acetyltributyl citrate, triethyl citrate, isobornyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, butyl glycol acetate, butyl diglycol acetate, and menthanol propionate. One type of ester compound may be used alone, or two or more types may be used in combination.

[0072] Examples of the ketone compounds include acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, etc. The ester compounds may be used alone or in combination of two or more.

[0073] <Plasticizer> The plasticizer is not particularly limited as long as it can adjust the viscosity, slump, hardness of the cured product, and mechanical properties (tensile strength, elongation, etc.) of the moisture-curable shoe composition. Examples include carboxylic acid ester compounds, sulfonic acid ester compounds, phosphate ester compounds, ether compounds, hydrocarbon compounds, epoxy plasticizers, and organic polymers that do not contain a crosslinkable silyl group. One type of plasticizer may be used alone, or two or more types may be used in combination.

[0074] Examples of the carboxylic acid ester compound include aromatic carboxylic acid ester compounds, alicyclic carboxylic acid ester compounds, aliphatic carboxylic acid ester compounds, polyhydric alcohol ester compounds, etc. One type of carboxylic acid ester compound may be used alone, or two or more types may be used in combination.

[0075] The aromatic carboxylic acid ester compound is not particularly limited as long as it is an ester compound of a carboxylic acid having an aromatic ring in the molecule. Examples include phthalate ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate, dioctyl phthalate, butyl benzyl phthalate, and diisoundecyl phthalate; terephthalate ester compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate (e.g., EASTMAN 168 (manufactured by EASTMAN CHEMICAL)); aromatic polybasic acid ester compounds having three or more basic acids such as trimellitic acid ester compounds and pyromellitic acid ester compounds; and aromatic carboxylic acid ester compounds from the ester compounds listed above for the diluent. The aromatic carboxylic acid ester compounds may be used alone or in combination of two or more.

[0076] The alicyclic carboxylic acid ester compound is not particularly limited as long as it is an ester compound of a carboxylic acid having an alicyclic ring in the molecule. Examples include cyclohexanedicarboxylic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester (e.g., Hexamoll DINCH (manufactured by BASF)) and 1,2-cyclohexanedicarboxylic acid dioctyl ester; and alicyclic carboxylic acid ester compounds among the ester compounds listed above as diluents. The alicyclic carboxylic acid ester compounds may be used alone or in combination of two or more.

[0077] The aliphatic carboxylic acid ester compound is not particularly limited as long as it is an ester compound of a saturated aliphatic carboxylic acid or an unsaturated aliphatic carboxylic acid. Examples include aliphatic dibasic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, tributyl acetylcitrate, and dibutyl adipate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; and aliphatic carboxylic acid ester compounds among the ester compounds listed for the diluent. The aliphatic carboxylic acid ester compounds may be used alone or in combination of two or more.

[0078] The polyhydric alcohol ester compound is not particularly limited as long as it is an ester compound of a polyhydric alcohol and a carboxylic acid. For example, glycol ester compounds such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, pentaerythritol ester, etc.; glycol ester compounds among the ester compounds listed as the diluents; etc. The ester compounds may be used alone or in combination of two or more.

[0079] Examples of sulfonate ester compounds include alkylsulfonic acid phenyl ester (Mesamoll (manufactured by LANXESS)). The sulfonate ester compounds may be used alone or in combination of two or more.

[0080] Examples of the phosphate ester compound include tricresyl phosphate, trioctyl phosphate, octyldiphenyl phosphate, tributyl phosphate, tricresyl phosphate, etc. The phosphate ester compounds may be used alone or in combination of two or more.

[0081] Examples of the ether-based compound include the glycol ether-based compounds listed above as diluents. The ether-based compounds may be used alone or in combination of two or more.

[0082] Examples of the hydrocarbon-based compound include hydrocarbon-based oils such as alkyldiphenyls and partially hydrogenated terphenyls. One type of hydrocarbon-based compound may be used alone, or two or more types may be used in combination.

[0083] The epoxy plasticizer is not particularly limited as long as it has an epoxy group in the molecule. Examples include epoxidized soybean oil, epoxidized linseed oil, and epoxy benzyl stearate. The epoxy plasticizer may be used alone or in combination of two or more.

[0084] Examples of organic polymers that do not contain crosslinkable silyl groups include vinyl organic polymers that do not contain crosslinkable silyl groups, polyester organic polymers that do not contain crosslinkable silyl groups, polyether organic polymers that do not contain crosslinkable silyl groups, etc. The organic polymers that do not contain crosslinkable silyl groups may be used alone or in combination of two or more.

[0085] The vinyl organic polymer not containing a crosslinkable silyl group is not particularly limited as long as it is an addition polymer of a vinyl monomer containing a carbon-carbon unsaturated bond. Examples thereof include polystyrene polymers such as poly-α-methylstyrene and polystyrene; ethylene-propylene copolymers; polybutadiene polymers; butadiene-acrylonitrile copolymers; polybutene polymers; hydrogenated polybutadiene polymers; hydrogenated polyisoprene polymers, polyisobutylene polymers; isobutylene-isoprene copolymers; polychloroprene polymers; polyisoprene polymers; isoprene and / or butadiene-acrylonitrile and / or styrene copolymers; hydrocarbon oligomers such as process oil; halogenated hydrocarbons such as chlorinated paraffin; (meth)acrylic acid ester polymers, hydroxyl group-containing (meth)acrylate polymers, carboxyl group-containing (meth)acrylate polymers, epoxy group-containing (meth)acrylate polymers; and diallyl phthalate polymers. The vinyl organic polymers not containing a crosslinkable silyl group may be used alone or in combination of two or more.

[0086] Examples of polyester-based organic polymers that do not contain a crosslinkable silyl group include polyester compounds obtained from a monomer component containing a dibasic acid and a dihydric alcohol, polyester compounds obtained from a monomer component containing a hydroxycarboxylic acid, etc. One type of polyester-based organic polymer that does not contain a crosslinkable silyl group may be used alone, or two or more types may be used in combination.

[0087] Examples of polyether-based organic polymers that do not contain a crosslinkable silyl group include polyether compounds obtained from a monomer component containing an alkylene oxide, such as polypropylene glycol derivatives and polyethylene glycol derivatives. One type of polyether-based organic polymer that does not contain a crosslinkable silyl group may be used alone, or two or more types may be used in combination.

[0088] The content of the diluent and / or plasticizer (C) in the moisture-curing shoe composition is not particularly limited. It can be, for example, 1 part by mass or more, preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, and can be, for example, 100 parts by mass or less, preferably 90 parts by mass or less, and more preferably 80 parts by mass or less, relative to 100 parts by mass of the total of the components (A) and (B) in the moisture-curing shoe composition. For example, 1 part by mass or more and 100 parts by mass or less, for example, 1 part by mass or more and 90 parts by mass or less, for example, 1 part by mass or more and 80 parts by mass or less, for example, 5 parts by mass or more and 100 parts by mass or less, for example, 5 parts by mass or more and 90 parts by mass or less, for example, 5 parts by mass or more and 80 parts by mass or less, for example, 10 parts by mass or more and 100 parts by mass or less, for example, 10 parts by mass or more and 90 parts by mass or less, for example, 10 parts by mass or more and 80 parts by mass or less.

[0089] [Component (D)] <Silica Powder> The moisture-curable shoe composition of the present invention may contain silica powder as component (D). Examples of silica powder include fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica, and crystalline silica. The shape of the silica powder is not particularly limited. It may be amorphous, spherical, flaky, fibrous, or the like.

[0090] The silica powder may be a surface-treated silica fine powder whose surface has been hydrophobized with a surface treatment agent. Specific examples of the surface treatment agent include silazanes such as hexamethyldisilazane and 1,1,3,3,5,5-hexamethylcyclotrisilazane; silane coupling agents such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, chloropropyltrimethoxysilane, trimethylsilanol, and hydroxypentamethyldisiloxane; and organosilicon compounds such as polymethylsiloxane and organohydrogenpolysiloxane. Alternatively, a surface-treated silica fine powder whose surface has been hydrophobized with these agents may also be used. Preferred surface treatment agents are silazanes or chlorosilanes.

[0091] <Specific Surface Area> The specific surface area of ​​the silica powder that may be contained in the moisture-curable shoe composition is not particularly limited. ２ / g or more, preferably 70m ２ / g or more, more preferably 90m ２ / g or more, for example, 400m ２ / g or less, preferably 380m ２ / g or less, more preferably 350m ２ / g or less, for example, 50m ２ / g or more 400m ２ / g or less, for example, 50m ２ / g or more 380m ２ / g or less, for example, 50m ２ / g or more 350m ２ / g or less, for example, 70m ２ / g or more 400m ２ / g or less, for example, 70m ２ / g or more 380m ２ / g or less, for example, 70m ２ / g or more 350m ２ / g or less, for example, 90m ２ / g or more 400m ２ / g or less, for example, 90m ２ / g or more 380m ２ / g or less, for example, 90m ２ / g or more 350m ２ The specific surface area of ​​the silica powder may be measured by the BET method, or when a commercially available product is used, the value listed in the catalog may be used.

[0092] <Content of Component (D)> The content of component (D) “silica powder” in the moisture-curable shoe composition is not particularly limited. It can be, for example, 0.5 parts by mass or more, preferably 2.5 parts by mass or more, and more preferably 5.0 parts by mass or more, and for example, 200 parts by mass or less, preferably 150 parts by mass or less, and more preferably 100 parts by mass or less, relative to 100 parts by mass of the total of components (A) and (B) in the moisture-curable shoe composition. For example, from 0.5 to 200 parts by mass, for example, from 0.5 to 150 parts by mass, for example, from 0.5 to 100 parts by mass, for example, from 2.5 to 200 parts by mass, for example, from 2.5 to 150 parts by mass, for example, from 2.5 to 100 parts by mass, for example, from 5.0 to 200 parts by mass, for example, from 5.0 to 150 parts by mass, for example, from 5.0 to 100 parts by mass.

[0093] [Component (E)] The moisture-curable shoe composition of the present invention may contain a curing catalyst as component (E). The curing catalyst is a catalyst for the moisture-curing reaction of the crosslinkable silyl group and is used for purposes such as accelerating the curing of the moisture-curable shoe composition. Examples of curing catalysts include organotin compounds, organotitanium compounds, organoaluminum compounds, organic carboxylic acid-organic amine reactants, organozirconium compounds, organoiron compounds, organic vanadium compounds, amine compounds, acidic phosphoric acid compounds, polyamide compounds, amine-epoxy reactants, and boron compounds. One type of curing catalyst may be used alone, or two or more types may be used in combination.

[0094] As the curing catalyst, it is preferable to use an organic tin compound and / or an organic titanium compound.As the organic tin compound, for example, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dineodecanoate (dioctyltin diversatate), dioctyltin oxide, the reaction product of dibutyltin oxide and phthalic acid ester, the reaction product of dioctyltin oxide and alkoxysilane, etc., tetravalent tin compounds, such as tin dioctylate, tin dinaphthenate, tin distearate, tin dineodecanoate (tin diversatate), etc., divalent tin compounds, such as tin dioctylate, tin dinaphthenate, tin distearate, tin dineodecanoate (tin diversatate), etc. In view of fast curing speed, dibutyltin maleate, reaction products of dibutyltin oxide with phthalic acid ester, dibutyltin diacetylacetonate, dioctyltin dineodecanoate, and reaction products of dioctyltin oxide with alkoxysilane are preferred.

[0095] Examples of the organic titanium compound include tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanium tetraacetylacetonate, and titanium chelate.

[0096] Examples of titanium-based compounds include one or more selected from the group consisting of titanium chelates represented by structural formula (8) and titanium chelates represented by structural formula (9). In structural formula (8), n6 R ８１ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and 4 to n6 R ８２ are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and 4 to n6 R ８３ and 4-n6 R ８４ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; and n6 is 0, 1, 2, or 3.

[0097] In structural formula (9), R ９１is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and two R ９２ are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and two R ９３ and two R ９４ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The titanium-based compounds may be used alone or in combination of two or more.

[0098] Examples of titanium chelates represented by structural formula (8) or structural formula (9) include titanium dimethoxide bis(ethylacetoacetate), titanium diethoxide bis(ethylacetoacetate), titanium diisopropoxide bis(ethylacetoacetate), titanium diisopropoxide bis(methylacetoacetate), titanium diisopropoxide bis(t-butylacetoacetate), titanium diisopropoxide bis(methyl-3-oxo-4 ,4-dimethylhexanoate), titanium diisopropoxide bis(ethyl-3-oxo-4,4,4-trifluorobutanoate), titanium di-n-butoxide bis(ethyl acetoacetate), titanium diisobutoxide bis(ethyl acetoacetate), titanium di-t-butoxide bis(ethyl acetoacetate), titanium di-2-ethylhexoxide bis(ethyl acetoacetate), titanium bis(1-methoxy-2-propoxide) bis (ethyl acetoacetate), titanium bis(3-oxo-2-butoxide) bis(ethyl acetoacetate), titanium bis(3-diethylaminopropoxide) bis(ethyl acetoacetate), titanium triisopropoxide(ethyl acetoacetate), titanium triisopropoxide(allyl acetoacetate), titanium triisopropoxide(methacryloxyethyl acetoacetate), 1,2-dioxyethane titanium bis(ethyl acetoacetate acetate), 1,3-dioxypropane titanium bis(ethyl acetoacetate), 2,4-dioxypentane titanium bis(ethyl acetoacetate), 2,4-dimethyl-2,4-dioxypentane titanium bis(ethyl acetoacetate), titanium tetrakis(ethyl acetoacetate), titanium bis(trimethylsiloxy)bis(ethyl acetoacetate), titanium bis(trimethylsiloxy)bis(acetylacetonate), etc. Among these, titanium diethoxide bis(ethyl acetoacetate), titanium diisopropoxide bis(ethyl acetoacetate), titanium dibutoxide bis(ethyl acetoacetate), etc. are mentioned, with titanium diisopropoxide bis(ethyl acetoacetate) being more preferred.The titanium chelates may be used alone or in combination of two or more.

[0099] Examples of chelating agents capable of forming chelating ligands for titanium chelates include β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, t-butyl acetoacetate, allyl acetoacetate, 2-methacryloxyethyl acetoacetate, methyl 3-oxo-4,4-dimethylhexanoate, and ethyl 3-oxo-4,4,4-trifluorobutanoate, with methyl acetoacetate and ethyl acetoacetate being preferred, and ethyl acetoacetate being more preferred. When two or more chelating ligands are present, the respective chelating ligands may be the same or different.

[0100] The content of the curing catalyst (component (E)) in the moisture-curable shoe composition is not particularly limited. For example, it can be 20 parts by mass or less, preferably 10 parts by mass or less, per 100 parts by mass of the total of components (A) and (B) in the moisture-curable shoe composition, and can be, for example, 0 parts by mass to 20 parts by mass, for example, 0 parts by mass to 10 parts by mass.

[0101] [Component (F)] The moisture-curable shoe composition of the present invention may contain an adhesion promoter as component (F). The adhesion promoter is used for the purpose of improving the adhesion of the moisture-curable shoe composition and accelerating curing. Examples of adhesion promoters include compounds represented by the following structural formula (10): Si(R １０１ ) ４－ａ１０ X １０１ ａ１０ ...(10) (In structural formula (10), R １０１ represents a hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, R １０２ ３ SiO-(R １０２ is R １０１ a triorganosiloxy group represented by the formula (same as above), or —CH ２ OR １０３ Group (R １０３ is R １０１ (same as R１０１ is a group in which at least one hydrogen atom on the 1st to 3rd carbon atoms is a halogen, -OR １０４ , -NR １０５ R １０６ , -N=R １０７ , -SR １０８ (R １０４ , R １０５ , R １０６ , R １０８ are each a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; R １０７ represents a hydrocarbon group having 1 to 20 carbon atoms, which may or may not have a divalent substituent, and represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a perfluoroalkyl group having 1 to 20 carbon atoms, a glycidyl group, an isocyanate group, or a cyano group. １０１ When there are two or more R １０１ may be the same or different. １０１ represents a hydroxyl group or a hydrolyzable group (such as a halogen group or an alkoxy group having 1 to 6 carbon atoms), and X １０１ If there are two or more X １０１ may be the same or different, and a10 is an integer of 0, 1, 2, or 3.

[0102] Examples of adhesion promoters include γ-aminopropyltrimethoxysilane (3-aminopropyltrimethoxysilane), γ-aminopropyltriethoxysilane (3-aminopropyltriethoxysilane), γ-aminopropylmethyldimethoxysilane (3-aminopropylmethyldimethoxysilane), γ-aminopropylmethyldiethoxysilane (3-aminopropylmethyldiethoxysilane), N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N- Isocyanurate silanes such as (β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane, and tris(3-trimethoxysilylpropyl)isocyanurate; N-benzyl-3-aminopropyltrimethoxysilane, N-vinylbenzyl-3-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis(3- amino group-containing silanes such as alkoxysilanes containing a secondary amino group and / or a tertiary amino group, such as N-ethyl-3-aminoisobutyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane), γ-glycidoxypropyltriethoxysilane (3-glycidoxypropyltriethoxysilane), γ-glycidoxypropylmethyldimethoxysilane (3-glycidoxypropylmethyldimethoxysilane), β-(3,4-epoxycyclohexyl) Epoxy group-containing silanes such as ethyltrimethoxysilane, 4-oxiranylbutyltrimethoxysilane, and 8-oxiranyloctyltrimethoxysilane; mercapto group-containing silanes such as alkoxysilanes containing a mercapto group, such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane;Vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-acryloyloxypropylmethyldimethoxysilane; chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, (isocyanatemethyl)trimethoxysilane, and (isocyanatemethyl)dimethoxymethylsilane. isocyanate-containing silanes such as methyldimethoxysilane, trimethoxysilane, and methyldiethoxysilane; hydrosilanes such as methyldimethoxysilane, trimethoxysilane, and methyldiethoxysilane; and tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, and tetra-t-butoxysilane. One type of adhesion promoter may be used alone, or two or more types may be used in combination.

[0103] The content of the adhesion promoter (F) in the moisture-curable shoe composition is not particularly limited. It can be, for example, 20 parts by mass or less, preferably 10 parts by mass or less, and can be, for example, 0 parts by mass or more and 20 parts by mass or less, for example, 0 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total of the components (A) and (B) in the moisture-curable shoe composition.

[0104] [Other Components] The moisture-curable shoe composition of the present invention may contain "other components" as necessary in addition to the components (A) to (F). Examples of the "other components" include crosslinkable silyl group-containing polymers other than the components (A) and (B), fillers other than the component (D), light stabilizers, ultraviolet absorbers, antioxidants, moisture absorbers, thixotropy-imparting agents (anti-sagging agents), colorants, antioxidants, tackifiers, flame retardants, release agents, lubricants, and anti-fungal agents. One type of the other components may be used alone, or two or more types may be used in combination.

[0105] <Moisture-Curable Polymer Other Than Component (A) and Component (B)> The moisture-curable shoe composition of the present invention may contain a moisture-curable polymer other than component (A) and component (B). Examples of the crosslinkable silyl group in the crosslinkable silyl group-containing polymer as the moisture-curable polymer other than component (A) and component (B) include the same crosslinkable silyl groups as described for component (A). The main chain skeleton in the crosslinkable silyl group-containing polymer as the moisture-curable polymer other than component (A) and component (B) is not particularly limited as long as it is a polymer other than a polysiloxane-based polymer. Examples of moisture-curable polymers other than component (A) and component (B) include crosslinkable silyl group-containing polymers such as crosslinkable silyl group-containing polyester polymers, crosslinkable silyl group-containing polysulfide polymers, crosslinkable silyl group-containing polyamide polymers, crosslinkable silyl group-containing polycarbonate polymers, and crosslinkable silyl group-containing diallyl phthalate polymers, in which the main chain skeleton is other than a polysiloxane polymer; moisture-curable urethane resins; moisture-curable cyanoacrylate resins; etc. The moisture-curable resins other than component (A) and component (B) may be used singly or in combination of two or more.

[0106] <Fillers other than component (D)> As fillers other than component (D) "silica powder", various shapes can be used, and either organic fillers or inorganic fillers other than silica can be used. Examples of fillers include calcium carbonate, magnesium carbonate, zinc carbonate, carbon black, clay, talc, kaolin, diatomaceous earth, zeolite, titanium dioxide, quicklime, iron oxide, zinc oxide, barium oxide, magnesium oxide, aluminum sulfate, vinyl chloride paste resin, resin particles, glass balloons, shirasu balloons, saran balloons, phenol balloons, vinylidene chloride resin balloons, vinylidene fluoride (co)polymer balloons, and fatty acid or fatty acid ester-treated products thereof. One type of filler may be used alone, or two or more types may be used in combination.

[0107] <Light Stabilizer> The moisture-curable shoe composition of the present invention may contain a light stabilizer. The light stabilizer is used for purposes such as improving the weather resistance of the cured product of the moisture-curable shoe composition. Examples of light stabilizers include benzotriazole-based light stabilizers, benzophenone-based light stabilizers, hindered amine-based light stabilizers, nickel-based light stabilizers, and benzoate-based light stabilizers. One type of light stabilizer may be used alone, or two or more types may be used in combination.

[0108] <Ultraviolet Absorber> The moisture-curable shoe composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is used to prevent ultraviolet degradation of the moisture-curable shoe composition and improve weather resistance. Examples of ultraviolet absorbers include benzotriazole-based, triazine-based, benzophenone-based, benzoate-based, salicylate-based, substituted tolyl-based, and metal chelate-based ultraviolet absorbers. One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.

[0109] <Antioxidant> The moisture-curable shoe composition of the present invention may contain an antioxidant. The antioxidant is used for the purpose of inhibiting oxidation of the moisture-curable shoe composition and improving weather resistance and heat resistance, etc. Examples of antioxidants include hindered phenol-based, hindered amine-based, phenol-based, organic sulfur-based, and organic phosphorus-based antioxidants. Of these, hindered phenol-based and / or hindered amine-based antioxidants are preferred. One type of antioxidant may be used alone, or two or more types may be used in combination.

[0110] <Moisture absorbent> The moisture-curable shoe composition of the present invention may contain a moisture absorbent. The moisture absorbent is used for the purpose of improving the storage stability of the moisture-curable shoe composition by absorbing moisture in the moisture-curable shoe composition. Examples of moisture absorbents include inorganic moisture absorbents such as zeolite, calcium oxide, magnesium oxide, and zinc oxide; and silane compound moisture absorbents such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane. One type of moisture absorbent may be used alone, or two or more types may be used in combination.

[0111] <Colorant> The moisture-curable shoe composition of the present invention may contain a colorant. The colorant is used for the purpose of coloring the moisture-curable shoe composition to a desired color tone, etc. Examples of colorants include inorganic pigments such as carbon black, red iron oxide, titanium dioxide, and zinc oxide; organic pigments; dyes; etc. One type of colorant may be used alone, or two or more types may be used in combination.

[0112] <Antiaging Agent> The moisture-curable shoe composition of the present invention may contain an antioxidant. The antioxidant is used for the purpose of preventing thermal degradation of the moisture-curable shoe composition and improving its heat resistance, etc. Examples of antioxidants include amine-ketone antioxidants, aromatic secondary amine antioxidants, benzimidazole antioxidants, thiourea antioxidants, and phosphite antioxidants. One type of antioxidant may be used alone, or two or more types may be used in combination.

[0113] <Tackifier> The moisture-curable shoe composition of the present invention may contain a tackifier. The tackifier is used for the purposes of improving the adhesion of the moisture-curable shoe composition and improving initial fixation, etc. Examples of tackifiers include terpene resins, aromatic modified terpene resins and hydrogenated terpene resins obtained by hydrogenating these, terpene-phenol resins obtained by copolymerizing a terpene compound with a phenol compound, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low-molecular-weight polystyrene resins, styrene copolymer resins, and petroleum resins (e.g., C ５ Hydrocarbon resin, C ９ Hydrocarbon resin, C ５ C ９ Examples of the tackifier include hydrocarbon copolymer resins, hydrogenated petroleum resins, dicyclopentadiene resins, etc. One type of tackifier may be used alone, or two or more types may be used in combination.

[0114] [Wear Mass of Cured Product in Taper Abrasion Test] The wear mass of the cured moisture-curable shoe composition of the present invention in a taper abrasion test (abrasive wheel material H22, applied force 9.8 N, test rotation speed 1,000 rpm) specified in JIS K 6264 is preferably 130 mg or less, more preferably 110 mg or less. This ensures that the cured product exhibits good abrasion resistance even when used to repair shoe soles. Furthermore, the cured moisture-curable shoe composition of the present invention preferably has a JIS A hardness of 10 or more in accordance with JIS S 5050. The cured product of the moisture-curable shoe composition of the present invention has excellent abrasion resistance and sufficient hardness, making it extremely suitable as a moisture-curable shoe composition.

[0115] [Form of Moisture-Curable Shoe Composition] The form of the moisture-curable shoe composition of the present invention is not particularly limited and can be appropriately determined depending on the intended use, constituent components, etc. For example, it can be a one-component moisture-curable shoe composition containing at least components (A) to (C), and optionally components (D) to (F) and other components. For example, it can be a two-component moisture-curable shoe composition consisting of a first component containing at least components (A) and (B) and a second component containing at least component (E). In this case, components (C), (D), (F), and other components may be contained in either or both of the first and second components. The moisture-curable shoe composition of the present invention is particularly suitable for use as a one-component composition.

[0116] The moisture-curable shoe composition of the present invention may be a room temperature curing type or a heat curing type. For example, if it can be cured at room temperature by moisture in the air, it can be a room temperature curing moisture-curable shoe composition. In this case, if necessary, the curing may be accelerated by heating. For example, it can be a heat curing moisture-curable shoe composition, which is obtained by adding moisture (water) to the moisture-curable shoe composition and then heating it to cure it.

[0117] [Method for Producing Moisture-Curable Shoe Composition] The method for producing the moisture-curable shoe composition is not particularly limited. The moisture-curable shoe composition can be produced by mixing the essential components (A) to (C) and, if necessary, one or more of the components (D) to (F) and other components in a container, followed by deaerating and stirring. When the moisture-curable shoe composition is a one-component type, for example, it can be produced by taking predetermined amounts of the components (A) to (C) and, if necessary, one or more of the components (D) to (F) and other components in a container, mixing them, and deaerating and stirring. The order in which the components are mixed is not particularly limited and can be set as appropriate. When the moisture-curable shoe composition is a two-component type, for example, the components (A) and (B) are used as a first part, and the component (E) (curing catalyst) is used as a second part, each of which is placed in a separate container. The components (C), (D), (F), and other components are mixed with either the first part and / or the second part.

[0118] The mixing step is, for example, a step of preparing a moisture-curing shoe composition by mixing the components of the moisture-curing shoe composition, which include at least components (A) to (C), using a conventionally known method. The mixing step does not require the use of a completely sealable mixing device, and can be carried out in the presence of air. However, the use of a completely sealable mixing device is not excluded. The moisture-curing shoe composition of the present invention must undergo a container filling step in the manufacturing process, in which the moisture-curing shoe composition is filled into a sealed container. The filling method can be a conventionally known method and is not particularly limited.

[0119] The moisture-curable shoe composition of the present invention is preferably stored in a sealed container to ensure storage stability, since the crosslinkable silyl groups cure through a crosslinking reaction caused by moisture in the air. The shape of the sealed container is not particularly limited as long as it can seal the moisture-curable shoe composition, and may be selected depending on the application. Examples include a pail can that can hold 3 L to 50 L of the moisture-curable shoe composition, and a cartridge container or tube container that can hold less than 1 L of the moisture-curable shoe composition.

[0120] [Uses of Moisture-Curable Shoe Composition] The uses of the moisture-curable shoe composition of the present invention are not particularly limited as long as they are used in shoes. Examples include shoe repair materials, sole-forming materials, shoe adhesives, sole coating materials, sole anti-wear agents, shoelace coating materials, shoelace impregnating materials, shoe stain-resistant materials, and shoe slip prevention agents. Among these, the moisture-curable shoe composition of the present invention can be suitably used as shoe repair materials, sole-forming materials, shoe adhesives, sole coating materials, and sole anti-wear agents, and is particularly suitably used as shoe repair materials, sole-forming agents, sole coating materials, and sole anti-wear agents. The moisture-curable shoe composition of the present invention can be applied to any type of shoe, such as men's shoes, women's shoes, sneakers, and sandals.

[0121] The moisture-curable shoe composition of the present invention has excellent surface abrasion resistance, is uniform without containing bubbles generated by reaction inside the cured product, and has excellent transparency. Therefore, even when used to repair shoe soles, etc., a cured product with excellent surface abrasion resistance can be formed immediately after repair. Even when worn over time, the cured product continues to exhibit its abrasion resistance because the interior of the cured product is uniform and bubble-free. Furthermore, because the cured product is transparent, it is possible to make the repaired area less noticeable without having to color-match the moisture-curable shoe composition, and it can be colored to any color tone as needed, making it an ideal moisture-curable shoe composition.

[0122] The moisture-curable shoe composition of the present invention can be used to repair damaged parts of shoes, such as repairing worn or missing parts of shoes, such as shoe soles, or gluing peeled parts. The shoe repair method for repairing a shoe sole using the moisture-curable shoe composition of the present invention is not particularly limited. For example, the repaired part of a shoe can be repaired by applying, injecting, or casting the moisture-curable shoe composition of the present invention to the repaired part of the shoe, forming a buildup, and, if necessary, shaping with a spatula or the like, and curing. When repairing the heel part of a shoe, it is preferable to attach a mold to the shoe sole, cast the moisture-curable shoe composition of the present invention, shape it with a spatula or the like, and cure it. During curing, the composition may be left at room temperature (ambient temperature), or, if necessary, heated by blowing hot air or using a heat source.

[0123] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass." In addition, the blending amounts of each component in Table 1 are all in parts by mass.

[0124] [Constituent Components] <Component (A)> Si-PE: Crosslinkable silyl group-containing polyether (SAX510 manufactured by Kaneka Corporation) Si-PU: Crosslinkable silyl group-containing polyurethane

[0125] <Component (B)> Si-VP: a crosslinkable silyl group-containing (meth)acrylate organic polymer

[0126] <Component (C)> DEGDEE: diethylene glycol diethyl ether DEGMBA: diethylene glycol monobutyl ether acetate MMB: 3-methyl-3-methoxybutanol DINCH: 1,2-cyclohexanedicarboxylic acid diisononyl ester PAc: polyacrylic acid polymer plasticizer EHPH-DEH: epoxyhexahydrophthalic acid di-2-ethylhexyl

[0127] <(D) component> SiO ２ -1: Hydrophilic fumed silica (volume average primary particle diameter 12 nm, BET specific surface area 200 m ２ / g) SiO ２ -2: Hydrophobic fumed silica (volume average primary particle diameter 16 nm, BET specific surface area 110 m ２ / g, dimethyldichlorosilane surface treatment) SiO ２ -3: Hydrophobic fumed silica (volume average primary particle diameter 16 nm, BET specific surface area 80 m ２ / g, dimethyl silicone oil surface treatment)

[0128] <Component (E)> CA: tin catalyst (dioctyltin dineodecanoate)

[0129] <Component (F)> A-Si: 3-aminopropyltrimethoxysilane

[0130] <One-component polyurethane-based moisture-curable resin composition> PU: One-component polyurethane-based moisture-curable resin composition obtained by Comparative Synthesis Example 1

[0131] Comparative Synthesis Example 1 (Production of a polyurethane-based one-component moisture-curable resin composition) Modified polytetramethylene glycol (Hodogaya Chemical Co., Ltd. "PTG-L2000") 450 parts and polypropylene glycol (Mitsui Chemicals Polyurethanes Inc. "Actocol P-23") 200 parts of a polyol component was placed in a stirrer equipped with a thermometer and dehydrated, followed by the addition of a polyisocyanate component consisting of 110 parts of xylylene diisocyanate, and the mixture was allowed to react for 5 hours at 70 ° C. to 90 ° C. under a nitrogen atmosphere to obtain a urethane prepolymer. To 100 parts of the obtained urethane prepolymer, 8 parts of fumed silica and 0.5 parts of dioctyl tin diversatate were added, and the mixture was stirred and mixed at 25 ° C. ± 5 ° C. (room temperature) under a nitrogen atmosphere to obtain a polyurethane-based one-component moisture-curable resin composition PU.

[0132] [Evaluation of moisture-curable shoe compositions] <Wear resistance of cured product> A 3 mm thick sheet-like cured product was prepared using the moisture-curable shoe composition of Example 1. The resulting sheet-like cured product was subjected to a taper abrasion test (abrasive wheel material H22, applied force 9.8 N, test rotation speed 1,000 rpm) specified in JIS K 6264 to measure the abrasion mass and evaluate the abrasion resistance of the cured product according to the following criteria. In the present invention, ratings of A and B indicate passing. The abrasion resistance of the cured products of the moisture-curable shoe compositions of Examples 2 to 11 and Comparative Example 1 was evaluated in the same manner as for the moisture-curable shoe composition of Example 1. The results are shown in Table 1. (Evaluation criteria) A: Abrasion mass 70 mg or less B: Abrasion mass more than 70 mg and less than 130 mg D: Abrasion mass more than 130 mg

[0133] <Transparency of Cured Product> (Preparation of Test Specimen) 1 mm spacers were fixed to both ends of a 40 mm x 40 mm x 3 mm float glass, and the moisture-curing shoe composition of Example 1 was placed in the center of the float glass, taking care not to trap bubbles. A float glass of the same dimensions was pressed onto the placed moisture-curing shoe composition of Example 1, and any excess was removed. The mixture was then cured at 23°C and 50% RH for one day to cure the adhesive, producing a test specimen with a 1 mm layer of the moisture-curing shoe composition of Example 1 between the float glass panes. Test specimens were also prepared for the moisture-curing shoe compositions of Examples 2 to 11 and Comparative Example 1 in the same manner as for the moisture-curing shoe composition of Example 1.

[0134] (Evaluation of Transparency of Cured Product) A haze meter "NDH 7000" manufactured by Nippon Denshoku Industries Co., Ltd. was used as a haze measurement tester. The float glass surfaces of the obtained test specimens were cleaned with acetone to remove dirt such as dust and fingerprints. Then, each test specimen was set in the haze measurement tester, and the haze value of each specimen was measured. The transparency of the cured product of the moisture-curable shoe composition of the present invention was evaluated according to the following criteria. In the present invention, A and B are acceptable. Each test specimen was also visually observed. The results are shown in Table 1. A: Haze value is 0 or more and 15 or less (visually transparent (visibility through the test specimen is clear)) B: Haze value is more than 15 and 30 or less (visually slightly transparent (visibility through the test specimen becomes blurred as the distance increases)) C: Haze value is over 30 (visually semi-transparent (transparency with a yellowish tint or that looks like frosted glass)) D: Haze value cannot be measured (light passes through, but is opaque to the naked eye (including conditions where measuring the film itself is difficult due to foaming, etc.))

[0135] Example 1 In a vessel equipped with a stirrer, a thermometer, a nitrogen inlet, component charging tubes, and a water-cooled condenser, 50 parts of Si-PE, 50 parts of Si-VP, 50 parts of DEGDEE, SiO ２ A moisture-curable shoe composition was prepared by adding 25 parts of PEG-2, 3 parts of A-Si, and 1 part of CA to the composition and stirring. The moisture-curable shoe composition was evaluated for surface abrasion resistance and transparency of the cured product. The results are shown in Table 1.

[0136] Examples 2 to 11, Comparative Example 1 Moisture-curable shoe compositions were obtained in the same manner as in Example 1, except that the components shown in Table 1 were used in the amounts shown in Table 1. The resulting moisture-curable shoe compositions were evaluated for surface abrasion resistance and transparency of the cured product. The results are also shown in Table 1.

[0137]

[0138] As shown in Table 1, the moisture-curable shoe compositions of Examples 1 to 11 according to the present invention all received a rating of A or B in the abrasion resistance of the cured product, and the cured product had excellent transparency with no bubbles observed inside. As shown in Table 1, the one-component polyurethane moisture-curable resin composition of Comparative Example 1 received a rating of C in the transparency of the cured product, indicating that the transparency of the cured product was poor.

Claims

1. A moisture-curing shoe composition comprising: (A) a crosslinkable silyl group-containing polyether and / or a crosslinkable silyl group-containing polyurethane; (B) a crosslinkable silyl group-containing vinyl organic polymer; and (C) a diluent and / or a plasticizer.

2. The moisture-curable shoe composition according to claim 1, wherein the abrasion mass in the taper abrasion test specified in JIS K 6264 (abrasive wheel material H22, applied force 9.8 N, test rotation speed 1,000 rpm) is 130 mg or less.

3. A moisture-curable shoe composition according to claim 1 or 2, wherein the diluent and / or plasticizer (C) has a boiling point of 150°C or higher.

4. The moisture-curable shoe composition according to claim 1 or 2, wherein the (C) diluent and / or plasticizer includes a plasticizer having a number average molecular weight of 3,000 or less.

5. A moisture-curable shoe composition according to claim 1 or 2, further comprising (D) silica powder.

6. A moisture-curable shoe composition according to claim 1 or 2, further comprising (E) a curing catalyst.

7. A shoe repair method using the moisture-curing shoe composition according to claim 1 or 2.

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