JPS6026866B2 - Fiber sheet material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fibrous sheet material that is uniformly colored and has a fluffy and soft texture.

Although various fibrous sheet-like products have been proposed in the field, a fibrous sheet-like product that is uniformly colored and has a fluffy/noft texture has not yet been obtained. In order to obtain a uniformly colored fiber sheet with a fluffy and soft texture, the present inventors have made extensive studies and found that the texture is determined by the presence of polyurethane elastic material in the fiber sheet. It has been shown that the degree of smearing and pore conditions at fiber junctions depends on the uniformity of the coloring, and that the uniformity of the coloring also depends on the dispersion of the pigment in the impregnating agent, and that these are largely controlled by the type of polyurethane elastomer. The present invention has the following heading and configuration.

A fiber sheet-like product obtained by impregnating a fiber aggregate with a composition consisting of a solution of a polyurethane elastic body A and a solution of a polyurethane elastic body B kneaded with a pigment, and wet-coagulating the composition, the polyurethane elastic body A comprising: A polyurethane elastomer consisting of a polymer diol, an organic polyisocyanate, and a chain extender, wherein 4% by weight or more of the polymer diol is a polyether diol, and the chain extender is an aromatic diamine. Polyurethane elastic body B is a polyurethane elastic body consisting of a polymer diol, an organic polyisocyanate, and a chain extender, and the polymer diol is a polyether and b polyester and/or polycarbonate. A fibrous sheet-like article characterized in that it is a polyurethane elastomer in which the chain extender is a lower aliphatic glycol and satisfies the following formula (1).

G^-1≦GB≦G^11 (1) In the formula, G^ is the gel point of polyurethane elastic body A. GB is the gel point of polyurethane elastic body B. Polyurethane elastic body A referred to in the present invention
The gelation points of and B are measured as follows.

Method for Measuring Gelation Point The polyurethane solution to be measured is diluted with N,N dimethylformamide (DMF) to make a 1% solution.

Place the above 1% solution in a 100mm Erlenmeyer flask, put a magnetic sieve in it, and add distilled water dropwise from a buret while stirring uniformly on a magnetic stirrer. The total volume (unit: ') of water added until the cloudiness associated with dripping of water no longer disappears at 25° C. is read from the scale of the buret, and this value is taken as the gel point. The polyether-based polyurethane elastomer A of the present invention, in which 4% by weight or more of the polymeric diol component is polyether diol, is a polyurethane elastomer consisting of a polymeric diol, an organic polyisocyanate, and a chain extender, At least 40% by weight, more preferably at least 5% by weight of the polymeric diol component has hydroxyl groups at both ends and has an average molecular weight of at least 500, preferably from 800 to 4000, preferably 70% by weight or more.
is a polyether diol having a melting point below qo,
The chain extender is an aromatic diamine.

Examples of these polyether diols include polypropylene glycol, polytetramethylene oxide glycol, and mixtures thereof. Of course, it may be a copolymerized polymeric diol with other components as long as the weight ratio in the polymeric diol used satisfies the above relationship. For example, poly(polypropylene oxide) organic dibasic acid estyl diol. Other polymer geo-
The diol is not particularly limited, but is preferably a commonly used polyester diol and/or polycarbonate diol. Examples of the polyester diol include polyethylene adibate diol, polypropylene adibate diol, polybutylene adibate diol, polyhexamethylene adibate diol, polycaprolactone diol, and mixtures thereof. Examples of the polycarbonate diol include polyethylene carbonate diol, polybutylene carbonate diol, polyhexamethylene carbonate diol, and mixtures thereof. If the polyether diol component in the polymer diol component is 4% by weight or less, when a solution of polyurethane elastomer A is wet-coagulated using a non-solvent for polyurethane elastomer such as water, Because shrinkage is large and sometimes a complete pig-clothing phenomenon occurs, after mixing a solution of polyurethane elastomer B kneaded with pigment, it is soaked into the fiber aggregate and wet coagulated, but the thickness retention rate is low and the density is high. It is not possible to obtain a sheet-like material that is soft, supple, and has a desirable texture.

Aromatic diamines as chain extenders include, for example, 4,4'-diaminodiphenylmethane, 3,3'-dichloro4,4
'-diaminodiphenylmethane, either alone or as a mixture.

Polyurethane elastomer A uses such an aromatic diamine as a chain extender, so it is preferable because it does not easily flatten even when pressed into a fiber sheet at high temperatures and can maintain softness and a fluffy feel. Methods using various coagulation regulators have been proposed to compensate for this drawback, but they are complicated and
Even after solidification, many of these cannot be removed simply by washing with water, and if many of these remain in the sheet-like material, they adversely affect the physical properties, which is undesirable.

The polyurethane elastomer B of the present invention is a polyurethane elastomer comprising a polymeric diol, an organic polyisocyanate, and a chain extender, wherein the polymeric diol is a polyether and b polyester and/or polycarbonate, and the chain This is a polyurethane elastomer whose elongating agent is lower aliphatic glycol.

The amount of the polyester diol component used is at least 5% by weight or more, preferably 1% by weight or more based on the total polymeric diol diol. If the amount of polyester diol used is less than these, there will be problems with processing properties such as increased viscosity due to moisture absorption and sometimes gelation during pigment kneading, and even if it is impregnated into the fiber aggregate. A sheet material with desirable properties cannot be obtained. Examples of the lower aliphatic glycol as a chain extender include ethylene glycol, propylene glycol, and 1,4-butanediol, either alone or as a mixture.

Polyurethane elastomer B uses such a lower aliphatic glycol as a chain extender, so it is preferable because pigments are unlikely to aggregate even when kneaded. Furthermore, although the polyurethane elastic body B is different from the polyurethane elastic body A, it must have an affinity with the polyurethane elastic body A, that is, it must satisfy the relational expression (1).

If the range of formula (1) is exceeded, the polyurethane elastomer A and polyurethane elastomer B from which pigments have been removed in the composition of the present invention will not form a homogeneous solution, but will increase in viscosity over time and phase separation will occur. In addition, sheet materials impregnated with these and wet-coagulated have a large thickness drop when dried, and therefore have a large density.
It has a hard and rough texture, which is undesirable. The pigment is kneaded with a solution of polyurethane elastomer B in order to uniformly disperse the pigment in the composition. In general, pigments have a large cohesive force and are difficult to disperse uniformly in an impregnating agent, so the fiber sheet obtained by impregnating a fiber aggregate with an impregnating agent and green coagulation is not uniformly colored and the color of the impregnating agent itself There is a problem that spots remain. As a method for dispersing pigments in impregnating agents, there is a kneading method in which the pigments are first dispersed in a small amount of polyurethane solution and then diluted with another polyurethane solution. It is extremely difficult to uniformly disperse pigments. This is because when a pigment is kneaded into a polyurethane solution, thickening and sometimes gelation occur due to absorption of water, etc., which prevents uniform dispersion of the pigment.

The present inventors have found that this phenomenon depends on the type of polyurethane and that it can be solved by using polyurethane elastic body B in which the polymeric diol is a polyether and b polyester and/or polycarbonate.

That is, when a pigment is kneaded with a solution of this polyurethane elastomer B, the pigment can be uniformly dispersed without thickening or gelling. Therefore, when a fiber aggregate is impregnated with the composition in which the pigment is uniformly dispersed and wet-coagulated, a uniformly colored fiber sheet can be obtained. The amount of polyurethane elastomer B is 0.1 to 5% by weight based on the pigment.
This is preferable because aggregation of the pigment can be prevented after the pigment is thickened. Furthermore, since the polymeric diol of polyurethane elastic body B consists of a polyether and b polyester and/or polycarbonate, it has extremely good processing characteristics and stability during pigment kneading. In a polyurethane elastomer in which the polymeric diol component is polyether diol alone, it gels too quickly during kneading, resulting in poor processing properties and making it impossible to obtain stable properties. On the other hand, a polyurethane elastomer in which the polymeric diol component is polyester alone has a high waist-wearing property, and when made into an impregnated fiber sheet, it is hard and has a poor feel. The type of pigment in the composition of the present invention is not particularly limited. This is because, in the present invention, microporous formation by wet coagulation is controlled by the type and combination of polyurethanes. Therefore, pigments that can be used include carbon black, titanium oxide,
Various materials such as cadmium sulfide and organic pigments can be used and are not particularly limited. The amount of pigment is preferably 0.01 to 3% by weight based on the polyurethane elastomer A, since this imparts appropriate strength to the fiber sheet, but the amount is determined depending on the desired color. Each solvent forming the solution of polyurethane elastic body A and the solution of polyurethane elastic body B of the present invention may be any solvent as long as it can dissolve each polyurethane elastic body, but it is limited to the solvents in the polyurethane elastic body A and polyurethane elastic body B compositions. It is necessary to form a homogeneous solution and to disperse the pigment.

For this reason, dimethylformamide, dimethylacetamide, diethylformamide, N-methylpyrrolidone, dioxane, dimethylsulfoxide, polytetrahydrofuran alone or a mixture thereof, and also a mixture with water etc. are preferred, but in particular dimethylformamide,
Dimethylacetamide is preferred. The fibers constituting the fiber aggregate of the present invention may be synthetic fibers, chemical fibers, or natural fibers, such as polyester, polyamide, polyacrylic, polyolefin, ring-containing pinyl polymer or copolymer, polyurethane, polyurea, Semi-synthetic fibers obtained from cellulose derivatives, cotton, hemp, wool natural fibers such as

The grade of the fibers constituting the fiber aggregate is not particularly limited, but as long as the fibers are ultrafine fibers of 0.5 denier or less, the fiber sheet can be
It is preferable because it has excellent flexibility and flexibility. Ultrafine fibers can be obtained by a method of removing or peeling one component from multicomponent fibers such as sea-island fibers, mixed spun fibers, special composite fibers, etc., or by a super draw method. The form of the fiber aggregate is woven fabric,
It can be arbitrarily selected from various materials such as knitted fabrics, nonwoven fabrics, or composites thereof depending on the intended use. The fiber sheet of the present invention is produced, for example, by impregnating a fiber aggregate with a composition consisting of a solution of polyurethane elastomer B and a solution of polyurethane elastomer A kneaded with a pigment, and wet-coagulating the composition. A preferred method for producing the fiber sheet of the present invention will be described below.

The pigment is kneaded in a solution of the polyurethane elastomer B to uniformly disperse the pigment, and then mixed with the polyurethane elastomer A solution to obtain the composition. Next, the fiber aggregate is impregnated with the composition and soaked in the non-solvent or solvent-non-solvent of polyurethane elastomers A and B, or wet coagulated in a steam atmosphere or the like to obtain a fiber sheet. The green coagulation rate composition is not particularly limited as long as it is a non-solvent for the polyurethane elastomer A and the polyurethane elastomer B and is miscible with the solvent in the composition. For reasons such as economic efficiency, it is preferable to use water and/or a mixture thereof. When the composition is used as in the present invention, the thickness retention rate of wet coagulation increases due to the combination of specific polyurethane elastomers A and B, so the resulting fiber sheet has a low density and is therefore plump and soft. It has a nice texture.

On the other hand, the combination of the specific polyurethane elastomers A and B makes it possible for the intertwined portions of the fibers to be moderate without causing any sagging. You can get it. In addition, the present invention allows the pigment to be uniformly kneaded with the polyurethane elastomer B without causing any build-up, and furthermore, since the solution of the polyurethane elastomer A having good affinity with the polyurethane elastomer B is blended, a composition in which the pigment is uniformly dispersed can be obtained. is obtained.

Therefore, the impregnated fiber sheet obtained from this composition is uniformly colored. The colored woven sheet of the present invention is uniformly colored and has a fluffy and soft texture, so it has a wide range of uses such as clothing, interior decoration, and industrial materials. The fiber sheet of the present invention can be used as it is, but if it is further subjected to a napping treatment, it will become suede-like artificial leather, or if it is coated with a polymer such as polyurethane, it will become grain-finished artificial leather. In particular, when a fiber sheet made of a fiber aggregate made of ultra-fine fibers is brushed, it has a noticeably fluffy and soft texture, has excellent flexibility and bending properties, and is composed of elegant downy naps. It is preferable because it becomes suede-like artificial leather with an excellent lighting effect. EXAMPLES The present invention will be specifically explained below with reference to Examples, but of course the present invention is not limited to the following Examples. In addition, the following abbreviations are used in the examples.
PTHF Polytetramethylene oxide glycol P
EA Polyethylene adipate glycol PBA Polybutylene adipate glycol PCL Polycaprolactone glycol MD1 4,4'-Diphenylmethane diisocyanate M Old A 4,4'-diaminophenylmethane DMF N,N-dimethylformamide DBA Dibutylamino mA In Propyl alcohol PBC Polybutylene carbonate glycol MOCA
3,3'-dichlorodiaminodipheni'remethane P
PG polypropylene oxide glycol (molecular weight 19
50) PBA polybutylene adipate glycol (
Molecular weight 2015) 1, Crab D 1,4-Butanediol Example 1 A thick film consisting of 50 parts of polyethylene terephthalate as the island component and 5 parts of polystyrene as the sea component, with 16 islands/filament stretched 2 or 3 times. A non-woven fabric with an apparent density of 0.170 is made by using polymer array fibers with a diameter of 3.4 denier, a length of 51 willow, and a crimp number of 15/inch, through the carding, cross wrapper, and needle punching processes. Obtained.

The nonwoven fabric was impregnated with a 20% aqueous solution of polyvinyl alcohol, dried, and then soaked in perchloroethylene to dissolve the polystyrene to obtain a nonwoven fabric in which the ultrafine fibers were entangled. PTHF with a molecular weight of 2030 (7% by weight) and 20
For a PCL of 60 (wt% of 3), twice the molar equivalent of M
After reacting with DI to obtain a prepolymer, 50
A DMF solution containing Mold A and DBA in a molar ratio of 96:4 was added in an equivalent molar amount to the remaining isocyanate groups, and reacted to obtain a 25% polyurethane [A] solution. On the other hand, PTHF with a molecular weight of 2030 (70% by weight) and PCL with a molecular weight of 2060 (3% by weight) were reacted with 3 times the molar equivalent of MDI to obtain a prepolymer, which was then diluted to 50% with DMF and EG A mixed solution containing IPA and IPA at a molar ratio of 99:1 was added in an amount of 0.97 molar equivalent to the remaining isocyanate groups, and the mixture was reacted at 30 qo for 2 hours.

The mixture was then diluted to 30% with DMF and reacted at 30°C for 8 hours. Polyurethane B obtained in this way: 15% by weight Polyurethane solid content equivalent amount, carbon black: 15% by weight
, DMF7 were kneaded in a super mixer to obtain a pigment composition. The nonwoven fabric was impregnated into a mixed polyurethane solution obtained by adding 3% by weight of the composition to a 13% DMF solution of polyurethane A, and the excess solution was removed by squeezing with a roll. Green coagulation was carried out for 1 hour, and the water temperature was raised to 8,000 ℃ to remove the solvent and polypynyl alcohol to obtain a sheet-like product. The thickness retention rate of this sheet-like material with respect to the nonwoven fabric before being impregnated with PoIJ urethane is 1
It was 0.6%. This sheet-like material was cut in two cases in each of the vertical and horizontal directions, and the tensile stress at 20% elongation was measured.
g/skin. In addition, it was cut into 2.5 mm in each of the vertical and horizontal directions, and
When the flexibility was measured by SEIKILTD),
It was 1.11 evening vertically and 0.85 evening horizontally. As listed in Table 1, these values indicate that a sheet-like material having remarkable flexibility compared to Comparative Examples 1 and 2 was obtained. Comparative Example 1 A sheet-like product was obtained in accordance with the conditions of Example 1, except that only PCL having a molecular weight of 2060 was used as the polymer diol instead of polyurethane B in Example 1.

As shown in Table 1, the sheet-like material is much harder than Example 1, and the thickness retention rate of the nonwoven fabric before polyurethane impregnation is 104.8%, which is the same as Example 1.
The value was smaller than that of . Comparative Example 2 As the polymer diol of polyurethane B, the molecular weight was 204
A sheet-like product was obtained according to all the conditions of Example 1 except that 0 PBA was used.

As listed in Table 1, the physical properties of this material were similar to those of Comparative Example 1, and it was harder than the Examples, and the thickness retention rate relative to the nonwoven fabric before impregnation with polyurethane was also small. Comparative Example 3 A sheet-like product was obtained by processing according to the conditions of Example 1 except that polyurethane 8 of Example 1 was used as polyurethane A.

This sheet-like material exhibited the physical properties listed in Table 1, but was unsatisfactory because the thickness decreased significantly and the texture changed to a hard texture when subjected to high-temperature treatment such as hot pressing. Example 2 The same as Example 1 except that PTHF (molecular weight 2030, 7% by weight) was used as the polymer diol of polyurethane B.
A sheet-like material was obtained by processing according to the conditions described in .

This sheet-like material had the physical properties shown in Table 1 and was fluffy and soft. Furthermore, even after high-temperature treatment such as heat pressing, the thickness did not decrease and the texture did not change. Example 3 Polymer diols of polyurethane B include PTHF (molecular weight 2030, 7% by weight), PCL (molecular weight 206Q
15% by weight) and PBC (molecular weight 1980, 15% by weight) were all treated according to the conditions of Example 1,
A sheet-like product was obtained.

This sheet-like material had the physical properties shown in Table 1 and was fluffy and soft. Furthermore, even after high-temperature treatment such as heat pressing, the thickness did not decrease and the texture did not change. Example 4 MOC as a chain extender for polyurethane A
A sheet-like product was obtained by processing according to the conditions of Example 1 except that A was used.

This sheet-like material had the physical properties shown in Table 1 and was fluffy and soft. Furthermore, even after high-temperature treatment such as heat pressing, the thickness did not decrease and the texture did not change. Example 5 A sheet-like product was obtained by processing according to the conditions of Example 1 except that the compositions shown in Table 1 were used as polyurethane A and polyurethane B.

This sheet-like material had the physical properties shown in Table 1 and was fluffy and soft. Comparative Example 4 A sheet-like product was obtained by processing according to the conditions of Example 1 except that the compositions shown in Table 1 were used as polyurethane A and polyurethane B.

This sheet-like material had physical properties as shown in Table 1, but was unsatisfactory because the thickness decreased significantly and the texture changed to a hard texture when subjected to high-temperature treatment such as hot pressing. Example 6 Consisting of 7 parts of polyethylene phthalate as the island component and 30 parts of polystyrene as the sea component, 2. Number of islands stretched by 1 orion: 36/filament thickness: 387 niel,
Using a polymer array fiber having a length of 51 ribs and a number of crimps of 15/inch, a nonwoven fabric having an apparent density of 0.260/inch was obtained through each process of carding, cross wrapping, and needle punching.

This nonwoven fabric was impregnated with a 15% aqueous solution of polyvinyl alcohol, dried, and then soaked in carbon tetrachloride to dissolve the polystyrene to obtain a nonwoven fabric in which the ultrafine fibers were entangled. Polyurethane A and polyurethane B having the compositions listed in Table 1 were used for this nonwoven fabric, and the concentration of polyurethane A was set to 1.
A sheet-like product was obtained by carrying out the treatment in accordance with the conditions of Example 1 except that the concentration was 4%. When the physical properties of this sheet-like material were measured according to Example 1, as shown in Table 1, a remarkable softening effect was observed, and the thickness retention rate was also high compared to the nonwoven fabric before impregnation with polyurethane. Comparative Example 5 A sheet-like product was obtained by carrying out the treatment according to the conditions of Example 6 except that polyurethane B having the composition shown in Table 1 was used.

The physical properties of this sheet-like material were measured according to Example 1, and as shown in Table 1, the softening effect was low, and the thickness retention rate relative to the nonwoven fabric before impregnation with polyurethane was also low. Example 7 The sheet-like product obtained in Example 1 was cut in half, and both sides were ground with sandpaper to obtain a sheet-like product having fluff on the surface.

The sheet-like material was dyed with a jet dyeing machine for 12,000 yen for 2 hours, and then subjected to finishing treatment to a thickness of 0.5 oz. as shown in Table 2.
A suede-like artificial leather having a density of 82 willow and a density of 0.261 m/m was obtained, which was much more flexible than that of Comparative Example 6 and had an excellent texture. When the cross section of the artificial leather was observed using SEM, it was found that the polyurethane of the comparative example contracted strongly and bound the ultra-fine loom east, whereas in the example, the polyurethane loosely surrounded the fiber east. Met.
Comparative Examples 6 and 7 Suede-like artificial leather was obtained from the sheet-like materials obtained in Comparative Examples 1 and 3 according to the conditions of Example 7.

Example 8 Polyurethane A of Example 1 was replaced with a polyurethane with a molecular weight of 2030.
Polyurethane A was obtained in the same manner except that only PTHF was used as the polymer diol.

Polyurethane B: 8 parts by weight of PTEF, 2 parts by weight of PCL
A pigment composition was prepared in the same manner as in Example 1 except that the parts by weight were changed to .

When a sheet-like product was produced using this in the same manner as in Example 1, a soft, delicate, and pliable sheet-like product could be obtained.

Gel point of polyurethane A 2.01 Gel point of polyurethane B 2. Thickness retention rate of planar sheet material 106% Stress at 20% elongation Vertical 4.20 Horizontal 2.62 (Soil 9
/ Adversary) Gurley bending stress Vertical 1.09 Horizontal 0.86
Comparative Example 8 When polyurethane A was used in place of polyurethane B in Example 8 and kneading of pigment was attempted, gelation occurred and a uniform kneaded composition could not be obtained.

Comparative example 9 As polyurethane B, PTHFSoPCLS.

Claims (1)

[Scope of Claims] 1. A fibrous sheet-like product obtained by impregnating a fiber aggregate with a composition consisting of a solution of polyurethane elastomer A and a solution of polyurethane elastomer B kneaded with pigment, and wet-coagulating the composition. , polyurethane elastomer A is a polyurethane elastomer made of a polymer diol, an organic polyisocyanate, and a chain extender, in which 40% by weight or more of the polymer diol is polyether diol, and the chain extender is an aromatic diamine. Polyurethane elastic body B is a polyurethane elastic body consisting of a polymeric diol, an organic polyisocyanate, and a chain extender, and the polymeric diol is a polyether, b polyester, and / or polycarbonate, a polyurethane elastomer whose chain extender is a lower aliphatic glycol, and which satisfies the following formula (I): G_A-1≦G_B≦G_A+1 (I)
(In the formula, G_A is the gel point of polyurethane elastic body A,
G_B is the gel point of polyurethane elastic body B. ).