JPH0458833B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to polyurethane compositions. [Prior Art] It has been known that polyurethane elastomer compositions (solutions) are used for producing porous sheet materials (Japanese Patent Publication No. 46-25269, Japanese Patent Publication No. 58-5931, etc.). [Problems to be Solved by the Invention] Polyurethane compositions used for such sheet materials are polyurethane compositions that provide a porous sheet material with excellent surface smoothness, low sheet density, and low shrinkage, so-called wet film forming properties. There is a demand for something superior. [Means for Solving the Problems] As a result of intensive study by the present inventors in order to disturb the polyurethane composition that satisfies these requirements, the present inventors found that a polyurethane composition containing a specific aluminum compound has an excellent wet processability. It was discovered that a porous sheet material having film-forming properties, excellent surface smoothness, and low sheet density could be provided, and the present invention was achieved. That is, the present invention is a polyurethane composition consisting of polyurethane and, if necessary, a melt-combed polyurethane composition, which is characterized by containing an aluminum compound (A) represented by the formula. [In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are straight chain or branched saturated or unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms; R is H or a straight chain having 1 to 20 carbon atoms or a branched saturated or unsaturated aliphatic hydrocarbon group. ] As the saturated or unsaturated aliphatic hydrocarbon group of R ₁ , R ₂ , R ₃ , R ₄ and R, methyl, ethyl, n
Alkyl groups such as - and iso-propyl, n-, iso-, sec- and tert-butyl, octyl, 2-ethylhexyl, pelagonyl, capryl, lauryl, tridecyl, myristyl, cetyl, stearyl, nonadecyl, arachidyl; vinyl, propenyl , butenyl, pentenyl, hexenyl, octenyl, decenyl, dodecenyl, tridecenyl, fiseteryl, pentadecenyl, zomaryl, oleyl, gadoleyl, linoleyl, and other unsaturated aliphatic hydrocarbon groups (alkenyl groups, etc.). Among these, methyl,
iso-propyl, octyl, lauryl, stearyl, dodecenyl, fiseteryl, pentadecenyl, oleyl, and linoleyl. A preferred group of aluminum compounds represented by the formula include those represented by the formula. [In the formula, R ₄ represents a straight chain or branched saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms. ] Specific examples of aluminum compounds represented by the formula include the following: Al compound (1): where R ₄ is Al compound (2): R ₄ is -(CH ₂ ) 8CH=CHCH ₂ CH=CH(CH ₂ ) ₄ CH ₃ . In the polyurethane composition of the present invention, a polyurethane made of an organic diisocyanate (a), a polymeric diol (b), and optionally a chain extender (c) can be used as the polyurethane. As the organic diisocyanate (a) used in the production of such polyurethane, those conventionally used in the production of polyurethane can be used. Such diisocyanates include aromatic diisocyanates having 60 to 20 carbon atoms (excluding the carbon in the NCO group), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, and 8 carbon atoms.
~15 araliphatic diisocyanates and modified products of these diisocyanates (modified products containing urethane groups, carbodiimide groups, allophanate groups, urea groups, Biuret groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone groups, etc.) . Specific examples of such diisocyanates include those described in JP-A-53-42294, such as 1,3- and 1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate (TD1 ), diphenylmethane-2,4'- and/or 4,
4'-diisocyanate (MDI), naphthylene-1,
Aromatic diisocyanates such as 5-diisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate; ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, 2,
6-diisocyanate methyl caproate, bis(2-isocyanate ethyl) fumarate, bis(2-isocyanate ethyl) carbonate, 2
Aliphatic diisocyanates such as -isocyanate ethyl-2,6-diisocyanate hexanoate; isophorone diisocyanate, dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanate ethyl ) Cycloaliphatic diisocyanates such as 4-cyclohexene-1,2-dicarboxylate: xylylene diisocyanate,
Aroaliphatic diisocyanates such as diethylbenzene diisocyanate; modified MDI (urethane modified
(MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and mixtures of two or more of these. Among these, aromatic diisocyanates, particularly MDI, are practically preferred. Examples of the polymer diol (b) used in the production of polyurethane include polyether diols, polyester diols, and mixtures of two or more thereof. Polyether diols include polymerized or copolymerized (block and/or Random addition)
For example, polyethylene glycol, polypropylene glycol, polyethylene-propylene (block and/or random) glycol, polytetramethylene ether glycol, polytetramethylene-ethylene (block and/or random) glycol, polytetramethylene-propylene (block and/or random) ) glycol, polyhexamethylene ether glycol,
Examples include polyoctamethylene ether glycols and mixtures of two or more thereof. Polyester diols include condensed polyester diols obtained by reacting low molecular weight diols and/or polyether diols with a molecular weight of 1000 or less with dicarboxylic acids, and polylactone diols obtained by ring-opening polymerization of lactones. Examples of the low molecular weight diols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-,1,
3-butanediol, neopentyl glycol,
1,6-hexanediol; low-molecular-weight diols having a cyclic group [for example, those described in Japanese Patent Publication No. 1474/1974: bis(hydroxymethyl)cyclohexane, bis(hydroxyethyl)benzene, ethylene oxide adduct of bisphenol A, etc. ],
and mixtures of two or more thereof.
Examples of polyether diols having a molecular weight of 1000 or less include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, and mixtures of two or more thereof. Dicarboxylic acids include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, etc.), aromatic dicarboxylic acids (terephthalic acid,
isophthalic acid, phthalic acid, etc.), and mixtures of two or more thereof; examples of the lactone include ε-caprolactone. Polyesters can be produced by conventional methods such as adding low molecular weight diols and/or polyether diols with a molecular weight of 1000 or less to dicarboxylic acids or their ester-forming derivatives [such as anhydrides (maleic anhydride, phthalic anhydride, etc.), lower esters (terephthalic anhydride, etc.)]. (dimethyl acid, etc.), halides, etc.], or their anhydrides and alkylene oxides (e.g., ethylene oxide and/or propylene oxide), or initiators (low molecular diols and/or polyamides with a molecular weight of 1000 or less). It can be produced by adding lactone to ether diol). Preferred among these polyester diols are polyethylene adipate, polybutylene adipate,
Polyhexamethylene adipate, polyneopentyl adipate, polyethylene propylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, polydiethylene adipate, poly(polytetramethylene ether) adipate, polyethylene azelate, polyethylene sebacate, polybutylene azelate,
polybutylene sebacate, and polycaprolactone diol. In addition, polymer diols obtained by polymerizing these diols (polyether diols and/or polyester diols and, if necessary, low-molecular diols) and ethylenically unsaturated monomers (acrylonitrile, styrene, etc.)
54-101899, JP-A No. 54-122396), polybutadiene diol, hydroxyl group-containing vinyl polymer (acrylic diol) such as those described in JP-A-58-57413 and JP-A-57414 can also be used. . The average molecular weight of the polymeric diol (b) is usually 500~
5000, preferably 1000-3000. The chain extender (c) used as necessary during the production of the polyurethane composition includes two active hydrogen atom-containing groups (hydroxyl group, amino group, mercapro group, etc.);
A low-molecular active hydrogen compound (molecular weight: usually 500 or less, preferably 60 to 400) having preferably a hydroxyl group and/or an amino group, particularly preferably a hydroxyl group
[Low molecular diols, amino alcohols, diamines, etc.] can be used. Examples of such low-molecular active hydrogen compounds include those described in JP-A-53-42294, such as low-molecular diols [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol,
Neopentyl glycol, hexanediol, polyethylene glycol and polypropylene glycol with a molecular weight of 200 to 400, low molecular weight diols having a cyclic group (for example, those described in Japanese Patent Publication No. 45-1474: propylene oxide adduct of bisphenol A, etc.), tertiary or quaternary nitrogen atom-containing low-molecular diols (e.g. those described in JP-A-54-130699: alkyl dialkanolamines and their quaternized products), thiodiethylene glycol, etc.]; cyamines, e.g. aliphatic Diamines (e.g. ethylene diamine), cycloaliphatic diamines (e.g. isophorone diamine), heterocyclic diamines (e.g. piperazine, aminoethylpiperazine), araliphatic diamines (e.g. xylylene diamine), aromatic diamines, hydrazine, hydrazide (adipic acid) dihydrazides, etc.); amino alcohols such as alkanolamines (monoethanolamine, monopropanolamine, etc.); and mixtures of two or more thereof. Among these, preferred are low molecular diols (especially ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol,
and mixtures of two or more of these). The molar ratio of the polymeric diol (b) to the chain extender (c) is usually 1:0 to 15, preferably 1:1 to 7. The overall average molecular weight of the polymeric diol (b) and chain extender (c) is usually 300 to 1000. Average molecular weight is 1000
If it is larger than 300, the wet film formability of the polyurethane decreases, and if it is smaller than 300, the wet film formability is good, but the bending resistance, particularly at low temperatures, becomes insufficient, which is not preferable. In producing polyurethane, the ratio of organic diisocyanate (a) to polymeric diol (b) and optionally chain extender (c) is such that the equivalent ratio of NCO group to active hydrogen-containing group is usually 0.9 to 1.1:1, preferably It is substantially 1. If the equivalent ratio is outside the above range, it will be difficult to obtain a polyurethane with a high degree of polymerization, which is not preferable. Polyurethane can be produced by a conventional method, such as a one-shot method in which an organic diisocyanate (a), a polymeric diol (b), and if necessary a chain extender (c) are simultaneously reacted, or (a) and (b). ) to produce an NCO-terminated prepolymer;
(c) includes a prepolymer method in which chain elongation is performed. Polyurethane production can be carried out in the presence or absence of solvents inert towards NCO groups. As such a solvent, those mentioned below can be used. When producing polyurethane, the reaction temperature is the same as the temperature normally employed in polyurethanization reactions, which is usually 20 to 100°C if a solvent is used, and usually 20 to 220°C if no solvent is used, preferably 150 to 200°C. . To accelerate the reaction, catalysts commonly used in polyurethane reactions [e.g., amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), tin-based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.)]
can be used as needed. In addition, if necessary, polymerization terminators [such as monohydric alcohols (methanol, butanol, cyclohexanol, etc.), monovalent amines (methylamine,
butylamine, cyclohexylamine, etc.)] can also be used. Polyurethane can be produced using commonly used production equipment. In the case of no solvent, for example, a device such as a kneader or an extruder can be used. Practically preferred polyurethanes produced in this manner have a solution viscosity of 2,000 to 1,000,000 cps at 20°C, measured as a 30% by weight DMF solution. The polyurethane solvent used if necessary in the polyurethane composition of the present invention includes an amide solvent [dimethylformamide (hereinafter referred to as DMF)].
), dimethylacetamide, etc.], sulfoxide solvents (dimethylsulfoxide, etc.), ether solvents (dioxane, tetrahydrofuran, etc.), ketone solvents (cyclohexanone, methyl ethyl ketone, etc.), ester solvents (ethyl acetate, etc.), aromatic solvents Examples include hydrocarbon solvents (such as toluene) and mixtures of two or more thereof. Practically preferred are amide solvents and sulfoxide solvents, particularly DMF. Polyurethane composition of the present invention (in the case of solution)
may be either a polyurethane solution prepared in the above-mentioned inert solvent or a polyurethane solution prepared in the above-mentioned solvent. The former is preferred. The concentration of the polyurethane solution is usually 5 to 40% by weight, preferably 10 to 30% by weight. The polyurethane composition of the present invention may optionally contain resins other than polyurethane, such as polyvinyl chloride, polyacrylic ester, polymethacrylic ester, polystyrene, polyacrylonitrile, acrylonitrile-vinylidene chloride copolymer, vinyl chloride-vinyl acetate. A copolymer can also be blended. The blending ratio (weight ratio) of polyurethane and other resins can be varied; for example, 20:80 to 100:0, preferably 50:50 to 100:0.
It can be done. In addition, if necessary, a coagulation regulator such as a higher alcohol (Special Publication No.
22719), Crystalline Organic Compounds (Special Publication No. 1983)
41652), hydrophobic nonionic surfactants (Japanese Patent Publication No. 45-39634 and Japanese Patent Publication No. 45-39635), silicone surfactants (polyoxyalkylene-modified dimethylpolysiloxane), urethane-modified silicones (Japanese Patent Publication No. 45-39634), Application No. 59-1148), etc. can be included. Among these coagulation regulators, urethane-modified silicone (Japanese Patent Application No. 59-1148) is preferred, and the amount added is usually 0.1 to 20% based on the solid content of the polyurethane solution.
% by weight, preferably 0.4-10% by weight. Furthermore, if necessary, safety agents [antioxidants such as 4,4'-butylidene bis(3'-methyl-6-t
- Hindered phenols such as (butylphenol); organic phosphites such as triphenylphosphite and trichloroethylphosphite; ultraviolet absorbers such as benzophenones, benzotriazoles, etc.; acidic substances such as carboxylic acids, oxycarboxylic acids, phosphoric acids, Halogenated phenols; epoxy compounds (e.g. JP-A-55-
60554), pigments (titanium oxide, iron oxide, carbon black, etc.), fillers (calcium carbonate, etc.), flame retardants, plasticizers, thixotropic agents, antistatic agents, bactericides, etc. You can also. The polyurethane compositions of the present invention are useful for porous sheet materials. Porous sheet materials are typically produced by applying a polyurethane solution to a substrate and wet processing.
Substrates used include nonwoven fabrics, woven fabrics, knitted fabrics, raised fabrics, paper (release paper, etc.), plastic films,
Examples include glass plates. Alternatively, the substrate may be resin-treated with a polymeric material in advance, such as non-woven fabric,
In the case of fibrous substrates such as woven fabrics, knitted fabrics, and raised fabrics, it is also possible to use substrates that have been resin-treated in advance with a polymeric substance (for example, a polyurethane with a composition different from that of the polyurethane in the polyurethane composition (with a different nitrogen content)). Examples of the resin processing method include a method in which the substrate is impregnated with a solution or dispersion of a polymeric substance, or a method in which the substrate is subsequently wet-processed. When applying the composition (polyurethane solution) of the present invention to a substrate and subjecting it to wet treatment, application (coating and/or impregnation) of the solution and wet treatment can be carried out by conventional methods. Liquids used in wet processing (nonsolvents include water, ethylene glycol, glycerin, ethylene glycol monoethyl ether, hydroxyethyl acetate, and mixtures of two or more of these. In addition, the above nonsolvents and the above solvents (polyurethane solvents) ) (weight ratio: 90:10 to 30:70, for example).Wet processing methods include immersing a substrate coated with a polyurethane solution in a coagulation bath, coagulating with water vapor, Examples include a method in which a polyurethane solution is partially coagulated with water vapor and then immersed in a coagulation bath, and a method in which a non-solvent is added to a polyurethane solution and applied to the substrate as a colloidal dispersion and then immersed in a coagulation bath. Such wet processing Specific methods include methods (a), (b), (c), and (d) in columns 10 to 11 of US Pat. , washed (with water, methanol, etc.), and dried. Anionic, nonionic, cationic, or amphoteric surfactants can also be used to promote solvent removal. Also,
Crosslinking treatment can also be carried out by the method described in British Patent No. 1168872. The obtained porous 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, glass plate, etc.). Such porous sheet materials include (a) coating the substrate with a polyurethane solution and wet processing;
One consisting of a porous polyurethane layer obtained by peeling off a substrate; (b) One consisting of a base layer and a porous polyurethane coating layer obtained by coating a substrate with a polyurethane solution and wet-processing; (c) One consisting of a porous polyurethane coating layer obtained by coating a substrate with a polyurethane solution; Consisting of a substrate layer with a porous polyurethane impregnated layer obtained by impregnation and wet processing; (d)
A base layer is pre-impregnated with a polyurethane solution and wet-treated if necessary, and () the polyurethane solution is applied thereon and then wet-treated, or () another base layer is coated on top of it. Examples include those having a resin-treated base layer and a porous polyurethane coating layer, which are obtained by laminating prepared wet-processed polyurethane films. Among these, (c) and (d) are preferred. [Example] The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. (The parts shown in the Examples represent parts by weight.) The coagulation regulators used in the Examples and Comparative Examples are as follows. Coagulation regulator (1): Urethane-modified silicone Coagulation regulator (2): Polyoxyalkylene-modified dimethylpolysiloxane Examples 1 to 2, Comparative Example 1 Polyethylene adipate 133 with an average molecular weight of 2220
g, ethylene glycol 15g and MDI 76g
In addition to 800 g of DMF, the solution was reacted in a dry nitrogen atmosphere to obtain a substantially linear polyurethane resin solution (a) having a resin concentration of 20% and a viscosity of 110 poise (20° C.). An Al compound and a coagulation regulator were added to this solution (a) to produce polyurethane compositions of the present invention having compositions as shown in Examples 1 and 2 of Table 1. Also, for comparison, Comparative Example 1 in which only the coagulation regulator was added to solution (a)
A solution with the following composition was prepared.

[Table] Examples 3 to 4, Comparative Example 2 122 g of PTMG with an average molecular weight of 2050, 16.5 g of 1,4-butylene glycol, and 61.5 g of MDI
In addition to 800 g of DMF, the mixture was reacted in a dry nitrogen atmosphere to obtain a substantially linear polyurethane resin solution (b) having a resin concentration of 20% and a viscosity of 50 poise (20° C.). An Al compound and a coagulation regulator were added to this solution (b) to produce polyurethane compositions of the present invention having compositions as shown in Examples 3 and 4 of Table 1. Also, for comparison, Comparative Example 2 in which only the coagulation regulator was added to solution (b)
A solution with the following composition was prepared.

[Table] Usage example (wet film formation test) Each of these solutions was applied to a thickness of 1 mm on a glass plate, and solidified by immersing it in a coagulation bath consisting of a 20% DMF aqueous solution adjusted to 30°C. . Then,
The porous sheet peeled off from the glass plate was washed in warm water at 30°C for 90 minutes and then dried with hot air at 80°C. The appearance and properties of the obtained porous sheet material are shown in Tables 3 and 4.

[Table] Note: *Apparent density

【table】

[Table] Note: *Apparent Density [Effects of the Invention] The polyurethane composition of the present invention provides very excellent wet film formability when used in the production of porous sheet materials. The relative wet film formability when manufacturing porous sheet materials is different when using polyester diol and polyether diol as the polymer diol, and generally speaking, when polyether diol is used, However, the effect of the present invention is remarkable not only in the case of polyester diol-based polyurethane but also in the case of polyether diol-based polyurethane. In addition, the polyurethane composition of the present invention has extremely excellent air permeability, hygroscopicity, texture, flexibility, and physical properties (tensile strength, elongation, abrasion resistance, bending resistance, etc.), and has a smooth surface. It provides a porous sheet material that is dense, has high strength, and has excellent internal air permeability and flexibility. Because of these effects, the polyurethane composition of the present invention is useful for porous sheet materials, and is suitable for use in artificial leather and synthetic leather (shoes, footwear, clothing, bags, furniture, car seats, etc.). Demonstrates usefulness.

Claims (1)

[Scope of Claims] 1. A polyurethane composition comprising polyurethane and, if necessary, a solvent thereof, characterized in that it contains an aluminum compound (A) represented by the formula. [In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are linear or branched saturated or unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms; R is H or a straight chain having 1 to 20 carbon atoms; Represents a chain or branched saturated or unsaturated aliphatic hydrocarbon group. 2. The composition according to claim 1, wherein the content of (A) is 0.05 to 5% by weight based on the solid content of the polyurethane composition. 3. The composition according to claim 1 or 2, wherein the polyurethane is a polyurethane made of an organic diisocyanate (a), a polymeric diol (b), and optionally a chain extender (c). 4. The composition of claim 3, wherein (b) is a polyalkylene ether diol. 5. Claims 1 to 5, wherein the polyurethane composition is a polyurethane solution containing a coagulation regulator.
The composition according to any one of Item 4. 6. The composition according to claim 5, wherein the coagulation regulator is a urethane-modified silicone.