JPS5831176A - Artificial leather - 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 relates to artificial leather. Traditionally,
Artificial leather is made by forming a resin layer of polyurethane, polyamide, polyvinyl chloride, etc. on a base fabric such as woven fabric or non-woven fabric (using polyurethane, polyacrylic acid ester, polyvinyl chloride as a finishing agent on the surface of A).

Manufactured by coating resin such as polyamino acid or polyamide. However, due to its rubbery elasticity, polyurethane resin, which is commonly used as a marking agent, has a rough pattern and a dry touch pattern cannot be obtained. Further, at high temperatures, it exhibits tackiness and has the disadvantage of causing so-called blocking, in which coated surfaces 4' and 11 adhere to each other.

The present inventor has already developed the patented St+, which improves the drawbacks of the above polyurethane resin and applies it to leather. (Japanese Patent Application Kokai Shoj, 2-Tata, 20/Yumi Publication Report) However, the polyurethane resin film used in this ≦6 light has the above-mentioned general polyurethane resin 1-hanari+Q,'l
+ is shown in I+, and there is a grain pattern, but it is shallow 1 (grain, and further improvement was desired.) As a result of the inventor's subsequent research, the adhesive layer with the base material (one layer of primer) The present invention has been completed based on the discovery that the properties of the resin make it possible to create deeper and clearer grain patterns, creating a surface appearance that more closely resembles natural leather.

To outline the present invention, (a) a polymer primer having a ratio of 10% elongation tensile strength/100% elongation tensile strength within the range of o, 5t-i, oo when the film is stretched; (b) on which, when the film is stretched, a polyurethane resin layer having a ratio of falling value/'-yield value within the range of 09t to 0 is formed. Regarding 1-ru.

To explain the present invention in detail, a single layer of primer is formed on a base material. A polymer suitable for the primer layer must have a ratio of 10% elongation tensile strength/100% elongation tensile strength within the range of 03j to 00 when the film is stretched.

Examples of polymers that satisfy the second condition include polyamide resins and specific polyurethane resins. Generally, polyamide resin has poor adhesion with polyurethane resin, so when polyurethane resin is used as a surface finishing layer, it is inappropriate to use it as a primer layer. However, according to the research of the present inventor, if the polyamide resin draws the specific film elongation curve,
Surprisingly, they found that the adhesion to polyurethane resin was good. Furthermore, when this polyamide resin is used as a primer layer, polyurethane II'1. 1-1 showed that it is possible to create a deeper and clearer grain pattern in the fat layer than in V.

The above-mentioned specific polyamide resin is, for example, produced by the condensation reaction of dimer acid and polyamine.
Plastic resin is suitable.

On the other hand, certain polyurethane resins that exhibit a film elongation curve similar to that of polyamide resins can also be used as the primer layer.

For example, polyurethane resins obtained from the following compounds are suitable.

Polyol: Molecular weight containing aromatics/0-20%:/θ00-2. Polyester with tOθ or polyether diisocyanate with molecular weight SOO~700: Example of fat ix diisocyanate Chip
- Hydrogenated compounds of diphenylmethane diisocyanate, hydrogenated compounds of xylylene diinocyanate, isophorone inosocyanate,
, /',5. -1゛- 111/ -2,-,,=/ ”” ””' (li) Chain extender: alicyclic diamine example, except g2-diphenylmethanediamine hydrogenation compound, ginilire/diamine hydrogenation An example of the production of the compound, inphorondiamine, is to react polyol and diisocyanate-1 for 1 hour at ~100°C in the presence of a tin-based catalyst, followed by reaction with a urethane such as dimethylporamide, j or methyl ethyl ketone. Add a solvent to melt the resin and reduce the solid content to -81. -! Hayabusa.

Subsequently, the viscosity is 2〇〇〇-, 20,000cpθ/
When the temperature reaches 30°C, add the alicyclic diamine little by little.

What is common to these polyamide layers and certain polyurethane resins is that they both have a relatively low value of 1 point.

In the present invention, the polymer is used as a film, and the film is stretched to have a tensile strength in the range of 0 to 100. The value of H is 0. When jt is less than 9, the surface finish layer (polyurethane resin) 1 grain pattern is difficult to form and becomes shallow and unclear. On the other hand, when the ratio value is greater than /θ, a grain pattern similar to natural leather cannot be obtained. Moreover, the texture of the artificial leather itself becomes hard, which is not desirable.

The primer layer is formed by applying a polymer solution that meets the above conditions onto the substrate. Application methods include tosoter knife and reverse coater.

Various methods such as gravure printer, spray, etc. can be used. The resin solid content of the polymer solution is 16-H weight f
It is appropriate to prepare a coating material of I-type and apply it on a substrate so that the dry coating thickness is approximately j to 7 (i).

In the present invention, a surface finishing layer is formed on the primer layer. The polyurethane resin used as the surface finishing layer is
When a film is stretched and its tensile strength curve is plotted on a graph, an upper yield value and an upper yield value appear, and the value of the ratio of upper yield value/lower yield value is within the range of 0 to 0. use something This particular polyurethane resin is described in Japanese Patent Application Laid-Open No. 2-2020,
Although it is disclosed in detail, it can be summarized as follows. For example, when a polyurethane resin film is stretched under the conditions shown in Table 1 below, it clearly has the lower yield point and lower yield point shown in Figure 1, and the ratio of lower yield value/upper yield value is: It is a specific polyurethane resin that has a temperature of 0 to 0.

Polyurethane resins with a ratio of lower yield value/upper yield value in the range of 0.1.0 have high crystallinity and are easily oriented, so the rubber-like elastic region is very narrow and the plastic deformation region It is characterized by its wide area. This has properties opposite to those of commonly used polyurethane resins.

Regarding the ten-loop value and the upper yield value, when a film of a certain thickness is stretched, the lower yield point is the point at which elongation rapidly increases from the elastic limit where permanent strain occurs when the load is increased. So, after passing the point of surrender,
The point at which the load once decreases and then increases by the amount of elongation h under a nearly constant stress is called the lower yield point.
The upper yield value and upper yield value mean the lower yield point and the first stress at the lower yield point, respectively.

The most commonly used polyurethane resin film Q! has the film properties of polyurethane resin in which the ratio of lower yield value to upper yield value is in the range of 06 to 0.9! ? When compared with Pc, it becomes as shown in Fig. 1.

The polyurethane resin used in the present invention having a lower yield value/ten yield value in the range of 06 to 0 is, for example, produced by the following method.

That is, (1) a polyol component having an average molecular weight of 1 so-ttoo regardless of the molecular weight distribution, (2) an aromatic and/or alicyclic incyanate, and (3) an agent added to the chain in a solvent. It is a polyurethane resin that reacts to a certain temperature.

The surface finishing layer is prepared by applying a single layer of primer with a polyurethane resin solution from Tokusou 17 above.
j? be done. As a coating method, various methods such as a doctor knife, reverse coater, gravure printer, and spray shade can be used. Polyurethane resin solution 'I'
lK fat solid content wog-/31kpr % I-,,pJ
1 Hayabusa': lte coating η7. It is appropriate to apply the coating so that the Jrp is 1 to 31tp.

In the present invention, after coating and forming a primer layer and a surface finishing layer, they are heated and dried. In the case of a single layer of primer, the conditions necessary for drying are 70~ioo℃ and 7~
3 minutes, for surface finishing layer, go ~/20℃, 2-3
It's a minute.

The material used in the present invention refers to base fabrics such as woven fabrics, non-woven fabrics, knitted fabrics, etc., and furthermore, those with a polymer layer such as polyvinyl chloride, polyurethane, polyamide, etc. formed on the base fabric, or
It refers to a foamed layer made of these polymers.

The artificial leather used in the present invention is characterized by the combination of forming a specific primer layer on the substrate and forming a specific polyurethane resin layer thereon as described above, and as a result, it is different from the conventional one. It has a deep and clear grain pattern that is not present in artificial leather, and the texture and feel are very similar to natural leather.

In order to explain the main point more specifically, hereafter,
Here is an example. In addition, in the examples, special feature 1: Unless otherwise specified, all parts are parts by weight.

[Polyurethane ranking solution A] 60 parts of polyether with average molecular weight 7Q Q, 11 addition of 1 water of quinrylene diisocyanate, 3 g parts of a compound of 11, 3 parts of inphorondiamifu, methyl ethyl ketone Using 1tIl-7 parts as a raw material, the resin r, f, and l forms are divided into 2 parts by l/1:
0 weight 1-ti [polyurethane l (i, l fat solution B, l
il, 1. l! li°1] 700 parts of polyester with an average molecular % of 1000 (1f<1 product name Pyro 7RU-, -X manufactured by Shakobo Co., Ltd.), 11. ++-diphenylmethanediynane-1· water f addition compound q'+++ ,! ;1
Part, xylylene dichloride 1/1 xylene dichloromethane additive 1
Using 1/3 part of polyurethane, 3 parts of dimethylformamide, 2 parts of methyl ethyl ketone and 2 parts of methyl ethyl ketone as raw materials, prepare a polyurethane resin solution of 1 part of resin solids and 0 parts of stock according to the conventional method I.
12.

[Preparation of polyurethane resin solution C]

200 parts of polyester with an average molecular weight of p12000 (trade name: Vylon RU-X manufactured by Toyobo Co., Ltd.), 3 g parts of a hydrogenated compound of xylylene diisocyanate, 73 parts of inphorondiamine, 20.2 parts of dimethylformamide, and 701 parts of methyl ethyl ketone were added to the raw material. And as always, he was adamant.

Actual No. 1 11 Example 1 On the surface of polyvinyl chloride leather, apply a 20% solution of polyamide resin (product name: Parsalon/73 to Henkel Nipponsha 111!) as a primer using a percoater so that the dry film Ire becomes j ~ 71r. It was coated and dried at goC for 7 minutes. Furthermore, as a surface finish, polyurethane resin (product name) Nidotsubu I10 (manufactured by Ni Kasei Co., Ltd.)
A 12% solution of was applied using a bar coater to a film thickness of λ to 3μ.

Next, the above surface treatment was applied to the IJ, and the polyvinyl chloride leather was heated at 200° C. for 70 seconds to foam, and then rubbed by hand. As a result, surface 1: deep, angular, and well-grained grains were formed, and artificial leather was obtained that had a texture that was harsher than that of natural leather.

In the method of Examples λ to 1, the polyurethane resins A to C were used instead of the polyamide resin.The same method was applied to all other parts except J. A deep and clear grain pattern is formed on the surface, and the artificial leather has a texture of 4!i, I-,
It's h.

Comparative Example/Example/Method C=, polyurethane M resin (trade name: Honey Ace tt! Manufactured by Honey Kosei Co., Ltd.) was used as a surface filler.
The same method was used for all steps 1' using .

What do these knots look like on the surface of the resulting artificial leather? (Only a vague grain pattern was formed.

The same method as in Comparative Example/Example/Example was carried out except that a polyurethane resin (trade name: Honey Semengutata/manufactured by Honey Kasei T1.) was used as the primer. As a result, a large grain pattern having direction 4'1 was formed on the surface of the obtained artificial leather, which was different from the surface of natural leather.

Comparative example 3 Example/person? 72, polyurethane resin (trade name: HAETOP 110 HONEY KASEI?1-
The same method was used except that the system was used.

As a result, only a large grain pattern with a hard texture was formed on the surface of the obtained artificial leather.

The rolling tensile strength of the primer resin and the elongation tensile strength of the surface finishing resin used in Example/-1' and Comparative Examples/--3 were as shown in Table 1 below.

Figure 17] A simple drawing shows a film of polyurethane resin for surface finishing used in the present invention. This is a graph comparing the film characteristics of 'r'.

In the figure, curve 9 M is a characteristic graph of the invented product, and curve N 8 is a characteristic graph of the commercially available product.

1 person from M Honey Kasei Co., Ltd. (/7) Section/Figure

Claims (1)

[Claims] When (a) the film is stretched on the base material, the ratio of 10% elongation FJ force/100% elongation Kp force is 0. j j〜／
(b) When a film is stretched on the primer, the lower yield value/upper yield value ratio is within the range of 0, 6-o. An artificial pressure chamber made of polyurethane resin 9.