WO2018181843A1

WO2018181843A1 - Urethane synthetic leather, production method for urethane synthetic leather, cosmetic puff, and member provided with synthetic leather

Info

Publication number: WO2018181843A1
Application number: PCT/JP2018/013509
Authority: WO
Inventors: 祐典岩口; 草川　公一
Original assignee: 日本発條株式会社
Priority date: 2017-03-31
Filing date: 2018-03-29
Publication date: 2018-10-04
Also published as: JP2018172822A; CN110461896A; JP6901894B2; CN110461896B

Abstract

Provided are: a urethane synthetic leather composed of a closed-cell foam which is a cured product of a composition that contains a high-molecular-weight polyol having a number average molecular weight of 2,000-12,000, a polyisocyanate, a low-molecular-weight polyol having a molecular weight of 60-300, a catalyst, and a foam stabilizer; a production method therefor; a urethane synthetic leather-provided member obtained by using said urethane synthetic leather; and a cosmetic puff.

Description

Urethane synthetic leather, method for producing urethane synthetic leather, cosmetic puff, and member with synthetic leather

This disclosure relates to urethane synthetic leather, a method for producing urethane synthetic leather, a cosmetic puff, and a member with synthetic leather.

In recent years, urethane synthetic leather has been used for various parts instead of natural leather because of its texture and durability.

As is well known, urethane synthetic leather is produced by the wet extraction method of dimethylformamide (DMF) solution of polyurethane, and it has been pointed out that there are operational and environmental problems such as harmful DMF treatment and post-use treatment. There was a need for improvements.
For example, Patent Document 1 states that “a prepolymer (A) obtained by reacting a diisocyanate compound with a polyol having a molecular weight of 500 to 3000, a crosslinking agent (B) having an average number of hydroxyl groups of 2 to 4 and comprising a polyol (B ) And water (C), a solvent-free polyurethane-urea foam formed by foaming air or an inert gas and then forming into a sheet and curing by heating. Synthetic leather comprising body sheets "is disclosed.

Patent Document 2 discloses a method for producing the following polyurethane foam sheet and synthetic leather having the polyurethane foam sheet as an intermediate layer.
“The diisocyanate compound (A-2) is added to the low molecular weight glycol (A-1) having a molecular weight of 60 to 250, the isocyanate group content is 20 to 25% by weight, the prepolymer and the unreacted free Producing a reaction product (A) containing a diisocyanate compound;
b) In the reaction product (A), a high molecular weight glycol (B-1) having 2 hydroxyl groups having a number average molecular weight of 800 to 3000, and a high molecular weight polyhydroxy compound having 3 hydroxyl groups having a number average molecular weight of 3000 to 8000 ( Mixing the liquid mixture (B) mainly comprising B-2);
c) further mixing an inert gas (C) to produce a mixed composition having an apparent isocyanate group content of 2.0 to 5.0% by weight; and
d) A method for producing a polyurethane foam sheet, comprising the steps of applying the above-mentioned mixed composition on a release film or release paper, heating in a moisture atmosphere, foaming and curing. "
All of these prior arts are solvent-free synthetic leathers, but all involve large amounts of urea bonds due to the reaction of water and isocyanate.

Patent Document 1: Japanese Patent No. 5465660 Patent Document 2: Japanese Patent Laid-Open No. 2014-12820

By the way, the conventional urethane synthetic leather is made of an open cell type urethane foam because it is made by a wet extraction method of a dimethylformamide (DMF) solution of polyurethane polymer. It was characterized by good moisture release due to sweating when applied to clothes. However, since it is open-celled, it has the properties of high permeability of liquids such as cosmetic liquids and high penetration of fine powders. Therefore, the conventional urethane synthetic leather has a problem that once the dirt adheres, the dirt is difficult to remove and the dirt resistance is low.

As a countermeasure for this problem, it is common to coat the surface of urethane synthetic leather with a non-foaming thin film, but the cost increases because of the increased number of processes.
In addition, there is an example in which urethane synthetic leather is composed of non-foamed urethane foam, but since it is non-foamed, there is a problem that the texture is poor, such as high hardness and poor familiarity (feel) to fingers. . Furthermore, the above-mentioned problems cannot be solved because the above-mentioned synthetic leather of the solventless type is essentially aimed at open cells.

Therefore, in view of the above problems, an object of one embodiment of the present disclosure is to provide a urethane synthetic leather excellent in dirt resistance while improving texture at low cost.
Moreover, the subject of 1 aspect of this indication is providing the manufacturing method of the urethane synthetic leather excellent in stain resistance, improving texture at low cost.
Moreover, the subject of 1 aspect of this indication is providing the member with urethane synthetic leather which has urethane synthetic leather excellent in stain resistance, improving texture at low cost.
Another object of one embodiment of the present disclosure is to provide a cosmetic puff having a backing material that is excellent in dirt resistance while enhancing texture at low cost.

The above problem can be solved by the following means.

<1>
A closed-cell type, which is a cured product of a composition comprising a high-molecular polyol having a number average molecular weight of 2000 to 12000, a polyisocyanate, a low-molecular polyol having a molecular weight of 60 to 300, a blowing agent, a catalyst, and a foam stabilizer. Urethane synthetic leather made of foam.
<2>
The urethane synthetic leather according to <1>, wherein the closed cell ratio is 10 to 60%.
<3>
A composition comprising a polymer polyol having a number average molecular weight of 2000 to 12000, a polyisocyanate, a low molecular polyol having a molecular weight of 60 to 300, a blowing agent, a catalyst, and a foam stabilizer is formed on the first continuous web. A coating process for continuously coating and forming a coating film;
A heating step of heating and curing the coating film on the first continuous web to form a closed cell foam;
Of urethane synthetic leather comprising
<4>
After the coating step, before the heating step, a second continuous web is supplied to the coating film on the first continuous web, and the coating film is sandwiched between two continuous webs. Including steps,
The method for producing urethane synthetic leather according to <3>, wherein the heating step is a step of forming the closed cell foam by heating and curing the coating film in a state sandwiched between the two continuous webs. .
<5>
<1> or the member with a urethane synthetic leather which has the urethane synthetic leather as described in <2> as a skin material.
<6>
The member with urethane synthetic leather according to <5>, wherein the urethane synthetic leather is heat-sealed to an adjacent member.
<7>
A cosmetic puff having the urethane synthetic leather according to <1> or claim 2 as a backing material.

According to one embodiment of the present disclosure, it is possible to provide a urethane synthetic leather that is excellent in dirt resistance while improving texture at low cost.
Moreover, according to one aspect of the present disclosure, it is possible to provide a method for producing a urethane synthetic leather that is excellent in dirt resistance while enhancing texture at low cost.
Moreover, according to one aspect of the present disclosure, it is possible to provide a member with a urethane synthetic leather having a urethane synthetic sun leather having excellent dirt resistance while enhancing texture at low cost.
In addition, according to one embodiment of the present disclosure, it is possible to provide a cosmetic puff having a backing material that is excellent in dirt resistance while enhancing texture at low cost.

It is a schematic diagram of an example of the device composition for carrying out the manufacturing method of the synthetic leather concerning this embodiment. It is a schematic sectional drawing which shows an example of the cosmetic puff which concerns on this embodiment. It is a figure which shows the cross-sectional SEM photograph of the synthetic leather of Example 6. FIG. It is a figure which shows the cross-sectional SEM photograph of the synthetic leather of the comparative example 2. It is a figure which shows the SEM photograph of the surface of the synthetic leather of Example 9 produced by the double method. It is a figure which shows the SEM photograph of the back surface of the synthetic leather of Example 9 produced by the double method. It is a figure which shows the SEM photograph of the surface of the synthetic leather of Example 13 produced by the single method. It is a figure which shows the SEM photograph of the back surface of the synthetic leather of Example 13 produced by the single method.

Hereinafter, an embodiment that is an example of the present disclosure will be described.

<Urethane synthetic leather>
The urethane synthetic leather according to this embodiment (hereinafter also referred to as “synthetic leather”) includes a high-molecular polyol having a number average molecular weight of 2000 to 12000, a polyisocyanate, a low-molecular polyol having a molecular weight of 60 to 300, a foaming agent, It consists of a closed-cell type foam which is a hardened | cured material of the composition containing a catalyst and a foam stabilizer.

The synthetic leather according to the present embodiment is made of a foam, so that the hardness is low and the familiarity (feel of touch) to fingers is improved. Further, by making the foam a closed-cell foam, it has a property that the permeability of the liquid and the penetration of the fine powder are low without coating the synthetic leather with a non-foamed thin film.
Therefore, the synthetic leather according to the present embodiment is a urethane synthetic leather that is excellent in dirt resistance while improving texture at low cost.

Hereinafter, the details of the synthetic leather according to this embodiment will be described.

The composition (hereinafter also referred to as “urethane raw material liquid”) for forming the synthetic leather (closed cell foam) according to the present embodiment includes a polymer polyol having a number average molecular weight of 2000 to 12000, a polyisocyanate, A low molecular polyol having a molecular weight of 60 to 300, a foaming agent, a catalyst, and a foam stabilizer. The urethane raw material liquid may contain other additives as necessary.

(Polymer polyol)
Examples of the polymer polyol include polyether-based polyols such as polyoxypropylene polyol (PPG), polyoxyethylene polyol (PEG), a copolymer of PPG and PEG, and polyoxytetramethylene polyol (PTMG).
In addition to polyether polyols, polymer polyols include dicarboxylic acids (adipic acid, sebacic acid, phthalic acid, dimer acid, etc.) and glycols (ethylene glycol, propylene glycol, 1.4-butanediol, 1.6-hexanediol) Polyester polyol (PES), polycaprolactone polyol (PCL), polycarbonate polyol (PCA), (hydrogenated) polybutadiene polyol, (hydrogenated) condensed with 2-methylpropanediol, 3-methylpentanediol, etc. Also known are well-known polymer polyols such as polyisoprene-based polyols.
A high molecular polyol may be used individually by 1 type, and may be used together 2 or more types.

Of these, polyether polyols (particularly PPG and PTMG) are preferred as the polymer polyol from the viewpoint of the feel, durability and cost of synthetic leather. Polyether polyols have the advantage of low viscosity and high handleability.

The number average molecular weight of the high-molecular polyol is 2000 to 12000, but 4000 to 12000 is more preferable in order to produce a “moist feeling” and softness as a hand feeling of the synthetic leather.
Here, the number average molecular weight is defined as the molecular weight obtained from the measured value of the hydroxyl value according to JIS K0070 (1992) and the number of functional groups. The number average molecular weights of other components are measured in the same manner.

-Polyisocyanate-
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, xylene-1,4-diisocyanate, 1,5 -Aromatic diisocyanates such as naphthylene diisocyanate, 1,4-naphthylene diisocyanate, 3,3'-dichloro-4,4'-diphenylmethane diisocyanate; hexamethylene diisocyanate, propylene-1,2 Aliphatic diisocyanates such as diisocyanate and butylene-1,2-diisocyanate; cycloaliphatic diisocyanates such as isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and cyclohexylene diisocyanate Known polyisocyanates such as nat; As, or may be used as a prepolymer.
A polyisocyanate may be used individually by 1 type, and may be used together 2 or more types.

Among these, as the polyisocyanate, diphenylmethane diisocyanate (MDI) -based isocyanate is preferable because of its high reactivity and high productivity.
Examples of MDI isocyanate include crude MDI (cr-MDI), 4.4′-diphenylmethane diisocyanate (4.4′-MDI), 2.4′-MDI, 2.2′-MDI, and carbodiimide modification. MDI, prepolymer modified MDI, etc. are mentioned.

The prepolymer is a prepolymer modified with a terminal NCO group by reacting with an isocyanate such as PDI glycol, PTMG glycol, polycarbonate glycol or the like having a molecular weight of 200 to 1000 as a diol and an MDI, TDI or HDI isocyanate. It is a modified isocyanate. A prepolymer obtained by reacting a small amount of a diol such as ethylene glycol, propylene glycol, 1,4-butanediol, or 1,6-hexanediol can also be applied to these prepolymers. The NCO content of the prepolymer is preferably 2.5 to 30% from the viewpoint of viscosity and strength, and most preferably 5 to 15% from the standpoint of ease of synthesis, handleability and strength.

(Low molecular polyol)
Examples of the low molecular polyol include bifunctional to tetrafunctional polyols.
Examples of the bifunctional polyol include aliphatic diols such as ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, and dodecanediol; cyclohexane Examples thereof include alicyclic diols such as diol and hydrogenated xylylene glycol; aromatic diols such as xylylene glycol; and polyether polyols obtained by addition polymerization of alkylene oxide (ethylene oxide, propylene oxide, etc.) to a divalent alcohol. . The addition polymerization of the plurality of types of alkylene oxides may be random addition polymerization or block addition polymerization.
Examples of the trifunctional polyol include trivalent alcohols having 3 to 10 carbon atoms such as glycerin and trimethylolpropane. Examples of the trifunctional polyol include polyether polyols obtained by addition polymerization of alkylene oxide (ethylene oxide, propylene oxide, etc.) to a trivalent alcohol. The addition polymerization of the plurality of types of alkylene oxides may be random addition polymerization or block addition polymerization.
Examples of the tetrafunctional polyol include polyether polyols obtained by addition polymerization of alkylene oxide to ethylenediamine, pentaerythritol, or the like.
Other examples of the low molecular polyol include ester-based polyols obtained by condensation of adipic acid and short-chain diols such as ethylene glycol and 1.4-butanediol with polyfunctional triols such as glycerin.
A low molecular polyol may be used individually by 1 type, may be used together 2 or more types, and may make it react with polyisocyanate beforehand as a prepolymer.

The molecular weight of the low molecular weight polyol is 60 to 300, and the reaction curability at the time of production, the strength / elongation of the synthetic leather, the hand feeling, and the low temperature characteristics are good. Among these, as the low molecular polyol, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and glycerin are preferable from the viewpoint of the strength and hand feeling of the synthetic leather.

(Foaming agent)
Examples of the foaming agent include water, halogenated alkanes (dichloromethane, monofluorinated trichloromethane, dichloride methane, etc.), low boiling point alkanes (butane, pentane, etc.), liquid carbon dioxide, and the like. Further, foaming by a so-called mechanical flossing method in which an inert gas such as air or nitrogen is agitated with a Oaks mixer or the like and bubbles are entrained in the raw material to be used is also preferable.
A foaming agent may be used individually by 1 type, and may be used together 2 or more types.
Among these, as the foaming agent, water is preferable from the viewpoints of handleability and expansion ratio.
When water is used as a blowing agent, the amount of closed cells decreases when the number of parts used is large. % Is preferable, and more preferably 0 to 0.2%. By reducing the number of water added in this way, urea bonds (urea bonds) in the synthetic leather are reduced, and the “moist feeling” of the hand feeling is not deteriorated by the urea bonds.
In the case where the number of water parts is very small, it is preferable to use an alkali halide, liquid carbon dioxide, mechanical floss method or the like alone or as a foaming agent to be used alone.

(catalyst)
Examples of the catalyst include an organometallic compound catalyst and an amine catalyst.
Examples of the organometallic compound-based catalysts include tin-based, titanium-based, bismuth-based, nickel-based and other organometallic catalysts, such as organotin compounds such as stannous octylate and dibutyltin dilaurate.
As the amine-based catalyst, tertiary amines are preferable, and amine-based catalysts such as monoamines, diamines, triamines, cyclic amines, alcohol amines, ether amines, and the like, for example, triethylenediamine, triethylamine, n -Methylmorpholine, n-ethylformoline, N, N, N ', N'-tetramethylbutanediamine and the like.
A catalyst may be used individually by 1 type and may be used together 2 or more types.

(Foam stabilizer)
Examples of the foam stabilizer include silicone compounds, fluorine compounds, and the like, which are representative examples of copolymers of polydimethylsiloxane and polyoxyalkylene polyol. One type of foam stabilizer may be used alone, or two or more types may be used in combination.

(Other additives)
Other additives include known additives such as flame retardants, antioxidants, colorants, ultraviolet absorbers, inorganic fillers such as calcium carbonate, and the like.

≪Content of each component in urethane raw material liquid≫
The content of the high molecular polyol is preferably 40 to 80% by weight, more preferably 40 to 70% by weight, based on the main raw material (high molecular polyol, low molecular polyol, isocyanate) of the urethane raw material liquid.
It is preferable that the content of the polymer polyol is in the above range because the resulting synthetic leather has good softness and feeling (moist feeling).

The content of the polyisocyanate is preferably 15 to 30% by weight, more preferably 20 to 29% by weight, based on the main raw material component of the urethane raw material liquid.
When the content of the polyisocyanate is within the above range, the synthetic leather has a high strength, a good hand feeling, and a good anti-absorbing property for skin lotion.

The content of the low molecular polyol is preferably 2 to 20% by weight, more preferably 4 to 10% by weight, based on the main raw material component of the urethane raw material liquid.
When the content of the low-molecular polyol is in the above range, the obtained synthetic leather is excellent in strength and elongation, and the touch feeling is moist, which is preferable.

The closed cell ratio can be controlled by the reactivity of the composition. For example, when the reaction between polyol and isocyanate proceeds fast, and the reaction between water and isocyanate delays, the closed cell ratio increases. On the other hand, when the water reactivity is fast, the gas generation rate is relatively high and open cells tend to be formed. . Therefore, the number of water parts has a great influence on the closed cell ratio, and less water is better to increase the closed cell ratio. However, if there is less water, the urea bond will decrease and the hardness and strength will decrease accordingly. When the amount is reduced, it is preferable to maintain the polar group concentration and the hardness by increasing the number of added low-molecular polyols. The low molecular polyol has an advantage that the “moist feeling” is hardly impaired even when the number of added parts is large. The foam stabilizer and catalyst used have a great effect on controlling the closed cell ratio. For example, if an amine catalyst that promotes the reaction between water and isocyanate is used, the closed cell ratio tends to decrease. Conversely, if a catalyst that promotes the reaction between polyol and isocyanate is used, such as an organotin catalyst, the closed cell ratio is It tends to increase. If a foam stabilizer that is difficult to dissolve in the polyol is used, it tends to become open cells, and in the opposite case, it tends to become closed cells.
Here, from the viewpoint of increasing the closed cell ratio and improving the stain resistance, the weight ratio of the low molecular polyol to the water as the foaming agent (low molecular polyol / foaming agent) is preferably 200 to 10, and preferably 100 to 20 More preferred.

(Characteristics of synthetic leather)
The closed cell type foam according to the present embodiment refers to a closed cell ratio of 5% or more, preferably 5 to 75%, more preferably 10 to 60%.
By setting the closed cell ratio of the synthetic leather to the above range, the permeability of the liquid and the penetration of the fine powder are lowered, and the stain resistance is easily improved. If the closed cell ratio exceeds 75%, shrinkage and wrinkles are likely to occur when the product is manufactured, but if it is 60% or less, the reaction curing is completed and the product is difficult to shrink to release the web. Therefore, productivity is good and preferable.

The closed cell ratio of the synthetic leather is measured according to the Beckman method (air comparison specific gravity measurement method: ASTM D 2856-70). Specifically, a sample having a size of 20 mm × 20 mm × thickness mm was cut out from the measurement object, and the volume (cm ³ ) of the obtained sample was measured using BECKMAN-TOSHIBA, LTD. Measured with an “air comparison type hydrometer 930 type” (pressurization method). The measured volume of the sample is taken as the measurement value. On the other hand, the volume was measured in a state where the sample was not put into the “air comparison type hydrometer 930 type”, and a background measurement value (blank value) was obtained. And the closed cell rate (closed cell rate per space volume) Vc (%) is calculated by the following formula.
Formula: Vc (%) = [(ΔV−E) / (V−E)] × 100
ΔV: {(measured value) − (blank value)} (cm ³ )
V: Apparent volume of sample by submersion method (cm ³ )
E: Volume of resin (polyurethane) (cm ³ ) = {(weight of sample) / (true specific gravity of sample)}

The C hardness of the synthetic leather according to this embodiment is preferably 15 to 60, and more preferably 25 to 45.
When the C hardness of the synthetic leather is within the above range, the hardness is low, the hand feeling is “moist”, and the texture is enhanced.

The C hardness of the synthetic leather is determined by measuring the C hardness of any five points of the test piece according to the physical test method for thermosetting polyurethane elastomer moldings described in JIS K 7312 (1996), and obtaining the average value.

Apparent density of the synthetic leather according to the present embodiment is preferably 200 ~ 800kg / ^{m 3,} more preferably 400 ~ 600kg / ^{m 3.}
When the apparent density of the synthetic leather is within the above range, the hardness is low, the hand feeling is improved, and the texture is enhanced.

The apparent density of the synthetic leather is measured by the following method.
First, a sample to be measured (approximate size: length 100 mm × width 100 mm × thickness measurement value) is prepared in an environment of 23 ± 3 ° C. Next, the weight of the sample is measured with a precision balance with an accuracy of 1/100 g. Next, using a digital gauge, the thickness of the sample is measured at nine locations with an accuracy of 1/100 mm using a probe having a diameter of 10 mm and a load of about 0.6 N, and an average value is obtained. The vertical dimension and the horizontal dimension of the sample are measured at three locations using a digital caliper, and the average is obtained. The volume of the sample is calculated from the obtained dimensions. Then, the apparent density is obtained by the formula: apparent density = weight / volume.

The tensile strength of the synthetic leather according to this embodiment is preferably 1.0 MPa or more, and more preferably 2.0 MPa or more.
If the tensile strength of the synthetic leather is higher than the above, the durability is enhanced.

The tensile strength of synthetic leather is measured according to JIS K 6400-5 (2012). In the measurement, the object to be measured is punched into a dumbbell No. 2, a sample is obtained, and the thickness is measured. The obtained sample is subjected to a speed of 300 mm / min by “Tensilon Universal Material Testing Machine UCT-500” manufactured by Oriontec Co., Ltd. And the intensity | strength at the time of a sample fracture | rupture is measured.

In addition, each said characteristic of the synthetic leather which concerns on this embodiment is obtained by adjusting the kind and quantity of the component for obtaining synthetic leather, and manufacturing conditions.

<Method for producing urethane synthetic leather>
There is no restriction | limiting in particular in the manufacturing method of the urethane synthetic leather which concerns on this embodiment. For example, the following method is mentioned as a manufacturing method of the synthetic leather which concerns on this embodiment.
A coating process for forming a coating film by continuously applying a urethane raw material liquid onto the first continuous web (band-shaped body), and heating and curing the coating film on the first continuous web to form a closed cell foam. A method for producing urethane synthetic leather comprising a heating step for forming a body. Synthetic leather made by this method has a different surface condition on the continuous web side (lower surface) on the opposite side (upper surface), and the upper surface has high density and unevenness, and the hand feeling is “grainy”. In general, the bottom surface is the bottom surface.

On the other hand, before the post-heating step after the coating process, the second continuous web (band-shaped body) is supplied to the coating film on the first continuous web (band-shaped body), and the coating film is sandwiched between the two continuous webs. The heating step includes two continuous web supply steps, and the step of heating and curing the coating film in a state sandwiched between two continuous webs to form a closed cell foam has many merits.
In particular, when the urethane raw material coating film is heated and cured in a state of being sandwiched between two releasable continuous webs to form a closed cell foam, the foam is sandwiched between two continuous webs. Therefore, since there is no scattering of the foaming agent, the expansion ratio increases (becomes low density), and a high closed cell foam (that is, synthetic leather) can be obtained with a small number of water parts, so that the soil resistance is good and the urea bond. Because there is less, the touch feels moist. A major feature is that a thin and smooth skin layer can be formed on both surfaces, and it is easy to obtain a closed-cell foam (that is, synthetic leather) that is well-fitted to fingers (moist touch) and has a high texture.

Hereinafter, a method for producing the synthetic leather of this aspect will be described with reference to the drawings.

FIG. 1 is a schematic diagram illustrating an example of a device configuration for carrying out the synthetic leather manufacturing method according to the present embodiment.
As shown in FIG. 1, the synthetic leather manufacturing apparatus 100 includes a first web roll 14 that sends out a first continuous web 14A, a coating apparatus 12 that applies a urethane raw material liquid onto the first continuous web 14A, A large-diameter roller 18 that guides the first continuous web 14A fed from one web roll 14 directly below the coating device 12, a second web roll 16 that feeds the second continuous web 16A, and a second continuous web 16A The guide roller 20 guided onto the coating film 10 on one continuous web 14A and the coating film 10 of the urethane raw material liquid sandwiched between the two

continuous webs

14A and 16A are guided to the heating device 22 and by the heating device 22 It was peeled off from the foamed urethane sheet 30 and the

transport rollers

28A and 28B for transporting the heated and cured foam (hereinafter referred to as “foamed urethane sheet”) 30. Continuous web 14A, the recovery roller 24, 26 to collect roll up 16A, and a.

(Coating process)
First, the urethane raw material liquid in which the raw material components are mixed and stirred is continuously applied onto the first continuous web 14 </ b> A to form the coating film 10.

For example, a resin film or a paper body is preferably used as the first continuous web 14.
The resin film is not particularly limited as long as it is not deformed by the application of the urethane raw material liquid and heating in the heating step, but from the viewpoint of resistance to the urethane raw material liquid, heat resistance, etc., a film of polyester, polypropylene, polymethylpentene, etc. Is preferred.
If necessary, the surface of the resin film may be subjected to corona discharge treatment, plasma treatment or the like to improve the adhesion to the urethane foam sheet.

Moreover, after manufacturing a foaming urethane sheet, you may use the resin film in which the surface in which the coating film of a urethane raw material liquid forms a mold release property so that a resin film may be peeled easily.
As a resin film having releasability, a method of applying a silicone release agent on one side of a resin film, a method of using a resin film having releasability such as polypropylene resin or polymethylpentene resin as it is, and having releasability There is a method of laminating a resin film on a polyester film or the like. Also, the surface of the release film or paper release paper can be matted or textured to enhance the design and texture.

When a paper body is used as the first continuous web 14A, a glassine paper or a high-quality paper whose surface is coated with polyethylene or polypropylene, or a resin coated with a silicone release agent is used.
As the first continuous web 14A used in the present disclosure, a resin film or a releasable resin film is preferable because the solidification speed of the foam is high and the thickness accuracy is high.

It is preferable to use a die coater, a roll coater, a knife coater, a comma coater, or the like as the coating device 12 for coating the urethane raw material liquid on the first continuous web 14A. A method in which a urethane raw material liquid is stirred with a mixing device, discharged from a discharge nozzle with a traverse (repetitive coating) device and thinly coated with a roll coater or a knife coater, or a urethane raw material liquid is introduced from a discharge nozzle into a die coater. A method of coating on top is also preferred.

The thickness of the coating film 10 may be determined according to the intended use of the foam (synthetic leather), but is preferably 0.1 to 2 mm from the viewpoint of the foaming ratio of the foamed urethane sheet and the desired thickness. .

(Second continuous web supply process)
The second continuous web 16A is supplied to the coating film 10 on the first continuous web 14A, and the coating film 10 is sandwiched between the two

continuous webs

14A and 16A.
As the second continuous web 16A, the resin film or paper exemplified in the description of the first continuous web 14A can be used. In addition, at least one continuous web of the first continuous web 14 </ b> A and the second continuous web 16 </ b> A is in contact with the coating film 10 from the viewpoint of easily peeling the continuous web on at least one side of the urethane foam sheet 30 after the heating step. It is preferable to use a continuous web whose surface has releasability.

The second continuous web 16A is continuously unwound from the second web roll 16 around which the second continuous web 16A is wound, and is placed on the coating film 10 on the first continuous web 14A. As a result, the coating film 10 is sandwiched between the two

continuous webs

14A and 16A.

In addition, although the apparatus shown in FIG. 1 is comprised so that the coating film 10 may be pinched | interposed by two

continuous webs

14A and 16A, after forming a coating film on the 1st continuous web 14A, the 2nd continuous web You may advance to the next heating process, without covering 16A.

(Heating process)
The coating film 10 is conveyed into the heating device 22 while being sandwiched between two

continuous webs

14A and 16A and cured by heating.
The heating temperature for curing is preferably 80 to 120 ° C., and curing is preferably performed at a temperature within this range in 5 to 20 minutes.
As the heating device 22, an infrared heater, an electric heater, a gas combustion furnace, or the like can be used.

(Peeling process)
The foamed urethane sheet 30 foamed and cured by the heating step may be wound while the

continuous webs

14A and 16A are in close contact with the foamed urethane sheet 30, or when the

continuous webs

14A and 16A are releasable webs, FIG. The release web is peeled off from the foamed urethane sheet 30 as shown in FIG. The collected

continuous webs

14A and 16A can be reused as the supply rolls 14 and 16.

Through the above steps, urethane synthetic leather made of a foamed urethane sheet (closed cell foam) can be continuously produced.

<Components with urethane synthetic leather>
The member with urethane synthetic leather according to the present embodiment (hereinafter also referred to as “member with synthetic leather”) has the synthetic leather according to the present embodiment as a skin material. Here, the skin material is a material constituting a surface on which a member is visually recognized and a surface that is touched by a person (such as a finger). That is, the skin material includes not only the material constituting the surface (front surface) but also the backing material.

The member with synthetic leather according to the present embodiment is a member having excellent stain resistance while enhancing the texture at low cost by applying the synthetic leather according to the present embodiment as a skin material.

Examples of the member with synthetic leather according to the present embodiment include a laminate having synthetic leather in at least one of the uppermost layer and the lowermost layer, and a molded body having synthetic leather on the surface of a molded body having a desired shape.

In the member with synthetic leather according to the present embodiment, the synthetic leather is preferably heat-sealed to an adjacent member. This heat fusion means that when the synthetic leather and the adjacent member are directly heat-sealed, the synthetic leather and the adjacent member are heat-sealed via an adhesive (hot melt adhesive or the like). Including both cases.
Here, when the member with synthetic leather is the laminated body, the member adjacent to the synthetic leather indicates a layer adjacent to the synthetic leather in the laminated body. Moreover, when the member with synthetic leather is the said molded object, the adjacent member shows a molded object main body.
In the member with synthetic leather according to the present embodiment, the synthetic leather is heat-sealed to the adjacent member. When the synthetic leather and the adjacent member are directly heat-fused, the synthetic leather is adjacent to the synthetic leather. This includes both cases where the member is thermally fused via an adhesive (hot melt adhesive or the like).
Here, when the member with synthetic leather is the laminated body, the member adjacent to the synthetic leather indicates a layer adjacent to the synthetic leather in the laminated body. Moreover, when the member with synthetic leather is the said molded object, the adjacent member shows a molded object main body.

Specific examples of the member with synthetic leather according to the present embodiment include a cosmetic puff, a bag, a sarifu, a glove, a book cover, a touch panel type mobile phone (smartphone) protective cover, a place mat, and the like.

Here, in particular, when the synthetic leather according to the present embodiment is applied as a backing material for a cosmetic puff, the cosmetic puff has a backing material excellent in stain resistance while improving texture at low cost.
In addition, the backing material made of synthetic leather composed of closed cell foam has low liquid permeability and fine powder penetration, so it can be used for liquid cosmetics (lotions, solid foundations, etc.), solid cosmetics (solid It is difficult to permeate foundations, powder foundations, etc. Therefore, the cosmetic puff having the backing material made of synthetic leather can suppress wasteful consumption of cosmetics. There is also an advantage in the hygiene aspect of cosmetic puffs.

Here, an example of the makeup puff will be described with reference to the drawings.
FIG. 2 is a schematic cross-sectional view showing an example of a cosmetic puff according to the present embodiment.
As shown in FIG. 2, a cosmetic puff 200 includes a surface material 202 that adsorbs or absorbs cosmetics (for example, open-cell foam, nonwoven fabric, flocked sheet, etc.), a backing material 204 made of synthetic leather, and a surface material. 202 and a cushioning material 206 (for example, a low density foamed polyurethane layer) provided between the backing material 204 and the backing material 204. The cosmetic puff 200 includes an adhesive layer 208A (for example, a hot melt adhesive) between the front material 202 and the cushion material 206, and an adhesive layer 208B (for example, a hot melt adhesive) between the backing material 204 and the cushion material 206. Etc.).
And the edge part of the makeup | decoration puff 200 has adhere | attached the surface material 202 and the backing material 204 directly through the contact bonding layer.

The cosmetic puff 200 is heated, for example, by punching a laminated body in which a backing material 204, an adhesive layer 208B, a cushion material 206, an adhesive layer 208A, and a surface material 202 are laminated in this order with a punching die. Is obtained.

The cosmetic puff 200 is not limited to the above configuration except that it has a backing material 204 made of synthetic leather, and may be configured according to the purpose.

Examples of the present disclosure will be described below, but the present disclosure is not limited to these examples. In the following description, unless otherwise specified, “parts” and “%” relating to blending amounts (contents and addition amounts) are all based on weight.

<Examples and Comparative Examples>
Stir the polymer polyol, low molecular weight polyol, foaming agent, foam stabilizer, and catalyst of the urethane raw materials having the compositions shown in Tables 1 to 3 to make A liquid, and make the isocyanate B liquid. It was transported to the mixing head by a pump and mechanically stirred.

Using a die coater, apply a stirred urethane material solution on the polyester film (Film A) so that the thickness after curing is 0.3 to 0.8 mm. Separate release film from above (Film B) was coated on the coating film so that the surface after the release treatment was in contact with the urethane raw material coating film. Next, the coating film of the urethane raw material liquid was heated and cured in an oven sandwiched between two release films under the conditions of 80 ° C. × 3 minutes and 100 ° C. × 5 minutes. Thereafter, the film A on both sides was peeled off to obtain a synthetic leather composed of a foamed urethane sheet (closed cell foam) having a thickness of about 0.3 to 0.8 mm. The method of curing the coating film sandwiched between film A and film B as in this example is called “double method”, and the method of coating on the surface of film A and curing as it is is called “single method”. I will call it.

<Evaluation>
In addition to measuring the properties of the synthetic leather obtained in each example, various tests were conducted and evaluated for stain resistance, hand feeling, and appearance.

(Characteristic measurement)
The properties (closed cell ratio, etc.) of the synthetic leather obtained in each example were measured according to the method described above.

(Stain resistance)
The stain resistance of the synthetic leather was evaluated by the skin water absorption rate of the synthetic leather.
The liquid absorption rate of the synthetic leather was measured as follows. The water absorption of the synthetic leather was measured as follows. Synthetic leather is cut to prepare a sample of 10 cm square, and the weight is measured to 1/100 g. Next, 10cm lotion is put into the water tank, and the synthetic leather is submerged to a depth of 10cm and left for 24 hours. After 24 hours, the lotion on the sample surface is wiped off, and the weight of the sample is measured to 1/100 g. Thereafter, the liquid absorption is measured by the following formula.
Liquid absorption rate (%) = (weight after liquid absorption−weight before liquid absorption) / weight before liquid absorption × 100

The liquid absorption rate was excellent from 0% to less than 10%, good from 10% to less than 15%, and poor from 15%.
The skin lotion used was Silk Skin Story Lotion V (Daichem Beauty Care Division). Ingredients are water, glycerin, sorbitol, BG, phenoxyethanol, trehalose, oleth 5, hydroxyethylcellulose, methylparaben, arnica extract, licorice extract, Dutch mustard extract, burdock extract, squirrel extract, garlic extract, pine extract, rosemary extract, roman Contains chamomile extract and ascorbyl phosphate Mg.

Moreover, about the synthetic leather of Example 6 and Comparative Example 2, the SEM photograph of the cross section which shows a mode that the foundation was lightly rubbed against the synthetic leather and it entered into the synthetic leather (dirt resistance) is shown in FIGS. 3 and 4 respectively. Show. 3 and 4, it can be seen that the synthetic leather of Example 6 has almost no powder penetration.

(Hand feel)
As for the hand feel (texture) of synthetic leather, the rate of 10% evaluated by the evaluators in the blindfold test is 70% or more is “excellent”, 50% or more is “good”, and less than that “Inferior”.

(appearance)
FIGS. 5 and 6 show SEM photographs of the front and back surfaces of a product (synthetic leathers of Examples 9 and 13) when synthetic leather is produced by the “double method” and “single method”, respectively. Both the front and back surfaces of the synthetic leather produced by the double method from FIGS. 5A and 5B show a smooth surface, but the back surface of the synthetic leather produced by the single method from FIGS. 6A and 6B is smooth but the surface is rough and rough. You can see that

Details of the above examples and comparative examples are listed in Tables 1 to 3.
In the table, as the overall evaluation, “Excellent”, “Good” and “Inferior” were evaluated in three stages.

From the above results, the synthetic leather of this example made of closed-cell foam has a texture and dirt resistance compared to the synthetic leather of the comparative example made of open-cell foam having a closed cell ratio of less than 5%. Both are high.

In the table, the notation “double” in the column of the Web method indicates that the synthetic leather was manufactured by heating and curing the coating film of the urethane raw material liquid while being sandwiched between two release films.
The notation “single” indicates that the synthetic leather was manufactured by heating and curing the coating film of the urethane raw material liquid in a state of being provided on one release film.
The “main raw material” indicates three types of a high-molecular polyol, a low-molecular polyol, and an isocyanate.
The “ratio of each component” is a weight ratio with respect to the main raw material.
“Left arrow (←)” indicates the same content as the left column.

Other details such as abbreviations in the table are as follows.

-Polymer polyol-
Polyol A: Polyether polyol obtained by addition polymerization of 15% ethylene oxide “functional group number f = 3, Mn = 6000”

-Low molecular polyol-
・ 1,4BD: 1,4-butanediol (Mitsubishi Chemical Corporation)

-Foam stabilizer-
SH-190, SF-2936, L-2937, L2938, SZ-1605: Silicone foam stabilizer manufactured by Toray Dow Corning Co., Ltd. L-684: Silicone foam stabilizer manufactured by Momentive

-catalyst-
・ 33-LV: Amine catalyst “DABCO 33-LV (manufactured by Air Products Japan)”
・ SO: Stanoct (API Corporation)
DBTDL: Dibutyltin dilaurate (Nitto Kasei Co., Ltd.)

-Isocyanate-
・ P-MDI: Monomeric MDI “Millionate MT (manufactured by Tosoh Corporation)”
Prepolymer A: 100 parts of polypropylene glycol having 2 functional groups and molecular weight of 600 and 121.6 parts of P-MDI reacted at 80 ° C. for 3 hours at 80 ° C. for NCO% (isocyanate weight ratio) of 13.5% polymer

In the following, description of symbols will be described.
DESCRIPTION OF SYMBOLS 10 Coating film 12 Coating apparatus 14 1st web roll 14A 1st continuous web 16 2nd web roll 16A 2nd continuous web 18 Large diameter roller 22 Heating device 24 1st collection roll 26 2nd collection roll 30 Closed cell type foaming Body (for example, urethane foam sheet)
100 Synthetic leather production equipment

The entire disclosure of Japanese Patent Application No. 2017-071918 is incorporated herein by reference.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

Claims

A closed-cell type, which is a cured product of a composition comprising a high-molecular polyol having a number average molecular weight of 2000 to 12000, a polyisocyanate, a low-molecular polyol having a molecular weight of 60 to 300, a blowing agent, a catalyst, and a foam stabilizer. Urethane synthetic leather made of foam.
The urethane synthetic leather according to claim 1, wherein the closed cell ratio is 10 to 60%.
A composition comprising a polymer polyol having a number average molecular weight of 2000 to 12000, a polyisocyanate, a low molecular polyol having a molecular weight of 60 to 300, a blowing agent, a catalyst, and a foam stabilizer is formed on the first continuous web. A coating process for continuously coating and forming a coating film;
A heating step of heating and curing the coating film on the first continuous web to form a closed cell foam;
Of urethane synthetic leather comprising
After the coating step, before the heating step, a second continuous web is supplied to the coating film on the first continuous web, and the coating film is sandwiched between two continuous webs. Including steps,
The method for producing urethane synthetic leather according to claim 3, wherein the heating step is a step of heating and curing the coating film in a state sandwiched between the two continuous webs to form a closed cell foam. .
A member with urethane synthetic leather having the urethane synthetic leather according to claim 1 or 2 as a skin material.
The member with urethane synthetic leather according to claim 5, wherein the urethane synthetic leather is heat-sealed to an adjacent member.
A cosmetic puff having the urethane synthetic leather according to claim 1 or 2 as a backing material.