JP2016047909A - Polyurethane foam, manufacturing method therefor, cup for clothing using the same and clothing having cup part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane foam having largely improved stretch property, elasticity and surface hardness and a manufacturing method therefor, and a clothing having a cup part close to tactile of skin of human.SOLUTION: There are provided a polyurethane foam by foaming polyether polyol and having (A) elongation percentage of 150 to 500%, (B) elasticity in a boll release test of 25 to 60%, (C) surface hardness of 10 to 50 kPa, a manufacturing method therefor, a cup for clothing using the same and clothing having a cup part.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a polyurethane foam, a method for producing the same, a garment cup using the same, and a garment having a cup portion. In particular, the present invention relates to a polyurethane foam having greatly improved stretchability, elasticity and surface hardness, a method for producing the same, and a garment having a cup and a cup portion close to the touch of human skin using the polyurethane foam.

Polyurethane foams are used for cushioning materials such as furniture, bedding and automobile seats depending on their elasticity. In addition, polyurethane foam is known to be used for clothing having a cup portion such as a pad of a brassiere because it has a high degree of freedom in shape and can be applied to various designs.
For example, Patent Document 1 describes that an external wire brassiere can be used to reduce pressure on the skin by using a low-resilience urethane foam having a delayed elastic recovery performance as a cup pad material. Further, for example, Patent Document 2 describes a flexible polyurethane foam using polyether polyol as a raw material, and this flexible polyurethane foam can be used for a brassiere pad.

JP 2003-193304 A Special table 2012-509368 gazette

  However, the low-resilience urethane foam described in Patent Document 1 is intended to absorb and disperse the pressure of the wire and relieve contact with the body, and the tactile sensation of the cup portion has not been studied. There's a problem. Moreover, since the flexible polyurethane foam described in Patent Document 2 has a low falling ball rebound resilience, there is a problem that even if it is used for a brassiere pad, it does not provide a human skin feel.

  The present invention has been made in view of the above-mentioned problems, and is close to the touch of a polyurethane foam and a method for producing the same, and a human skin using the polyurethane foam having greatly improved stretchability, elasticity and surface hardness. It is an object of the present invention to provide a clothing having a clothing cup and a cup portion.

  As a result of intensive studies to achieve the above object, the present inventors have adjusted the balance of the elongation rate, elastic modulus and surface hardness of the polyurethane foam, and devised various processes during the production of the foam. By doing so, it is possible to obtain a polyurethane foam having greatly improved stretchability, elasticity and surface hardness, a method for producing the same, and a garment having a garment cup and a cup portion close to the touch of human skin using the same. As a result, they have reached the present invention.

That is, the present invention relates to a polyurethane foam obtained by foaming polyether polyol and having the following characteristics.
(A) Elongation rate is 150-500%
(B) Elasticity of ball flip test is 25-60%
(C) Surface hardness of 10-50 kPa

  The present invention also relates to a method for producing a polyurethane foam obtained by foaming a polyether polyol, the step of introducing a raw material containing the polyether polyol into a foaming container, and the inside of the foaming container at 15 to 30 ° C. A step of adding an additive containing a catalyst and a foam stabilizer, a step of stirring and foaming the raw material at 4000 to 8000 rpm, and a step of curing the foamed raw material over 20 hours. It is related with the manufacturing method of the polyurethane foam characterized by providing.

The present invention also relates to a clothing cup using a polyurethane foam, wherein the thickest portion of the polyurethane foam in the clothing cup has the following characteristics.
(A) Work of compression (WC value) is 4 to 20 gf · cm / cm ²
(B) Hardness at 40% compression is 1 to 40 kPa

  Furthermore, this invention relates to the clothing which has a cup part characterized by using the said cup for clothing.

  As described above, according to the present invention, a polyurethane foam having greatly improved stretchability, elasticity, and surface hardness, a method for producing the same, and a clothing cup and cup close to the touch of human skin using the same. A clothing having a part can be provided.

It is the perspective view which showed the brassiere cup used in Experimental example 2. FIG. It is sectional drawing along the A-A 'line | wire in FIG.

[Polyurethane foam]
(A) Elongation rate of the polyurethane foam of the present invention is 150 to 500%, more preferably 250 to 450%, and particularly preferably 350 to 400%. If the elongation is less than 150%, when the cup part of the garment is manufactured, the attachment of the cup part tends to deteriorate, which is not preferable. Moreover, when elongation rate is larger than 500%, there exists a tendency for the function as a cup part to fall, and it is unpreferable. The elongation can be measured based on ISO 1798, 2008.

  Moreover, the elastic modulus of the (B) ball flip test of the polyurethane foam of the present invention is 25 to 60%, more preferably 30 to 55%, and particularly preferably 40 to 50%. Even if the elastic modulus is smaller than 25% or larger than 60%, it is not preferable because the haptic feeling of human skin is not produced when the cup part of clothing is manufactured. The elastic modulus can be measured based on ISO 1798, 2008.

  Moreover, (C) surface hardness of the polyurethane foam of this invention is 10-50 kPa, 20-40 kPa is more preferable, 25-35 kPa is especially preferable. When the surface hardness is less than 10 kPa, the function as the cup part tends to be lowered when the cup part of clothing is manufactured, which is not preferable. Moreover, when surface hardness is larger than 50 kPa, there exists a tendency for the attachment comfort of a cup part to worsen and it is unpreferable. The surface hardness can be measured based on ISO 1798, 2008.

[Production method of polyurethane foam]
The polyurethane foam of the present invention can be produced by mixing, stirring and foaming a polyether polyol, a polyisocyanate, and various other additives as required. Specifically, (1) a step of introducing a raw material containing polyether polyol into a foaming container, (2) a step of bringing the inside of the foaming container to 15 to 30 ° C., and (4) a catalyst and a foam stabilizer A step of adding an additive containing, (5) a step of stirring the raw material at 4000 to 8000 rpm and foaming, and (6) a step of curing the foamed raw material over 20 hours or more. It can be manufactured by a method. Moreover, it is preferable to provide the process of (3) introduce | transducing nitrogen gas into this foaming container between a process (2) and a process (4).

(1) Step of introducing raw material containing polyether polyol into foaming container In the present invention, examples of the polyether polyol used as a raw material for polyurethane foam include alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.). And / or obtained by polymerizing or copolymerizing a heterocyclic ether (such as tetrahydrofuran), specifically, polyethylene glycol, polypropylene glycol, polyethylene glycol-polytetramethylene glycol (block or random), polytetramethylene Examples include ether glycol and polyhexamethylene glycol. These polyether polyols can be used singly or in combination of two or more, but it is particularly preferable to use polypropylene glycol alone.

  The number average molecular weight of the polyether polyol is preferably 6,000 to 10,000, and more preferably 7,000 to 9000. By increasing the number average molecular weight, the softness of the polyurethane foam can be improved.

  Further, the degree of unsaturation of the polyether polyol is preferably 0.001 to 0.01 mmol / g, and more preferably 0.003 to 0.007 mmol / g. By reducing the degree of unsaturation, the softness of the polyurethane foam can be improved.

  In the present invention, as the polyisocyanate used as a raw material for the polyurethane foam, any of the polyisocyanates conventionally used for producing polyurethane can be used, and is not particularly limited. For example, preferred are toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy -1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4′-methylenebis (phenylene isocyanate) (MDI), durylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, Examples include aromatic diisocyanates such as benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4′-diisocyanate dibenzyl. Of these, toluene-2,4-diisocyanate is particularly preferable.

  The polyisocyanate is preferably added in a range of 0.02 to 1.0% with respect to the total amount of raw materials. Usually, when producing polyurethane foam, polyisocyanate is generally added in an amount of 3.0% or more of the total amount of raw materials. However, if the amount of polyisocyanate used is too large, the foamed foam becomes hard. End up. In the present invention, the foamed foam can be kept in a soft state by making the polyisocyanate used in a range of 0.02 to 1.0% and less than the generally used amount.

(2) The process which makes the inside of the foaming container 15-30 degreeC The hardness of a polyurethane foam can be lowered | hung by making the inside of the foaming container after raw material injection into a low temperature state of 15-30 degreeC. As a low temperature state, 20-25 degreeC is preferable and 23-25 degreeC is more preferable. In the present invention, it is more preferable that the temperature is not only low but also a constant temperature state, and it is particularly preferable that the temperature is kept at 24 ° C. ± 1 ° C. The maintenance time is preferably 7 to 9 hours, more preferably 8 to 9 hours.

(3) Step of introducing nitrogen gas into the foaming container In the present invention, the step of introducing nitrogen gas may affect the improvement of the flexibility of the polyurethane foam. 2) It is preferable to provide a step of introducing nitrogen gas after the step. In the process of manufacturing polyurethane foam, the temperature of air varies depending on time and environment, but by introducing nitrogen gas, the temperature condition of foaming can be kept constant, even if the foaming start time and location are different, as much as possible There can be no fluctuation of softness. As an example, a polyurethane foam with no nitrogen gas (A) having an elongation of 208.4%, (B) an elastic modulus of a ball flip test of 30% or more, and (C) a surface hardness of 50 ± 5 kPa is produced. When nitrogen gas is introduced under the conditions, (A) Elongation rate 382.05%, (B) Elastic modulus 48% of ball flip test, (C) Surface hardness 20 ± 5 kPa to produce a polyurethane foam It has been confirmed that
The introduction of nitrogen gas is preferably performed at a pressure of 1 to 3 MPa, and 10 to 30% of the foaming container is preferably replaced.

(4) Step of adding an additive containing a catalyst and a foam stabilizer In the present invention, various additives such as a catalyst and a foam stabilizer can be added. By adding various additives and promoting the foaming of the raw material sufficiently uniformly, abnormalities in density and hardness generated in a part of the polyurethane foam can be reduced. Other additives that can be used in the present invention include softeners, brighteners, crosslinking agents, flame retardants, pigments, ultraviolet absorbers, antioxidants (antioxidants), and the like. These additives can be used in an amount that does not impair the object of the present invention.

<Catalyst>
The catalyst is not particularly limited as long as it is a catalyst that is usually used in the production of polyurethane foam. For example, triethylenediamine, triethylamine, tripropylamine, triisopnopalamine, tributylamine, trioctylamine, Hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, trimethylaminoethylethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, diethylenetriamine, N, N, N′-trimethyl-2-hydroxyethylpropylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ′ -Tetramethylbuta Diamine, N, N, N′N′-tetramethyl-1,3-butanediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, bis- (2-dimethylaminoethyl) ether, N, Formate and other salts of N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N, N ′, N′N ″ -pentamethyldiethylenetriamine, stanaoctate, dibutyltin diacetate, dibutyltin dilaurate Organic tin compounds such as di (2-ethylhexanoic acid) tin (II) can be used.

  Moreover, a catalyst may be used individually by 1 type, or may use 2 or more types together. The amount of the catalyst used may be a necessary amount corresponding to the target curing time, and is preferably 0.01 to 10.0 parts by weight, more preferably 100 parts by weight of the total polyether polyol used as a raw material. Is 0.05 to 5.0 parts by weight, more preferably 0.1 to 4.0 parts by weight.

  When a hydrolyzable compound such as an organic tin compound is used as a catalyst, the water component and the organic tin catalyst component are separated from each other and mixed with a mixing head of a foaming machine in order to avoid contact with water. It is preferable.

<Foam stabilizer>
There is no restriction | limiting in particular as a foam stabilizer, A conventionally well-known foam stabilizer can be used, For example, a silicone type foam stabilizer, a fluorine-containing compound type foam stabilizer, a well-known surfactant, etc. can be mentioned. In the present invention, it is preferable to use an organosilicon surfactant.

  A foam stabilizer may be used individually by 1 type, or may use 2 or more types together. The amount of the foam stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total polyether polyol used as a raw material.

<Softener>
As the softening agent, a mixture of polyether, water, propylene glycol, dipropylene glycol and N, N-dimethylcyclohexylamine can be preferably used. By using a softening agent, the usage-amount of polyisocyanate can be reduced rather than usual and the hardness of a polyurethane foam can be reduced.

(5) Step of stirring and foaming the raw material at 4000 to 8000 rpm In the present invention, the raw material mixed with the above additives is stirred at 4000 to 8000 rpm, more preferably stirring at 5000 to 8000 rpm. 7000 rpm is more preferable. By stirring the raw material at a high speed, a fine structure (bubbles) can be made and the softness of the polyurethane foam can be improved. When the stirring speed is slower than 4000 rpm, the structure (bubbles) is rough and the polyurethane foam becomes hard, which is not preferable. The stirring time is preferably 1 to 5 minutes, more preferably 1 to 2 minutes.

(6) Step of curing the raw material after foaming for 20 hours or more The softness of the polyurethane foam obtained from the raw material after foaming varies depending on the difference in curing time. In the present invention, curing is preferably performed over 20 hours, more preferably 40 to 100 hours, and particularly preferably 45 to 60 hours. By curing for 20 hours or longer, the foamed raw material can be completely chemically reacted. In addition, the quality of each lot can be stabilized. In the production of the polyurethane foam of the present invention, since the raw material after foaming is completely chemically reacted, a longer curing time than usual is required.

[Clothing cup]
The cup for clothing according to the present invention can be suitably manufactured by molding a polyurethane foam by hot pressing using a desired mold.
When the polyurethane foam of this invention is used as a polyurethane foam, 160-250 degreeC is preferable and the press temperature in hot press molding has more preferable 180-200 degreeC. The pressing pressure is preferably 2 to 6 MPa, and more preferably 3.5 to 4.5 MPa. The pressing time is preferably 60 to 120 seconds, and preferably 80 to 100 seconds. By hot press molding under the above conditions, a clothing cup close to the feel of human skin can be produced.

  In the present invention, a handy compression tester (KES-G5) manufactured by Kato Tech Co., Ltd., which has been conventionally known as an apparatus for evaluating the texture of a fabric, is used as an indicator of whether a clothing cup is close to the touch of human skin. It can be used to measure the compression characteristics and hardness of clothing cups. Further, in the clothing cup according to the present invention, the thickest part of the polyurethane foam in the clothing cup indicates a portion having the thickest thickness in the normal direction. For example, in the case of a brassiere cup, the outermost portion of the cup Located in one of the lower halves. The outer lower half of the cup is the part that can lift the chest up and move it to the inside, and at the same time, it is also the part that most affects the feel of the cup. Therefore, in the present invention, the physical properties of the polyurethane foam in the cup for clothing are measured around the thickest part, and if necessary, the compression characteristics of each part such as the thinnest part where the thickness in the normal direction is the thinnest And hardness was measured. Here, the thickness of the thickest part of the polyurethane foam is not particularly limited, but is usually preferably within a range of 1 to 30 mm, and particularly preferably within a range of 10 to 20 mm. Further, the thickness of the thinnest part of the polyurethane foam is not particularly limited, but is usually preferably within a range of 1 to 10 mm, and particularly preferably within a range of 1 to 6 mm. In addition, the thickest part and the thinnest part of the polyurethane foam referred to in the present invention are areas inside the margin of the peripheral edge of the clothing cup, and mean each part in the area functioning as a cup.

  In the clothing cup according to the present invention, the compression hardness (LC value) of the thickest part of the polyurethane foam in the clothing cup is preferably 0.83 to 1.20, and 0.85 to 1.15 is More preferred is 0.90 to 1.10. The LC value indicates compressibility with a small force, and the larger the value, the harder the compression. When the LC value is too small, it becomes easy to compress (easy to be crushed) in the initial stage of compression, and is not suitable for a cup for clothing.

Moreover, the compression work (WC value) of the thickest part of the polyurethane foam in the clothing cup is 4 to 20 gf · cm / cm ² , preferably 5 to 17 gf · cm / cm ² , and 6 to 14 gf · cm ^2. / Cm ² is more preferable. The WC value indicates the work of compression, and the larger the value, the softer in the thickness direction and the easier it is to compress.

  Moreover, it is preferable that the compression recovery property (RC value) of the thickest part of the polyurethane foam in a clothing cup is 55 to 80%, and more preferably 57 to 75%. The larger the RC value, the better the recoverability.

  Moreover, the hardness at the time of 40% compression of the thickest part of the polyurethane foam in a clothing cup is 1-40 kPa, It is preferable that it is 3-35 kPa, and it is more preferable that it is 5-30 kPa. Furthermore, the hardness at 40% compression of the thinnest portion of the polyurethane foam in the clothing cup is preferably 40 to 110 kPa, and more preferably 45 to 100 kPa. In addition, if the difference between the hardness of the thickest part and the hardness of the thinnest part of the polyurethane foam in the garment cup is too large, it affects the comfort of the garment having the cup part. It is preferable that

[Clothing with cup part]
In the present invention, specific examples of the clothing having a cup portion include a brassiere, a camisole with a cup, a swimsuit, a leotard, and a hip pad. The cup part obtained by this invention is close to the touch of human skin, and can be applied to various aspects.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, these do not limit the objective of this invention. First, the measurement methods used in the examples are shown below.

(Elongation Elongation)
Based on ISO 1798 and 2008, the sample was sandwiched between dedicated elongation measuring machines, the sample was stretched at 200 mm / min, and the maximum elongation immediately before the sample was measured was measured.

(Elastic modulus Rebound)
Based on ISO 1798, 2008, the ball was applied to the urethane surface and the elasticity of the urethane against the ball was measured.

(Surface hardness Hardness)
Based on ISO 1798, 2008, the sample was placed in a dedicated measuring instrument (bag-shaped), compressed at 200 mm / min, and measured by checking the measured display value when the sample height reached 40% of the normal state. .

(Compression characteristics)
A KES-G5 handy compression tester (manufactured by Kato Tech Co., Ltd.) was used, and measurement was performed under the following conditions.
Pressure plate: 2 cm ² (circular, standard)
Compression speed: 0.05 cm / sec
Compressive load: 50 gf / cm ²
Measurement sensitivity: SENS 2
Measurement control: FORCE
Number of measurements: 3 times (results are average values)
Measurement items: LC (linearity of compression load-compression strain curve), WC (compression work), RC (compression resilience), T ₀ (thickness when pressure is 0.5 gf / cm ² ), T _M (pressure 50 gf) / Thickness at cm ² )

(Hardness test)
A KES-G5 handy compression tester (manufactured by Kato Tech Co., Ltd.) was used, and measurement was performed under the following conditions.
Measurement method: Calculated from the maximum compression load of the 4th time when the compression distance is repeatedly compressed 4 times under the following conditions. Friction size: 2 cm ² (circular, standard)
Compression speed: 0.1 cm / sec
Compression distance: Calculated by 60% of the T ₀ value obtained from the compression characteristic test so that the thickness at the time of compression is 40%. Measurement sensitivity: SENS 10
Measurement control: DEF
Number of measurements: 3 times (results are average values)

(Experimental Example 1: Production of polyurethane foam)
(Example 1)
Polypropylene glycol (manufactured by Dow Chemical Company 5603, molecular weight: 8000, unsaturation: 0.005 mmol / g) 100 kg, toluene-2,4-diisocyanate 30 g is put in the tank, and the temperature in the tank is 24 (± 1) ° C. The raw material was kept in the tank until stable. Next, nitrogen gas was injected at a pressure of 2 MPa to replace 20% of the foaming container and stored for 8 hours. Then, 1.8 kg of a foam stabilizer (surfactant of organosilicon compound manufactured by Momentive) was used as an additive. , 0.1 kg of low-volatile amine (A230 manufactured by Dow Chemical Company), 0.14 kg of catalyst (D-19 manufactured by Momentive), 2 kg of softening agent (manufactured by APCI), 0.08 kg of whitening agent (manufactured by APCI) Antioxidant (manufactured by APCI) (0.08 kg) was added, and the polyurethane foam was foamed by high-speed stirring at 6000 r / min for 1 minute and 30 seconds. After foaming, it was cured over 48 hours to obtain a polyurethane foam. The resulting polyurethane foam was measured for elongation, elastic modulus, and surface hardness, and the results are shown in Table 1.

(Example 2)
100 kg of polypropylene glycol (containing 80% by weight of 5603 manufactured by Dow Chemical Company and 20% by weight of 2045 manufactured by Shanghai Takahashi Petrochemical Co., Ltd.) and 30 g of toluene-2,4-diisocyanate are placed in a tank, and the temperature in the tank is 20 to 24 ° C. It was confirmed that. Next, as an additive, a foam stabilizer (surfactant of organosilicon compound manufactured by Momentive) 1.3 kg, an additive (A33 manufactured by APCI) 0.14 kg, a catalyst (P-9 manufactured by Momentive) 0.02 kg , 0.15 kg of whitening agent (manufactured by APCI) and 0.15 kg of antioxidant (manufactured by APCI) were added, and the polyurethane foam was foamed by stirring at 4000 r / min for 1 minute 30 seconds. It was. After foaming, it was cured over 24 hours to obtain a polyurethane foam. The resulting polyurethane foam was measured for elongation, elastic modulus, and surface hardness, and the results are shown in Table 1.

(Example 3)
100 kg of polypropylene glycol (containing 20 wt% 5603 manufactured by Dow Chemical Company and 80 wt% 2045 manufactured by Shanghai Takahashi Petrochemical Co., Ltd.) and 35 g of toluene-2,4-diisocyanate are placed in a tank, and the temperature in the tank is 20-24 ° C. It was confirmed that. Next, as an additive, a foam stabilizer (surfactant of organosilicon compound manufactured by Momentive) 1.3 kg, an additive (A33 manufactured by APCI) 0.14 kg, a catalyst (P-9 manufactured by Momentive) 0.02 kg , 0.15 kg of whitening agent (APCI) and 0.15 kg of antioxidant (APCI) were added, and high speed stirring was performed at 4800 r / min for 1 minute 30 seconds to foam the polyurethane foam. It was. After foaming, it was cured over 24 hours to obtain a polyurethane foam. The resulting polyurethane foam was measured for elongation, elastic modulus, and surface hardness, and the results are shown in Table 1.

Example 4
100 kg of polypropylene glycol (5603 manufactured by Dow Chemical Company) and 30 g of toluene-2,4-diisocyanate were placed in the tank, and the temperature in the tank was confirmed to be 20 to 24 ° C. Next, as an additive, a foam stabilizer (surfactant of organosilicon compound manufactured by Momentive) 1.4 kg, an additive (33 LV manufactured by APCI) 0.13 kg, a catalyst (P-9 manufactured by Momentive) 0.02 kg , 0.15 kg of whitening agent (APCI) and 0.15 kg of antioxidant (APCI) were added, and high speed stirring was performed at 4800 r / min for 1 minute 30 seconds to foam the polyurethane foam. It was. After foaming, it was cured over 24 hours to obtain a polyurethane foam. The resulting polyurethane foam was measured for elongation, elastic modulus, and surface hardness, and the results are shown in Table 1.

(Example 5)
100 kg of polypropylene glycol (containing 20% by weight of 5603 manufactured by Dow Chemical Company and 80% by weight of 2045 manufactured by Shanghai Takahashi Petrochemical Co., Ltd.) and 27 g of toluene-2,4-diisocyanate are placed in a tank, and the temperature in the tank is 20 to 24 ° C. It was confirmed that. Next, as an additive, a foam stabilizer (surfactant of organosilicon compound manufactured by Momentive) 1.4 kg, an additive (33 LV manufactured by APCI) 0.13 kg, a catalyst (P-9 manufactured by Momentive) 0.02 kg , 0.15 kg of whitening agent (APCI) and 0.15 kg of antioxidant (APCI) were added, and high speed stirring was performed at 4800 r / min for 1 minute 30 seconds to foam the polyurethane foam. It was. After foaming, it was cured over 24 hours to obtain a polyurethane foam. The resulting polyurethane foam was measured for elongation, elastic modulus, and surface hardness, and the results are shown in Table 1.

(Comparative Example 1)
100 kg of polypropylene glycol (5603 manufactured by Dow Chemical Company) and 80 g of toluene-2,4-diisocyanate were placed in the tank, and it was confirmed that the temperature in the tank was 20 to 24 ° C. Next, as additives, foam stabilizer (surfactant of organosilicon compound manufactured by Momentive) 1.3 kg, low volatile amine (A230 manufactured by Dow Chemical Company) 0.06 kg, catalyst (P-9 manufactured by Momentive) 0.13 kg, whitening agent (manufactured by APCI) 0.08 kg, antioxidant (manufactured by APCI) 0.1 kg are charged, and polyurethane foam is obtained by high-speed stirring at 4000 r / min for 1 minute 30 seconds. Was foamed. After foaming, it was cured over 24 hours to obtain a polyurethane foam. The resulting polyurethane foam was measured for elongation, elastic modulus, and surface hardness, and the results are shown in Table 1.

(Comparative Example 2)
100 kg of polypropylene glycol (5603 manufactured by Dow Chemical Company) and 60 g of toluene-2,4-diisocyanate were placed in the tank, and it was confirmed that the temperature in the tank was 20 to 24 ° C. Next, as additives, foam stabilizer (surfactant of organosilicon compound manufactured by Momentive) 1.4 kg, low volatile amine (A230 manufactured by Dow Chemical Company) 0.08 kg, catalyst (P-9 manufactured by Momentive) 0.16 kg, whitening agent (manufactured by APCI) 0.08 kg, antioxidant (manufactured by APCI) 0.12 kg, and polyurethane foam by high-speed stirring at 4000 r / min for 1 minute 30 seconds Was foamed. After foaming, it was cured over 24 hours to obtain a polyurethane foam. The resulting polyurethane foam was measured for elongation, elastic modulus, and surface hardness, and the results are shown in Table 1.

(Comparative Example 3)
100 kg of polypropylene glycol (5603 manufactured by Dow Chemical Company) and 40 g of toluene-2,4-diisocyanate were placed in the tank, and it was confirmed that the temperature in the tank was 20 to 24 ° C. Next, nitrogen gas was injected at a pressure of 2 MPa to replace 20% of the foaming container and stored for 8 hours. Then, 1.8 kg of a foam stabilizer (surfactant of organosilicon compound manufactured by Momentive) was used as an additive. , 0.1 kg of low-volatile amine (A230 manufactured by Dow Chemical Company), 0.14 kg of catalyst (D-19 manufactured by Momentive), 2 kg of softening agent (manufactured by APCI), 0.08 kg of whitening agent (manufactured by APCI) Antioxidant (manufactured by APCI) (0.08 kg) was added, and the polyurethane foam was foamed by high-speed stirring at 6000 r / min for 1 minute and 30 seconds. After foaming, it was cured over 48 hours to obtain a polyurethane foam. The resulting polyurethane foam was measured for elongation, elastic modulus, and surface hardness, and the results are shown in Table 1.

(Comparative Example 4)
Polypropylene glycol (5603 manufactured by Dow Chemical Company) and 30 g of toluene-2,4-diisocyanate were placed in the tank, and the temperature in the tank was confirmed to be 20 to 24 ° C. Next, nitrogen gas was injected at a pressure of 2 MPa to replace 20% of the foaming container and stored for 6 hours. Then, 1.6 kg of foam stabilizer (surfactant of organosilicon compound manufactured by Momentive) was used as an additive. 0.13 kg of additives (33 LV manufactured by APCI), 0.13 kg of catalyst (T950 manufactured by Momentive), 0.08 kg of whitening agent (manufactured by APCI), and 0.09 kg of antioxidant (manufactured by APCI) The polyurethane foam was foamed by high-speed stirring at 6000 r / min for 1 minute 30 seconds. After foaming, it was cured over 48 hours to obtain a polyurethane foam. The resulting polyurethane foam was measured for elongation, elastic modulus, and surface hardness, and the results are shown in Table 1.

(Experimental example 2: production of brassiere cup)
Using the polyurethane foam of Experimental Example 1, hot press molding was performed to produce a brassiere cup 1 shown in FIGS. The molding temperature was 190 ° C., the pressure was 4 MPa, and the press time was 90 seconds. In addition, as a conventional brassiere cup having a normal tactile sensation, a brass cup 4014111200 manufactured by Sunworld Co., Ltd. was prepared (Comparative Example 5).
With respect to the brassiere cup 1 and the brassiere cup according to comparative example 5, the sensory test of tactile sensation and attachment feeling was performed. Specifically, 10 adult women in their 20s to 60s were selected and evaluated for the feel when the thickest part of the brassiere cup was touched by hand and the comfort of the brassiere using the brassiere cup. It was. The evaluation method is as shown below, and the evaluation was made with a total score of 40 points. The results are shown in Table 2.

<Tactile sense>
4: Appropriately elastic but soft and has a touch close to human skin (chest).
3: It is moderately elastic and has a touch slightly close to human skin (chest).
2: It is hard to say that the touch is not very elastic and is close to the human skin (chest).
1: Elasticity is not felt and it cannot be said that it is close to human skin (chest).
0: It is hard and does not feel elasticity at all, and cannot be said to be the touch of human skin (chest).
<Comfort>
4: The elongation of the cup portion is good and the feeling of attachment is very good.
3: The cup portion is moderately stretched and is comfortable to wear.
2: The cup portion does not stretch so much, and the comfort is somewhat bad.
1: There is little elongation of a cup part, and attachment feeling is bad.
0: The cup portion does not stretch and the feeling of attachment is very bad.

  Further, the compression characteristics and hardness of the brassiere cup 1 and the brassiere cup according to Comparative Example 5 were measured, and the results are shown in Tables 3 to 6. The measurement position is the thickest part of the polyurethane foam in the brassiere cup (in this example, the part closer to the lower edge than the top part of the cup), and the thinnest part of the polyurethane foam in the brassiere cup (this implementation) In the example, a portion closer to the upper end edge side than the top portion of the cup), and a top portion (top portion) which is the tip of the cup.

From the above, in Examples 1 to 5 where the WC value satisfies ⁴ to ²⁰ fg · cm / cm ² , both the tactile sensation and the feeling of attachment are excellent, and the WC values deviate from ⁴ to ²⁰ fg · cm / cm ^2. Then, it was found that both the tactile sensation and the wearing comfort were inferior.

  As described above, the LC value needs to have a certain height at the thinnest part and the thickest part that adjust the shape of the chest, but at the top part that does not affect the shaping of the chest, Then, it turned out that the lower one is preferable.

From the above, the RC value needs a high value in order to create the feel of human skin, particularly in the thickest part that affects the feel of the cup, but the RC value is low and the thickness T ₀ value is small in the top part. It has been found that it is preferable for obtaining good comfort.

From the above, in Examples 1 to 5 where the hardness of the thickest part satisfies 1 to 40 kPa, the tactile sensation and the feeling of attachment are excellent, and in Comparative Examples 1 to 5 where the hardness of the thickest part deviates from 1 to 40 kPa, It was found that both the tactile sensation and the feeling of attachment were inferior.

Claims (7)

A polyurethane foam obtained by foaming a polyether polyol and having the following characteristics.
(A) Elongation rate is 150-500%
(B) Elasticity of ball flip test is 25-60%
(C) Surface hardness of 10-50 kPa   The polyurethane foam according to claim 1, wherein the polyether polyol has a molecular weight of 6000 to 10,000 and an unsaturation degree of 0.001 to 0.01 mmol / g. A method for producing a polyurethane foam obtained by foaming a polyether polyol,
Introducing a raw material containing polyether polyol into a foaming container;
A step of bringing the inside of the foaming container to 15 to 30 ° C .;
Adding an additive comprising a catalyst and a foam stabilizer;
Stirring the raw material at 4000 to 8000 rpm for foaming;
Curing the raw material after foaming over 20 hours;
A process for producing a polyurethane foam, comprising:   The method for producing a polyurethane foam according to claim 3, further comprising a step of introducing nitrogen gas into the foaming container simultaneously with or after the step of bringing the inside of the foaming container to 15 to 30 ° C. A cup for clothing using polyurethane foam,
A clothing cup, wherein the thickest portion of the polyurethane foam in the clothing cup has the following characteristics.
(A) Work of compression (WC value) is 4 to 20 gf · cm / cm ²
(B) Hardness at 40% compression is 1 to 40 kPa   The cup for clothing according to claim 5, wherein the polyurethane foam is obtained from the polyurethane foam according to claim 1. A clothing having a cup portion, wherein the clothing cup according to claim 5 or 6 is used.

Images