JPH02264085A - Production of sheet material - Google Patents

Abstract

PURPOSE:To obtain a porous sheet by applying a liquid mixture consisting of a specific polyurethane elastomer, a solvent and specific weight ratios of a specific modified silicone oil and a block copolymer to a fibrous substrate, coagulating the liquid and peeling the formed elastic coating film. CONSTITUTION:A liquid mixture produced by compounding (A) a polyurethane elastomer composed of (i) a polyester diol having a number-average molecular weight of 500-4,000 and produced by the polycondensation reaction of 1,9- nonanediol and/or 2-methyl-1,8-octanediol and a dicarboxylic acid, (ii) a polyoxyalkylene glycol having a number-average molecular weight of 300-5,000, (iii) an organic diisocyanate and (iv) a chain extender. (B) a silicone oil modified with a polyether, (C) a polyoxyethylene-polyoxypropylene block polymer and (D) a solvent of said elastomer is applied to a fibrous substrate and coagulated. The formed elastomer coating film is peeled off from the substrate to obtain a porous sheet having spongy structure with excellent smoothness and flexibility. The sum of B and C is 0.5-50wt.% based on A and the weight ratio of B/C is 1/20-5/1.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing a sheet-like article.

The sheet material produced according to the present invention has a sponge structure exhibiting good smoothness and soft texture, has excellent hydrolysis resistance, and is suitable as a surface layer of a leather-like sheet.

[Conventional technology]

BACKGROUND ART Conventionally, it is known to apply a solution of a polymer mainly composed of polyurethane elastomer onto a base material, solidify it, and peel off the formed coating layer from the base material to obtain a porous sheet.

1.9-nonanediol and /l& is 2-methyl-1
, 8-octanediol and dicarboxylic acid (hereinafter referred to as P
It has been reported that a polyester-based polyurethane elastomer obtained by reacting NOA (abbreviated as NOA), an organic diisocyanate, and a chain extender is used as a coating agent impregnating agent or a texture control agent for synthetic leather and artificial leather. (1!#Refer to JP-A-61-185520 and JP-A-62-22817).

Furthermore, it is known that polyurethane containing polyoxyalkylene glycol such as polyoxytetramethylene glycol as a soft segment-forming polymer diol component can be used for hydrolysis resistance (Japanese Patent Publication No. 59-2003
(See Publication No. 0).

[Problem to be solved by the invention]

The conventional method was carried out using PNOA-polyoxyalkylene glycol polyurethane, probably because polyurethane containing PNOA and polyoxyalkylene glycol as soft segment-forming polymer diol components has a faster solidification rate than conventional polyester polyurethane. In some cases, only sheet-like materials having a collapsed sponge structure and a less smooth surface have been obtained.

However, when producing leather-like sheets, usually at least 2
Using a multi-component fine fiber obtained by spinning different kinds of polymers as a base fiber, this fiber is impregnated with polytalethane elastomer and coagulated, and then at least one component of the multi-component fiber is treated with a solvent or a decomposer. An operation is performed to remove the polyurthane elastomer and change the fiber morphology, but in this process, the sponge structure formed by the polyurthane elastomer is often deformed by the action of the treatment agent.

An object of the present invention is to provide a method for producing a perforated sheet material having a sponge structure exhibiting good smoothness and soft texture.

[Means to solve the problem]

According to the invention, the above object is obtained by the condensation polymerization of dicarboxylic acids with diols based on (a) 119-nonanediol and/or 2-methyl-1,8-octanediol; Average molecule 1soo~4,
000 polyester diol, number average molecular weight 300~
5,000 polyoxyalkylene glycol, an organic diisocyanate, and a chain extender, (b) a polyether-modified silicone oil, (c) a polyoxyethylene-polyoxypropylene block copolymer, and (d) a polyoxyethylene-polyoxypropylene block copolymer. poly9
Consisting of each component of the solvent for the urethane elastomer, the total amount of component ib) and component (c) is 0.5 to 50% relative to component ib).
A polyurethane elastomer composition liquid having a weight ratio of 1/20 to 5/1 of component (b) to component (c) is applied onto a substrate, and coagulated with a non-solvent of the polyurethane elastomer. This is achieved by providing a method for producing a sheet-like article, which is characterized in that the polyurethane elastomer coating layer formed on the base material is then peeled off from the base material.

The above polyester diol is produced by condensation polymerization of a diol containing 1,9-nonanediol and/or 2-methyl-1,8-octanediol as a main component and a dicarboxylic acid according to a conventional method. Examples of raw material diols include ethylene glycol, propylene gelol, nonanediol, hexanediol, and 3-methyl-
It may contain a small amount of diol such as 1,5-bentanediol, 1,4-cyclohexanediol, and xylene glycol. Examples of dicarboxylic acids include aliphatic dicarboxylic acids such as adipic acid, pimelic acid, speric acid, azelaic acid, and sebacic acid; and aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid. Or used in any combination of two or more types. The polyester diol used has a number average molecular weight determined from the hydroxyl value in the range of 500 to 4,000. The number average molecular weight is preferably in the range of 900 to 3,000.

Further, as the above-mentioned polyoxyalkylene glycol, for example, polyoxy7ethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, etc. are used. Polyoxyalkylene glycol has a number average molecular weight of 300 to 5,0 determined from the hydroxyl value.
A value in the range of 00 is used. Its number average molecular weight is 5
00~a,oo.

It is preferable that it is in the range of .

The polyurethane distomer used in the present invention is produced by reacting the above polyester diol, polyoxyalkylene glycol, organic diisocyanate, and chain extender in a desired ratio according to a conventional method. The ratio of polyester diol and polyoxyalkylene glycol used is determined so that the excellent properties of polyurethane, which uses polyester diol as a soft segment-forming polymer diol component, are not impaired, and the modifying effect of polyoxyalkylene glycol is fully exhibited. stipulated in

The ratio of polyester diol to polyoxyalkylene glycol (weight ratio) is preferably in the range of about 5/1 to 115. Examples of organic diisocyanates include 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and xylylene diisocyanate. Aromatic diisocyanates such as isocyanate; aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, inphorone diisocyanate), 4,4-dicyclohexylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, etc. In addition, as a chain extender, a compound having two active hydrogen atoms, such as ethylene glycol, propylene glycol, butanediol, hexanediol, 3-methyl-1,5-bentanediol,
1. Diols such as 4-cyclohexanediol and xylene glycol; diamines such as ethylene diamine, propylene diamine, xylylene diamine, inphorone diamine, piperazine, phenylene diamine, tolylene diamine, and inphoron diamine; hydrazine; adipic acid dihydrazide, inphthalic acid Examples include hydrazides such as dihydrazide. These organic diisocyanates and chain extenders may be used alone or in combination of two or more.

As the polyurethane elastomer, it is desirable to use a polyurethane elastomer whose solution viscosity in a 10% by weight solution of dimethylformamide at 30 DEG C. is at least 1 void, preferably in the range of 2 to 10 voids.

When a solution having a low viscosity is used, the sponge structure of the resulting sheet material may not have sufficient strength or bending fatigue resistance. On the other hand, a polyurethane elastomer having too high a solution viscosity does not have poor processability, and it is certain that a sponge structure with good uniformity can be imparted to a sheet-like product. Further, other polymers may be mixed with the polyurethane elastomer at a ratio of 40% by weight or less. When mixing the polyoxyethylene glycol polycrethane elastomer obtained by polymerizing polyoxyethylene glycol as a diol component with the above polyurethane elastomer in an amount of less than 10% by weight, a non-solvent, especially When coagulating the polyurethane elastomer in a coagulating solution containing water, it is not only possible to coagulate uniformly, but also to improve the dyeability of the polyurethane elastomer, and to provide a sheet-like product with a soft and moist texture. is obtained.

Examples of the solvent for the polyurethane elastomer include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, etc., but dimethylformamide is preferably used.

The polyurethane disstomer composition liquid used in the present invention is a polyether-modified silicone oil (hereinafter referred to as (b)) which is a copolymer of siloxane and polyoxyalkylene.
) and polyoxyethylene-polyoxypropylene block copolymer (hereinafter referred to as component (e)) in a specific ratio gives the sheet-like material a stable sponge structure. Yes, it is necessary.

The weight ratio of component (b) and component (c) is 1/20 to 5/1.
is within the range of A porous sheet-like material with good smoothness cannot be obtained either when the ratio of the component (b) is higher than this or when the ratio of the component (c) is higher than this. The weight ratio of component (b) and component (c) is preferably in the range of 1/10 to 2/1. Examples of the component (b) include Chrisbon Assister 5D-7 (Dainippon Ink & Chemicals @'11), and examples of the component (c) include Chrisbon Assister f3D-14 (manufactured by Dainippon Ink & Chemicals @'11). ), etc. The total amount of components (b) and (c) is 0.5 to 50% by weight based on the polyurethane elastomer. If the total amount is less than 0.5% by weight,
The sheet does not have a good spongy structure or a homogeneous spongy structure. In addition, if the total amount is more than 50% by weight, the diaphragm in the sponge structure of the sheet-like material may not be thin or the diaphragm may become too microporous, resulting in poor mechanical strength and swelling resistance of the sheet-like material. will be low.

As the base material (or support) to which the polyurethane elastomer composition is applied, sheets, plates, fiber structures, etc. made of materials that are not affected by polyurethane elastomer solvents are used, such as polyethylene sheets, polypropylene sheets, and polyester sheets. , polyamide sheets, synthetic rubber sheets, fabrics made of organic or inorganic fibers, fabrics obtained by adding silicone resin, fluororesin, etc. to these fabrics, sheets or plate-like products such as glass plates; natural fibers, recycled fibers , woven fabrics using single-component synthetic fibers obtained by conventional spinning methods, multi-component fibers obtained by spun at least two polymers with different physical or chemical properties through a single nozzle, etc. Examples include fibrous structures such as knitted fabrics, fiber-napped knitted and woven fabrics, fiber-entangled nonwoven fabrics, and fibrous structures in which these fibrous structures contain polymers.

When producing a porous sheet material for use as a surface coating layer of a leather-like sheet, a porous or core fiber structure made of multicomponent fibers or a core fiber structure is coated with a polymer mainly composed of polyurethane elastomer as a base material. It is particularly preferable to use a material contained in a non-porous state. When such a base material is used, a sheet-like product having flexibility and good secondary processability can be obtained.

The polyurethane elastomer composition liquid is coagulated by the non-solvent of the polyurethane elastomer. Water is used as the non-solvent for the polyurethane elastomer, and an aqueous solution of the above-mentioned solvent for the polyurethane elastomer is used. As the non-solvent, it is preferred to use an approximately 20-40% aqueous solution of dimethylformamide. The solidification temperature affects the sponge structure formed in the sheet material. When the solidification temperature is high, the entire material solidifies slowly, forming a fine, uniform sponge structure. On the other hand, if the solidification temperature is low.

It forms a dense skin layer on the surface, and the inside solidifies into a huge, uniform sponge structure. The solidification temperature is about 25-75°C to form the preferred sponge structure.
It is sufficient to select within the range of °C.

The polyurethane elastomer coating layer obtained by coagulation on the base material is peeled off from the base material, washed with water, and dried to obtain a porous sheet-like material having a surface with good smoothness.

Since the sheet-like material obtained by the present invention has a stable sponge structure and good surface smoothness and flexibility, the sheet-like material can be subjected to coloring treatment, rubbing salt, printing of patterns, etc. After being subjected to a finishing treatment, it can be used, for example, as a wall covering material, an interior decoration material, and for the decoration of various articles. Furthermore, the sheet-like material obtained in the present invention can be adhered to a flexible fibrous base material to form a grain layer of a leather-like sheet.

〔Example〕

The present invention will be specifically explained below with reference to Examples.

In addition, parts and parts in the examples represent parts by weight and weight % unless otherwise specified.

Example 1 Number average molecular weight 2,000 obtained by condensation polymerization of a mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol (molar ratio 50150) and adipic acid
polyester diol, polyoxytetramethylene glycol with a number average molecular weight of 2,000, 4,4-diphenylmethane diisocyanate and 1.4-butanediol (molar ratio 0.6:0.4:6:5, soft segment ratio 50. Polyurethane elastomer obtained by reacting 8% nitrogen based on isocyanate groups (1t4.31) (concentration 10% in tidimethylformamide solution)
The solution viscosity at
Mixture of D-7C (as described above, component (b)) and Crisbon Assister 5D-14 (component (e) as described above) [component (b)/component (c) (weight ratio) 1/2 ]
To the polyurethane elastomer, add 20% of carbon black as a coloring agent to the polytalethane elastomer to prepare a polyurethane elastomer composition liquid.

A liquid amount of 500 f/rl (polyurethane elastomer amount 62 f/d) was applied onto the base material of this polyurethane elastomer composition at-polyethylene sheet by a casting method, and then the base material was coated with dimethylformamide 25 % aqueous solution (liquid temperature 40°C) to ensure solidification. The obtained polyurethane elastomer ff-film layer was peeled off from the base material and heated at 80°C.
The solvent was removed and washed in hot water, followed by drying to obtain a sheet-like product. The obtained sheet-like material had a basis weight of 70 f/♂ and a thickness of 0.33.
■.

It had an apparent density of 0.23 f/cIA, had a sponge structure with long pores almost perpendicular to the surface, and was flexible with a smooth surface.

The surface of this porous sheet that was in contact with the base material was adhered to the nylon tricot using a cross-linked polyurethane adhesive, and then the surface was polished with sandpaper to a depth of approximately 0.04 to Q5 mm to expose the internal pores. By the way.

A suede-like sheet material with a beautiful appearance formed by uniform pores was obtained. This sheet-like material was flexible and drapable, and could be used as a material for black clothing.

Further, - this sheet-like material showed no abnormalities in a hydrolysis resistance test using a jungle tester for 6 weeks in an atmosphere of 95% humidity and 70° C., and the surface smoothness was also good.

Comparative Example 1 The same procedure as in Example 1 was carried out except that a polyurethane elastomer composition liquid was used in which the fA heating mixture addition amount of Chrisbon Assister 5D-7 and Chrisbon Assister 5D-14 was 0.41 to the polyurethane elastomer. The sheet-like material obtained by performing the same processing operation as in Example 1 had a basis weight of 68 V/rl, a thickness of O, 19 m, and an apparent density of 0.4.
It is 5P/crA, and the surface has irregularities like fine wrinkles, and the sponge structure has unevenly shaped pores. An attempt was made to prepare a suede-like sheet by treating this sheet in the same manner as in Example 1, but
The obtained sheet-like product had a poor appearance and a hard texture.

In addition, when the amount of the additive mixture added is 50% higher than that of the polyurethane elastomer and the polyurethane composition liquid is used, although a flexible porous sheet material is obtained, the pores are large. In addition, because the partition walls between the pores are thin, the sheet-like material easily separates into two pieces between the front layer and the back layer.

Examples 2 to 4 and Comparative Examples 2 and 3 A 13% dimethylformamide solution of the same poly9 urethane elastomer as obtained in Example 1 was added with an additive mixture of the weight shown in Table IK at 20% of the poly9 urethane elastomer. % to prepare each polyurethane elastomer composition liquid.

Margin table below 1 Comparative example 2 0.4% 19.6%
0.02 Example 2 1.9% 18.1
% 0.1 Example 3 10.0%
10.0% 1.0 Example 4 13.3
H 6.7% 2.0 Comparative Example 3
17.1chi 2.9% 6.0
These polyurethane elastomer composition liquids were applied onto a polyethylene sheet substrate at a liquid volume of 600 f/rr! of dimethylformamide, and then the substrate was coated with a 25% aqueous solution of dimethylformamide (
It was immersed in a solution at a temperature of 40°C to solidify. The polyurethane elastomer coating layer formed on the base material was peeled off from the base material, solvent removed and washed in SO"C hot water, and dried to obtain a sheet-like product. Table 2 shows the sponge condition and appearance.

Table Example 2 0.32 Good, glossy and uniform micropores Good flexibility Example 3 0.29 #, #
# #Example 4 0.24
&, # l # These porous sheet-like materials were made of fibers with a thickness of 1.2 mm obtained by incorporating polyester polyurethane into a pre-prepared nylon-6 ultrafine fiber bundle fiber entangled nonwoven fabric. It was adhered to a base material using a solvent adhesive method, a coloring agent was applied to the surface, and a two-boss process was performed to obtain a silver-finished leather-like sheet-like material. The sheet-like material obtained using the porous sheet-like material of the example was given a good embossed pattern and had many long and thin folds,
In contrast to the leather-like sheet-like material that looks heavy, the sheet-like material obtained using the porous sheet-like material of the comparative example has poor embossed pattern imparting properties and does not wrinkle easily. there were.

Example 5 and Comparative Examples 4 and 5 Nine numbers obtained by condensation polymerization of a mixture W of 1,9-nonanediol and 2-methyl-1,8-octanediol (molar ratio 30/70) and adipic acid Average molecule [1,500
polyester diol, polyoxytetramethylene glycol with a number average molecular weight of 1.500, 4,4-diphenylmethane diisocyanate, and ethylene glycol (
Molar ratio 0.6:0.4:3.7:2.7, soft segment ratio 57.81 Nitrogen amount based on incyanate group 4
．． Polyurethane elastomer caii obtained by reacting 01).

A 13% dimethylformamide solution was prepared from the solution viscosity (3 voids) at 30°C of a thidimethylformamide solution, and to this solution were added Crisbon Assister 5D-7 (as described above, component (b)) and Crisbon Assister 5D-14.
(as above, component (c)) mixture (component (b)/
A polyurethane elastomer composition liquid was prepared by adding 20% of component (c) (weight ratio: 8/10) to the polyurethane elastomer.

This polyurethane elastomer composition liquid was applied onto a base material under the same conditions as in Example 2, solidified, the polyurethane elastomer coating layer formed on the base material was peeled off from the base material, solvent removed, washed, and dried. A sheet-like product was obtained.

For comparison, a polyurethane distomer (
Molar ratio 0.6:0.4:1.5:0.5. Soft segment ratio 61.51 Nitrogen amount based on incyanate group 4
．． Polyurethane elastomer obtained using polyester diol with a number average molecular weight of 4,050 and polyoxytetramethylene glycol with a number average molecular weight of 4,050 C molar ratio 0.6: 0.4: 10.5
: 9.5, a soft segment ratio of 55.7%, and a sheet-like product was obtained by the same operation except that the amount of nitrogen based on incyanate groups was 4.01. Table 3 shows the sponge state, appearance, etc. of the obtained sheet-like material.

Table 3 Example 50.26 Good, gloss ib Uniform micropores
Good Flexibility Reference Example 1 A polyurethane elastomer composition liquid was prepared in the same manner as in Example I except that 2 parts of titanium oxide was added to the polyurethane elastomer instead of carbon black as the colorant. This polyurethane elastomer composition liquid was applied in a liquid amount onto a fibrous base material with a thickness of 1.2 cm obtained by incorporating polyester polyurethane into a pre-prepared nylon-6 ultrafine fiber bundle fiber entangled nonwoven fabric. 850
f/r! ! The base material was then immersed in a 30% dimethylformamide aqueous solution (liquid temperature: 40°C) to solidify.Then, the solvent was removed and washed in hot water at 80°C, and dried to obtain a fiber-purifying base material. A porous sheet material having a porous polyurethane elastomer coated thereon was obtained.

The surface of this porous sheet-like material had good smoothness.

A white ink was prepared using the same polyurethane elastomer as obtained in Example 1 as a base material and a pigment mainly composed of titanium oxide. Using this white ink, the surface of the above porous sheet is colored with a 140-mesh gravure roll, and after drying, it is embossed with a rough pattern (cowhide) and rubbed to form a silver-tone sheet. Gaining or mourning something. This product has good appearance, texture, and wrinkle resistance, and has good bending fatigue resistance, making it suitable as a material for men's shoes and sports shoes.

〔Effect of the invention〕

According to the present invention, a porous sheet material having a stable texture with good smoothness, excellent flexibility and drapability, and excellent bending resistance and hydrolysis resistance is manufactured. Ru. The manufactured sheet material has excellent light and weather resistance and low-temperature properties. The silvered leather-like sheet material obtained from this sheet material has a good appearance with folded wrinkles and embossed fixation, and the suede-like sheet material has good napping properties. In addition, these sheet-like products have excellent secondary processability, such as cutting processability, sewing processability, plowing processability, embossing processability, etc.

Patent applicant RiRashi Co., Ltd.

Claims (1)

[Claims] (a) Polyester having a number average molecular weight of 500 to 4,000 obtained by condensation polymerization of a diol containing 1,9-nonanediol and/or 2-methyl-1,8-octanediol as a main component and dicarboxylic acid. A polyurethane elastomer obtained by reacting a diol, a polyoxyalkylene glycol with a number average molecular weight of 300 to 5,000, an organic diisocyanate, and a chain extender, (b) polyether-modified silicone oil, (c) polyoxyethylene-polyoxypropylene It consists of each component of a block copolymer and (d) a solvent for the polyurethane elastomer, the total amount of components (b) and (c) is 0.5 to 50% by weight based on component (a), and (b) A polyurethane elastomer composition liquid having a weight ratio of component () to component (c) of 1/20 to 5/1 is applied onto a substrate, coagulated with a non-solvent for the polyurethane elastomer, and then formed on the substrate. A method for producing a sheet-like article, characterized by peeling off an elastomer coating layer from a base material.