Moisture-curing shoe composition and shoe repair method

Abstract

The objectives are to provide a moisture-curing shoe composition that exhibits excellent abrasion resistance in the cured product, suppresses the generation of air bubbles within the cured product, and has excellent transparency in the cured product, and to provide a shoe repair method using a moisture-curing shoe composition that exhibits excellent abrasion resistance in the cured product, suppresses the generation of air bubbles within the cured product, and has excellent transparency in the cured product. As a solution, a moisture-curing shoe composition is provided that contains (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.

Description

[Technical Field]

[0001] The present invention relates to a moisture-curing shoe composition and a shoe repair method. More specifically, the present invention relates to a moisture-curing shoe composition that has excellent surface abrasion resistance of the cured product, suppresses the generation of air bubbles inside the cured product, and has excellent transparency of the cured product, and to a shoe repair method using the same. [Background technology]

[0002] In recent years, shoe compositions for repairing worn-out soles have become known. When repairing shoe soles using a shoe composition, the damaged portion of the sole can be repaired by applying the shoe composition to the area to be repaired, or by injecting the shoe composition into a mold and leaving it to dry and harden at room temperature.

[0003] Patent Document 1 discloses a shoe sole repair agent containing rubber, a reinforcing agent such as carbon black, and a hydrocarbon solvent, wherein the hydrocarbon solvent content is 35 to 65 wt%, preferably 40 to 60 wt%. This shoe sole repair agent is said to be easy to use as it can repair worn shoe soles regardless of the sole shape simply by directly building up the material, has excellent workability, becomes a rubbery elastic body after hardening to obtain a finish indistinguishable from a normal shoe sole, has excellent usability, and is a one-component shoe sole repair agent that does not require mixing of its components and has excellent handling properties. Patent Document 2 discloses a shoe sole repair agent characterized by comprising a one-component thermosetting composition mainly composed of a terminal isocyanate group-containing urethane prepolymer and / or a polyisocyanate compound and a latent curing agent. This shoe sole repair agent is for repairing the soles and heels of shoes, and is said to have no solvent volatilization problems, be able to cure in a short time, have almost no deformation or shrinkage associated with curing, and be able to repair to the desired shape in a single repair operation. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2002-60552 [Patent Document 2] Japanese Patent Publication No. 2006-34882 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The sole repair agent described in Patent Document 1 is a solvent-based sole repair agent, and as the solvent evaporates during drying and curing, there were problems in terms of odor, working environment, and safety and hygiene. In addition, it takes a long time to dry and cure, and as it dries and cures, there is a risk that the repaired area will shrink, making it impossible to repair to the desired shape in a single repair, and sometimes requiring repeated repair work. The sole repair agent described in Patent Document 2 is said to have no solvent evaporation problems, can harden in a short time, and exhibits almost no deformation or shrinkage during hardening, and can repair to the desired shape in a single repair operation. However, because it is a urethane-based sole repair agent, it contains air bubbles generated during the reaction within the hardened material. When the surface of the hardened material in the repaired area wears down, it causes problems with the appearance of the repaired area, and furthermore, it accelerates the wear of the repaired area. Furthermore, the shoe sole repair agents described in Patent Document 1 and Patent Document 2 both had problems in terms of the transparency of the cured product.

[0006] The problem that this invention aims to solve is to provide a moisture-curing shoe composition that has excellent abrasion resistance in the cured product, suppresses the generation of air bubbles inside the cured product, and has excellent transparency in the cured product. The problem that the present invention aims to solve is to provide a shoe repair method using a moisture-curing shoe composition that exhibits excellent wear resistance in the cured product, suppresses the generation of air bubbles within the cured product, and has excellent transparency in the cured product. [Means for solving the problem]

[0007] The inventors of the present invention conducted diligent studies to solve the above problems and found that the above problems can be solved by a moisture-curing shoe composition of a specific composition and a shoe repair method using said moisture-curing shoe composition, thus completing the present invention. Specifically, it is as follows: [Item 1] (A) Crosslinkable silyl group-containing polyether and / or crosslinkable silyl group-containing polyurethane, (B) Crosslinkable silyl group-containing vinyl organic polymer, and (C) Diluents and / or plasticizers, A moisture-curing shoe composition containing the following: [Item 2] The wear mass in the tapered wear test specified in JIS K 6264 (abrasive wheel material H22, applied force 9.8N, test rotation speed 1,000 rpm) is 130 mg or less. The moisture-curing shoe composition described in item 1. [Item 3] The moisture-curing shoe composition according to item 1 or 2, wherein the (C) diluent and / or plasticizer has a boiling point of 150°C or higher. [Item 4] The moisture-curing shoe composition according to any one of items 1 to 3, wherein the (C) diluent and / or plasticizer comprises a plasticizer with a number average molecular weight of 3,000 or less. [Item 5] (D) A moisture-curing shoe composition according to any one of items 1 to 4, further comprising silica powder. [Item 6] (E) A moisture-curing shoe composition according to any one of items 1 to 5, further comprising a curing catalyst. [Item 7] A method for repairing shoes using a moisture-curing shoe composition described in any one of items 1 to 6. [Effects of the Invention]

[0008] The present invention provides a moisture-curing shoe composition that exhibits excellent surface abrasion resistance of the cured product, suppresses the generation of air bubbles within the cured product, and results in a cured product with excellent transparency. The present invention provides a shoe repair method using a moisture-curing shoe composition that exhibits excellent surface abrasion resistance of the cured product, suppresses the generation of air bubbles within the cured product, and results in a cured product with excellent transparency. The moisture-curing shoe composition of the present invention does not cause odor, environmental problems, or safety and hygiene issues due to solvents that volatilize during drying and curing, unlike conventional solvent-based shoe sole repair agents. Furthermore, because the drying and curing time is short and there are no shrinkage problems associated with drying and curing, the desired shape can be repaired in a single repair operation. In addition, because the cured product has excellent transparency, the repaired area can be made inconspicuous without coloring the moisture-curing shoe composition, and it can also be colored to any desired shade as needed. Moreover, because the generation of air bubbles inside the cured product is suppressed, wear resistance can be maintained even inside the cured product, extending the time between repairs. [Modes for carrying out the invention]

[0009] The moisture-curing shoe composition and shoe repair method of the present invention will be described in detail below. These are illustrative examples, and it goes without saying that various modifications are possible as long as they do not deviate from the technical concept of the present invention.

[0010] {Moisture-curing shoe composition} The moisture-curing shoe composition of the present invention is 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 a plasticizer. The moisture-curing shoe composition of the present invention may further contain (D) silica powder. The moisture-curing shoe composition of the present invention may further contain (E) a curing catalyst. The moisture-curing shoe composition of the present invention may have a cured mass of 130 mg or less in a tapered abrasion test (abrasive wheel material H22, applied force 9.8 N, test rotations 1,000 rpm) as specified in JIS K 6264.

[0011] [(A) component] Component (A) constituting the moisture-curing type 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, may consist of a crosslinkable silyl group-containing polyurethane, or may consist of 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 position of the crosslinkable silyl group is on the side chain and / or the terminal of the molecule, and preferably on the terminal 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 capable of crosslinking by forming a siloxane bond. As the crosslinkable silyl group, for example, a group represented by the structural formula (1) is preferable. -Si(R 11 ) 3-a1 X 11 a1 ···(1) In the structural formula (1), R 11 is 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 3SiO-(R 11 is as defined above) represented by a triorganosiloxy group, or a -CH2OR 11 group (R 11 is as defined above). Further, R 11 is such that at least one hydrogen atom on the carbon atom at the 1st to 3rd positions is halogen, -OR 12 , -NR 13 R 14 , -N=R 15 , -SR 16 (R12 , R 13 , R 14 , R 16 Each is a hydrogen atom, or a hydrocarbon group having or without substituents with 1 to 20 carbon atoms, R 15 R is a hydrocarbon group having 1 to 20 carbon atoms with a divalent substituent or without a substituent. It also refers to a perfluoroalkyl group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a cyano group. Among these, R 11 A methyl group is preferred. 11 If there are two or more R 11 They may be the same or different. 11 X indicates a hydroxyl group or a hydrolyzable group. 11 If there are two or more X 11 They may be the same or different. a1 is an integer of 0, 1, 2, or 3. Considering curability, in order to obtain a moisture-curing shoe composition with a sufficient curing rate, it is preferable that a1 is 2 or more in structural formula (1).

[0014] Hydrolyzable groups and hydroxyl groups can be bonded to a single silicon atom in a range of 1 to 3 groups. When two or more hydrolyzable groups or hydroxyl groups are bonded to a crosslinkable silyl group, they may be the same or different. The silicon atoms forming the crosslinkable silyl group may be one or two or more.

[0015] X 11The hydrolyzable group represented by is not particularly limited as long as it is not a fluorine atom. For example, hydrogen atoms, halogen atoms (chlorine atoms, bromine atoms, iodine atoms), alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups, etc. Of these, hydrogen atoms, halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups are preferred, and alkoxy groups, halogen atoms, amide groups, and aminooxy groups are more preferred. From the viewpoint of mild hydrolysis and ease of handling, alkoxy groups are 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 carbon atoms in the alkoxy group, the higher the reactivity, and the reactivity decreases as the number of carbon atoms increases, in the order of methoxy group > ethoxy group > propoxy group. While the choice depends on the purpose and application, methoxy and ethoxy groups are typically used.

[0016] Specific structures of crosslinkable silyl groups include trialkoxysilyl groups such as trimethoxysilyl and triethoxysilyl groups [-Si(OR)3], and dialkoxysilyl groups such as methyldimethoxysilyl and methyldiethoxysilyl groups [-SiR 1 (OR)2] is an example. A trimethoxysilyl group is preferred when the reactivity is high, and a dialkoxysilyl group is preferred when the reactivity is suppressed. 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-curing shoe composition and / or cured product, the crosslinkable silyl group is preferably a trimethoxysilyl group. The crosslinkable silyl group may be used alone or in combination of two or more types.

[0017] The crosslinkable silyl groups may be present at the ends of the main chain and / or side chains of the polyether molecular chain. In particular, it is preferable that the crosslinkable silyl groups are present only at the ends of the main chain of the polyether molecular chain. In this case, the effective network length of the polyether molecular chains contained in the final cured product is increased, resulting in superior properties in terms of adhesion, weather resistance, mechanical strength, etc. Furthermore, multiple crosslinkable silyl groups represented by structural formula (1) may be linked to one another.

[0018] In the moisture-curing shoe composition of the present invention, the number of crosslinkable silyl groups contained in one molecule of the crosslinkable silyl group-containing polyether, which is component (A), is not particularly limited. For example, the number of crosslinkable silyl group-containing polyether molecules can be, for example, an average of 0.5 or more, preferably an average of 1.0 or more, 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 average number of crosslinkable silyl groups contained in one molecule is less than 0.5, the curing ability will be insufficient, which may cause problems in terms of adhesion and curing properties. If the average number of crosslinkable silyl groups contained in one molecule exceeds 5.0, manufacturing will be difficult, and the high curing ability may reduce storage stability and handling, or the cured film may become hard and brittle.

[0019] (Polyether skeleton) Examples of polyether skeletons constituting crosslinkable silyl group-containing polyethers include structural formula (2): -OR 21 - ···(2) A skeleton having repeating units represented by is preferred. The polyether skeleton may consist of only one type of repeating unit, or it may consist of two or more types of repeating units. In structural formula (2), R 21 R is a divalent organic group. 21This can be, for example, a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 2 to 4 carbon atoms. A specific example of the repeating unit shown in structural formula (2) is preferably a polyoxyalkylene repeating unit. Examples of polyoxyalkylene repeating units include one or more selected from the group consisting of -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(C2H5)O-, -CH2C(CH3)2O-, -CH2CH2CH2O-, -CH2CH2CH2CH2CH2O-, -CH2CH2CH2CH2CH2CH2O-, etc. In the present invention, in the crosslinkable silyl group-containing polyether, it is preferable that the polyether skeleton be composed of a polyoxyalkylene polymer consisting of polyoxyalkylene repeating units, and more preferably a polyoxypropylene polymer.

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

[0021] (Method for producing crosslinkable silyl group-containing polyethers) 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 functional group that is reactive to the functional group of the polyoxyalkylene polymer and a crosslinkable silyl group is reacted.

[0022] Specific examples of polymer reaction methods include a method in which an unsaturated group-containing polyoxyalkylene polymer is reacted with a hydrosilane having a crosslinkable silyl group or a mercapto compound having a crosslinkable silyl group to perform hydrosilylation or mercaptolation, thereby obtaining a polyoxyalkylene polymer containing a crosslinkable silyl group. An 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 that reacts to this functional group and an unsaturated group. Other specific examples of polymer reaction methods include reacting a polyoxyalkylene polymer having hydroxyl groups at its termini with a compound having isocyanate groups and crosslinkable silyl groups, or reacting a polyoxyalkylene polymer having isocyanate groups at its termini with a compound having active hydrogen groups such as hydroxyl groups and amino groups and crosslinkable silyl groups. Using isocyanate compounds, polyoxyalkylene polymers having crosslinkable silyl groups can be easily obtained.

[0023] (number average molecular weight) In the moisture-curing shoe composition, component (A), "crosslinkable silyl group-containing polyether," may be either a linear polymer or a branched polymer. The number-average molecular weight of the crosslinkable silyl group-containing polyether, which is component (A) of the moisture-curing shoe composition of the present invention, is not particularly limited. In terms of polystyrene equivalent in GPC, it can be, for example, 1,000 or more, preferably 2,000 or more, for example 100,000 or less, preferably 50,000 or less, more preferably 40,000 or less, for example 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, 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 during shoe repair.

[0024] <Crosslinkable silyl group-containing polyurethane> Crosslinkable silyl group-containing polyurethanes are compounds having crosslinkable silyl groups and a polyurethane skeleton within the molecule. The crosslinkable silyl groups are located in the side chains and / or terminals of the molecule, preferably at the terminals. Crosslinkable silyl group-containing polyurethanes may be used individually or in combination of two or more types.

[0025] (Crosslinkable silyl group) The crosslinkable silyl groups constituting the crosslinkable silyl group-containing polyurethane are groups that have a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond. Examples of crosslinkable silyl groups include those similar to the crosslinkable silyl groups described in (crosslinkable silyl groups) in the <crosslinkable silyl group-containing polyether> above. Note that the crosslinkable silyl groups of the crosslinkable silyl group-containing polyether and the crosslinkable silyl group-containing polyurethane may be the same or different from each other.

[0026] The crosslinkable silyl groups may be present at the ends of the main chain and / or side chains of the polyurethane molecular chain. In particular, it is preferable that the crosslinkable silyl groups are present only at the ends of the main chain of the polyurethane molecular chain. In this case, the effective network length of the polyurethane molecular chains contained in the final cured product is increased, resulting in superior properties in terms of adhesion, weather resistance, mechanical strength, etc. Furthermore, multiple crosslinkable silyl groups represented by structural formula (1) may be linked to one another.

[0027] In the moisture-curing shoe composition of the present invention, the number of crosslinkable silyl groups contained in one molecule of the crosslinkable silyl group-containing polyurethane, which is component (A), is not particularly limited. For example, the number of crosslinkable silyl groups in one molecule of the crosslinkable silyl group-containing polyurethane can be, for example, an average of 0.5 or more, preferably an average of 1.0 or more, 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 an average of 0.5, 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 exceeds an average of 5.0, manufacturing will be difficult, and storage stability and handling may be reduced due to excessively high curability.

[0028] (Polyurethane skeleton) Examples of polyurethane skeletons constituting crosslinkable silyl group-containing polyurethanes include structural formula (3): -OR 31 -OC(=O)-NH-R 32 -NH-C(=O)- ...(3) A skeleton having repeating units represented by is preferred. The polyurethane skeleton may consist of only one type of repeating unit, or it may consist of two or more types of repeating units. In structural formula (3), R 31 is a polyol residue, R 32This is a polyisocyanate residue. Polyol residues are groups derived from polyols, which will be described later, and polyisocyanate residues are groups derived from polyisocyanates, which will be described later.

[0029] In crosslinkable silyl group-containing polyurethanes, the method for synthesizing the polyurethane polymer constituting the polyurethane skeleton is not particularly limited. For example, it can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule with an optional chain extender. Known urethane catalysts and organic solvents can also be used in the synthesis of the polyurethane polymer.

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

[0031] • Polyisocyanate compounds The polyisocyanate compound used in the synthesis of polyurethane polymers is not particularly limited as long as it is a compound having two or more isocyanate groups. For example, aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, and the like 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, and 1,4-tetramethylene diisocyanate. Examples of alicyclic polyisocyanate compounds include norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexylene diisocyanate, bis(isocyanate methyl)cyclohexane, and dicyclohexylmethane diisocyanate. Polyisocyanate compounds may be used individually or in combination of two or more.

[0032] • Chain extender The chain extenders used as needed in the synthesis of polyurethane polymers are not particularly limited, as long as they are compounds having two or more reactive groups with an isocyanate group. Examples include low molecular weight polyols with 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. The chain extenders may be used alone or in combination of two or more.

[0033] (Method for producing crosslinkable silyl group-containing polyurethane) The method for producing crosslinkable silyl group-containing polyurethane is not particularly limited. For example, a crosslinkable silyl group-containing polyurethane can be obtained by introducing functional groups such as unsaturated groups, hydroxyl groups, epoxy groups, or isocyanate groups into the polyurethane polymer as needed, and reacting the polymer with a compound having a functional group that is reactive to the functional groups of the polyurethane polymer and a crosslinkable silyl group.

[0034] In particular, either (i) a method of reacting a hydroxyl group-containing polyurethane polymer obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule with an optional chain extender in such a way that there is an excess of hydroxyl groups, with a compound having a functional group that is reactive to hydroxyl groups and a crosslinkable silyl group, or (ii) a method of reacting an isocyanate group-containing polyurethane polymer obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule with an optional chain extender in such a way that there is an excess of isocyanate groups, with a compound having a functional group that is reactive to isocyanate groups and a crosslinkable silyl group, is preferred.

[0035] Examples of compounds having functional groups that are reactive to the functional groups of polyurethane polymers and crosslinkable silyl groups include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxy-ethoxy)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-isocyanatetopropyltrimethoxysilane, and 3-isocyanatetopropyltriethoxysilane. Compounds having a functional group that is reactive to the functional group of a polyurethane polymer and a crosslinkable silyl group may be used individually or in combination of two or more.

[0036] (number average molecular weight) In the moisture-curing shoe composition, component (A), "crosslinkable silyl group-containing polyurethane," may be either a linear polymer or a branched polymer. The number average molecular weight of the crosslinkable silyl group-containing polyurethane, which is component (A) of the moisture-curing shoe composition of the present invention, is not particularly limited. In terms of polystyrene equivalent in GPC, it can be, for example, 1,000 or more, preferably 2,000 or more, for example 100,000 or less, preferably 75,000 or less, more preferably 50,000 or less, for example 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, 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 during shoe repair.

[0037] <(A) Content of ingredient> The content of component (A), "crosslinkable silyl group-containing polyether and / or crosslinkable silyl group-containing polyurethane," in the moisture-curing shoe composition is not particularly limited. It can be, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, or, for example, 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less, or, for example, 5% by mass or more and 90% by mass or less, for example, 5% by mass or more and 85% by mass or less, for example, 5% by mass or more and 80% by mass or less, for example, 10% by mass or more and 90% by mass or less, for example, 10% by mass or more and 85% by mass or less, for example, 10% by mass or more and 80% by mass or less, for example, 15% by mass or more and 90% by mass or less, for example, 15% by mass or more and 85% by mass or less, for example, 15% by mass or more and 80% by mass or less.

[0038] [(B) Component] Component (B) of the moisture-curing 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 backbone within its molecule. The crosslinkable silyl group is located in the side chain and / or terminal of the molecule, preferably in the side chain and / or terminal. One crosslinkable silyl group-containing vinyl organic polymer may be used alone, or two or more may be used in combination.

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

[0040] In the moisture-curing 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, which is 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, 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. (B) The crosslinkable silyl group-containing vinyl organic polymer may include, for example, one that contains 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 in the molecular side chains. In the moisture-curing shoe composition of the present invention, the crosslinkable silyl group-containing vinyl organic polymer, which is component (B), preferably includes, for example, a polymer containing 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 in the molecular side chains.

[0041] <Main chain> The vinyl organic polymer constituting the main chain of a 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 polymer constituting the main chain of a crosslinkable silyl group-containing vinyl organic polymer may be used alone or in combination of two or more types. Of these, the vinyl organic polymer constituting the main chain of the crosslinkable silyl group-containing vinyl organic polymer preferably includes (meth)acrylate polymers and / or hydrocarbon polymers, and more preferably includes (meth)acrylate polymers.

[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 monomer components containing (meth)acrylate monomers. The (meth)acrylate monomer is not particularly limited as long as it has 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-containing (meth)acrylates such as γ-(methacryloyloxypropyl)trimethoxysilane and γ-(methacryloyloxypropyl)dimethoxymethylsilane; (meth)acrylic acid; fluorine-containing (meth)acrylates; and the like. (Meth)acrylate monomers may be used individually or in combination of two or more. The monomer component may contain (meth)acrylate monomers. Examples of monomers other than (meth)acrylate monomers include styrene, maleic anhydride, vinyl acetate, etc. Monomers other than (meth)acrylate monomers may be used individually or in combination of two or more.

[0043] In the present invention, examples of (meth)acrylate polymers constituting the main chain of a crosslinkable silyl group-containing vinyl organic polymer include (i) a (meth)acrylate polymer composed of (meth)acrylate monomers, and (ii) a (meth)acrylate polymer obtained by using one or more alkyl (meth)acrylate monomers and, if necessary, other (meth)acrylate monomers. By using silyl group-containing (meth)acrylate monomers as (meth)acrylate monomers, the number of silicon groups in the (meth)acrylate polymer can be controlled. In this specification, (meth)acrylate means acrylate and / or methacrylate.

[0044] (Hydrogen polymers) 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 monomer components containing hydrocarbon monomers. As the hydrocarbon polymer, saturated hydrocarbon polymers are preferred. Examples of hydrocarbon monomers include olefin monomers with 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, and isobutylene; and diene monomers, such as butadiene and isoprene. A single hydrocarbon monomer may be used, or two or more may be used in combination. Of these, isobutylene polymers and hydrogenated polybutadiene polymers are preferred, with isobutylene polymers being particularly preferred, because they allow for easy introduction of functional groups at the terminals, easy control of molecular weight, and easy increase in the number of terminal functional groups.

[0045] <Method for producing crosslinkable silyl group-containing vinyl-based organic polymers> The method for producing a crosslinkable silyl group-containing vinyl-based organic polymer is not particularly limited. As a method for synthesizing crosslinkable silyl group-containing (meth)acrylate polymers, for example, radical polymerization using radical polymerization reactions can be used. Examples of radical polymerization methods include radical polymerization (free radical polymerization) in which a polymerization initiator is used to copolymerize a predetermined monomer, and controlled radical polymerization in which crosslinkable silyl groups are introduced at controlled positions such as terminals.

[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, initiator 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 allows for the polymerization of polymers with molecular weights of approximately 500 to 100,000 with a molecular weight distribution of 1.5 or less, and enables the introduction of various functional groups at the molecular ends. Another example is cationic polymerization, which uses a combination of an organic halogen compound that generates a stable carbon-cation and a Friedel-Claft acid catalyst as a polymerization initiator.

[0047] Free radical polymerization, used as a synthesis method for crosslinkable silyl group-containing (meth)acrylate polymers, is a method of copolymerizing a vinyl monomer with a crosslinkable silyl group-containing vinyl monomer using a polymerization initiator. Examples of polymerization initiators include azo compound polymerization initiators and peroxide polymerization initiators, with the use of 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. Free radical polymerization offers a relatively broad molecular weight distribution, excellent workability due to its moderate fluidity, and the absence of catalyst-derived metal components in the polymer. This allows for improvements in issues such as inhibition of crosslinking reactions and discoloration, and enables the application of a suitable pot life.

[0048] Examples of azo compound polymerization initiators 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-carbonitride), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, and 2,2'- Examples include zobis(2-amidinopropane)dihydrochloride, 2,2'-azobis(N,N'-dimethylene isobutylamidine), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(isobutylamide)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 peroxide-based polymerization initiators include benzoyl peroxide and laurium peroxide. These polymerization initiators may be used individually or in combination of two or more. When using polymerization initiators, the entire amount may be added at once or added sequentially in multiple steps. In the present invention, it is preferable to use a free radical polymerization method using an azo compound, peroxide, or the like as a polymerization initiator to introduce a crosslinkable silyl group to the molecular side chain, and then to introduce a crosslinkable silyl group to the molecular terminal.

[0049] Controlled radical polymerization methods used for the synthesis of crosslinkable silyl group-containing (meth)acrylate polymers include free radical polymerization and living radical polymerization, which polymerize vinyl monomers using chain transfer agents having specific functional groups. Living radical polymerization methods such as reversible addition-fragmentation chain transfer (RAFT) polymerization and transition-metal-mediated living radical polymerization using transition metal complexes are more preferred. Reactions using thiol compounds having crosslinkable silyl groups, as well as reactions using thiol compounds having crosslinkable silyl groups and metallocene compounds, are also suitable.

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

[0051] In structural formula (4), M is a metal selected from the group consisting of metals from 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 Each of these is independently at least one group selected from the group consisting of aliphatic hydrocarbon groups that may have substituents, alicyclic hydrocarbon groups that may have substituents, aromatic hydrocarbon groups that may have substituents, and silicon-containing groups that may have substituents, or a hydrogen atom or a single bond. Furthermore, R 31 and R 32These may be working together to bond two five-membered rings in the compound represented by structural formula (3). In structural formula (4), b1 and b2 are each independently integers from 1 to 4, X is a hydrocarbon group or halogen atom in which at least some of the hydrogen atoms may be substituted with halogen atoms, and n is 0 or an integer with a valence of -2 of metal M.

[0052] Examples of metallocene compounds 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-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluoro-3-(pyru-1-yl)-phen-1- Titanocene compounds such as yl; 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-difluorophenyl-1-yl, dicyclopentadi Zirconocene compounds such as en-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-(pyru-1-yl)-phenyl-1-yl;Examples include dicyclopentadienyl-V-chloride, bismethylcyclopentadienyl-V-chloride, bispentamethylcyclopentadienyl-V-chloride, dicyclopentadienyl-Ru-chloride, and dicyclopentadienyl-Cr-chloride. The metallocene compounds may be used individually or in combination of two or more.

[0053] The metallocene compound can be used in a normal catalytic amount, for example, 0.001 parts by mass or more, preferably 0.005 parts by mass or more, for example, 1.0 parts by mass or less, preferably 0.01 parts by mass or less, for example, 0.001 parts by mass or more and 1.0 parts by mass or less, for example, 0.001 parts by mass or more and 0.01 parts by mass or less, for example, 0.005 parts by mass or more and 1.0 parts by mass or less, for example, 0.005 parts by mass or more and 0.01 parts by mass or less.

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

[0055] Examples of compounds 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, and 3-mercaptobutyl-trimethoxysilane. The crosslinkable silyl group-containing thiol compounds may be used individually or in combination of two or more.

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

[0057] The amount of metallocene compound used has little effect on the molecular weight of the resulting polymer, but without it, the reaction does not proceed effectively. Increasing the amount of thiol compound used increases the polymerization rate. From these trends, it is thought that in the catalyst used in the production of component (B) of the present invention, the metallocene compound acts as an activating catalyst throughout the reaction, and the thiol compound exerts a polymerization initiating effect (acting as a polymerization initiating species). In the catalyst used in the preparation of component (B) of the present invention, the amount of crosslinkable silyl group-containing thiol compound used is considered to be a law governing the molecular weight and polymerization rate.

[0058] The amount of crosslinkable silyl group-containing thiol compound used can be appropriately determined considering the molecular weight of the polymer to be obtained, the polymerization rate, etc. In order to ensure the reaction proceeds smoothly and to prevent it from running out of control, the metallocene compound and the crosslinkable silyl group-containing thiol compound can be used in a molar ratio of metallocene compound:crosslinkable silyl group-containing thiol compound, for example, in the range of 100:1 to 1.0:50,000, preferably in the range of 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, reacting for a desired time, and then adding the crosslinkable silyl group-containing thiol compound further, or (iii) adding both the crosslinkable silyl group-containing thiol compound and the (meth)acrylate monomer. By adding the crosslinkable silyl group-containing thiol compound in this way, or by adding the crosslinkable silyl group-containing thiol compound and the (meth)acrylate monomer, the polymerization rate can be improved.

[0060] As polymerization catalysts, a metallocene compound represented by structural formula (4) and a crosslinkable silyl group-containing thiol compound represented by structural formula (5) are used. In the presence of these catalysts, a (meth)acrylate monomer having a polymerizable unsaturated bond is polymerized to obtain a crosslinkable silyl group-containing vinyl organic polymer, in which at least one terminal is a residue (-SR) obtained by removing a hydrogen atom from the crosslinkable silyl group-containing thiol compound used as a catalyst. 51 ) is joined. Note that -R 51 This 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. When polymerizing a (meth)acrylate monomer having polymerizable unsaturated bonds in the presence of these catalysts, it is also possible to use in combination, in addition to the crosslinkable silyl group-containing thiol compound, alkyl thiol compounds that do not have functional groups other than thiol groups, such as ethyl mercaptan, butyl mercaptan, hexyl mercaptan, tert-decyl mercaptan, n-decyl mercaptan, and octyl mercaptan; aromatic thiol compounds that do not have functional groups other than thiol groups, such as phenyl mercaptan and benzyl mercaptan; thiol compounds that have 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 polymer-type thiols having active thiol groups, such as polysulfide polymers.

[0062] In the present invention, in order to adjust the polymerization rate and degree of polymerization, sulfide compounds such as disulfide compounds, trisulfide compounds, and tetrasulfide compounds can be used in addition to metallocene compounds and crosslinkable silyl group-containing thiol compounds. 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. The sulfide compounds may be used individually or in combination of two or more. Such sulfide compounds can be used in the polymerization of the present invention in an amount that does not deactivate the polymerization. Specifically, they 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] <Example of component (B)> Examples of crosslinkable silyl group-containing vinyl organic polymers, which are component (B), include crosslinkable silyl group-containing (meth)acrylate polymers. For example, a crosslinkable silyl group-containing (meth)acrylate polymer has a crosslinkable silyl group and its main chain is structured as shown in structural formula (6): -CH2-C(R 61 )(COOR 62 )- ···(6) (In the formula, R 61 R is a hydrogen atom or a methyl group. 62 (This indicates an alkyl group with 1 to 5 carbon atoms.) (Meth)acrylate monomer units represented by structural formula (7): -CH2-C(R 71 )(COOR 72 )- ···(7) (In the formula, R71 is the aforementioned R 61 It is the same as R 72 (This indicates an alkyl group with 6 or more carbon atoms.) Examples include polymers containing (meth)acrylate monomer units represented by . R in structural formula (6) 62 Examples 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 methyl, ethyl, propyl, n-butyl, and t-butyl groups, and there are multiple R 62 These may be the same or different from each other. R in structural formula (7) 72 Examples include long-chain alkyl groups with 6 or more carbon atoms, usually 7 to 30 carbon atoms, preferably 8 to 20 carbon atoms, such as 2-ethylhexyl group, lauryl group, and stearyl group, and there are multiple R 72 They may be the same or different from one another.

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

[0065] <Content of component (B)> The content of component (B) "crosslinkable silyl group-containing vinyl organic polymer" in the moisture-curing shoe composition is not particularly limited. For example, it can be 25 parts by mass or more, preferably 40 parts by mass or more, per 100 parts by mass of (A) crosslinkable silyl group-containing polyether, 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.

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

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

[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 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 mono Examples include glycol ether compounds such as phenyl ether, ethylene glycol mono-2-ethyl butyl 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. Alcohol compounds may be used individually or in combination of two or more.

[0069] Examples of aliphatic hydrocarbon compounds include saturated hydrocarbon compounds such as normal paraffins and isoparaffins, and α-olefin derivatives such as linear aldendimer (a trade name of Idemitsu Kosan Co., Ltd.). Aliphatic hydrocarbon compounds may be used individually or in combination of two or more.

[0070] Examples of aromatic hydrocarbon compounds include toluene and xylene. Aromatic hydrocarbon compounds may be used individually 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 menthonol propionate. Ester compounds may be used individually or in combination of two or more.

[0072] Examples of ketone compounds include acetone, 2-butanone, methyl ethyl ketone, and methyl isobutyl ketone. Ester compounds may be used individually 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-curing 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 crosslinkable silyl groups. The plasticizer may be used alone or in combination of two or more types.

[0074] Examples of carboxylic acid ester compounds include aromatic carboxylic acid ester compounds, alicyclic carboxylic acid ester compounds, aliphatic carboxylic acid ester compounds, and polyhydric alcohol ester compounds. Carboxylic acid ester compounds may be used individually or in combination of two or more.

[0075] Aromatic carboxylic acid ester compounds are not particularly limited as long as they are ester compounds of carboxylic acids 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 of three or more basic acids such as trimellitic acid ester compounds and pyromellitic acid ester compounds; aromatic carboxylic acid ester compounds among the ester compounds listed in the diluents above; and so on. Aromatic carboxylic acid ester compounds may be used individually or in combination of two or more.

[0076] Alicyclic carboxylic acid ester compounds are not particularly limited as long as they are ester compounds of carboxylic acids 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; alicyclic carboxylic acid ester compounds among the ester compounds listed in the diluents; and so on. Alicyclic carboxylic acid ester compounds may be used individually 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 in the diluent. The aliphatic carboxylic acid ester compound 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. Examples include glycol ester compounds such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and pentaerythritol ester; and glycol ester compounds among the ester compounds listed in the diluent. The ester compound may be used alone or in combination of two or more.

[0079] Examples of sulfonic acid ester compounds include alkylsulfonic acid phenyl esters (Mesamoll (manufactured by LANXESS)). Sulfonic acid ester compounds may be used individually or in combination of two or more.

[0080] Examples of phosphate ester compounds include tricresyl phosphate, trioctyl phosphate, octyldiphenyl phosphate, tributyl phosphate, and tricresyl phosphate. A single phosphate ester compound may be used, or two or more may be used in combination.

[0081] Examples of ether compounds include the glycol ether compounds mentioned above in the diluents. The ether compounds may be used individually or in combination of two or more.

[0082] Examples of hydrocarbon compounds include hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls. A single hydrocarbon compound may be used, or two or more may be used in combination.

[0083] The epoxy plasticizer is not particularly limited as long as it is a plasticizer having an epoxy group in its 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 types.

[0084] Examples of organic polymers that do not contain crosslinkable silyl groups include vinyl-based organic polymers that do not contain crosslinkable silyl groups, polyester-based organic polymers that do not contain crosslinkable silyl groups, and polyether-based organic polymers that do not contain crosslinkable silyl groups. Organic polymers that do not contain crosslinkable silyl groups may be used individually or in combination of two or more types.

[0085] Vinyl organic polymers that do not contain crosslinkable silyl groups are not particularly limited as long as they are vinyl organic polymers that are addition polymers of vinyl monomers containing carbon-carbon unsaturated bonds. Examples 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 oils; halogenated hydrocarbons such as chlorinated paraffins; (meth)acrylic acid ester polymers, hydroxyl group-containing (meth)acrylate polymers, carboxyl group-containing (meth)acrylate polymers, epoxy group (meth)acrylate polymers; diallyl phthalate polymers; and the like. Vinyl organic polymers that do not contain crosslinkable silyl groups may be used individually or in combination of two or more types.

[0086] Examples of polyester organic polymers that do not contain crosslinkable silyl groups include polyester compounds obtained from monomer components containing a dibasic acid and a dihydric alcohol, and polyester compounds obtained from monomer components containing a hydroxycarboxylic acid. Polyester organic polymers that do not contain crosslinkable silyl groups may be used individually or in combination of two or more types.

[0087] Examples of polyether-based organic polymers that do not contain crosslinkable silyl groups include polyether compounds obtained from monomer components containing alkylene oxides, such as polypropylene glycol derivatives and polyethylene glycol derivatives. Polyether-based organic polymers that do not contain crosslinkable silyl groups may be used individually or in combination of two or more types.

[0088] The content of component (C) "diluent and / or plasticizer" 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, more preferably 10 parts by mass or more, for example 100 parts by mass or less, preferably 90 parts by mass or less, more preferably 80 parts by mass or less, for example 1 to 100 parts by mass, for example 1 to 90 parts by mass, for example 1 to 80 parts by mass, for example 5 to 100 parts by mass, for example 5 to 90 parts by mass, for example 5 to 80 parts by mass, for example 10 to 100 parts by mass, for example 5 to 90 parts by mass, for example 5 to 80 parts by mass, for example 10 to 100 parts by mass, for example 10 to 90 parts by mass, for example 10 to 80 parts by mass.

[0089] [(D) component] <Silica powder> The moisture-curing 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, flake-shaped, fibrous, or any other form.

[0090] For silica powder, surface-treated silica fine powder, in which the surface has been hydrophobized with a surface treatment agent, can be used. Specific examples of surface treatment agents 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. Surface-treated silica fine powder, whose surface has been hydrophobized with these agents, can also be used. Silazanes or chlorosilanes are preferred as surface treatment agents.

[0091] <Specific surface area> The specific surface area of ​​the silica powder that may be contained in the moisture-curing shoe composition is not particularly limited. For example, 50 m². 2 / g or more, preferably 70m 2 / g or more, more preferably 90m 2 It can be 400m or more. 2 Less than or equal to / g, preferably 380m 2 / g or less, more preferably 350m 2 It can be less than / g, for example 50m 2 / g or more 400m 2 Less than / g, for example, 50m 2 / g or more 380m 2 Less than / g, for example, 50m 2 / g or more 350m 2 Less than / g, for example, 70mg 2 / g or more 400m 2 Less than / g, for example, 70mg 2 / g or more 380m 2 Less than / g, for example, 70mg 2 / g or more 350m 2 Less than / g, for example, 90mg 2 / g or more 400m 2Less than / g, for example, 90mg 2 / g or more 380m 2 Less than / g, for example, 90mg 2 / g or more 350m 2 It can be less than / g. The specific surface area of ​​silica powder may be measured by the BET method, or, if using a commercially available product, the catalog value may be adopted.

[0092] <(D) Content of ingredient> The content of component (D) "silica powder" in the moisture-curing 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, more preferably 5.0 parts by mass or more, per 100 parts by mass of the total of components (A) and (B) in the moisture-curing shoe composition, for example, 200 parts by mass or less, preferably 150 parts by mass or less, more preferably 100 parts by mass or less, for example, 0.5 parts by mass or more and 200 parts by mass or less, for example, 0.5 parts by mass or more and 150 parts by mass or less, for example, 0.5 parts by mass or more and 100 parts by mass or less, for example, 2.5 parts by mass or more and 200 parts by mass or less, for example, 2.5 parts by mass or more and 150 parts by mass or less, for example, 2.5 parts by mass or more and 100 parts by mass or less, for example, 5.0 parts by mass or more and 150 parts by mass or less, for example, 5.0 parts by mass or more and 100 parts by mass or less.

[0093] [(E) component] The moisture-curing 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 crosslinkable silyl groups and is used for purposes such as accelerating the curing of moisture-curing shoe compositions. Examples of curing catalysts include organotin compounds, organotitanium compounds, organoaluminum compounds, organocarboxylic acid-organoamine reaction products, organozirconium compounds, organoiron compounds, organovanadium compounds, amine compounds, acidic phosphoric acid compounds, polyamide compounds, amine-epoxy reaction products, and boron compounds. The curing catalyst may be used individually or in combination of two or more types.

[0094] It is preferable to use organotin compounds and / or organotitanium compounds as the curing catalyst. Examples of organotin compounds include tetravalent tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dieodecanate (dioctyltin diversatate), dioctyltin oxide, reaction products of dibutyltin oxide and phthalate esters, and reaction products of dioctyltin oxide and alkoxysilane; and divalent tin compounds such as tin dioctylate, tin dinaphthenate, tin distearate, and tin dieodecanate (dinosatinate). Dibutyltin maleate, reaction products of dibutyltin oxide and phthalate esters, dibutyltin diacetylacetonate, dioctyltin dieodecanate, and reaction products of dioctyltin oxide and alkoxysilane are preferred due to their fast curing speed.

[0095] Examples of organotitanium compounds 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). [ka] In structural formula (8), n6 R 81 These are each independently substituted or unsubstituted hydrocarbon groups with 1 to 20 carbon atoms, and 4-n6 R 82 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, either substituted or unsubstituted, and 4-n6 R 83 and 4-n6 R 84 Each of these is an independently substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and n6 is 0, 1, 2, or 3.

[0097] [ka] In structural formula (9), R 91 This is a substituted or unsubstituted divalent hydrocarbon group with 1 to 20 carbon atoms, and has two R 92 Each is 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 These are each independently substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms. The titanium-based compounds may be used individually or in combination of two or more.

[0098] Examples of titanium chelates represented by structural formula (8) or structural formula (9) include titanium dimethoxybis(ethyl acetate), titanium diethoxidebis(ethyl acetate), titanium diisopropoxidebis(ethyl acetate), titanium diisopropoxidebis(methyl acetate), titanium diisopropoxidebis(t-butyl acetate), and titanium diisopropoxidebis(methyl-3-oxo-4). Titanium diisopropoxide bis(ethyl-3-oxo-4,4,4-trifluorobutanoate), titanium di-n-butoxide bis(ethyl acetate), titanium diisobutoxide bis(ethyl acetate), titanium di-t-butoxide bis(ethyl acetate), titanium di-2-ethylhexoxide bis(ethyl acetate), titanium bis(1-methoxy-2-propoxide)bis (Ethyl acetate), Titanium bis(3-oxo-2-butoxide)bis(ethyl acetate), Titanium bis(3-diethylaminopropoxide)bis(ethyl acetate), Titanium triisopropoxide (ethyl acetate), Titanium triisopropoxide (allyl acetate), Titanium triisopropoxide (methacryloxyethyl acetate), 1,2-dioxyethanetitanium bis(ethyl acetate) Examples include titanium acetate, 1,3-dioxypropantanitanium bis(ethyl acetate), 2,4-dioxypentanetitanium bis(ethyl acetate), 2,4-dimethyl-2,4-dioxypentanetitanium bis(ethyl acetate), titanium tetrakis(ethyl acetate), titanium bis(trimethylsiloxy)bis(ethyl acetate), and titanium bis(trimethylsiloxy)bis(acetylacetonate). Among these, titanium diethoxide bis(ethyl acetate), titanium diisopropoxide bis(ethyl acetate), and titanium dibutoxide bis(ethyl acetate) are examples, with titanium diisopropoxide bis(ethyl acetate) being more preferred.The titanium chelate may be used alone or in combination of two or more.

[0099] Examples of the chelating reagent capable of forming the chelate ligand of the titanium chelate include β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, t-butyl acetoacetate, allyl acetoacetate, (2-methacryloxyethyl) acetoacetate, methyl 3-oxo-4,4-dimethylhexanoate, ethyl 3-oxo-4,4,4-trifluorobutanoate, etc. Methyl acetoacetate and ethyl acetoacetate are preferred, and ethyl acetoacetate is more preferred. When there are two or more chelate ligands, each chelate ligand may be the same or different.

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

[0101] [(Component (F))] The moisture-curable shoe composition of the present invention may contain an adhesion promoter as the component (F). The adhesion promoter is used for the purpose of improving the adhesion of the moisture-curable shoe composition and promoting curing. Examples of the adhesion promoter include the following structural formula (10): Si(R 101 ) 4-a10 X 101 a10 ···(10) (In the structural formula (10), R 101 is 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 3SiO-(R 102 is the same as R 101 ) represented by a triorganosiloxy group, or -CH2OR103 The group (R 103 is the same as R 101 ). Also, in R 101 , at least one hydrogen atom on the carbon atoms at the 1st to 3rd positions is 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 hydrocarbon group with or without a substituent having 1 to 20 carbon atoms, R 107 is a hydrocarbon group with or without a divalent substituent having 1 to 20 carbon atoms.). 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 is shown. When there are two or more R 101 , the plurality of R 101 may be the same or different. X 101 represents a hydroxyl group or a hydrolyzable group (a halogen group, an alkoxy group having 1 to 6 carbon atoms, etc.). When there are two or more X 101 , the plurality of X 101 may be the same or different. a10 is any integer of 0, 1, 2, or 3.). An alkoxysilane compound represented by

[0102] Examples of adhesion-imparting agents 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- (β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate and other isocyanurate silanes; 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 trimethoxysilylpropyl amine, N-ethyl-3-aminoisobutyltrimethoxysilane, and alkoxysilanes containing secondary and / or tertiary amino groups; γ-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane), γ-glycidoxypropyltriethoxysilane (3-glycidoxypropyltriethoxysilane), γ-glycidoxypropylmethyldimethoxysilane (3-glycidoxypropylmethyldimethoxysilane), β-(3,4-epoxycyclohexyl) Silanes containing epoxy groups such as ethyltrimethoxysilane, 4-oxyranylbutyltrimethoxysilane, and 8-oxyranyloctyltrimethoxysilane; silanes containing mercapto groups such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane;Silanes containing vinyl-type unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-acryloyloxypropylmethyldimethoxysilane; silanes containing chlorine atoms such as γ-chloropropyltrimethoxysilane; γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, γ-isocyanatetopropylmethyldimethoxysilane, 3-isocyanatetopropylmethyldimethoxysilane, (isocyanatetomethyl)trimethoxysilane, (isocyanatetomethyl)dimethoxymethylsilane Examples include isocyanate-containing silanes such as lan, (isocyanate-methyl)triethoxysilane, and (isocyanate-methyl)diethoxymethylsilane; hydrosilanes such as methyldimethoxysilane, trimethoxysilane, and methyldiethoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, and tetra-t-butoxysilane; and others. The adhesion-imparting agent may be used alone or in combination of two or more types.

[0103] The content of component (F), "adhesion granulator," in the moisture-curing shoe composition is not particularly limited. It can be, for example, 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-curing shoe composition, and can be, for example, 0 parts by mass or more and 20 parts by mass or, for example, 0 parts by mass or more and 10 parts by mass or less.

[0104] [Other ingredients] The moisture-curing shoe composition of the present invention may contain, as necessary, "other components" in addition to the components (A) to (F) described above. Examples of "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, thixotropic agents (anti-sagging agents), colorants, anti-aging agents, tackifiers, flame retardants, mold release agents, lubricants, antifungal agents, and the like. The other components may be used individually or in combination of two or more.

[0105] <Moisture-curing polymers other than component (A) and component (B)> The moisture-curing shoe composition of the present invention may contain moisture-curing polymers other than component (A) and component (B). In crosslinkable silyl group-containing polymers other than component (A) and component (B) as moisture-curing polymers, the crosslinkable silyl groups are the same as those described for component (A) above. The main chain skeleton of the crosslinkable silyl group-containing polymers other than component (A) and component (B) as moisture-curing polymers is not particularly limited as long as it is a polymer other than a polysiloxane polymer. Examples of moisture-curing 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 not a polysiloxane polymer; moisture-curing urethane resins; moisture-curing cyanoacrylate resins; and the like. Moisture-curing resins other than component (A) and component (B) may be used individually or in combination of two or more.

[0106] <Fillers other than component (D)> (D) In ​​addition to component "silica powder", various types of fillers can be used, and either organic fillers or inorganic fillers other than silica may 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-curing 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-curing 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] <UV absorber> The moisture-curing shoe composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is used to prevent ultraviolet degradation of the moisture-curing shoe composition and improve its 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-curing shoe composition of the present invention may contain an antioxidant. The antioxidant is used to suppress oxidation of the moisture-curing shoe composition and to improve weather resistance and heat resistance, etc. Examples of antioxidants include hindered phenol-based, hindered amine-based, phenol-based, organic sulfur-based, and organophosphorus-based antioxidants. Of these, hindered phenol-based and / or hindered amine-based antioxidants are preferred. The antioxidant may be used alone or in combination of two or more types.

[0110] <Moisture absorbent> The moisture-curing shoe composition of the present invention may contain a moisture absorbent. The moisture absorbent is used to improve the storage stability of the moisture-curing shoe composition by absorbing moisture in the composition. Examples of moisture absorbents include inorganic moisture absorbents such as zeolite, calcium oxide, magnesium oxide, and zinc oxide; and silane compound-based 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] <Coloring agent> The moisture-curing shoe composition of the present invention may contain a coloring agent. The coloring agent is used for purposes such as coloring the moisture-curing shoe composition to a desired shade. Examples of colorants include inorganic pigments such as carbon black, red iron oxide, titanium dioxide, and zinc oxide; organic pigments; dyes; and so on. A single colorant may be used, or two or more may be used in combination.

[0112] <Anti-aging agent> The moisture-curing shoe composition of the present invention may contain an anti-aging agent. The anti-aging agent is used for purposes such as preventing thermal degradation of the moisture-curing shoe composition and improving its heat resistance. Examples of anti-aging agents include amine-ketone-based anti-aging agents, aromatic secondary amine-based anti-aging agents, benzimidazole-based anti-aging agents, thiourea-based anti-aging agents, and phosphite-based anti-aging agents. Anti-aging agents may be used individually or in combination of two or more types.

[0113] <Adhesion agent> The moisture-curing shoe composition of the present invention may contain a tackifier. The tackifier is used for purposes such as improving the tackiness of the moisture-curing shoe composition and improving its initial fixation. Examples of tackifiers include terpene resins, aromatically modified terpene resins and hydrogenated terpene resins obtained by hydrogenating these, terpene-phenol resins obtained by copolymerizing terpene compounds with phenol compounds, 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, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, and dicyclopentadiene resins. The tackifier may be used alone or in combination of two or more types.

[0114] [Wear mass of hardened material in tapered wear test] The moisture-curing shoe composition of the present invention exhibits a cured mass of preferably 130 mg or less, and more preferably 110 mg or less, in a tapered abrasion test (polishing wheel material H22, applied force 9.8 N, test rotation speed 1,000 rpm) as specified in JIS K 6264. As a result, even when the moisture-curing shoe composition is used to repair shoe soles, the cured product will exhibit good abrasion resistance. Furthermore, the moisture-curing shoe composition of the present invention preferably has a JIS A hardness of 10 or higher in accordance with JIS S 5050 for its cured product. The moisture-curing shoe composition of the present invention is extremely suitable as a moisture-curing shoe composition because its cured product has excellent abrasion resistance and sufficient hardness.

[0115] [Form of moisture-curing shoe composition] The form of the moisture-curing shoe composition of the present invention is not particularly limited and can be appropriately determined depending on the application, components, etc. For example, it can be a one-component, moisture-curing shoe composition containing at least components (A) to (C), and optionally components (D) to (F) and other components. For example, the composition may be a two-component moisture-curing shoe composition comprising a first agent containing at least component (A) and component (B), and a second agent containing at least component (E). In this case, component (C), component (D), component (F), and other components may be contained in either the first agent or the second agent, or in both. The moisture-curing shoe composition of the present invention can be preferably used as a one-component type.

[0116] The moisture-curing shoe composition of the present invention may be room-temperature curing or heat-curing. For example, if it is possible to cure at room temperature due to moisture in the air, it can be made into a room-temperature curing, moisture-curing shoe composition. In that case, curing may be accelerated by heating as needed. For example, a heat-curing type of moisture-curing shoe composition can be obtained by adding moisture (water) to a moisture-curing shoe composition and then heating it to cure it.

[0117] [Method for manufacturing moisture-curing shoe composition] The method for producing moisture-curing shoe compositions is not particularly limited. They can be produced by mixing essential components (A) to (C) and, if necessary, one or more of components (D) to (F) and other components in a container, and then degassing and stirring. If the moisture-curing shoe composition is a one-component type, it can be manufactured, for example, by taking predetermined amounts of components (A) to (C), and optionally one or more of components (D) to (F) and other components, mixing them in a container, and then degassing and stirring. There are no particular restrictions on the order in which the components are added, and they can be set as appropriate. If the moisture-curing shoe composition is a two-component type, for example, components (A) and (B) may be used as the first agent, and component (E) (curing catalyst) as the second agent, each in a separate container, and components (C), (D), (F), and other components may be mixed with either the first agent or the second agent.

[0118] The mixing step is 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), by a conventionally known method. The mixing step does not require the use of a completely sealed mixing apparatus and can be carried out in the presence of air. However, this does not preclude the use of a completely sealed mixing apparatus. The moisture-curing shoe composition of the present invention requires 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 any conventionally known method and is not particularly limited.

[0119] Since the moisture-curing shoe composition of the present invention hardens through a crosslinking reaction of crosslinkable silyl groups in response to moisture in the air, it is preferable that it be stored in a sealed container to ensure storage stability. The shape of the airtight container is not particularly limited as long as it can seal the moisture-curing shoe composition, and can be selected according to the application. Examples include pails that can hold 3 to 50 liters of the moisture-curing shoe composition, and cartridge or tube containers that can hold less than 1 liter of the moisture-curing shoe composition.

[0120] [Uses of moisture-curing shoe composition] The uses of the moisture-curing shoe composition of the present invention are not particularly limited as long as they are related to shoes. Examples include shoe repair materials, sole forming materials, shoe adhesives, sole covering materials, sole wear inhibitors, shoelace covering materials, shoelace impregnation materials, shoe stain repellents, and shoe slip inhibitors. Of these, the moisture-curing shoe composition of the present invention can be suitably used as a shoe repair agent, sole forming agent, shoe adhesive, sole covering material, and sole wear inhibitor, and is particularly suitably used as a shoe repair agent, sole forming agent, sole covering material, and sole wear inhibitor. The moisture-curing shoe composition of the present invention can be applied to any type of shoe, including men's shoes, women's shoes, sneakers, and sandals.

[0121] The moisture-curing shoe composition of the present invention exhibits excellent surface abrasion resistance of the cured product, is uniform in its cured product without containing air bubbles formed by reaction within the cured product, and has excellent transparency. Therefore, even when used for repairing shoe soles, it is possible to form a cured product with excellent surface abrasion resistance immediately after repair, and even when worn over time, the abrasion resistance of the cured product is continuously maintained because the inside of the cured product is uniform and does not contain air bubbles. Furthermore, because the cured product is transparent, it is possible to make the repaired area inconspicuous without coloring the moisture-curing shoe composition, and it is also possible to color it to any desired shade as needed, thus possessing optimal characteristics as a moisture-curing shoe composition.

[0122] The moisture-curing shoe composition of the present invention can be used to repair damaged parts of shoes, such as worn or damaged soles, or to bond detached parts. The method of repairing shoe soles using the moisture-curing 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-curing shoe composition of the present invention to the repair area of ​​the shoe, building up the material, shaping it with a spatula or the like as needed, and then curing it. When repairing the heel of a shoe, it is preferable to attach a mold to the sole, pour in the moisture-curing shoe composition of the present invention, shape it with a spatula or the like, and then cure it. During curing, the material may be left at room temperature (ambient temperature), or, if necessary, heated by blowing hot air or using a heat source. [Examples]

[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 "mass percent" and "parts" means "parts by mass". Also, the amounts of each component in Table 1 are all in parts by mass.

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

[0125] <(B) component> Si-VP: Crosslinkable silyl group-containing (meth)acrylate-based organic polymer

[0126] <(C) component> 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: Di-2-ethylhexyl epoxyhexahydrophthalate

[0127] <(D) component> SiO2-1: Hydrophilic fumed silica (volume average primary particle size 12 nm, BET specific surface area 200 m²) 2 / g) SiO2-2: Hydrophobic fumed silica (volume-average primary particle size 16 nm, BET specific surface area 110 m²) 2 ( / g, dimethyldichlorosilane surface treatment) SiO2-3: Hydrophobic fumed silica (volume-average primary particle size 16 nm, BET specific surface area 80 m²) 2 ( / g, dimethyl silicone oil surface treatment)

[0128] <(E) component> CA: Tin catalyst (dioctyl tin dionedecanoate)

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

[0130] <Polyurethane-based one-component moisture-curing resin composition> PU: Polyurethane-based one-component moisture-curing resin composition obtained by Comparative Synthesis Example 1

[0131] <Comparative Synthesis Example 1> (Manufacturing of polyurethane-based one-component moisture-curing resin compositions) A polyol component consisting of 450 parts of modified polytetramethylene glycol (Hodogaya Chemical Co., Ltd. "PTG-L2000") and 200 parts of polypropylene glycol (Mitsui Chemicals Polyurethane Co., Ltd. "Actcol P-23") was placed in a stirrer equipped with a thermometer and dehydrated. Then, a polyisocyanate component consisting of 110 parts of xylylene diisocyanate was added, and the mixture was reacted at 70°C to 90°C under a nitrogen atmosphere for 5 hours 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 diversate were added and stirred and mixed at 25°C ± 5°C (room temperature) under a nitrogen atmosphere to obtain a polyurethane-based one-component moisture-curing resin composition PU.

[0132] [Evaluation of moisture-curing shoe composition] <Abrasion resistance of hardened material> A sheet-like cured material with a thickness of 3 mm was prepared using the moisture-curing shoe composition according to Example 1. The obtained sheet-like cured material was subjected to a taper abrasion test specified in JIS K 6264 (polishing wheel material H22, applied force 9.8 N, test rotation speed 1,000 rpm), and its abrasion mass was measured to evaluate the abrasion resistance of the cured material according to the following criteria. In the present invention, evaluations A and B are considered acceptable. The abrasion resistance of the cured materials of the moisture-curing shoe compositions according to Examples 2 to 11 and Comparative Example 1 was evaluated in the same manner as the moisture-curing shoe composition according to Example 1. The results are shown in Table 1. (Evaluation Criteria) A: Wear mass 70mg or less B: Wear mass more than 70mg and less than 130mg D: Wear mass exceeding 130mg

[0133] <Transparency of hardened material> (Preparation of test specimens) A 1mm spacer was fixed to both ends of a 40mm x 40mm x 3mmt float glass, and the moisture-curing shoe composition according to Example 1 was applied to the center of the float glass, ensuring that no bubbles were present. A float glass of the same dimensions was pressed onto the applied moisture-curing shoe composition according to Example 1, and the excess was removed. The mixture was then cured at 23°C and 50% RH for one day to allow the adhesive to harden, creating a test specimen with a 1mm layer of the moisture-curing shoe composition according to Example 1 between the float glass pieces. Test specimens were prepared for the moisture-curing shoe compositions according to Examples 2-11 and Comparative Example 1 in the same manner as for the moisture-curing shoe composition according to Example 1.

[0134] (Evaluation of the transparency of the cured material) A haze meter, the "NDH 7000," manufactured by Nippon Denshoku Industries Co., Ltd., was used as the haze measurement test equipment. The float glass surfaces of the obtained test specimens were cleaned with acetone to remove dust, fingerprints, and other contaminants. Then, each test specimen was placed in a haze measuring machine, and the haze value was measured for each specimen. The transparency of the cured product of the moisture-curing shoe composition of the present invention was evaluated according to the following criteria. In this invention, A and B are considered acceptable. Visual observation was also performed on each test specimen. The results are shown in Table 1. A: Haze value is between 0 and 15 (visually transparent (clear view through the test specimen)) B: Haze value between 15 and 30 (slightly transparent to the naked eye (the view through the test specimen becomes blurry as the distance increases)) C: Haze value over 30 (visually semi-transparent (yellowish transparency or transparency that looks like frosted glass)) D: Haze value cannot be measured (It transmits light but is opaque to the naked eye (including cases where measuring the film itself is difficult due to foaming, etc.))

[0135] [Example 1] A moisture-curing shoe composition was prepared by adding 50 parts of Si-PE, 50 parts of Si-VP, 50 parts of DEGDEE, 25 parts of SiO2-2, 3 parts of A-Si, and 1 part of CA to a container equipped with a stirrer, thermometer, nitrogen inlet, component charging tube, and water-cooled condenser, and stirring and mixing the mixture. The surface abrasion resistance and transparency of the cured product were evaluated for the obtained moisture-curing shoe composition. The results are shown in Table 1.

[0136] [Examples 2-11, Comparative Example 1] A moisture-curing shoe composition was 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 surface abrasion resistance and transparency of the cured product of the obtained moisture-curing shoe composition were evaluated. The results are also shown in Table 1.

[0137] [Table 1]

[0138] As shown in Table 1, the moisture-curing shoe compositions of Examples 1 to 11 according to the present invention all received an A or B rating for the abrasion resistance of the cured product, demonstrating excellent abrasion resistance, no air bubbles were observed inside the cured product, and the cured product exhibited excellent transparency. As shown in Table 1, the polyurethane-based one-component moisture-curing resin composition in Comparative Example 1 had a transparency evaluation of C for the cured product, indicating poor transparency.

Claims

1. (A) Crosslinkable silyl group-containing polyether and / or crosslinkable silyl group-containing polyurethane, (B) Crosslinkable silyl group-containing vinyl-based organic polymers, and (C) Diluents and / or plasticizers, It contains, The wear mass in the tapered wear 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. Moisture-curing shoe composition.

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

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

4. (D) The moisture-curing shoe composition according to claim 1 or 2, further comprising silica powder.

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

6. (A) Crosslinkable silyl group-containing polyether and / or crosslinkable silyl group-containing polyurethane, (B) Crosslinkable silyl group-containing vinyl-based organic polymers, and (C) Diluents and / or plasticizers, A shoe repair method using a moisture-curing shoe composition containing [a specific substance].

7. (A) Crosslinkable silyl group-containing polyether and / or crosslinkable silyl group-containing polyurethane, (B) Crosslinkable silyl group-containing vinyl-based organic polymers, and (C) Diluents and / or plasticizers, A moisture-curing shoe repair composition containing [the specified ingredient].