JPH11189715A - Polyol stock solution for shoe sole and shoe sole using the same - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To improve the dispersion stability of a pigment blended in a polyetherpolyol stock solution, and to improve the conventional stability life of several hours,
It is an object of the present invention to provide a pigment-dispersed polyetherpolyol stock solution stabilized for several days or more and a shoe sole using the same. An EO content of 5 to 30% and a molecular weight of 3,000 to a polyether-based undiluted solution for shoe soles.
8000 tetrafunctional PPG, EO content 5-30%, molecular weight 3000-7000 trifunctional PPG and EO
Content is 5-30% and molecular weight is 1000-6000
A pigment dispersion-stabilized shoe sole polyol stock solution obtained by adding a mixture of a pigment and a vehicle consisting of two or three kinds of the PPG containing the tetrafunctional PPG as an essential component among the bifunctional PPGs; It is a shoe sole formed using this.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stock solution of polyol for shoe soles and a shoe sole using the same, and more particularly, to a stock solution of polyetherpolyol for shoe soles stabilized with pigment dispersion and a shoe sole using the same.

[0002]

2. Description of the Related Art In recent years, one of the raw materials for polyols, which is a raw material of polyurethane material which occupies most of sole materials, is polyetherpolyol stock, which has excellent hydrolysis resistance and liquid at room temperature. It has been adopted from the viewpoint of ease of handling due to the fact that it is widely used, while the diversification of personal preferences has led to colorization and multicoloring of shoe soles, and gray and brown other than black The soles are increasing.

[0003] However, when a shoe sole becomes multicolored, it is necessary to mix various coloring pigments with the polyol stock solution. Particularly, when such a pigment is mixed with the polyetherpolyol stock solution, the number of pigments increases. Because the pigment in the storage tank separates and settles due to aggregation in time, the hue of the stock solution changes,
Therefore, there was a problem that the hue of the molded shoe sole also changed.

For example, in the case of intermediate colors toned by mixing 4 to 5 pigments such as gray and brown, the pigments are blended with a stock solution of polyether polyol, and the stock solution is used for a few hours after putting it in a tank. Then, the hue of the molded shoe sole changes as compared with the case where the shoe is used immediately after being put into the tank. Therefore, the tank can store only a minimum amount of the pigment-containing polyetherpolyol stock solution (for example, two 18 kg cans). However, it was an obstacle in increasing the molding efficiency (productivity) of shoe soles.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention improves the dispersion stability of a pigment blended in a polyetherpolyol stock solution and reduces the conventional stability life of several hours to a problem in forming shoe soles. It is an object of the present invention to provide a pigment-dispersed polyetherpolyol stock solution which is stabilized for a period of time, that is, several days or more, and a shoe sole using the same.

[0006]

As a result of diligent studies to achieve the above object, the conventional polyether stock solution for polyether-based urethane soles has compatibility, handleability and bending resistance of soles. In consideration of the above, a bifunctional PPG (including an EO-containing PPG) was used as a vehicle for the pigment, but two or three types of 2- to 4-functional EO-containing PPG containing a tetrafunctional EO-containing PPG as an essential component were used. A seed PPG is used as a pigment vehicle, and a mixture of the pigment and a pigment is added to a conventional polyetherpolyol stock solution for a polyether-based urethane shoe sole, while the pigment dispersion stability of the stock solution is remarkably improved. The present inventors have found that a shoe sole having almost the same bending resistance as that obtained when bifunctional PPG is used as a vehicle can be obtained, and the present invention has been completed.

That is, the present invention according to claim 1 of the present invention relates to a polyether-based polyol stock solution for shoe soles,
O content is 5 to 30% and molecular weight is 3,000 to 800
0 of the trifunctional PPG having an EO content of 5 to 30% and a molecular weight of 3000 to 7000 and the bifunctional PPG having an EO content of 5 to 30% and a molecular weight of 1000 to 6000. A pigment dispersion-stabilized shoe sole polyol solution obtained by adding a mixture of two or three kinds of PPGs containing a functional PPG as an essential component and a pigment.

Here, PPG and EO stand for polypropylene glycol and ethylene oxide, respectively, and the molecular weight means the number average molecular weight. Propylene oxide was addition-polymerized using a bifunctional PPG using an initiator having 2 functional groups, a trifunctional PPG using an initiator having 3 functional groups, and a 4-functional PPG using an initiator having 4 functional groups. Polyol. Here, initiators having two functional groups include ethylene glycol, propylene glycol, and 1,4-butanediol, and initiators having three functional groups include glycerin, trimethylolpropane, and triethanolamine. However, examples of the initiator having four functional groups include pentaerythrol and quadrol. The EO content is
In the PPG obtained by addition polymerization of EO, the ratio of the added EO to the average molecular weight of the PPG is represented by% by weight.

The tetrafunctional PPG used in the present invention is
O content is 5 to 30% and molecular weight is 3,000 to 800
It is necessary to use a trifunctional PPG having an EO content of 5 to 30% and a molecular weight of 3,000 to 7000, and a bifunctional PPG having an EO content of 5 to 30%.
It is necessary to use those having a molecular weight of 1,000 to 6,000, and as the vehicle of the pigment, among these PPGs, those PPs containing the tetrafunctional PPG as an essential component
It is necessary to use a mixture of two or three types of G.
This is because the dispersion stability of the pigment is sufficiently maintained and the flex resistance of the molded shoe sole is not impaired. The mixing ratio of the pigment to the vehicle is preferably 5 to 50% by weight.

The polyetherpolyol for shoe soles to which the mixture of the pigment and the vehicle is added in the present invention is not particularly limited as long as it is conventionally referred to as polyetherpolyol. Is polyethylene glyco-
, Polypropylene glycol, polytetramethylene glycol, and the like.Exemplary additives such as a chain extender, a surfactant, a weathering agent, a catalyst, and an antioxidant may be added according to the purpose. Good. Examples of the pigment used in the present invention include carbon black, titanium dioxide, benzimidazolone carmine HF3C (CIName; PR176), and diazoiello-HR.
(CIName; PY83), Phthalocyanine-R (CIN
ame; PB15: 2).

By forming as described above, it has been common sense to use a trifunctional or less functional PPG as a pigment vehicle from the viewpoint of prioritizing flex resistance. By the above configuration used as an essential component, polyether polio for shoe soles
In addition, the dispersion stability of the undiluted solution was greatly improved, and the soles produced using the same were almost equivalent to those using conventional bifunctional PPG without impairing the flex resistance.

The amount of the mixture of the vehicle and the pigment may be 0.5 to 10% by weight based on the undiluted polyetherpolyol solution for a shoe sole.
It is preferred that If it is less than 0.5% by weight, the coloring power (or hiding power) of the pigment on the shoe sole tends to be insufficient, and if it exceeds 10% by weight, the bending resistance of the shoe sole manufactured using this tends to be impaired. Because it is in.

Next, the average number of functional groups of the vehicle composed of two or three kinds of 2- to 4-functional PPG containing 4-functional PPG as an essential component is 3 to 3 as in the invention of claim 3.
It is preferably 3.5. If less than 3, polye for shoe sole-
This is because the dispersion stability of the terpolyol stock solution tends to be insufficient, and if it exceeds 3.5, the bending resistance of the shoe sole manufactured using the same tends to be impaired.

Here, the average number of functional groups is P
The molecular weight of PG is M2, that of 3 functional groups is M3, that of 4 functional groups is M4, the blending amount of PPG with 2 functional groups is W2, that of 3 functional groups is W3, and that of 4 functional groups is W4.
Then, it is obtained by the following equation (1). Average number of functional groups = (2 (W2 / M2) +3 (W3 / M3) +4 (W4 / M4)) / ((W2 / M2) + (W3 / M3) + (W4 / M4)) (1)

According to a fourth aspect of the present invention, there is provided a sole formed by using the undiluted polyester solution for a sole according to the first, second or third aspect.

In this case, the polyisocyanate used in producing the polyurethane shoe sole of the present invention by reacting the undiluted polyester solution for a shoe sole according to the first, second or third aspect of the present invention by a conventional method is isocyanate. Any known aliphatic, alicyclic, or aromatic organic polyisocyanate having two or more amino groups in the molecule may be used, and in particular, 4,4'-diphenylmethane diisocyanate (hereinafter referred to as MDI). ), P-phenylene diisocyanate, tolylene diisocyanate and polyester polyols or polyether polyols
For example, a prepolymer of a terminal polyisocyanate obtained by subjecting a polyisocyanate such as MDI to a urethanation reaction with a polyisocyanate such as MDI is exemplified. The bending resistance of the sole formed in this manner is almost the same as the bending resistance of the conventional polyurethane sole using only bifunctional PPG.

[0017]

Embodiments of the present invention will be described below. The pigment dispersion-stabilized shoe sole polyetherpolyol stock solution according to the present invention is obtained as follows.
4-functional PPG, which has 4-functional PPG as an essential component
A mixture of two or three kinds of tetrafunctional PPGs and a pigment, which is added to a conventional polyetherpolyol stock solution, and stirred to mix, can be produced. Where P
The method of mixing the pigment and the vehicle composed of two or three types of PG is not particularly limited. For example, a predetermined amount of each component may be introduced into a container and then stirred and mixed at the same time, or two or three types of PPG may be mixed. After stirring and mixing, a pigment may be added thereto and mixed.

The bifunctional PPG is obtained by subjecting polypropylene oxide or polyethylene oxide to addition polymerization using ethylene glycol, propylene glycol or 1,4-butanediol having two functional groups as an initiator, and having an EO content by a conventional method. It is manufactured so as to have a molecular weight of 5 to 30% and a molecular weight of 1000 to 6000. As such a PPG having 2 functional groups, EL-510 manufactured by Asahi Glass Co., Ltd. (initiator: propylene glycol, molecular weight: 4,000, EO
EL-550 (initiator; propylene glycol, molecular weight: 1,000, EO)
Content: 20%) or MF-1 manufactured by Takeda Pharmaceutical Co., Ltd.
2 (initiator: propylene glycol, molecular weight: 4,000
0, EO content; 15%).

Trifunctional PPG is prepared by using glycerin, trimethylolpropane or triethanolamine having 3 functional groups as an initiator in the same manner so that the EO content is 5 to 30% and the molecular weight is 3000 to 7000. Adjust and manufacture. As such a PPG having 2 functional groups, EL-82 (initiator; glycerin, molecular weight; 4,900, EO content; 15%) manufactured by Asahi Glass Co., Ltd. or EL-84 (initiator; glycerin, molecular weight; 6,50
0, EO content: 30%) or GS-92 manufactured by Takeda Pharmaceutical Co., Ltd. (initiator; glycerin, molecular weight: 4,000)
0, EO content; 15%).

The tetrafunctional PPG is prepared by using pentaerythritol or quadrole having 4 functional groups as an initiator, similarly having an EO content of 5 to 30% and a molecular weight of 3000 to 8
000. Such PPG having 4 functional groups is MF- manufactured by Takeda Pharmaceutical Co., Ltd.
83 (initiator: pentaerythritol, molecular weight: 5,0
00, EO content; 15%).

The thus-produced 2- to 4-functional PP
Among G, a mixture of a pigment and a vehicle composed of two or three of these PPGs containing the tetrafunctional PPG as an essential component is produced. In this case, the PP constituting the vehicle
As a combination of G, 4-functional and 3-functional, 4-functional and 2-functional
Functional, tetrafunctional, trifunctional, and difunctional are considered, and the mixing ratio of each component is not particularly limited, but it is preferable to mix them so that the average number of functional groups is 3 to 3.5.

The mixing ratio of the pigment to the vehicle is preferably 5 to 50% by weight, more preferably 10 to 30% by weight. The amount of the mixture of the vehicle and the pigment to be added to the undiluted polyetherpolyol solution for shoe soles is preferably 0.5 to 10% by weight, more preferably 1 to 6% by weight.

The polyurethane shoe sole according to the present invention has an MD
I, a prepolymer of p-phenylene diisocyanate or tolylene diisocyanate or a terminal diisocyanate (this is a polyester polyol or a polyether polyol and a polyisocyanate such as MDI, And a mixture of a polyol stock solution for pigment dispersion-stabilized shoe soles manufactured as described above, a foaming agent such as water, and an amine catalyst (commonly referred to as R solution). ) In such a manner that the molar ratio of isocyanate to active hydrogen capable of reacting with isocyanate is approximately 1 to 1 (normally, hydroxyl groups are used in excess), and this is injected into the mold. It is manufactured by foaming. The R solution may contain a low molecular weight polyol as a chain extender, or may further contain a surfactant, a weathering agent and other additives.

[0024]

Next, the present invention will be described more specifically with reference to examples. Hereinafter, “parts” means “parts by weight”.

(Example 1) The number of functional groups is 4, and the molecular weight is 500.
0, 70 parts of PPG (MF-83 manufactured by Takeda Pharmaceutical Co., Ltd.) having an EO content of 15%, a functional group number of 2, and a molecular weight of 400
0, 30 parts of PPG having an EO content of 15% (MF-12 manufactured by Takeda Pharmaceutical Co., Ltd.) and 100 parts of titanium white (CR-90 manufactured by Ishihara Sangyo Co., Ltd.) are mixed (using the formula (1)). The average number of functional groups of the vehicle determined by the above method is 3.3), and this is added to a stock solution of polyetherpolyol (T-1291RNC manufactured by Toyo Tire & Rubber Co., Ltd.) so as to be 4% by weight, followed by stirring and mixing. Thus, a pigment dispersion was obtained.

Next, using a PEC MU-203H type urethane foaming machine (manufactured by Polyurethane Engineering Co., Ltd.), the above pigment dispersion was used as an R liquid in an R liquid tank, and P
In a liquid tank, diisocyanate (T-1285P manufactured by Toyo Tire & Rubber Co., Ltd.) is charged as P liquid, and a gear pump for P liquid and R liquid is set to (active hydrogen capable of reacting with isocyanate) / (isocyanate). ) = 1.0 and the mixed liquid discharge amount of the P liquid and the R liquid is adjusted so as to be 45 g / sec, and the mixed liquid is discharged at a mixer rotation speed of 5,000 and injected into the mold. Then, a molded product of the shoe sole was obtained. However, for the evaluation of the bending resistance of the sole, JIS K 6301 (15.
The test piece specified in the bending test was molded in the same manner as described above, and the test piece was used.

(Example 2) The number of functional groups is 4, and the molecular weight is 500.
0, 55 parts of PPG (MF-83 manufactured by Takeda Pharmaceutical Co., Ltd.) having an EO content of 15%, a functional group number of 2, and a molecular weight of 400
0, PPG with EO content of 15% (MF-12 manufactured by the company)
35 parts, 10 parts by weight of PPG (GS-92 manufactured by the company) having 3 functional groups, molecular weight of 4000 and EO content of 15%, and titanium white (CR-90 manufactured by Ishihara Sangyo Co., Ltd.) 100
(The average number of functional groups in the vehicle determined by using the formula (1) is 3.1).
It was added so as to be 4% by weight with respect to the terpolyol stock solution, and stirred and mixed to obtain a pigment dispersion.

Next, this pigment dispersion was used as the R liquid in the R liquid tank of the urethane foaming machine, and Example 1 was stored in the P liquid tank.
The diisocyanate was charged as a liquid P, and a molded article of a shoe sole was obtained and a test piece for evaluating flex resistance was obtained in the same manner as in Example 1.

(Comparative Example 1) Number of functional groups: 4, molecular weight: 500
0, 100 parts of PPG having an EO content of 15% (MF-83 manufactured by Takeda Pharmaceutical Co., Ltd.) and 100 parts of titanium white (CR-90 manufactured by Ishihara Sangyo Co., Ltd.) were mixed. 4% by weight based on the polyetherpolyol stock solution
And stirred and mixed to obtain a pigment dispersion.

Next, this pigment dispersion was used as the R liquid in the R liquid tank of the urethane foaming machine, and the P dispersion was used in Example 1 in the P liquid tank.
The diisocyanate was charged as a P solution, and a test piece for evaluating the bending resistance of the shoe sole was obtained in the same manner as in Example 1.

(Comparative Example 2) The number of functional groups is 2, and the molecular weight is 400.
0, 100 parts of PPG (MF-12, manufactured by Takeda Pharmaceutical Co., Ltd.) having an EO content of 15% and 100 parts of titanium white (CR-90, manufactured by Ishihara Sangyo Co., Ltd.) were mixed. 4% by weight based on the polyetherpolyol stock solution
And stirred and mixed to obtain a pigment dispersion.

Next, this pigment dispersion was used as the R liquid in the R liquid tank of the urethane foaming machine, and the P liquid tank was used in Example 1.
The diisocyanate was charged as a P solution, and a test piece for evaluating the bending resistance of the shoe sole was obtained in the same manner as in Example 1.

(Comparative Example 3) Number of functional groups: 3, molecular weight: 400
0, 100 parts of PPG (GS-92, manufactured by Takeda Pharmaceutical Co., Ltd.) having an EO content of 15% and 100 parts of titanium white (CR-90, manufactured by Ishihara Sangyo Co., Ltd.) The pigment dispersion was added at 4% by weight to the stock solution and mixed with stirring to obtain a pigment dispersion.

Next, this pigment dispersion was used as the R liquid in the R liquid tank of the urethane foaming machine, and the P liquid tank was used in Example 1.
The diisocyanate was charged as a P solution, and a test piece for evaluating the bending resistance of the shoe sole was obtained in the same manner as in Example 1.

(Physical property test method used in this example) The dispersion stability of the pigment was evaluated by adding the pigment dispersion liquid of the above-described example and comparative examples (to a 500 cc cup, immediately after adding the mixture of the vehicle and the pigment, and before stirring the stock solution). Thing) 100cc
After stirring at a rotation speed of 0 to 5000 rpm for 10 to 15 seconds,
This pigment dispersion is placed in a test tube (10φ × 15 cm) so that the height becomes 10 cm, and the change with time of the dispersion in an atmosphere of 45 ° C. and standing is visually observed. The following four-step evaluation was performed in relation to the sedimentation property of the pigment and the elapsed time. ×: After 3 hours, sedimentation and separation of the pigment and clear aggregation of the pigment were confirmed. Δ: Aggregation of the pigment was partially observed after 3 hours. ：: After 3 hours, a slight separation of the pigment was observed, but no aggregation of the pigment was observed. A: After 3 hours, the state of uniform dispersion of the pigment was maintained.

The evaluation of the bending resistance of the shoe sole was performed according to JIS K using the test pieces for evaluating the bending resistance of the above Examples and Comparative Examples.
A bending test based on the bending test method specified in 6301 was performed, and the presence or absence of a notch and the growth length of the notch were observed on the test piece after 100,000 times of bending. X: Notch growth length is 5 mm or more. Δ: Notch growth length is between × and ○. ：: The growth length of the notch is within 2 mm. A: It is recognized that no notch is formed.

[0037]

[Table 1]

From the physical properties shown in Table 1, the pigment dispersion-stabilized polyol stock solution (Examples 1 and 2) according to the present invention is a conventional polyol stock solution and Comparative Example 2 having poor pigment dispersion stability is Of course, only PPG having 3 functional groups was used, and Comparative Example 2 was used.
Comparative Example 3 in which dispersion stability was improved, and only PPG having 4 functional groups was used. Dispersion stability is very good.

On the other hand, when the bending resistance of the shoe sole formed by using these polyols was evaluated, as apparent from comparison with Comparative Example 2 having a high evaluation of the bending resistance, it was clear that the number of functional groups was 3 or 4. In Comparative Examples 1 and 3 using only PPG, the flex resistance was deteriorated as the number of functional groups was increased. However, those in Examples 1 and 2 were Comparative Example 2 as conventional products. It exhibited the same bending resistance as.

[0040]

As described above, although it has been common knowledge that trifunctional or less functional PPG is conventionally used as a pigment vehicle from the viewpoint of emphasizing flex resistance, tetrafunctional PPG is an essential component. By using the pigment dispersion-stabilized polyol stock solution having the above-described structure, the dispersion stability of the pigment in the polyetherpolyol stock solution for shoe soles is greatly improved, and the pigment dispersion-stabilized polyol is used. The shoe sole manufactured using the undiluted solution had the same bending resistance as that of the conventional bifunctional PPG, and the bending resistance was not impaired.

Claims (4)

[Claims] 1. An EO content of 5 to 30% and a molecular weight of 3000 to a stock solution of polyetherpolyol for shoe soles.
8000 tetrafunctional PPG, EO content 5-30%, molecular weight 3000-7000 trifunctional PPG and EO
Content is 5-30% and molecular weight is 1000-6000
A stock solution of a pigment dispersion-stabilized shoe sole obtained by adding a mixture of a pigment and a vehicle consisting of two or three kinds of the above-mentioned PPG containing the above-mentioned four-functional PPG as an essential component. 2. The addition amount of the mixture of a vehicle and a pigment is 0.5 to the undiluted polyetherpolyol solution for shoe soles.
2. The undiluted polyol solution for pigment-stabilized shoe soles according to claim 1, wherein the amount is 10 to 10% by weight. 3. The vehicle according to claim 3, wherein the vehicle has an average number of functional groups of 3 to 3.
3. The undiluted polyol solution for shoe soles according to claim 1 or 2, wherein the pigment dispersion is stabilized. 4. A sole formed by using the undiluted polyester solution for a sole according to claim 1, 2 or 3.