JPS58169576A - Sheet-like article - 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 a sheet-like product which has excellent properties such as hand feel and rebound resilience, and which properties do not deteriorate even when subjected to heat treatments such as dyeing, ironing, and pressing.

Various sheet-like products made from a combination of a fiber sheet and a polyurethane elastic body have been proposed so far, and have attracted particular attention as an excellent material for use in artificial leather. Artificial leather, especially suede-like artificial leather, has features such as surface quality due to its elegant raised appearance and excellent color development, texture, easy care, pleochroism, dye fastness, lightness, and good processability. It has been widely praised as an excellent clothing material that is different from natural products.

However, in addition to the above-mentioned features, suede-like artificial leather is required to have high flexibility, moderate rebound, strength, and ease of high-order processing. In order to satisfy these requirements, various studies have been made from the aspect of polyurethane elastomer, but no artificial leather that satisfies all of these requirements has yet been obtained. In other words, various organic diamines have been proposed as chain extenders for polyurethane elastomers composed of polymeric polyols, organic polyisocyanates, and chain extenders. There are problems with the strength of the object, fading, etc. Products that use low-molecular-weight diols as chain extenders still have excellent strength, but have poor rebound properties.In order to provide appropriate rebound properties, it is necessary to reduce the amount of organic polyisocyanate used below a certain level, or use polymer It is necessary to appropriately reduce the amount of diol, but a glycol-based polyurethane elastomer that satisfies these conditions has a low softening point, so if it goes through a dyeing process at high temperatures, surface quality such as smoothness will deteriorate. Occasionally, the problem of "tearing" occurs, and there are also problems such as the texture being significantly damaged due to ironing, pressing, etc. during high-order processing.

The present inventors used polyurethane to obtain a sheet material for artificial leather that is flexible, has excellent rebound resilience, and has an elegant surface quality, and which does not lose its excellent properties through heat treatment such as dyeing, pressing, and ironing. The present invention was arrived at as a result of extensive research from the perspective of elastic bodies.

The gist of the present invention is as follows.

In a sheet-like product formed by impregnating and/or coating a fiber sheet with a polyurethane elastic material, the polyurethane elastic material has a molecular weight that includes (a) a polyester obtained by reacting a compound represented by formula [1] with an organic carboxylic acid; 500 or more polymeric diol, (b) organic polyisocyanate, and (C)
The sheet-like material of the present invention is characterized by being a polymer synthesized from a chain extender. It has excellent features that cannot be achieved with conventional artificial leather, such as hardening or softening of the texture and deterioration of the surface quality when the sewn products are ironed or pressed. have. The above-mentioned excellent properties that could not be achieved with conventional artificial leathers can only be achieved by combining a specific polyurethane elastic material and a fiber sheet.

Producing a polyurethane elastomer consisting of a polymeric diol, an organic polyisocyanate, and a glycol chain extender,
Impregnating and/or coating fiber sheets with polyurethanes is already known and has been put to practical use in some artificial leathers.

However, although sheet-like products using conventional glycol-based polyurethane elastomers have excellent strength, they have poor rebound and flexibility; on the other hand, glycol-based polyurethane elastomers designed to overcome these drawbacks have a softening point. It was not suitable for the purpose of the present invention because problems during dyeing and changes in thickness, texture, and surface quality occurred due to ironing, pressing, etc. of sewn products.

The present inventors discovered a special spiroglycol represented by formula [1], namely 2,4,8.10-tetraoxaspiro(
5,5) Tsuy7-Kafu! 1. A sheet-like material in which a fiber sheet is combined with a polyurethane elastomer containing a polyester diol containing diol residues of 9-jetanol and/or its derivatives has the above-mentioned excellent strength. It has excellent texture, surface quality, and rebound resilience, as well as excellent thermal properties. Therefore, it has good stability during dyeing processing, and its texture does not change due to ironing or pressing during sewing or wearing of the product. They discovered that the fabric has less scarlet and exhibits excellent sewn products and cord properties over a long period of time. This cannot be predicted simply from the properties of the polyurethane elastomer.
Its excellent properties are exhibited only when it is combined with a fiber sheet.

The polyurethane elastomer containing the polyol having a spiro ring in its molecular chain is, for example, U, 8. P, 2.945,
008 (1960), etc., but there is no description or suggestion of the combination with a fiber sheet or sorted material as in the present invention, and there is no mention of the strong stability, rebound and impact properties of such a sheet material. The effect of improving texture retention was unexpected.

The polymeric diol constituting the polyurethane elastomer of the present invention has a molecular weight of 500 or more and includes a polyester obtained by reacting a compound represented by formula (1) with an organic carboxylic acid and/or an ester or anhydride thereof. It is a high molecular weight diol.

As the compound represented by formula (1) of the present invention, R1 to R1
Compounds in which o is a hydrogen atom, an alkyl group of 00 to 2, particularly a hydrogen atom, or an alkyl group of 01 to 2 are preferred.

Specifically, 2, 4, 8. '10-Tetraoxaspiro (
5,5'l undecane-3,9-jethanol, β, β
'-Dimethyl-2,4,8,10-tetraoxaspiro(5,5':l undecane-6,9-jetanol, β
, βI diethyl-2.4.8°10-tetraoxaspiro[5,5)undecane-3,9-jetanol, β,
β,β'βI-tetramethyl-2.4.8.10-tetraoxaspiro[:5.5)undecane-3,9-jetanol,β,β'-cymey-ruβ,β'-diethyl-2゜4.8.10-Tetraoxaspiro(5,5)
Undecane-3,9-jetanol, α,α′-dimethyl-2.4,8.10-tetraoxaspiro(5,5)
Undecane-5,9-jetanol, α, a', β, β
'-tetramethyl-2.4.8.10-tetraoxaspiro[5,5)undecane-3,9-jetanol,
α,α′-dimethyl-β.

β'-diethyl-2,4,8,10-tetraoxaspiro C5,5) undecanni-3,9-jetanol, α,
α′, β, β, β′, β′-hexamethyl-2,4,8
,10-tetraoxaspiro[5゜5]undecane-3
, 9-jetanol, α.

α′, β, β′-tetramethyl-β, β′-diethyl-
2,4,8,10-tetraoxaspiro[5゜5]undecane-6,9-jetanol and the like are preferred, especially 2,
4,8.10 Tetraoxaspiro(5,5') undecane-6,9-jetanol and/or β, β, β'
, β'-tetramethyl-2,4,8,10-tetraoxaspiro(5,5)undecane-6,9-jetanol are preferred. More preferably β, β, β′, β′−
Tetramethy/l/21 4+ 81 10-tetraoxa(5,5)undecane-ro, 9-jetanol.

A polyester diol using this compound can be produced by heating and condensing the compound and, if necessary, another low-molecular-weight diol with an organic dicarboxylic acid and/or an ester or anhydride thereof, adding a catalyst if necessary. You can get it.

Low-molecular diols are preferably aliphatic diols with a molecular weight of 550 or less, such as ethylene glycol,
Propylene glycol, buta/diol, bentanediol, hexanediol, cyclohexanediol, octanediol, diethylene glycol, triethylene glycol, etc. or mixtures thereof.

The organic carboxylic acid preferably has 2 to 12 carbon atoms, and more preferably succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, inphthalic acid, etc. or a mixture thereof.

Of course, other polymeric diols can also be used.

These polymeric diols have a molecular weight of 500 or more, preferably 500 to 4000, more preferably 800 to 30
00 and preferably has a melting point of 70°C or less, polyester glycol, polyether glycol,
Typical examples of polyester ether glycol, polyacetal glycol, polybutadiene glycol, etc. are polyethylene adipate, polypropylene adipate, polytetramethylene adipate, polyhexamethylene adipate, polycaprolactone glycol, and poly(ethylene oxide) glycol. , poly(
Propylene oxide) glycol, poly(tetramethylene oxide) glycol, etc. or mixtures thereof can be used.

Spi, F glycol represented by formula (1) is represented by formula (It)
As shown in , sheet-like materials impregnated and/or coated with a polyurethane elastomer made of a polymeric diol containing a certain amount or more have no problems such as unevenness or tearing even when dyed, etc., and are easy to sew. It is preferable because it has the advantage that the excellent feel is not impaired even if it is pressed or ironed when worn.

W, XW2≧0.2 ・・・・・・・・・・・・
. . . [■] It is preferable that the product of Wl and W2 is 0.2 or more, more preferably 0.5 or more. If the size is smaller than this, the resulting sheet-like product will have poor surface quality due to unevenness caused by the dyeing process, and may sometimes have problems such as tearing. Also, when sewing or wearing secondary sewn products, press processing or It is undesirable because the texture changes greatly due to ironing.

Further, if necessary, other polyester diols and polyether diols may be mixed with the above polyester diol and applied as the polymer diol component of the present invention.

The organic polyisocyanate used in the present invention includes:
Phenyl diisocyanate, toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, naphthylene diisocyanate, diphenyldiisonanate, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene Cyinoneanate, lysine diincyanate, inphorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexyldimethylmethane-4,4'
- Organic diisocyanates consisting of diisocyanates, xylylene diisocyanates, etc. and mixtures thereof, and also reaction products of these organic diinsyanates and polyhydroxy compounds, polyinsyanates containing isocyanate groups such as those obtained by trimerization of organic diisocyanates. , or German Patent Specification No. 110139
These include biuret group-containing polyisocyanates such as those obtained by method No. 4. Preferred are organic diincyanates, and more preferred are aromatic organic diisocyanates and alicyclic organic diisocyanates. Particularly preferable from the strength, rebound, and stain resistance of the sheet-like material are:
Toluylene diisocyanate, diphenylmethane-4,
4'~Diincyanate, diphenyldimethylmethane-
4,4'-diincyanate, naphthylene diincyanate, dicyclohexylmethane-4,4'-diincyanate, dicyclohexyldimethylmethane-4,4'-
diisocyanates, or mixtures thereof.

In order to obtain a sheet material having a certain level of strength, appropriate rebound, and sufficient heat resistance and stain resistance, the organic diincyanate is preferably added in an amount of 1.7 to 6 molar equivalents relative to the polymeric diol. is used in an amount of 1.8 to 5 molar equivalents.

The chain extender used in the present invention is preferably a low-molecular compound having two functional groups that react with commonly used organic polyinsyanates, such as glycols, diamines, amino alcohols, etc.

Glycol chain extenders used in the present invention include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-bentanediol, nepeo-based glycol, hexanediol, Cyclo-＼
These include xanediol, 1,4-bis(β-hydroxyethoxy)benzene, N,N'-bis(β-hydroxyethyl)aniline, diethylene glycol, triethylene glycol, etc., or mixtures thereof.

Specific examples of the organic diamine chain extender used in the present invention include P-phenylene diamine, m-phenylene diamine, tolylene diamine, naphthylene diamine, 4,4
'-cyaminodiphenylmethane, 4.4'-cya□
Minodiphenyl ether, 4,4'-diaminodiphenyl thioether, 4,4'diaminodiphenyl sulfone, 4゜4'-diamino-6,3'-dimethyldiphenylmethane, 4,4'-diamino-6,3'-dichlor Aromatic organic diamines such as diphenylmethane, 4,4'-diaminodiphenyldimethylmethane, ethylenediamine,
Propylene diamine, menthane diamine, isophorone diamine, cyclohexylene diamine, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3
, 3'-dimethyldicyclohexylmethane, aliphatic organic diamines such as xylylene diamine, or mixtures thereof.

Of course, the compound represented by formula (1) of the present invention may be used as a chain extender.

The characteristics of the compound represented by formula [I] are more effectively exhibited when a glycol-based chain extender is used.

As a solvent for the polyurethane of the present invention, 2. /Ane is not particularly limited as long as it does not react with the group. Preferably, dimethylformamide, diethylformamide, dimethylacetamide, hexamethylphosphoramide, N-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran,
Dioxane, etc., or a mixture thereof.

When producing the polyurethane elastomer of the present invention, in order to adjust the degree of polymerization to a desired degree, a commonly used monofunctional monofunctional compound having 14# of amine groups or hydroxyl groups can be used. .

The polyurethane elastomer of the present invention can be obtained by adding and reacting a polymeric diol, an organic polyisocyanate, a chain extender, and, if necessary, a terminal capping agent, all at once, as is generally practiced. It is also possible to use a so-called prepolymer method in which a polymeric diol and an organic polyisocyanate are reacted in advance to synthesize a so-called prepolymer, and then extended with a chain extender.

In order to accelerate the reaction rate when synthesizing the polyurethane of the present invention, for example, S, L, Reegen and K.
, O.

Fr1sch, -Advances in Uret
hane 5science and Technology
ogy, '1, (1971) Technomic
,Pub.

It is of course possible to add a 6th class amine such as triethylenediamine as described in Oo-Inc, +, or an organometallic compound such as dilauryl diptyltin.

Of course, the prepolymer is synthesized according to the above method, and if necessary, it is synthesized in an aqueous solvent using an appropriate emulsifier.
・ ・ ・ ・ A method is also adopted in which A is chain extended with a chain extender to synthesize an aqueous polyurethane emulsion and used for impregnation. Although it is not as good as the solution type polyurethane in terms of mechanical properties, etc., it is very advantageous in producing fiber sheets, as will be described later.

As already known, weathering agents such as various antioxidants and ultraviolet absorbers, organic and inorganic pigments, carbon black, titanium oxide, and coagulation regulators are added to the solution of the polyurethane elastomer of the present invention. You can also add some medicine.

The fiber sheet in the present invention includes nonwoven fabrics, woven fabrics, knitted fabrics, and laminates thereof. There may be piloerection. The type of fibers constituting the fiber sheet is not particularly limited. That is, synthetic fibers, regenerated fibers, natural fibers, etc. can all be used, but synthetic fibers such as polyamide and polyester are preferred.

The fineness of the fiber is not particularly limited, but is 1.5 denier or less, preferably 0.8 denier. Denier or less is preferable.
If it is 2 denier or less, the feel and flexibility of the sheet-like material will be improved.

These fibers may form a bundle or may exist individually.

In the present invention, it is preferable to apply a fiber sheet made of ultrafine fibers, and the ultrafine fibers can be obtained by removing one component from ultrafine fiber-generating fibers such as composite fiber polymer array fibers or mixed spun fibers, or Directly by exfoliating each component using mechanical action, super draw, etc. Manufactured by a method to obtain fine fibers.

The sheet-like product of the present invention can be obtained by dissolving or dispersing the hapolyurethane of the present invention in a fiber sheet, impregnating or coating, or impregnating and coating, and then wet-coagulating or dry-solidifying.

The sheet-like material of the present invention is made of artificial leather because it is made of a specific polyurethane, so it is flexible and has appropriate rebound resilience, and its excellent properties are not impaired by heat treatment such as dyeing, pressing, and ironing. As such, it is particularly suitable for use in artificial leather for clothing.

That is, the sheet-like material of the present invention has strength, appropriate hardness,
In addition to having flexibility and texture, there is little shine or hardening of the texture due to ironing, there is little decrease in thickness or hardening of texture due to pressing, and there is no bubbling (small irregularities on the surface) and the initial It has the advantage of maintaining excellent surface quality that is almost unaffected by high-order processing.

The present invention will be specifically explained below using examples. The following measuring method was used to evaluate the sheet-like products in the examples.

Tensile test: A sample of 20 x 100 mm was prepared and measured using a Tensilon UTM-m-ioO tensile tester manufactured by Toyo Baldwin ■.

Flexibility (Clark method) 01arkS manufactured by Nidaiei Kagaku Seiki Co., Ltd.
JISL-10 using ofness Te5ter
It was measured by a method according to the 6/22/30 method (Clark method) of 79-1976.

Ironing: Use an electric steam iron (heatless iron) set at 140℃ (approximately 120℃), use a Teflon ironing cover, remove the cloth ironing cover from the ironing board and use it as a pad, and iron while applying vacuum suction. I ran a cliff.

Press test JAN-670-8Fu-s manufactured by Nitokyo Heavy Industries
ing and collar molding pr
Using an essing machine, the temperature was 130°C.
Pressure 2Kg/cm2, steam 3 seconds, baking 5
The treatment was carried out under the condition of vacuum for 5 seconds.

In the Examples, the following abbreviations were used.

SG β, β, β', β'-tetramethyl-2.4
．． Polyester diol PEA containing 8,10-tetraoxaspiro[5,5]undecane BG 114-butanediol EG ethylene glycol PSA 8G
Polyethylene adipate diol POL Polycaprolactone diol P TMG Polytetramethyleneoxyglycol MDI Diphenylmethane-4,4'-diisocyanate IPA Isopropyl alcohol DMF N,N-dimethylbormamide Example 1 β2βtβ'tβ'-tetramethyl-2,4,8゜10
-tetraoxaspiro(5,5)undecane(1o,3
g), 1,4-butanediol (31 g) and adipic acid (85 g) were heated and stirred at 21o C for 4 hours to condense,
A polymeric diol (PSA-1) with an average molecular weight of 198° was obtained.

PTMG (50% by weight) with a molecular weight of 20% and PSA-
1 (50% by weight), 5 times molar equivalent of MD
After reacting I to obtain a prepolymer, it was diluted to 50% with DMF, and DMF containing EG and IPA at a molar ratio of 99:1.
The solution was added in an amount of 0.97 molar equivalent based on the remaining incyanate groups, and reacted at 30°C for 200 hours. The mixture was then diluted to 50% with DMF and reacted at 30° C. for 8 hours.

The softening point of the polyurethane dry film was 130°C.

Consisting of 50 parts of polyethylene terephthalate as the island component and 50 parts of polystyrene as the sea component, 16 high fibers/filament stretched 2°3 times, thickness 3', 4 denier, length 51 length, number of crimps 15/inch Using the polymer array fiber of 2. −
Apparent density 0.170g/c through each step of Dolpanchino
I got J's non-woven fabric. The nonwoven fabric was impregnated with a 2° aqueous solution of polyvinyl alcohol, dried, and then immersed in perchloroethylene to dissolve the polystyrene to obtain a nonwoven fabric in which bundles of ultrafine fibers were entangled.

After immersing the nonwoven fabric in a 13% DMF solution of the polyurethane elastomer and squeezing it with a roll to remove excess solution,
Wet coagulation was carried out in water for 1 hour, the bath temperature was raised to 80°C, and the solvent and polyvinyl alcohol were removed to obtain a sheet-like product. The resulting sheet was sliced to a thickness of 1.1 tnm, and the surface was buffed with sandpaper. The thickness of the sheet after puffing is 0.8! lfi toshida. This sheet was dyed at 125°C for 1 hour using Kayalon Polyester Gray NG (disperse dye) 2 parts o, w, f dye solution in a high temperature, high pressure jet dyeing machine.The resulting sheet was brushed to obtain a raised sheet material of the present invention having an apparent density of 0.260 g/crII.

Examples 2 to 4 and Comparative Examples 1 to 3 Sheet-like products were produced in the same manner as in Example 1, except that a polyurethane elastomer synthesized using the polyurethane composition shown in Table 1 was used.

The properties of the obtained sheet-like material are listed in Table 1.

It is clear from the measurement results listed in Table 1 that the sheet-like article of the present invention using a polyurethane elastic body having a structure in which a certain amount or more of polyester diol containing a specific spiroglycol is used can be sewn. (Refer to tensile properties such as sufficient strength for the original fabric, appropriate hardness and 20% modulus)
In addition to having excellent flexibility, texture, and surface quality, there is little hardening of the texture when ironing. It is clear that the material has the advantage that there is no occurrence of unevenness (irregularities), and the initial excellent surface quality is maintained almost unaffected by high-order processing.

Furthermore, it is clear from Comparative Example 3 that polyurethane elastomers with a lower molecular weight of polymeric diol or with a larger amount of organic diisocyanate have a harder initial texture.
It has the disadvantage of poor flexibility.

Procedural amendment 1. Indication of the case Patent Application No. 47255 filed in 1982 2. Name of the invention: Sheet-like product 5. Name of the person making the amendment (315) Higashi Shi Co., Ltd. Company 41. Date of the amendment order: Voluntary 5. Invention increased by the amendment. Number None & Contents of amendment 1 in column 7 of “Claims” and “Detailed Description of the Invention” of the specification to be amended, “Claims” on page 1, line 4 to page 2, line 6 of the specification ” shall be amended as shown in the attached sheet.

2. "Organic carboxylic acid" on page 4, line 15 and page 8, line 2 of the specification shall be changed to "organic dicarboxylic acid."

3. Change "Among the diol residues in the diol" to "Among the low molecular weight diol residues in the diol" on page 12 of the specification, line 8.

4 Specification page 24 line 10 ``Boriesteg'' is changed to ``Polyestag''.

Attachment Claims In the sheet-like product obtained by impregnating and/or coating a polyurethane elastic material on a fiber notebook, the polyurethane elastic material is composed of (a) a compound represented by formula C13, an organic dicarboxylic acid, and an ester or ester thereof; A sheet-like polymer synthesized from a polymeric diol having a molecular weight of 500 or more containing a polyester obtained by reacting an anhydride, (b) an organic polyisocyanate, and (C) a chain extender. thing

Claims (1)

[Scope of Claims] In a sheet-like article formed by impregnating and/or coating a fiber sheet with a polyurethane elastic material, the polyurethane elastic material comprises: (a) a compound represented by formula [I] and an organic carboxylic acid and/or the like; (b) an organic polyisocyanate, and (C) a polymeric diol with a molecular weight of 500 or more containing a polyester obtained by reacting an ester or anhydride of
It is a polymer synthesized from a chain extender.