JPS61126147A - Production of sheet material - Google Patents

Abstract

PURPOSE:To obtain a sheet material which has excellent resistance to hydrolysis and wet-process film-moldability, by applying a soln. of a polyurethane obtd. from an org. diisocyanate, a high-molecular diol, a chain extender, etc., to a substrate and treating the substrate in a wet process. CONSTITUTION:A polyurethane is prepd. by using an org. diisocyanate (A) (e.g.4,4'-diphenylmethane diisocyanate), a high-molecular diol (B) consisting of a polyethylene/tetramethylene ether diol (e.g. tetrahydrofuran/ethylene oxide block copolymer) and optionally other diol (e.g. ethylene glycol) and optionally a chain extender (C) (e.g. ethylenediamine). A soln. of the polyurethane is applied to a substrate such as nonwoven fabric or synthetic resin film and the substrate is treated in a wet process by using a soln. such as water or ethylene glycol to obtain the desired sheet material.

Description

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

[Conventional technology]

Conventionally, there has been a method of producing a sheet material by wet processing a polyurethane entomer made from polyalkylene ether glycol or/and polyester glycol (for example, Japanese Patent Publication No. 46-25269 and Japanese Patent Publication No. 58-5981). Shikaya Shiko's sheet materials did not have sufficient wet film formability or hydrolysis resistance.

[Problem that the invention seeks to solve]

The present inventors have conducted intensive studies to obtain a sheet material with excellent wet film formability and hydrolysis resistance, and as a result, have arrived at the present invention.

[Means to solve the problem]

The present invention relates to organic diisocyanate fA), polyethylene/
A solution of polyurethane consisting of tetramethylene ether diol (b,) and optionally another polymeric diol (b2) and optionally a chain extender (q) is applied to the substrate. , followed by wet processing.

The polyethylene/tetramethylene ether diol (b1) used in the polyurethane of the present invention includes a block copolymer and a random copolymer of tetrahydrofuran (hereinafter abbreviated as TI-IF) and ethylene oxide (hereinafter abbreviated as EO). included.

In (b1), the weight ratio of oxyethylene groups to oxytetramethylene groups is usually 5:95 to 70:30.

The ratio is preferably 10:90 to 50:50. When the proportion of oxytetramethylene groups exceeds the above range, the wet film forming property, that is, the ability to form microporous cells when a sheet is created by a wet processing method, decreases, and when the proportion of oxyethylene groups exceeds the above range, Wet film forming properties and the hydrolysis resistance of the sheet material are reduced.

(bυ can be produced by various methods. For example, block copolymers can be obtained by adding EO to polytetramethylene ether glycol (hereinafter abbreviated as PTMG) or by adding THF to polyoxyethylene glycol. The above-mentioned PTMG can be used as a usual one, such as FTMO described in JP-A-58-29816.The EO addition method can be carried out using a usual alkali catalyst (KOf(
, Na0f1, etc.) under pressure. Further, the method of adding THF may be a method of adding in the presence of a catalyst (such as a Lewis acid). A random copolymer can also be obtained by reacting THF and EO in the presence of an initiator (water, ethylene glycol, 1°4-butanediol, etc.) and a catalyst (Lewis acid, etc.). (b
The average molecular weight of ``1'' is usually 500 to 5,000, preferably 1.0(X) to 3,000. Among (b), preferred is a block copolymer of THF and EO.

Other polymers Geo-1v (
As b2), polyester l/l/ is preferred. Examples of polyester diols include condensed polyester diols obtained by reacting with low molecular weight diols or polyalkylene ether glycol tan dicarboxylic acids having a molecular weight of 100 or less, and polyester diols obtained by ring-opening polymerization of lactones. can give.

The low molecular diols mentioned above include ethylene glycol and propylene glycol.

t,a-butanediol, 1,4-butanediol.

1.6-hexanediol, diethylene glycol.

Dipropylene glycol, neopentyl glycol, bis(hydroxymethyl)cyclohexane.

Examples include bis(hydroxyethyl)benzene and mixtures of two or more thereof. As polyalkylene ether glycol with a molecular weight of 1000 or less, PTMG
, polypropylene ether glycol, polyethylene ether glycol, and mixtures of two or more thereof. Dicarboxylic acids include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid,
cepatic acid), aromatic dicarboxylic acids (terephthalic acid, etc.).

isophthalic acid, etc.), and mixtures of two or more of these. The method for obtaining the condensed polyester diol may be the same as the conventional method, in which a low molecular diol or a polyalkylene ether glycol with a molecular weight of 1000 or less and a dicarboxylic acid are reacted under normal reaction conditions to form a terminal hydroxyl group. Bye. Furthermore, the method for obtaining polyester resin 7 obtained by ring-opening polymerization of lactone may be the same as the conventional method, for example, using an initiator (
It is obtained by addition polymerizing lactone (for example, C-caprolactone, etc.) to glycols, etc.). Preferred among these polyester di-7s are polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene propylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, and polydiethylene adipate. , poly(bori-tetramethylene ether/L/) adipate, bori-ethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, and polycaprolactone diol obtained by ring-opening polymerization of ε-caprolactone. The average molecular weight of the polyester diol is usually 500 to 5.000, preferably 1.000 to 3.0.
It is 00.

The weight ratio of (b1) and (b1) in the polymer Geo-tI/(B) used in the present invention is usually 100:O~
10: 90° preferably go: 20-20:
It is 30. When (b1) is less than 10, the hydrolysis resistance of the sheet material decreases when polyester diol is used as (b1). The average molecular weight of (B) is usually 500-s, ooo, preferably 1.000-3.0
It is 00.

The organic diisocyanates (A) used in the present invention include) aromatic diisocyanates (4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, etc.), araliphatic diisocyanates (quinolyl diisocyanate, etc.) to aliphatic diisocyanates (hexamethylene diisocyanate, etc.) .

lysine diisocyanate, etc.), alicyclic diisocyanates (isophorone diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, etc.), and the like. Details are described in Japanese Patent Application Laid-Open No. 51-42294. Among these, aromatic diisocyanates are practically preferred, and 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) is particularly preferred.

Chain extenders (9) used as necessary in the present invention include those described in JP-A-51-42294, such as low molecular weight di-/L/(ethylene glycol, propylene glycol-/L', 1,4 -butanediol, 1,6-hexanediol, etc.), aliphatic diamines (ethylenediamine, etc.), alicyclic diamines (isophoronediamine, etc.)
, aromatic diamines (such as 4,4'-diaminodiphenylmethane), araliphatic cyamines (such as xylene diamine), alkanolamines (such as ethanolamine), hydrazine, dihydrazide (such as adipic acid dihydrazide), and two or more of these. A mixture of Among these, preferred is low molecular weight glyco-1V
and particularly preferred is ethylene glycol, 1
．． These include 4-butanediol, 1,6-hexanediol, and mixtures of two or more thereof.

The molar ratio of the polymeric diol (B) and the chain extender (q is usually 1.~1°, preferably 1.2~5. (The average molecular weight of the diol combined with Bl and (C)' is 1 Usually 300 to 300.The average molecular weight of the diol is 30
If it is thicker than 0, the wet film formability of polyurethane will deteriorate, and if it is smaller than 300, the wet film formability of polyurethane will be good, but a hard polyurethane will be obtained, and the bending resistance, especially at low temperatures, will be poor. Not sexual enough.

When producing polyurethane, organic diisocyanate (
The ratio of A) to the polymeric diol (evenly and the chain extender (q) used if necessary is usually isocyanate group: active hydrogen-containing group = 0.9 to 1.1: 1 (equivalent ratio), preferably substantially If the ratio is outside the above-mentioned normal range, it is difficult to produce polyurethane with a high degree of polymerization.

The method for producing polyurethane may be any known method (
b) One-shot method, for example, organic diisocyanate (A
) and polymeric di-/v (B) and, if necessary, a chain extender (q), (b) a prepolymer method, for example, reacting (A) and (B) to form a terminal NCO precipitate. Examples include a method in which a polymer is obtained and the chain is extended with (C). Among these, the one-shot method is preferred.

The above production can be carried out in the presence or absence of a solvent inert to isocyanate groups. Suitable solvents in the presence of a solvent include amide solvents [dimethylformamide (hereinafter abbreviated as DMF), dimethylacetamide, etc.], 1-sulfoxide solvents (dimethylsulboquine, etc.), and ether solvents (dioxane, tetrofluorocarbons, etc.). (hydrofuran, etc.), ketone solvents (cyclohexanone, methyl ethyl ketone, etc.), ester solvents (ethyl acetate, etc.), aromatic hydrocarbon solvents (toluene, etc.), and two or more of these solvents.

Practically preferred solvents are amide solvents and sulfoxide solvents, and particularly preferred is DMF.

In the production of polyurethane, the reaction temperature may be the same as the temperature normally employed in the polyurethanization reaction in the industry, and when a solvent is used, the temperature is usually 20 to 100.
°C, typically 20-220 °C if no solvent is used.
°C1 Preferably it is 150-200 °C.

In order to accelerate the reaction, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.) and tin-based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.) used in normal polyurethane reactions may be used. Furthermore, if necessary, a polymerization terminator such as a monohydric alcohol (methanol, butanol, cyclohexanol, etc.), a monohydric amine (methylamine, butylamine, cyclohexylamine, etc.) can also be used.

Polyurethane can be produced using production equipment commonly employed in the industry. In addition, when a solvent is not used, a manufacturing device such as a kneader or an extra/L/-der can be used. The polyurethane produced in this way has a solution viscosity of 2,000 to 1,000,000 measured as a DMF solution (weight%) (solid content).
cps/20°C is practically preferred.

As the polyurethane solution used in the production of the solvent, it is possible to use a polyurethane solution produced in the presence of a solvent inert to the isocyanate groups, or a polyurethane solution prepared by dissolving the polyurethane in the solvent. You can also use it.

The concentration of the solution is usually 5 to 30% by weight, preferably 10 to 3%.
It is 0% by weight.

The polyurethane solution contains resins other than polyurethane resins, such as polyvinyl chloride, polyacrylic acid ester, polymethacrylic acid ester, polystyrene, polyacrylonitrile, acrylonitrile-vinylidene chloride copolymer, vinyl chloride-vinylacetate μ copolymer. can also be blended. In addition, if necessary, antioxidants such as C4,4'-butylidene-bis(-3-methy/l'-6-t-butylpheno-)L/); triphenyl phosphite, trichloroethyl phosphite, etc. organic phosphite], ultraviolet absorber (benzophenone type.

benzotriazole type, etc.), carboxylic acid, phosphoric acid.

Stabilizers such as oxycarboxylic acids and halogenated phenols, and pigments (titanium oxide, carbon black, etc.).

Fillers (calcium carbonate, etc.), plasticizers, antistatic agents, bactericides, and known coagulation regulators [higher alcohols/L/(
(Japanese Patent Publication No. 42-22719) crystalline organic metal compounds (Japanese Patent Publication No. 55-41652), hydrophobic nonionic surfactants (Japanese Patent Publication No. 45-39634 and Japanese Patent Publication No. 45-39685), Oxyalkylene-modified dimethylpolysiloxane (Special Publication Showa 5g-89451
(Japanese Patent Application Publication No. 2003-110000), etc.) can be added.

Examples of the substrate include two nonwoven fabrics, a woven fabric, a raised fabric (such as release paper), a plastic film, and a glass plate. Alternatively, the substrate may be resin-treated with a polymeric substance in advance, such as a nonwoven fabric.

In the case of fibrous substrates such as knitted fabrics, woven fabrics, raised fabrics, polymeric substances (polyurethanes such as conventional polyurethanes and the polyurethanes according to the invention from polyether polyols and/or polyester polyols, chain extenders and organic diiso7anates) are used beforehand. etc.) can also be used. Examples of resin processing methods include a method of impregnating the substrate with a solution or dispersion of a polymeric substance, or a subsequent wet treatment method.A method of applying a polyurethane solution to the substrate includes coating and/or impregnation. can be given.

Next, wet processing is performed. Liquids (nonsolvents) used in wet processing include water, ethylene glycol, glycerin, ethylene glycol monoethyl ether, hydroxyethyl acetate, and mixtures thereof. Further, a mixture of the above-mentioned non-solvent and the above-mentioned solvent (mixing ratio: 90:10 to go:70) can also be used.

Preferred among these are mixtures of water and solvents and water.

Wet processing methods include conventional methods, such as immersing a substrate coated with a polyurethane solution in a coagulation bath, coagulating it with steam, partially coagulating it with steam, and then immersing it in a coagulation bath. There is a method in which a colloidal dispersion is added to the substrate, which is then applied to the substrate and immersed in a coagulation bath. A conventional wet processing method is described in U.S. Patent No. f11284274, columns 10-11 (
It is also described as the method of a) t (b) , (cl , (di).

After the wet treatment, the solvent is removed, washed (with water, methanol, etc.), and dried in the usual manner. Anionic, nonionic, cationic or amphoteric surfactants can also be used to promote solvent removal. Further, crosslinking treatment can also be carried out by the method described in British Patent No. 1,168,872.

The obtained sheet material may be used as it is or after being peeled off from the substrate (in the case of using a plastic film, release paper, or glass plate).

The sheet material obtained by the method of the present invention includes (a) a porous polyurethane layer obtained by coating a substrate with a polyurethane solution, subjecting it to wet treatment, and then peeling off the substrate; (b)
A material consisting of a base layer and a porous polyurethane coating layer obtained by coating a base with a polyurethane solution and wet-processing;
C) A base layer having a porous polyurethane-impregnated layer obtained by impregnating a base with a polyurethane solution and wet-processing; 2) Preparing a base layer impregnated with a resin solution and wet-processing if necessary 1) Either apply a polyurethane solution on it and then wet-process it, or 11)
It can be obtained by laminating a wet-processed polyurethane film made by coating on another substrate on top of it.
Examples include those having a resin-treated base layer and a porous polyurethane coating layer. Among these, the preferred one is (
c) and ii).

〔Example〕

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Production example 1 Molecular weight 2000 OPTMG 400,1il (0,
2-E-tLi ) and potassium hydroxide 0.49 (0,
007 mo/L/) was placed in an autoclave with an internal volume of 11, and after uniformly mixing, 106 g (2.4 moles) of EO was reacted while maintaining the pressure r:, kg/crfl and temperature 140-160"C. .After the reaction, neutralize the alkali, door to door,
After dehydration, an EO adduct of about 5009 PTMG (block copolymer of THF and EO, EO content 20 T)
I got it. This was a white solid at 20°C and had a hydroxyl number of 45.

Obtained EO adduct 25 of P'rMG with a molecular weight of 2500
0, @(01 mo/L/) and polyethylene adipes with a molecular weight of 2000) 2009 (0,1 mo/I/) and ethylene glycol s-/L/309 (0,48 mo/I/) After adding 1520 g of DMF and dissolving it uniformly, MDI 170 J (068 mo/I/) was added and reacted at 60 to 70°C. Eight hours after the start of the reaction, a transparent and uniform polyurethane solution with a viscosity of 80,000 CI) S/20°C was obtained.

Production example 2 Molecular weight force 1400 OPTMG 230 j/ (0,
2%#) and potassium hydroxide 0.39 (0,005
mol) into an autoclave with an internal volume of 11, and after uniformly mixing, EO124.9 (2.8 mol) was placed at a pressure of 5 kg/
crd, and the reaction was carried out while maintaining a temperature of 14o - 160"O. After the reaction, the EO adduct of about 4009 FTMO (THF and E
A block copolymer of O, EO content: JOq6) was obtained.

This is a white solid at 20°C, hydroxyl number = 5
It was 6.

Obtained EO adduct 20 of P'rMG with a molecular weight of 2000
01 (0,1 mo) V ) and polyethylene adipate with a molecular weight of 1000. ! ? (0.1 mol) and 1.4
-Butanedio-/I/44/! (0.49 mol) and 8
After adding 1204g of DMF and dissolving it uniformly, 4172g (069 mol) of MD was added. The reaction was carried out at 60-70°C. Eight hours after the start of the reaction, the viscosity was 100,000 cps/20. A transparent homogeneous polyurcitane solution was obtained at ℃.

Production example 3 THF 216J (3 mo/v) and ethylene glycol-t
L/9. J9 (0.15 mol) and BF3・TH1i'
21.9 (0.15 mol) was placed in an autoclave with an internal volume of 11, and after uniformly mixing, EO54,p (1,2
3 mol) was reacted while maintaining a pressure of 1 kg/a/l and a temperature of 20-30°C. After the reaction, neutralize the acidic catalyst, and
After dehydration, a random copolymer of approximately 2709 THF/EO (EO content: 20 cm) was obtained.

This product was a colorless and transparent liquid at 20°C and had a hydroxyl value of 62.

The obtained THF/EO random copolymer with a molecular weight of 1300 130. p(0,1 mo/L/) and molecular weight is 2500
polybutylene adipate 250. p(0,1mo/L/
) and ethylene glyco-I s5. rp (0,58mo/
I/) into 31 Kolben and 1540p DM
After adding F and dissolving it uniformly, MD1194g (0
, 78 mol) was added thereto, and the reaction was carried out at 60-70''C.

12 hours after the start of the reaction, a transparent and uniform polyurethane solution with a viscosity of 100,000 cps/2oC was obtained.

Production example 4 THF 216. ! li' (3 mo/L/), water 21, BF, and 8.4 g (0.06 mole) of THF were placed in an autoclave with an internal volume of 11, and after uniformly mixing, the mixture was heated to EO93.
, 9 (2,11 mo IL/) at pressure x kg/crt! The reaction was carried out while maintaining the temperature at 20-30°C. After the reaction, approximately 300g of T was neutralized and dehydrated.
A random copolymer of HF/EO (EO content: 30) was obtained. This product was a colorless and transparent liquid at 20°C and had a hydroquine value of 56.

The obtained random copolymer of THF/EO with a molecular weight of 2000.9 (0.1 mol) and polyethylene adipate with a molecular weight of 2000. il (0,1mo/L
/) and 1,4-butanediol 49.4 g (0,55
mole) into 3g of Kolben, and 1487g of DM
After adding F and dissolving it uniformly, MDI 188gC0
, 75 mol) and reacted at 60-70°C. After 11 hours from the start of the reaction, a transparent and uniform polyurethane solution with a viscosity of 90,000 cps/20°C was obtained.

Production Example 5 The EO adduct soog (0.2 mo/L/) of PTMG with a molecular weight of 2500 obtained in Production Example 1 and 43.8 g (0.71 mole) of ethylene glycol were put into a 31-kolben, and 1300 g After adding DMF and dissolving it uniformly,
Add MDI 227 jj (0.91 mo/L/), 6
The reaction was carried out at 0-70"C. Eight hours after the start of the reaction, a transparent and uniform polyurethane solution with a viscosity of 100,000 cps/20C was obtained.

Production Example 6 Random co-electrolyte compound of THF/EO of the molecular weight obtained in Production Example 4 400.9 (0.2 mol) and 1.4
65.9 g (0.18 mol) of -Ftandio-/V was put into a 31st Colben, 1630 g of DMF was added, and after uniformly dissolving, 233 g (0.93 mol/L) of MIII was added. was added and reacted at 60-70"C.

Seven hours after the start of the reaction, a transparent and uniform polyurethane solution with a viscosity of 90,000 cps/20°C was obtained.

Comparative Example 1 PTMG 200 i (0.1 mo/L/) with a molecular weight of 2000, 200 g (0.1 mole) of polyethylene adipate with a molecular weight of 2000, and "・"-7'9'y
) f -#"&(0,55-etv") 2- is put into the Kolben of °' 1, 1487/! DMF of
was added and dissolved uniformly, then 188 g of MDI (0,
75 mol) was added and reacted at 60-70°C. A transparent and uniform polyurethane solution with a recovery degree of 100,000 cps/20°C was obtained 8 hours after the start of the reaction.

Comparative Example 2 400 g (0.2 moles) of FTMO with a molecular weight of 2000 and 42.4.9 (0.68 moles) of ethylene glycol were placed in a 31-kolben, 1548 g of DMF was added, and the mixture was uniformly dissolved. , MDI 221.3g (0,8
9 mol) and reacted at 60-70''C. Ten hours after the start of the reaction, a transparent and uniform polyurethane solution with a viscosity of 100,000 cps/20°C was obtained.

Comparative Example 3 Polyethylene Adipes with a molecular weight of 2000) 400!
! (0,2mo)v) and 1,4-butanediol49.
4. @ (0.55 mol) was put into a 3e Kolben, 1486.9 DMF was added, and after uniformly dissolving it,
MDI 187.8. ! i! (0.75 mo/I/) was added and reacted at 60-70°C. Ten hours after the start of the reaction, a transparent and uniform polyurethane solution with a viscosity of 90,000 cps/20°C was obtained.

Example 1 To 100 parts of the 20% DMF solution of the polyurethane solutions obtained in Production Examples 1 to 6 and Comparative Examples 1 to 3, 1 g of a coagulation regulator (MDI modified product of polyether modified silicone) was added to each. The polyester film was immersed in a 204DMF water bath for 10 minutes to simulate coagulation, and then the porous sheet was peeled off from the polyester film and further immersed in warm water at 20-30°C for 90 minutes. After washing at 100°C,
It was dried with hot air for 0 minutes. The appearance and characteristics of the obtained porous notebook were as shown in Table 1.

In addition, the porous sheet obtained above was 70″C995%R.
, H for two weeks in a constant temperature and humidity chamber.

The tensile strength of the porous sheet before and after this test was measured, and its retention rate was determined. The results were as shown in Table-2.

The porous material of the present invention has excellent surface smoothness, a uniform microporous layer without curling phenomenon, and good hydrolysis resistance, whereas the polyurethane solutions of Comparative Examples 1 to 3 Those that yield good porous sheets have poor hydrolysis resistance, and those that have good hydrolysis resistance cannot yield good porosity, and have poor wet film forming properties and hydrolysis resistance. It did not combine the excellent performance of both.

[Effects of the Invention] The sheet material obtained by the present invention has very excellent wet film formability and hydrolysis resistance. It also has excellent air permeability, and is also excellent in moisture absorption, texture, flexibility, and physical properties (tensile strength, elongation, abrasion resistance, bending resistance, etc.). Furthermore, the surface is dense and has high strength, and the interior has excellent air permeability and flexibility.

Since it exhibits the above effects, the notebook material obtained by the present invention is useful for artificial leather and synthetic leather (shoes, clothing, bags, furniture, automobile seats, etc.).

Claims (1)

[Scope of Claims] 1. A polymeric diol (B) consisting of an organic diisocyanate (A), a polyethylene/tetramethylene ether diol (b_1), and optionally another polymeric diol (b_2), and optionally a chain extender (C ) A method for producing sheet materials, characterized in that a solution of polyurethane from ) is applied to a substrate, followed by wet processing. 2. The manufacturing method according to claim 1, wherein the other polymeric diol (b_2) is a polyester diol. 3. The manufacturing method according to claim 1 or 2, wherein the weight ratio of oxyethylene groups to oxytetramethylene groups in (b_1) is 5:95 to 70:30. 4. Claims 1 to 4, wherein (b_1) is a block copolymer of tetrahydrofuran and ethylene oxide.
The manufacturing method according to any one of paragraph 3.