JPS59173381A - Synthetic leather having moisture permeability and excellentin high frequency weldability - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention The present invention provides a soft segment constituting polyurethane that is made of polyurethane containing (at least) polyethylene glycol as a component of polymer glycol and a fluorocarbon water-repellent resin, and is non-porous and transparent. The present invention relates to synthetic leather that has excellent moisture resistance and a high frequency of rotation.

BACKGROUND ART Polyurethane synthetic leather has traditionally been used for clothing as a leather substitute because of its excellent appearance, texture, drapability, etc.

However, these f-urethane synthetic leathers have no or very little moisture permeability, and when worn, they can become stuffy and sticky due to sweat generated depending on the amount of exercise9. Comfort and comfort (I was not completely satisfied with it.

However, the method for imparting moisture permeability to these polyurethane synthetic leathers K and S'' is to mix a third substance into the polyurethane elastomer, and then remove the third substance by eluting it with a trowel in the liquid. Methods such as the method of releasing the third substance by rubbing, or the method of releasing the third substance by stretching are discouraged, but these methods can obtain a reasonable degree of moisture permeability, but because of the force exertion for removing the third substance. It is far from traditional synthetic leather, as its appearance is significantly impaired.

In addition, polyurethane synthetic leather has traditionally had excellent waterproof properties due to its structure with a non-porous film, but due to its functional requirements, some polyurethane synthetic leathers have a waterproof effect when used as clothing. In order to provide a sealing tape after sewing, or one-frequency welding without sewing, the sealing tape peeled off during use, and the polyurethane and base material were separated during the high-frequency one-coating process. Because the balance between the softening point and the melting point of the bath was inappropriate, one coating was insufficient or overcoat, and the fused part peeled or tore during use, causing the original function to be lost. I was not able to fully accomplish this.

In addition, conventional polyurethane synthetic leather is now a non-porous film! Therefore, it is waterproof, but when water droplets from rain etc. adhere to it, a continuous film of water tends to form on the entire surface, resulting in an unsightly appearance.
Furthermore, it has the disadvantage that it becomes easy to become dirty gradually during use due to the adhesion of dirt, dust, foreign matter, etc.

The present invention was developed because conventional polyurethane-based synthetic leathers have the above-mentioned drawbacks in terms of roughness.

In other words, as a result of intensive research, the Ministry of the Invention and others has developed a polyurethane component that forms a non-toxic polyurethane film layer on a substrate! Molded with a specific polyurethane, and furthermore, the softening point of the polyurethane component, the material of the base material, the bath melting point or fraction! By limiting the temperature and further coating the laminate with a fluorine-based water-repellent resin, the above-mentioned conventional drawbacks are overcome, and the original functionality of polyurethane-based synthetic leather is water-resistant and urine-resistant. In addition to heat and windproof properties, this synthetic leather has been newly added with moisture permeability and high frequency non-adhesion properties.

That is, the present invention provides a synthetic leather formed by laminating and integrating at least a polyurethane film layer on the surface of a base material, wherein the polyurethane film layer is a polyurethane containing polyethylene glycol as a component of the polymer glycol as a soft segment, and has a softening point of 150. Thermal oJ [formed of polyurethane, the water-repellent resin layer is fluorine-based water-repellent on both sides, and the base material has a softening point of polyurethane film layer of 30 °C or higher, or a temperature of 30 °C or higher] 911 It is a synthetic leather that is made of synthetic fibers, semi-synthetic fibers, or natural fibers with dots (IL: %) and has excellent moisture permeability and high frequency weldability.

In this study, as the polymer glycol that can be used together with polyethylene glycol, which becomes the soft segment of polyurethane, polyester diols and polyether diols can be used alone, or mixed or copolymerized.

Polyester thread diols include hydroxyl compounds with a carbon number of 2 or more, such as ethylene glycol and dibasic diol,
For example, a polyester obtained by further adding ε-cablocktone to a polyether obtained by a complete reaction with adipic acid can be used, and polyether glycols such as polypropylene 5♂ yakol, polytetrametherene ether glycol, etc. can be used. Permanent methylene ether glycol can be used.

Polyethylene glycol, which is the soft segment of polyurethane, provides flexibility and hydrophilicity, and has a direct effect on water vapor permeability.

The average molecular weight of the polyethylene glycol that becomes the soft segment is 400 to 1,500. Preferably 600-1
,000. When the average molecular weight of polyethylene glycol increases, the mechanical strength of the product decreases.

In order to obtain moisture permeability, the amount of polyethylene glycol used is 20 to 80 weight, preferably 30 to 70 weight, based on the total amount of polymer glycol. The amount of polyethylene glycol used is 2 based on the total amount of polymer glycol.
If the weight is less than 0 weight φ, sufficient moisture permeability cannot be obtained,
If the weight is higher than that, the moisture permeability is excellent, but on the other hand, the hydrophilicity is too strong, so swelling by water is likely to occur, which is not preferable.

The amount of polyethylene glycol used in the soft segment is determined by the desired properties of the product and the average molecular weight of the polyethylene glycol used. When using low-molecular-weight polyethylene glycol, a much larger amount is required to obtain the same moisture permeability as that obtained using a small amount of a high-molecular-weight polyethylene glycol. It is also possible to use a mixture of polyethylene glycols having different average molecular weights.

As for the solid diisocyanate used as the hard segment, diphenylmethane diisocyanate,
Aromatic diisocyanates such as diphenyl diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and naphthylene diisocyanate; other aliphatic diisocyanates such as hexamethylene diisocyanate and decamethylene diisocyanate; and other diisocyanates such as dicyclohexylmethane and inphorone diisocyanate. Alicyclic diincyanates such as nates are also used.

Chain extenders having two active hydrogens in the Cerevitino 7 reaction used for chain extension include glycols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, ethylene diamine, hexamethylene diamine, Diamines such as P,P'-diaminophenylmethane, m-phenylenediamine, and 4-methyl-m-phenylenediamine can be used.

The polyurethane that forms the film is 1, with a softening point of 150.
The polyurethane must have a temperature of -230°C or less, preferably 160 to 200°C. Softening point is 15
At temperatures below 0°C, the coating layer is heated above its softening point during high-frequency fusing layer processing, resulting in poor melting of the polyurethane that saturates the coating layer, resulting in a decrease in fusion strength and poor texture. In addition, cracks are likely to occur in the fused part, and the effect of complete waterproofing is significantly reduced.If the softening point is 230°C or higher, the frequency fusion properties are poor and the fusion strength is weak. This is because the fused surface tends to peel off during use, reducing the complete waterproof effect.

The polyurethane forming the polyurethane film layer further contains 1
00 thymodylus must have a mass of 30 to 20 oKg/ca. If 100 Timodilus is less than 30Kg/c++1, the strength of the skin RS layer will be weak and practical synthetic leather will not be obtained.If it is more than 2ooQ/-, the texture will become extremely hard and the characteristics of synthetic leather will be lost. be.

Note that materials, dyes, and other various stabilizers can be added to the polyurethane film layer for coloring.

As for the coating method, a dilute solution of the polyurethane is coated onto a support having mold releasability using a doctor knife coater, a reverse roll coater, a floating knife coater, or the like.

The coating amount of the polyurethane is 5 to 8゜y/l in terms of solid content.
, for girls 1o~5o2/? ? It is 12.

If the weight of the fallen fabric is less than by/rd, the mechanical strength will be significantly reduced and the synthetic leather will no longer function as it should. If the fabric weight is 80v/door or more, the texture will be extremely hard and the synthetic leather will lose its appeal.

The base material can be synthetic fibers, such as polyamide, polyester, vinylon, acrylonitrile, etc., semi-synthetic fibers, such as rayon, cupro, acetate, etc., or natural fibers, ν.
For example, knitted fabrics made of silk, wool, cotton, linen, etc., nonwoven fabrics, impregnated fabrics, etc. can be used.

The substrate must have a melting point or decomposition point that is at least 30°C higher than the softening point of the polyurethane coating layer.

If the difference between the bath melting point or decomposition point of the base material and the softening point of the polyurethane film layer is 30°C or less, the heat generated by high frequency will cause the base of the fused portion to melt before the polyurethane skin layer is fused. If the material is bath-fused, or even if it is not bath-melted, the texture of the base material becomes significantly hard, resulting in a significant difference in texture between the fused area and the non-layered area. This is because there is.

The material used for the added leather of the present invention does not have to be used under any particularly limited specifications, and may be made of polyvinyl chloride film sheets, polyvinyl chloride leather, etc. Ordinary machines used for high frequency fusion can be used as is.

When the synthetic leather of the present invention is fused using high frequency waves, the seam portions can be fused after sewing, and it is also possible to fused the synthetic leather without sewing.

In the above example, we explained the case where the base material and the coating layer are laminated together without intervening any adhesive between them. can also be stacked.

As the adhesive layer, polyurethane having the same soft segment component as the film layer can be used.
It is also possible to add lfi agents, catalysts, dyes, pigments, and other additives.

Preferred examples of crosslinking agents used include polyisocyanates having a tertiary or higher functional level. Further, as a catalyst, a tertiary amine, an organic tin compound, or an organic tin compound is used.

The polyurethane constituting the adhesive layer must also have a softening point of 140°C or higher, preferably 160°C or higher. If the softening point is below 140°C, the adhesive layer will be heated above the softening point during high-frequency fusion processing, so the polyurethane forming the adhesive layer will penetrate into the base material and cause the contact between the base material and the coating layer. This is because the layer strength decreases and the bond becomes hard, resulting in the inconvenience of losing the characteristics of synthetic leather.

The polyurethane layer forming the polyurethane contact layer must have physical properties ranging from 0 to 000Rf/ctA. When the 100-thread modulus is less than 10 to 9/cnf, the peel strength is weak <, 100 Lq/
This is because if it exceeds crA, the synthetic leather becomes hard and loses its length as a synthetic leather.

In addition, pigments, dyes, and other stabilizers can be added to the polyurethane adhesive to prevent corrosion.

The coating method is to apply a diluted solution that will become the polyurethane adhesive layer onto the polyurethane film formed on the support having mold releasability using a doctor knife coater or a reverse roll coater.
, float ink knife coater, etc.

The wall covering amount of the polyurethane contact layer is 5 to B 0 in terms of solid content.
f/? 71', preferably 10-609/n? It is.

If the coating weight is less than 5t/7Fr'', the adhesive strength will be significantly reduced, and if it is more than 80f/Tr?, the texture of the synthetic leather will become hard and the characteristics of synthetic leather will be lost.

Water repellency @ fat is a fluorine-based resin that not only has water repellency that is effective in repelling water droplets, but also has oil repellency to prevent dirt, dust, and oil from adhering to the surface.

As the fluororesin, resins having a ζ-fluoroalkyl group in the side chain and the main chain of which is acrylic ester, methacrylic ester, polyurethane, polyester, etc. can be used, and the main chain is polyurethane. Fluororesins are preferred. These resins, emulsions or organic
It is used as a solution of agent, 'dipping method, gravure roll 7
It is applied onto the synthetic leather by a coating method, a spray method, or the like.

Is the basis weight of water-breaking resin 0.1 to 5 y/lr in terms of solid content? is within the range of If the basis weight is less than o, 1y/lri'', the water repellency and oil repellency of the synthetic leather will be significantly reduced, and 5
17n? If it is more than that, the high frequency weldability will deteriorate, which is not preferable.

Synthetic leather of dud (7) has the structure described above, so it has excellent flexibility, has a strong texture, texture, etc. that closely resembles natural leather, and has moisture permeability similar to natural leather. Because of its high-frequency adhesion properties, waterproofing is suitable for applications that require cold protection, and is suitable for use in various sportswear such as windbreakers, ground coats, marine wear, ski wear, etc., and rainwear. It is a synthetic leather that I like.

Examples of the present invention are listed below, but the present invention is not limited to these Examples.

Example 1 Polyethylene glycol/polytetramethylene glycol (with a 100% modulus of '70 K9/C4 and a softening point of 165°C) was deposited on a smooth support with mold release properties.
A polyurethane resin solution prepared by adding an eyebrow coloring agent to a polyurethane made of polymer glycol (37/6s heavy weight) is applied so that the floating layer of the polyurethane skin becomes 35 μm, and the polyurethane skin layer is heated and semi-dry. A stretch knitted fabric made of polyamide fibers having a melting point of 215° C. was laminated as a base material while still containing gold in the bath agent 7c, and after drying by heating, it was peeled off from the support to obtain synthetic leather.

Emulsion of synthetic skin 44 fluorine-based water repellent (product name:
Deitku Guard F-'70. After soaking in Inu Nippon Ink KK) and squeezing the liquid until the basis weight of the fluororesin becomes O, St/- in terms of solid content, it is dried on a dry bed at 140℃ for 2 minutes to ensure water rupture and oil repellency. Synthetic leather was obtained. The obtained synthetic leather was made to be flexible and had excellent texture, touch, and drapability, and was suitable as a material for clothing as it had excellent heat retention, windproof properties, moisture permeability, and high-frequency fusion properties. This was sewn into a windbreaker, and the seams were subjected to high-frequency welding processing to create a product. The measurement results of moisture permeability, high frequency weldability, tear strength and flexibility of the fused portion of this material are shown in Table 1.

Example 2 Polyethylene glycol/polybutylene adipate glycol (-/
A polyurethane resin solution made by adding a coloring agent to polyurethane made from polymer glycol (41.
Coat the layer so that the thickness of the layer becomes 20 μm, heat and dry it to form a polyurethane layer, and use it as an adhesive on top of the polyurethane layer with a 100% modulus of 20/c.
d. Polyethylene glycol/Voriglobin V glycol (-65/35 Judo 6I) with a softening point of 165°C
) was coated with a polyquintane resin solution consisting of polymer glycol to a dry thickness of 30 μtn, and then heated and dried. While the adhesive was still sticky, polyamide fibers with a melting point of 250°C were used as a profit. After the stretchable knitted fabric was completely laminated and the encrusting layer was solidified, it was peeled off from the support to obtain synthetic leather 4.

The Gono Ebisu leather was subjected to solvent dissolution of a fluorine-based water-breaking agent (product name: Disoku Guard F-32'7, manufactured by Dainichi Fu Ink KK) using a gravure roll so that the basis weight of the fluorine-based resin was o in terms of solid content.
sr/rr? I coated it to make it look like this. after that,
The synthetic leather was dried at 140° C. for 2 minutes to obtain water- and oil-repellent synthetic leather.

The obtained synthetic leather was made to be flexible and had a texture, touch, and appearance that closely resembled natural leather, and was suitable as a material for clothing as it had excellent moisture permeability and high frequency fusion properties. This was made into a product using only one wave welding force as Rainwooer. The measurement results of moisture permeability, high frequency weldability, tear strength and flexibility of the welded portion of this material are shown in the following-1.

Ratio 1 Squeezing Example 1 A polyurethane resin m liquid from which the colorant has been removed is applied to a polyurethane made of polymer glycol of polyethylene adipate glycol having a 100% modulus of 55 Kg10+f and a softening point of 170°C on a diaphragm support with full mold releasability. It was applied so that the taste was 25 μm VC, and this was heated and dried to form a polyurethane film layer, and a layer with a 100% modulus of 25 K was applied as a layer on the polyurethane film layer.
g / c, m z Dry a polyurethane resin bath liquid consisting of polymer glycol of polyethylene-butylene adipate glycol with a softening point of 165 ° C) to a thickness of 30 μm, and while it has a viscous layer, the base material A stretchable knitted fabric made of polyamide fibers having a melting point of 215° C. was pasted on nine boards, and after the adhesive layer was solidified, it was peeled off from the support to obtain synthetic leather.

Table 1 shows the measurement results of the moisture permeability, 7u wave resistance, tear strength and flexibility of the melting layer of the obtained synthetic leather.

Comparison Tari 2 A coloring agent was added to polyurethane made of polymer glycol of polyethylene butyne/adipate glycol having a 100-fiber modulus of l l Oy, g/cd, and a softening point of 190°C on a support with a diaphragm that improves mold release properties. A polyurethane resin bath solution was applied so that the dry thickness was 20 μm, and this was heated and dried to form a polyurethane film layer.
A polyurethane resin solution consisting of a polymer glycol of polyethylene adipate glycol with a 100% modulus of 35 Kq/crL and a softening point of 170° C. was applied as an adhesive onto the polyurethane film layer so that the dry thickness was 32 μm, and while it had adhesive properties, A stretchable i-cloth made of polyamide/spandenox fiber having a melting point of 200 to 215°C was laminated to the base material, and after the adhesive layer was solidified, it was peeled off from the support to obtain synthetic leather. Emulsion of synthetic leather fully fluorine water repellent (Product name: Daytsu Guard F-
'70. After soaking in Inu Nippon Ink KK) and squeezing out the liquid until the basis weight of the fluororesin becomes 0.75 y/door in terms of solid content, drying at 140°C for 2 minutes will break the water and produce a synthetic resin with no oily residue. Obtained leather. The moisture permeability, high-frequency fusion properties, tear strength and flexibility of the fused portion of the obtained synthetic leather were measured and the results are shown in Cloth-1.

The methods for measuring the still frequency fusion properties, tear strength and flexibility of the fused portions of the synthetic leathers used in the above Examples and Comparison C are as follows.

■Measuring method of cylindrical frequency fusion property A 3-inch-wide test piece is taken from a sample that has been fused using high-frequency tB bonding by aligning the surface of the synthetic leather with the butt, and the fused surface is destroyed using a tensile tester. The strength at the time was measured.

◎ Method for measuring the tear strength of the fused part A test piece was taken from a sample of six sides of synthetic leather that was fused using a high-frequency 1-layer machine in accordance with J-Ko SK-6/'l'2. Then, the tear strength of the agglomerated portion was measured using a tensile test.

◎ Method for measuring the flexibility of the fused part A test piece was taken from a sample of synthetic leather that was fused together using a high-frequency wave pattern, and the tensile strength was measured using an Olzen bending tester. The test was performed at IK7.5000 times, and the flexibility of the fused portion was observed.

From Table 1, I am unsure about the moisture permeability due to the smoothness,
The synthetic leather of the present invention has excellent water-breaking properties and good frequency fusion properties, and is shown in Example 2. Wakame seaweed is suitable as a material for clothing that requires special care.

Patent applicant Achilles Co., Ltd. j ゛＼－ノ' Procedural amendment book 1978 Mokukaku'! jfZ1-l! l"r 1i'11i' L＜Kanwakasugi Kazuo Tono 1・I
f (Table of 'l/I' Tokugansho, No. 58-45604 (both IC14,) Higashi 5 + Eto tjJi-ku, Hitokyo-cho 22, 5/1r Yama 1
11 examples of 1'' life <n jizuoke 0勺5, drawn] 1. χ1 (1) Delete the word ``(at least)'' in the first line of page 2 of the specification2).

(2) In the eighth negative line of the specification, the phrase [~chroma] is corrected to "formation."

Claims (1)

[Claims] (1) In synthetic leather in which a polyurethane film layer and a water-repellent resin layer are sequentially laminated on the surface of a base material, (1) the polyurethane film layer is made of polyurethane having polyethylene glycol as one component of the polymer glycol constituting the soft segment; It is made of thermoplastic polyurethane with a softening point of 150°C or more; ■ The water-repellent resin layer is a fluorine-based water-based resin; ■
Synthetic fibers with excellent moisture permeability and high-frequency weldability, in which the base material is made of synthetic fibers, semi-synthetic fibers, or natural fibers that have a melting point or decomposition point 30°C or more higher than the softening point of the polyurethane film layer. leather.