JP5106801B2 - One-part room temperature and moisture-curing shoe repair agent and shoe repair method - Google Patents

Description

  The present invention relates to a one-component moisture-curing shoe repair agent capable of easily repairing a worn portion or a peeled portion of a shoe such as a shoe sole, and a shoe repair method using the shoe repair agent.

  As a method for repairing a shoe sole, a method has been proposed in which a mold is attached to the shoe sole and repaired by casting rubber or resin (see, for example, Patent Document 1). Patent Document 1 describes, as rubber or resin, a two-component reaction type such as an epoxy resin or a urethane resin, a high-temperature solution such as polyamide, polypropylene, or polyethylene, a rubber latex, a rubber solution, and is naturally cured at room temperature. It is disclosed to cure by heating. However, the two-component reaction type has a problem that the two components need to be mixed immediately before the repair and the work becomes complicated, and heat curing has a problem in terms of safety.

  As a sole repair agent that cures at room temperature in a one-pack type, Patent Document 2 proposes a sole repair agent containing rubber, a reinforcing agent, and a hydrocarbon solvent. However, the shoe sole repair agent has an environmental problem because it uses an organic solvent, and the cured product shrinks due to the volatilization of the organic solvent, and the wear resistance is not sufficient.

In addition, as a solvent-free one-pack type shoe sole repair agent, Patent Document 3 is mainly composed of a terminal isocyanate group-containing urethane prepolymer and / or a polyisocyanate compound and a latent curing agent obtained by inactivating an amine compound. However, since the shoe sole repair agent is heated and cured using hot water, there is a problem in terms of safety.
JP 52-76149 A Japanese Patent Laid-Open No. 2002-6052 JP 2006-34882 A

  The present invention relates to a one-part moisture-curing shoe repair agent that has good adhesion to rubber, natural leather and synthetic leather, has excellent wear resistance, and can be cured at room temperature in a solvent-free system, and a shoe repair method using the shoe repair agent. The purpose is to propose.

The one-component room temperature moisture-curing shoe repair agent of the present invention is obtained by reacting a polyol containing a modified polytetramethylene glycol having a copolymer structure of tetramethylene ether and an alkylene ether having a side chain with a polyisocyanate compound. The abrasion mass obtained by the Taber abrasion test (Test conditions: grinding wheel H22, load 9.8 N, number of tests 1000 times) specified in JIS K 6264 is 70 mg or less. It is characterized by being.

The one-component moisture-curing shoe repair agent of the present invention preferably further contains a curing catalyst.
In addition, it is preferable that the one-component moisture-curing shoe repair agent of the present invention further includes a thixotropic agent.
It is preferable that the polyol further contains a polyester polyol and / or a hydroxyl group-containing liquid diene polymer.
The one-component moisture-curing shoe repair agent of the present invention preferably has an SVI value of 2 or more and 8 or less.

  The shoe repairing method of the present invention is characterized by repairing a shoe at room temperature using the one-component moisture-curing shoe repairing agent of the present invention.

  The one-component moisture-curing shoe repair agent of the present invention does not use an organic solvent and is a one-component room-temperature curing type, so it has excellent workability with no environmental and safety problems, and rubber, natural leather and Good adhesion to synthetic leather and excellent wear resistance. According to the shoe repair method of the present invention, a shoe can be repaired simply and safely.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

  The shoe repair agent of the present invention is a one-part moisture curable composition containing, as a main component, a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyol with a polyisocyanate compound, , One or more selected from the group consisting of polytetramethylene glycol and modified polytetramethylene glycol.

  The total amount of the polytetramethylene glycol and the modified polytetramethylene glycol is preferably 10% by mass or more, more preferably 30% by mass or more based on the total polyol. Only one of the polytetramethylene glycol and the modified polytetramethylene glycol may be used or may be used in combination, but it is more preferable to use the modified polytetramethylene glycol from the viewpoint of workability.

  As the polytetramethylene glycol, known tetrahydrofuran polymers can be widely used. The molecular weight of the polytetramethylene glycol is not particularly limited, but it is preferable to use one having a number average molecular weight in the range of 500 to 5,000, more preferably in the range of 500 to 2,000. The polytetramethylene glycol may be used alone or in combination of two or more.

  The modified polytetramethylene glycol is a copolymer of tetramethylene ether and alkylene ether, and the alkylene ether preferably has a side chain. Examples of the modified polytetramethylene glycol include a copolymer of tetrahydrofuran and an alkyl-substituted tetrahydrofuran, a copolymer of tetrahydrofuran and an alkylene oxide, a copolymer of tetrahydrofuran and an alkylene ether having a side chain, and the like. Suitable examples of the copolymer of tetrahydrofuran and alkyl-substituted tetrahydrofuran include, for example, a copolymer of tetrahydrofuran and 3-alkyltetrahydrofuran described in JP-A No. 63-235320.

  The molecular weight of the modified polytetramethylene glycol is not particularly limited, but it is preferable to use a number average molecular weight in the range of 500 to 5000, more preferably 1000 to 3000. The modified polytetramethylene glycol may be used alone or in combination of two or more.

In this invention, you may mix | blend polyols other than the said polytetramethylene glycol and modified polytetramethylene glycol as a polyol component. The polyol may be any active hydrogen-containing compound having two or more active hydrogen groups, and is not particularly limited. For example, other polyether polyols such as trifunctional or higher polyhydric alcohols and diols, polypropylene glycol (PPG), Examples include polyester polyols, polybutadiene polyols, polyisoprene polyols, polyolefin polyols, polycarbonate polyols, polymer polyols, polycaprolactone polyols, and polyacrylic ester polyols. These polyols may be used alone or in combination of two or more. May be.
In particular, in order to improve the adhesion to fibers, synthetic leather, rubber, etc., a liquid diene-based polymer containing a hydroxyl group such as a polyester polyol obtained by reaction of a polyvalent carboxylic acid and a polyol, a polybutadiene polyol or a polyisoprene polyol. 1 to 50% by mass, preferably 5 to 30% by mass, based on the total polyol component.

  More specifically, examples of the polyether polyol include diols such as ethylene glycol, propylene glycol and butylene glycol, triols such as glycerin and trimethylolpropane, and one or two amines such as ammonia and ethylenediamine. Examples include polyether polyols such as random or block copolymers obtained by ring-opening polymerization of propylene oxide and / or ethylene oxide in the presence of more than one species. Polyester polyol is obtained by polycondensation of polyvalent carboxylic acids such as adipic acid, sebacic acid and terephthalic acid in the presence of polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4 butanediol and neopentyl glycol. Other examples include low-molecular active hydrogen compounds having two or more active hydrogen groups such as bisphenol A and ramester of castor oil. As the above compound, those having a molecular weight of usually 100 to 7000 and 2 to 4 OH groups in one molecule can be preferably used.

  The polyisocyanate compound is not particularly limited, and examples thereof include aromatic polyisocyanates such as diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, and hexamethylene diisocyanate (HDI). ), Aliphatic polyisocyanates such as lysine methyl ester diisocyanate, and alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, and hydrogenated tolylene diisocyanate. As the isocyanate compound, MDI is preferable from the viewpoint of cost and reactivity, but XDI is preferable in consideration of discoloration such as yellowing.

A method for reacting the polyol component and the polyisocyanate compound is not particularly limited, and a known method can be used. Specifically, a polyol component having two or more hydroxyl groups (OH) and a polyisocyanate compound having two or more isocyanate groups (NCO) are used so that the isocyanate groups become excessive, that is, the NCO / OH equivalent ratio is 1 By making it react so that it may become larger, the urethane prepolymer which has an isocyanate group at the terminal is obtained.
The reaction conditions are not particularly limited. For example, the NCO / OH equivalent ratio is 1.3 to 10.0, more preferably 1.5 to 5.0, in a nitrogen or dry air stream. It is produced by reacting at ~ 100 ° C for several hours. When the NCO / OH equivalent ratio is less than 1.3, the viscosity of the prepolymer becomes high, causing a problem in workability, and when it exceeds 10, a problem may occur due to foaming.

The one-component moisture-curing shoe repair agent of the present invention preferably further contains a curing catalyst. The curing catalyst is a catalyst for promoting curing of the urethane prepolymer, and examples thereof include organometallic compounds and amines.
The blending ratio of the curing catalyst is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

  Examples of the organometallic compound include divalent organic tin compounds such as tin octylate and tin naphthenate; dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, Tetravalent organic tin compounds such as dioctyltin diversate, dibutyltin oxide, dibutyltin bis (triethoxysilicate), reaction product of dibutyltin oxide and phthalate; organic acid lead salts such as lead octylate and lead naphthenate A titanate such as tetra-n-butyl titanate and tetrapropyl titanate; an organic bismuth compound such as bismuth octylate, bismuth neodecanoate and bismuth rosinate; an organic zirconium compound such as zirconium octylate; Organic cobalt compounds; organic zinc compounds; organic manganese compounds; organic iron compounds; tin-based chelate compounds such as dibutyltin bis (acetylacetonate), zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), Examples include chelate compounds of various metals such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetone nickel, acetylacetone zinc, and acetylacetone manganese. Of these, organic tin compounds and metal chelate compounds are preferred, and tin-based chelate compounds are more preferred because of their high reaction rate and relatively low toxicity and volatility.

  Examples of the amines include primary amines such as butylamine and octylamine, secondary amines such as dibutylamine and dioctylamine, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, diethylenetriamine, Examples include primary amines such as triethylenetetramine, tertiary amines such as triethylamine, tributylamine, triethylenediamine, and N-ethylmorpholine, or salts of these amines and carboxylic acids. .

  Moreover, you may mix | blend latent hardening agents, such as a compound which produces | generates an amine by hydrolysis, with the said 1 liquid moisture hardening type shoe repair agent. Preferred examples of the compound that generates an amine by hydrolysis include dehydration reaction products of amines such as ketimine compounds, enamine compounds, and aldimine compounds and carbonyl compounds, and the like are reaction products of polyamines and aldehydes. Some polyaldimines are more preferred. By using the latent curing agent, the low-temperature curability can be improved and the workability in winter can be further enhanced. Furthermore, the use of a latent curing agent also has an effect of suppressing foaming.

  The blending ratio of the latent curing agent is not particularly limited, but when using a compound such as polyaldimine that hydrolyzes to produce amines, it is included in the number of amino groups of amines produced by hydrolysis and the urethane prepolymer. It is desirable that the ratio of the number of isocyanate groups to be produced is 0.1 to 1.0, more preferably 0.2 to 0.6.

When a latent curing agent such as polyaldimine is blended with the one-component moisture-curing shoe repair agent, it is preferable to further blend a compound that promotes hydrolysis of the latent curing agent. As a compound which accelerates | stimulates this hydrolysis, a hydrolysable SL compound, p-toluenesulfonyl isocyanate, etc. are mentioned, for example. These compounds can be used alone or in combination of two or more. When two or more types are used in combination, the combination is not particularly limited, and for example, a hydrolyzable ester compound and p-toluenesulfonyl isocyanate may be used in combination.
The hydrolyzable ester compound is hydrolyzed with water to produce a free acid, and promotes hydrolysis of aldimine. For example, esters such as methyl formate, orthoformate such as methyl orthoformate and ethyl orthoformate Acetals such as esters and cyclohexanone dimethyl acetal are preferred in terms of storage stability.

The one-part moisture-curing shoe repair agent of the present invention has a structural viscosity index (SVI value: Structural Viscosity Index, hereinafter referred to as SVI value) of 2 or more from the viewpoint of workability during shoe repair. Preferably, it is 3 or more. The upper limit of the SVI value is not particularly limited, but is preferably 8 or less. In the present invention, the SVI value means a numerical value calculated by the following method. First, in accordance with 6.3 viscosity of JIS K 6833, using a B-type viscometer (manufactured by Toki Sangyo, BS rotor No. 7), the viscosity after 120 seconds at 1 rotation and 10 rotations Measure (measurement temperature 23 ° C.). From the measured viscosity, an SVI value is calculated by the following formula (1).
S = η ₁ / η ₂ (1)
In the formula (1), S: SVI value, η ₁ : viscosity at 1 rotation, η ₂ : viscosity at 10 rotations.

  The method for improving the SVI value is not particularly limited, but it is preferable to improve the SVI value by adding a thixotropic agent. As the thixotropic agent, for example, various kinds of materials such as surface-treated calcium carbonate, fine powder silica, and fatty acid amide can be used. The mixing ratio of the thixotropic agent is not particularly limited, but it is preferable to select and mix appropriately so that the SVI value of the one-part moisture-curing shoe repair agent of the present invention is 2 or more.

  In addition to the above components, the one-component moisture-curing shoe repair agent of the present invention includes, as necessary, a filler, a plasticizer, a colorant, a discoloration preventing agent, an adhesion-imparting agent, a physical property adjusting agent, a release agent, Contains various additives such as lubricants, dehydrating agents (storage stability improvers), tackifiers, anti-sagging agents, UV absorbers, antioxidants, flame retardants, radical polymerization initiators, and diluents such as high-boiling solvents. May be. As the colorant, a dye or pigment corresponding to the color of the shoe sole or shoe repair portion may be appropriately selected and used.

  Examples of the filler include organic or inorganic materials of various shapes, such as calcium carbonate, magnesium carbonate, and zinc carbonate; carbon black; clay; talc; fumed silica, calcined silica, precipitated silica, pulverized silica, and fused silica. Kaolin; diatomaceous earth; zeolite; titanium oxide, quicklime, iron oxide, zinc oxide, barium oxide, magnesium oxide; aluminum sulfate; vinyl chloride paste resin; glass balloon, shirasu balloon, saran balloon, phenol balloon, vinylidene chloride resin balloon Inorganic balloons, organic balloons, etc .; or these fatty acids, fatty acid ester-treated products, etc. can be mentioned, and these can be used alone or in combination. As the filler, it is preferable to use fine powder silica in order to increase transparency. Moreover, it is preferable to use inorganic hollow fillers, such as a glass balloon and a silica balloon, and organic hollow fillers, such as a polyvinylidene fluoride and a polyvinylidene fluoride copolymer. The use of the hollow filler can reduce the weight of the shoe repair agent of the present invention. In particular, from the viewpoint of maintaining the flexibility of the cured product, for example, an organic hollow filler such as MFL-80GCA (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) is suitable.

  Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dilauryl phthalate (DLP), butyl benzyl phthalate (BBP), dioctyl adipate, diisononyl phthalate, diisodecyl adipate, diisodecyl phthalate, and trioctyl phosphate. , Tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, propylene glycol adipate polyester, butylene glycol adipate polyester, alkyl epoxy stearate, epoxidized soybean oil, etc., used alone or in combination Can do.

The one-part moisture-curing shoe repair agent of the present invention has a wear mass of 70 mg or less obtained by a Taber abrasion test (test conditions: grinding wheel H22, load 9.8 N, number of tests 1000 times) specified in JIS K 6264. It is preferable.
In addition, the one-component moisture-curing shoe repair agent of the present invention preferably has a JIS A hardness of 60 or more based on JIS S 5050.
The cured product of the one-component moisture-curing shoe repair agent of the present invention has excellent wear resistance and sufficient hardness, and is extremely suitable as a shoe repair agent.

  Since the shoe repair agent of the present invention is a one-component system and cures at room temperature by moisture in the air, the shoe repair part can be repaired simply, easily and safely. The method of using the shoe repairing agent of the present invention is not particularly limited, and can be used for repairing damaged parts of shoes, such as repairing worn or missing parts of shoes such as shoe soles and adhesion of peeled parts. When the shoe sole is repaired using the shoe repair agent of the present invention, the repair method is not particularly limited. For example, the shoe repair agent of the present invention is applied to the repaired portion of the shoe, poured or cast, and then is overlaid. Then, by repairing at room temperature, the repaired portion of the shoe can be repaired. When repairing the heel part of a shoe, it is preferable to attach a mold to the shoe sole, cast the shoe repairing agent of the present invention, mold it with a spatula, etc., and cure at room temperature.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

(Synthesis Examples 1 to 11) Synthesis of Prepolymers A to K The compositions of the prepolymers are shown in Tables 1 and 2. After adding a predetermined amount of a polyol component to a stirrer equipped with a thermometer and dehydrating, a predetermined amount of an isocyanate component was added and reacted at 70 to 90 ° C. for 5 hours in a nitrogen atmosphere to obtain urethane prepolymers A to K. . The terminal isocyanate contents of the obtained urethane prepolymer are shown in Tables 1 and 2 together.

The compounding amounts of the compounding substances in Tables 1 and 2 are expressed in parts by mass, and * 1 to 10 are as follows.
* 1) Modified polytetramethylene glycol: manufactured by Hodogaya Chemical Co., Ltd., trade name PTG-L2000, a chain diol composed of a random copolymer of tetramethylene ether and a modified tetramethylene ether having a side chain, molecular weight 2000 .
* 2) Modified polytetramethylene glycol: manufactured by Asahi Kasei Co., Ltd., trade name PTXG-1800, a chain diol composed of a random copolymer of tetramethylene ether and neopentyl glycol, molecular weight 1800.
* 3) Polytetramethylene glycol: manufactured by Hodogaya Chemical Co., Ltd., trade name PTG-2000, molecular weight 2000.
* 4) Polypropylene glycol: manufactured by Mitsui Chemicals Polyurethane Co., Ltd., trade name Actol P-23, molecular weight 3000, bifunctional.
* 5) Polyester polyol: Kuraray Co., Ltd., trade name Kuraray polyol P-2010, adipic acid polyester polyol.
* 6) Polybutadiene glycol: Nippon Soda Co., Ltd., trade name NISSO PB G-1000.
* 7) XDI: xylylene diisocyanate * 8) MDI: 4,4'-diphenylmethane diisocyanate * 9) Polypropylene glycol: manufactured by Mitsui Chemicals Polyurethanes, Inc., trade name Actol Diol 2000, molecular weight 2000, bifunctional.
* 10) Polypropylene glycol: manufactured by Mitsui Chemicals Polyurethane Co., Ltd., trade name Actol 79-56, molecular weight 3000, trifunctional.

(Examples 1-7 , Experimental example 1 and Comparative examples 1-3)
In the formulation shown in Table 3, after stirring and mixing the urethane prepolymer and the thixotropic agent at room temperature under a nitrogen stream, a curing catalyst is added and stirring and mixing is performed at room temperature under a nitrogen stream to obtain a one-part moisture curable composition. Obtained.

The compounding amounts of the compounding substances in Table 3 are shown in parts by mass, and * 11 to 23 are as follows.
* 11-21) Urethane prepolymers A to K: The urethane prepolymers obtained in Synthesis Examples 1 to 11.
* 22) Thixotropic agent: Nippon Aerosil Co., Ltd., trade name Aerosil RY200S, fumed silica.
* 23) Curing catalyst: Sansha Kikai Co., Ltd., trade name STANN BL, dioctyltin diversate.

The following test was done with respect to the obtained one-component moisture-curable composition. The results are shown in Table 4.
1. Adhesion test Using the one-component moisture-curable composition, the adherends having a width of 25 mm and the materials shown in Table 4 were bonded to each other, and a 180 ° peel test was conducted after 7 days at 23 ° C and 50% RH. The evaluation criteria are as follows.
A: Peeling strength 0.6 N / 25 mm or more or destruction of the adherend.
○: Peel strength 0.3N / 25mm or more and less than 0.6N / 25mm.
Δ: Peel strength of 0.1 N / 25 mm or more and less than 0.3 N / 25 mm.
X: Peel strength of less than 0.1 N / 25 mm.

2. Abrasion Resistance A sheet having a thickness of 2 to 3 mm was prepared using the one-component moisture-curable composition, and the abrasion mass was measured by a Taber abrasion test specified in JIS K 6264. The test conditions were a grinding wheel H22 and a test number of 1000 with a load of 9.8 N.

3. Measurement of SVI value In accordance with 6.3 viscosity of JIS K 6833, using a B-type viscometer (manufactured by Toki Sangyo, BS rotor No. 7), after 120 seconds at 1 rotation and 10 rotations The viscosity was measured (measurement temperature: 23 ° C.), and the SVI value was calculated by the following formula (1).
S = η ₁ / η ₂ (1)
In the formula (1), S: SVI value, η ₁ : viscosity at 1 rotation, η ₂ : viscosity at 10 rotations.

4). Hardness measurement Based on JIS S5050, the JIS A hardness was measured with respect to the hardened | cured material after 23 degreeC50% RH 7 days of the said one-component moisture hardening type composition.

As shown in Table 4, the compositions of Examples 1 to 7 have excellent adhesion to any material of rubber (NR, NBR), natural leather (cowhide) and plastic (EVA, soft PVC). It has been found that it is suitable as a repair agent for shoes made of rubber, natural leather and synthetic leather. Further, the cured product of the composition of Example 1-7 has achieved the following and hardness 60 or more wear mass 70 mg, had excellent wear resistance and hardness.

  In addition, a shoe repair test was performed on the one-component moisture-curable compositions of Examples 1 to 3 and Comparative Examples 1 and 3. Specifically, a mold is placed on the side of the sole of a leather shoe with a worn sole, and the compositions of Examples 1 to 3 and Comparative Examples 1 and 3 are cast and repaired, and left at room temperature for 72 hours. did. After that, repaired leather shoes were used for 3 months and the condition was confirmed. Although the repair part of the shoes of Examples 1 to 3 maintained a good state without being worn, wear of the repair parts of the shoes of Comparative Examples 1 and 3 was recognized.

Claims (5)

Containing a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyol containing a modified polytetramethylene glycol having a copolymer structure of tetramethylene ether and an alkylene ether having a side chain, and a polyisocyanate compound;
One-part, room temperature, moisture-curing shoe repair characterized by a wear mass of 70 mg or less obtained by a Taber abrasion test (test conditions: polishing wheel H22, load 9.8 N, test number 1000 times) specified in JIS K 6264 Agent.   The one-component room temperature moisture-curing shoe repair agent according to claim 1, wherein the SVI value is 2 or more and 8 or less.   The one-component room temperature moisture-curing shoe repair agent according to claim 1 or 2, further comprising a curing catalyst.   The one-component room temperature moisture-curing shoe repair agent according to any one of claims 1 to 3, further comprising a thixotropic agent.   A shoe repairing method comprising repairing a shoe at room temperature using the one-component room temperature moisture-curing shoe repair agent according to any one of claims 1 to 4.