JPH0586160A - Water-base o/w dispersion of polyurethane resin - Google Patents

Abstract

PURPOSE:To prepare the title dispersion which gives a molded article having high elasticity, shape memory properties, and self-healing ability by dispersing a specific polyurethane resin prepd. from an org. polyisocyanate and an active hydrogen component comprising a specific polyol. CONSTITUTION:A polyurethane resin prepd. from an org. polyisocyanate [e.g. 4,4'-methylenebis(cyclohexyl isocyanate)] and an active hydrogen component comprising at least one polyol selected from the group consisting of polyols of formulas I, II, and III[wherein A3 is-SO2-.-CO-, or-C(R1)(R2)-(wherein R1 and R2 are each H, 1-3C alkyl, F, or CL); A1 and A2 are each 2-4C alkylene; 2<=m+n<=10; 0<=o+p<=10; 0<=q+r<=10; and X is H or CH3] and contg. at least 10wt.% at least one kind of group derived from the polyol and selected from the group consisting of groups of formulas IV, V, and VI is dispersed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane resin type O / W type aqueous dispersion which can be used as a resin having a shape memory property and is useful for resin processing of textiles, film, paint and the like. Is.

[0002]

2. Description of the Related Art Conventionally, as a shape memory resin, a norbornene type shape memory resin having a number average molecular weight of 1,000,000 or more (for example, Japanese Patent Laid-Open No. 59-53528) or a urethane resin type shape memory resin (for example, Japanese Patent Laid-Open Publication No. Hei. No. 2-92914) is known, but the form before molding or before obtaining a coating film was a solvent solution or pellets.

[0003]

However, when a textile product is resin-processed or a coating film is formed using a shape-memory resin in the form of a solvent solution, the solvent scatters, so measures for handling dangerous materials and explosion-proof equipment are required. And exhaust equipment were required. Further, in the case of the pellet form, it is necessary to dissolve in a solvent and use it as a solution, or an extra process or equipment for melt molding is required. The present invention provides a polyurethane resin-based aqueous dispersion that can be used as a shape-memory resin, that is, it eliminates the problem of handling dangerous substances and the need for the above equipment, and obtains a product that is easier to handle than before. The purpose is to

[0004]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventors have found a polyurethane resin-based O / W type aqueous dispersion which can be used as a shape memory resin, and have found the present invention. Arrived That is, the present invention is derived from an organic polyisocyanate (a) and an active hydrogen component (b) consisting of one or more polyols (b1) represented by any one of the following general formulas 7 to 9 and having in the molecule A polyurethane resin system O / containing a polyurethane resin containing at least 10% by weight of one or more groups represented by any one of the following general formulas 10 to 12 derived from the polyol (b1) in a dispersed state. It is a W-type aqueous dispersion.

[0005]

[Chemical 7]

[0006]

[Chemical 8]

[0007]

[Chemical 9]

[0008] An alkyl group having 1 to 3 carbon atoms, fluorine or chlorine), A ₁ and A ₂ are alkylene groups having 2 to 4 carbon atoms, m and n
Is a positive integer satisfying 2 ≦ m + n ≦ 10, o and p
Is 0 or a positive integer that satisfies 0 ≦ o + p ≦ 10, q
And r are 0 or a positive integer satisfying 0 ≦ q + r ≦ 10, and X represents hydrogen or a methyl group. ]

[0009]

[Chemical 10]

[0010]

[Chemical 11]

[0011]

[Chemical formula 12] [In the above formulas, A ₃ , R ₁ and R ₂ , A ₁ and A ₂ , m
And n, o and p, q, r, and X are the same as those in the general formulas 7 to 9, respectively. ]

The polyurethane resin-based O / W type aqueous dispersion of the present invention can be a resin having a shape memory property. Here, the shape memory property referred to in the present invention refers to a primitive shape [a shape of a molded article as it is, for example, a sheet shape obtained by drying the aqueous dispersion of the present invention on a glass plate, etc.]
When the molded body of No. 1 is deformed at a temperature of from room temperature to 130 ° C, it can be fixed by bringing its shape to room temperature (for example, less than 40 ° C), or near room temperature (for example, less than 40 ° C).
The deformed shape can be maintained by, and further, a series of characteristics can be restored to the original shape in a short time (for example, within 5 minutes) by heating (for example, 40 ° C. or higher) a molded body with the deformed shape fixed. Ordinary plastic does not have the above-mentioned shape memory. For example, the deformed shape of ordinary plastic can be fixed, but the original shape cannot be recovered even when heated to 40 ° C. or higher, and the deformed shape of rubber cannot be fixed at room temperature.

In the present invention, the organic polyisocyanate (a) may be any one generally used in the synthesis of polyurethane resins, and specific examples thereof include 4,4 '.
-Diphenyl methane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, xylylene diisocyanate, modified aromatic polyisocyanate [ Aromatic polyisocyanates such as 4,4′-diphenylmethane diisocyanate modified to have carbodiimide groups, uretdione groups, and uretoimine groups] and the like; hexamethylene diisocyanate (HD
I), aliphatic polyisocyanates such as water-crosslinked polyisocyanates of hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate (IPDI), 4,4′-methylenebis (cyclohexyl isocyanate); and combinations of two or more of these. Can be mentioned. Of these, 4,4 'from the viewpoint of shape memory
-Diphenyl methane diisocyanate and 4,4 '
-Methylenebis (cyclohexyl isocyanate) is preferred, and particularly preferred is 4,4'-methylenebis (cyclohexyl isocyanate).

In general formulas 7 to 9, among R ₁ and R ₂ ,
Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group and a butyl group. It is preferable that both R ₁ and R ₂ are methyl groups in terms of good shape memory. ₂ to 4 carbon atoms represented by A ₁ and A ₂ in the general formulas 7 to 9
Examples of the alkylene group include ethylene group, propylene group and butylene group. Among these, ethylene group is preferable from the viewpoint of elastic retention at high temperature. M and n in the general formula 7 are usually 2 ≦ m + n ≦ 10, preferably 2 ≦ m + n
≦ 4, more preferably a positive integer satisfying 2 ≦ m + n ≦ 2.5 (where m + n = 2.5 means, for example, a mixture of 2 mol adduct and 3 mol adduct in equimolar amounts). ..
O and p in the general formula 8 are 0 or a positive integer which usually satisfies 0 ≦ o + p ≦ 10, preferably 0 ≦ o + p ≦ 4, and o + p is more preferably 0. Q and r in the general formula 9 are usually 0 ≦ q + r ≦ 10, preferably 0 ≦ q
+ R ≦ 4, which is 0 or a positive integer, and q + r
Is more preferably 0.

Among the polyols (b1), the polyol represented by the general formula 7 is, for example, 4,4'-methylenebisphenol, 4,4'-isopropylidenebisphenol, 4,4'-hydroxybisphenol,
A diol obtained by subjecting a bisphenol such as 4,4′-sulfonyl bisphenol and 4,4′-hydroxybenzophenone to an addition reaction with an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and butylene oxide Can be mentioned. Specifically, 2,4'-methylene bisphenol ethylene oxide 2 mol adduct, 4,4'-methylene bisphenol propylene oxide 2 mol adduct,
2,4'-isopropylidene bisphenol ethylene oxide 2 mol adduct, 4,4'-isopropylidene bisphenol propylene oxide 2 mol adduct,
4,4'-Isopropylidene bisphenol ethylene oxide 1 mol, propylene oxide 1 mol adduct, 4,4'-hydroxybisphenol ethylene oxide 2.2 mol adduct, 4,4'-sulfonyl bisphenol propylene Examples thereof include an oxide 3 mol adduct, 4,4′-hydroxybenzophenone ethylene oxide 2 mol adduct, and 4,4′-hydroxybenzophenone butylene oxide 4 mol adduct.

Among the polyols (b1), specific examples of the polyol represented by the general formula 8 include hydrogenated bisphenols obtained by further hydrogenating the bisphenols exemplified in the section of the polyol represented by the general formula 7. [Bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane, 3,3-bis (4-hydroxycyclohexyl) pentane, etc.] and the hydrogenated bisphenols represented by the general formula 7 As the case of the polyol to be used, those obtained by adding alkylene oxide can be mentioned. Specific examples of the alkylene oxide adduct include an adduct of bis (4-hydroxycyclohexyl) methane with 2 moles of ethylene oxide, an adduct of bis (4-hydroxycyclohexyl) methane with 2 moles of propylene oxide, and a 2,2-bis (4- Hydroxycyclohexyl) propane ethylene oxide 2 mol adduct, 2,2-bis (4-hydroxycyclohexyl) propane propylene oxide 2 mol adduct, 2,2-bis (4-hydroxycyclohexyl)
Propylene butylene oxide 2 mol adduct, 2,2-bis (4-hydroxycyclohexyl) propane ethylene oxide 1 mol. Propylene oxide 1 mol adduct, 3,3-bis (4-hydroxycyclohexyl)
Examples include 4-mol ethylene oxide adduct of pentane.

Among the polyols (b1), the polyol represented by the general formula 9 is cyclohexanedimethanol or its alkylene oxide adduct. Specific examples of the alkylene oxide adduct include a cyclohexanedimethanol 2-mol adduct of ethylene oxide and a cyclohexanedimethanol 2-mol adduct of propylene oxide. Further, two or more kinds of the above-exemplified polyol (b1) may be used in combination.

The polyol (b) in the polyurethane resin
The amount of one or more groups represented by any one of the general formulas 10 to 12 derived from 1) is usually at least 10% by weight, preferably 15% by weight or more, more preferably 20% by weight or more. If it is less than 10% by weight, sufficient shape memory property cannot be obtained.

In order to further improve the impact resistance and cold resistance of the shape memory polyurethane resin obtained from the aqueous dispersion of the present invention, the number average molecular weight of the active hydrogen component (b) is usually the same as that of the polyol (b1). 600-8000
It is preferable to use a long-chain polyol (b2) whose molecular weight is determined from the OH value. Examples of (b2) include polyether polyol (b2-1), polyester polyol (b2-2), and polybutadiene glycol (b2-).
3), polymer polyol (b2-4) and the like having the above-mentioned molecular weight. You may use these 2 or more types together.

Specific examples of (b2-1) include polyethylene glycol, polypropylene glycol, polyoxyethylene-oxypropylene (random and / or block) glycol, polytetramethylene ether glycol, polytetramethylene ether-oxyethylene (random). And / or block) glycol,
Examples thereof include polytetramethylene ether-oxypropylene (random and / or block) glycol, polyhexamethylene ether glycol and the like.

(B2-2) is produced by ring-opening polymerization of polyester polyols and lactones obtained by reacting dihydric alcohols and / or polyether diols having a number average molecular weight of 1000 or less with dicarboxylic acids. And a polycarbonate diol obtained by reacting a dihydric alcohol such as 1,6-hexanediol with phosgene.
Examples of the dihydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,3-pentanediol. .. You may use these 2 or more types together. As the polyether diol having a number average molecular weight of 1,000 or less, polyethylene glycol, polypropylene glycol, polyoxyethylene-oxypropylene (random and / or block) glycol, polytetramethylene ether glycol, polytetramethylene ether-oxyethylene (random and / or Or block) glycol, polytetramethylene ether-oxypropylene (random and / or block) glycol, polyhexamethylene ether glycol and the like. You may use these 2 or more types together. Examples of dicarboxylic acids include aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.) and the like. .. You may use these 2 or more types together. Examples of lactones include ε-caprolactone, γ
Examples include valerolactone. Specific examples of the polyester polyol (b2-2) include polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, polydiethylene adipate, poly (polytetramethylene ether) adipate, polyethylene azelate,
Polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol,
Examples thereof include polyhexamethylene carbonate.

As (b2-3), a polybutadiene homopolymer having hydroxyl groups at both ends, a polybutadiene copolymer having hydroxyl groups at both ends (styrene butadiene copolymer, acrylonitrile butadiene copolymer, etc.)
And those obtained by hydrogenating a part or all of these unsaturated double bonds. You may use these 2 or more types together. Specifically, Poly B from ARCO, USA
Examples include d series, G series and GI series of NISSO-PB manufactured by Nippon Soda Co., Ltd.

As (b2-4), (b2-1)-
The polymer polyol obtained by polymerizing an ethylenically unsaturated monomer (acrylonitrile, styrene, etc.) in any of (b2-3) is mentioned. You may use these 2 or more types together.

In order to further improve the properties such as hardness and heat resistance of the shape-memory resin obtained from the aqueous dispersion of the present invention, the molecular weight of 400 (this molecular weight is OH) together with (b1) and optionally (b2). The chain extender (b3) selected from the following polyhydric alcohols (determined by the valency or amine number), polyhydric amines and water is preferably used. (B
Specific examples of 3) include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol; glycerin, triglyceride. Trihydric or higher alcohols such as methylolpropane and pentaerythritol; amino alcohols such as monoethanolamine and diethanolamine; aliphatic amines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; isophoronediamine, 4,4′-methylenebis (cyclohexylamine) A) alicyclic amines such as hydrazine, carbohydrazide, dibasic acid di-hydrazine (adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide) , Isophthalic acid dihydrazide, etc.)
And water. You may use these 2 or more types together.

A monofunctional active hydrogen compound such as monoalcohol, monoamine, aminoalcohol or asymmetric dimethylhydrazine is added to a part of the active hydrogen component (b) for the purpose of molecular weight adjustment during prepolymer synthesis or chain extension. It can be used or can be additionally used when the desired molecular weight is reached.

The polyurethane resin is obtained by subjecting (a) and (b) to a urethane reaction. NCO group in the organic polyisocyanate (a) used in producing the polyurethane resin and NCO in the active hydrogen component (b)
The equivalent ratio of the active hydrogen group capable of reacting with the group is usually 0.8 to
It is 1.2: 1.0, preferably substantially 1.0: 1.0. The method for producing the polyurethane resin includes (a)
And a one-shot method of simultaneously reacting all of the components (b) to obtain the polyurethane resin, (a), and the components (b)
There is a prepolymer method in which a part of the above is reacted to produce a prepolymer, and then the rest of the component (b) is added to cause a chain extension reaction to obtain the polyurethane resin, and any of these can be produced. In the above prepolymer method, the equivalent ratio of the NCO group in (a) used for producing the prepolymer to the active hydrogen group capable of reacting with the NCO group of the component (b) is usually 1.1 to 2.5: 1.0, preferably 1.1-2.
It is 0: 1.0, and more preferably 1.2 to 1.8: 1.0. If the ratio of NCO groups in this equivalent ratio is smaller than 1.1, the viscosity of the prepolymer becomes too high and a special disperser is required for dispersion, and the dispersion stability of the resulting aqueous dispersion becomes poor. Occurs, and when it exceeds 2.5, the film forming temperature of the dispersion becomes too high,
Since the ratio of the isocyanate (a) constituting the polyurethane resin is large, it is disadvantageous in terms of cost.

A catalyst can be used, if necessary, in the synthesis of the polyurethane resin by the one-shot method and the synthesis of the above prepolymer. Specific examples of the catalyst include lead octylate, dibutyltin dilaurate, dioctyltin dilaurate, stanas octoate and other salts of organic and inorganic acids, and organic metal derivatives; organic tertiary amines such as triethylenediamine and triethylamine; Examples thereof include diazabicycloundecene catalyst.

The polyurethane resin can be synthesized by the one-shot method and the prepolymer can be synthesized without solvent or in a solvent. As this solvent, those usually used for the synthesis of urethane resin can be used. Preferred solvents include solvents that are inert to NCO groups or less active than the reaction components. Specifically, ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.), aliphatic hydrocarbon solvents (n
-Hexane etc.), alcohol solvents (isopropyl alcohol, ethanol etc.), ether solvents (dioxane, tetrahydrofuran etc.), ester solvents (ethyl acetate, cellosolve acetate etc.), amide solvents (dimethylformamide, dimethylacetamide etc.), Examples thereof include sulfoxide type solvents (dimethyl sulfoxide and the like), lactam type solvents (n-methyl-2-pyrrolidone and the like) and the like. Among these, acetone and methyl ethyl ketone are particularly preferable from the viewpoints of solvent evaporation, solubility of the polyurethane resin or prepolymer, dispersibility in water, and the like. Although the solvent may remain in the O / W type aqueous dispersion of the present invention,
Usually, it is removed after forming a dispersion. When removing, it is heated and distilled under normal pressure, or it is heated and distilled under reduced pressure for distillation.

The polyurethane resin can be made into a self-emulsifying type by introducing into the molecule a cation group such as a quaternary ammonium group or a hydrophilic group such as an anion group such as a tertiary amine salt of carboxylic acid. The self-emulsifying type is preferable because the dispersion stability of the O / W type aqueous dispersion of the present invention is improved.

As a specific example of the method of introducing an anion group into the molecule, α, α'-dimethylolalkanoic acids are used as a part of the component (b), and the polyurethane resin is prepared from the components (a) and (b). And a method of introducing a carboxyl group into the molecule during synthesis of a prepolymer and then neutralizing with a amino compound. Specific examples of the α, α′-dimethylolalkanoic acids include α, α′-dimethylolpropionic acid, α, α′-dimethylolacetic acid and the like, and combinations thereof. Of these, α, α'-dimethylolpropionic acid is preferred. Further, as the above-mentioned amino compound used for neutralization, triethylamine, ammonia, 2
-Amino-2-methylpropanol, diethanolamine, dibutylamine, monoethanolamine, and the like, and combinations of these are included. As a specific example of the method of introducing a cationic group into the molecule, a quaternary nitrogen-containing polyol is used as a part of the component (b), and when the polyurethane resin or prepolymer is synthesized from (a) and the component (b). A cationic group is introduced into the molecule or a tertiary amino group-containing polyol is used as a part of the component (b), and when the polyurethane resin or prepolymer is synthesized from (a) and the component (b),
A method of introducing a secondary amino group into the molecule and then quaternizing with an alkylating agent or neutralizing with an acid can be mentioned. In the above, as the tertiary amino group-containing polyol, N, N
-Dialkylmonoalkanolamines (N, N-dimethylethanolamine, N, N-diethylethanolamine, etc.), N-alkyldialkanolamines (N-methyldiethanolamine, N-butyldiethanolamine, etc.), trialkanolamines (triethanolamine) , Tripropanolamine, etc.) or their alkylene oxide adducts having 2 to 4 carbon atoms, and the like. You may use together 2 or more types of these. Of these, preferred are N-alkyl dialkanol amines. Four
Examples of the secondary nitrogen-containing polyol include those obtained by quaternizing the above tertiary amino group-containing polyol with an alkylating agent. Examples of the alkylating agent and the alkylating agent used for quaternizing the tertiary amino group in the polyurethane resin or prepolymer include dialkyl sulfuric acid (dimethyl sulfuric acid, diethyl sulfuric acid, etc.), aralkyl halide (benzyl chloride, benzyl). Bromide), alkyl halides (methyl chloride, methyl iodide, ethyl chloride, etc.) and the like. You may use these 2 or more types together. 3 in the above polyurethane resins and prepolymers
Examples of the acid used for neutralizing the primary amino group include formic acid, lactic acid, acetic acid and the like. You may use these 2 or more types together.

In the O / W type aqueous dispersion of the present invention, the polyurethane resin obtained by the one-shot method or the prepolymer method is dispersed in water under proper stirring, or
Alternatively, it can be obtained by using a prepolymer intermediately obtained by the prepolymer method, dispersing it in water and extending the chain. Examples of the method of dispersing in water include a method of adding water to the polyurethane resin or prepolymer with appropriate stirring, or conversely, a method of dispersing the polyurethane resin or prepolymer in water. When dispersing the prepolymer, the chain extension reaction is carried out with water simultaneously with the dispersion. The chain extension reaction may be carried out using a chain extender other than water. In this case, in (b3), NCO is more preferable than water.
It is advisable to select and use a compound having high reactivity with the group.

The concentration of the resin component in the O / W type aqueous dispersion of the present invention can be usually 0.1 to 95% by weight, but 10 to 50% is preferable and 20 to 40% is particularly preferable in terms of production.

If necessary, the O / W type aqueous dispersion of the present invention may contain various additives for the purpose of improving weather resistance and the like. The additive may be usually added at the time of synthesizing the polyurethane resin or the prepolymer, but when the additive is water-soluble or reacts with a reaction component such as the organic polyisocyanate (a), an aqueous dispersion of the polyurethane resin And then add it. Specific examples of various additives include antioxidants (hindered phenol-based, phosphite-based, thioether-based, etc.), ultraviolet absorbers (benzophenone-based, benzotriazole-based, oxalic acid anilide-based, salicylate-based, salicylate-based, etc.), Light stabilizer (hindered amine type), NOx gas stabilizer (hydrazine type, semicarbazilo type, etc.), metal deactivator (nickel complex salt type, etc.), flame retardant (organic halogen type, etc.), antistatic agent, softening treatment Agents, water repellent treatment agents and the like.

The O / W type aqueous dispersion of the present invention can be used by adding a coloring agent such as a dye or a pigment, a filler, a modifier and the like, if necessary, according to the purpose. Examples of the dye include direct dyes, acid dyes, basic dyes, reactive dyes, metal complex salt dyes and the like. As the pigment, carbon black, titanium oxide,
Inorganic pigments such as iron oxide, chromium oxide, mica, zinc oxide, and navy blue and organic pigments such as coupling azo, condensed azo, anthraquinone, perylene, quinacridone, thioindigo, dioxazine, and phthalocyanine Can be mentioned. As the filler, calcium carbonate, silica, talc, inorganic filler such as glass beads, fluorine resin, silicone resin, polyamide resin, styrene resin,
Examples include fine powders of urethane resin and beads, organic fillers such as hollow beads, and the like. As the modifier, polyacrylic acid ester, polystyrene, polyacrylonitrile,
Aqueous dispersions such as acrylonitrile-vinylidene chloride copolymer, acrylonitrile-styrene copolymer vinyl chloride-vinyl acetate copolymer and the like can be mentioned.

The aqueous dispersion of the present invention can be used by adding a crosslinking agent if necessary. Specific examples of the cross-linking agent include compounds such as melamine, epoxy, and block isocyanate, and combinations of two or more of these. As a method of using these, for example, for the purpose of improving water resistance and the like, a hydroxyl group in the molecule of the polyurethane resin,
Examples include a method of introducing a carboxyl group, an amino group and the like, and crosslinking with the above-mentioned crosslinking agent at the time of processing.

If necessary, the aqueous dispersion of the present invention may contain a small amount of the following solvents according to the purpose. That is, when a solvent is used as a so-called film forming agent for the purpose of obtaining a uniform film or coating film, a high boiling point solvent such as dimethylformamide or n-methyl-2-pyrrolidone is preferable. When a solvent is used as a penetrant or an antifoaming agent, an alcohol solvent such as isopropanol is preferable.

The aqueous dispersion of the present invention is coated on a releasable substrate, dried, and optionally heat-treated, and then peeled off from the substrate to give a film or sheet of shape-memory resin, adhesion or impregnation. It can be used as a paint or a composite by coating or impregnating it on a substrate having properties, drying it, and then heat treating it if necessary. Drying is usually 0-130
C., preferably 50 to 130.degree. C., and dried for 1 minute to 1 hour. If necessary, this is further heat-treated at 130 to 220 ° C. for 1 minute to 1 hour. Examples of the releasable substrate include release paper, glass plates, various plastic films, metal plates surface-treated with a releasable agent, and the like. Examples of the adhesive and impregnating base material include various synthetic and natural fibers and fabrics, metal plates, plastic films, concrete, wood boards, various artificial and natural leathers, and the like. The polyurethane resin-based molded products of various shapes obtained from the aqueous dispersion of the present invention have shape memory properties. When the molded product is thermoplastic, it can be stored in a desired shape, and the shape can be stored as a primitive shape by holding at 130 to 220 ° C for 1 minute to 1 hour. In addition, this molded product usually deforms to a desired shape at 130 ° C or below,
The deformed shape can be retained below 0 ° C, and the retained deformed shape can be restored to the original shape by heating to 40 ° C or higher.

[0038]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. Hereinafter, parts are parts by weight. The abbreviations used in the examples have the following meanings.

(Organic polyisocyanate) MDI-H: 4,4'-methylenebis (cyclohexylisocyanate) (Active hydrogen component) BPEO: 4,4'-isopropylidene bisphenol, about 2 mol of ethylene oxide Adduct amount = 319.0 Hydroxyl value = 351.7 PC-2000: Polycarbonate diol [Nippon Polyurethane Industry Co., Ltd., product name: Nipporan 980R] Molecular weight = 1996 Hydroxyl value = 56.2 PCL-2000: Polycaprolactone diol [Daicel Chemical Industries Co., Ltd., product name: Praxel 220] Molecular weight = 1989 Hydroxyl group value = 56.4 PBA-1000: Polybutyrea dipate molecular mass = 1020 Hydroxyl group value = 110.0 DMPA: Dimethylol propionic acid n-MDA : N-methyl-diethano Amine CDH: carbohydrazide (quaternary agent) DMS: dimethylsulfate (neutralizer) TEA: triethylamine (reaction terminator) MEA: monoethanolamine (solvent) MEK: methyl ethyl ketone DMK: acetone (other components) M-3 : Sumitomo Chemical Co., Ltd. melamine resin (Product name: Sumitex resin M-3)

Example 1 PC-2000: 13 was placed in a reaction can which was replaced with dry nitrogen gas.
7.7 parts, BPEO: 236.7 parts, DMPA: 25.
3 parts,: MDI-H: 308.4 parts, MEK: 303.
About 4 parts were charged, and the reaction system temperature was 50 ° C to 100 ° C for about 15 minutes.
NCO% 1.47%
A prepolymer solution of was obtained. After cooling this to 40 ℃, TE
A: 19.1 parts were charged and stirred for 30 minutes, then ion-exchanged water: 1840 parts were charged under high speed stirring and stirred at about 40 ° C. for about 5 hours to carry out water elongation reaction together with emulsification. Next, a distiller was attached, the temperature was raised to 80 ° C, and the pressure was gradually reduced to remove MEK by distillation to remove the resin, the resin concentration was 29.8%, the viscosity was 9.5cps / 20 ° C (b
An O / W type aqueous dispersion of a polyurethane resin (containing 23.6% by weight of the group represented by Chemical Formula 4 derived from Component 1) was obtained. The O / W type aqueous dispersion of the polyurethane resin was used to prepare a mixed solution having the following formulation. O / W type aqueous dispersion of polyurethane resin: 90.0 parts Water: 4.0 parts The above compounded solution was cast on a glass plate and dried at room temperature for 24 hours.
It was dried at 0 to 120 ° C. for 2 hours to completely dry the water.
After heat treatment at 150 ℃ for 15 minutes, the thickness is about 0.2
A film of mm was obtained. This film (cut into a width of 1 cm and a length of 10 cm) was cooled to about 25 ° C. while being bent at 70 ° C. and 180 ° to fix the deformed shape. When this was immersed in warm water at about 80 ° C., it was almost completely restored to its original shape within 2 seconds. Another piece left bent at about 25 ° C. was still bent after one month, but when immersed in warm water at about 80 ° C., it was almost completely restored to its original shape within 2 seconds.

Example 2 Using the O / W type aqueous dispersion of the polyurethane resin obtained in Example 1, the following formulation liquid was prepared. O / W type aqueous dispersion of polyurethane resin: 90.0 parts M-3: 3.0 parts Isopropyl alcohol: 3.0 parts n-methyl-2pyrrolidone: 3.0 parts The above-mentioned compounded liquid has a thickness of about 1.2 mm. , Apparent density about 0.3g
It was immersed in / cm ₃ of a polyester nonwoven fabric, about 1:80
It was completely dried at 20 ° C. to obtain a sheet having a thickness of 1.1 mm and an apparent density of about 0.6 g / cm ₃ . Cut this sheet (1 cm wide, 10 cm long) at 90 ° C for 1
While being bent at 80 °, the deformed shape was fixed by cooling to about 25 ° C. When this was immersed in warm water of about 90 ° C., it was almost completely restored to its original shape within 30 seconds. Another section left bent at 180 ° C at about 25 ° C remained bent even after 1 month, but when immersed in warm water at about 65 ° C, 30
Within a second, it was almost completely restored to its original shape.

Example 3 PCL-2000: 1 was added to a reaction can which was replaced with dry nitrogen gas.
02.9 parts, PBA-1000: 44.1 parts, BPE
O: 227.8 parts, DMPA: 25.6 parts,: MDI-
H: 315.4 parts and MEK: 307 parts were charged and a prepolymerization reaction was performed at a reaction system internal temperature of 50 ° C. to 110 ° C. for about 15 hours to obtain a prepolymer solution with an NCO% of 1.68%. After cooling this to 40 ° C., TEA (23.2 parts) was charged, the mixture was stirred for 30 minutes, and then ion-exchanged water (189) under high-speed stirring.
0 parts and: MEA: 2.49 parts, and CDH: 16.5.
A 20% aqueous solution prepared by mixing 4 parts was continuously charged. Next, attach a distiller and raise the temperature to 80 ° C and gradually reduce the pressure to MEK.
Is removed by distillation, resin concentration is 31.2%, viscosity is 12.5 cps
/ 20 ° C. (the group represented by the formula 4 derived from the b1 component is 2
An O / W type aqueous dispersion of a polyurethane resin (containing 2.0% by weight) was obtained. The O / W type aqueous dispersion of the polyurethane resin was used to prepare a compounding solution having the following formulation. O / W type aqueous dispersion of polyurethane resin: 90.0 parts isopropyl alcohol: 3.0 parts n-methyl-2pyrrolidone: 3.0 parts The above compounded solution was cast on a glass plate and dried at room temperature for 24 hours.
The water was completely dried at 0 to 120 ° C. Then 150
After heat treatment at 15 ° C. for 15 minutes, a film having a thickness of about 0.2 mm was obtained. This film (cut to a width of 1 cm and a length of 10 cm) was bent at 90 ° and heated at 160 ° C for 30 minutes to memorize the shape. 180 ° at 80 ° C
The bent shape was cooled to about 25 ° C. to fix the deformed shape. When this was immersed in warm water of about 80 ° C., it was restored to a memory shape bent almost 90 ° within 30 seconds. 18
Another section left bent at 0 ° C. at about 25 ° C. was still bent after one month, but when immersed in warm water at about 65 ° C., it almost completely recovered to the memory shape within 30 seconds.

Example 4 An O / W type aqueous dispersion of the polyurethane resin obtained in Example 3 was used to prepare a mixed solution having the following formulation. O / W type aqueous dispersion of polyurethane resin: 85.0 parts Titanium oxide fine powder: 5.0 parts Isopropyl alcohol: 3.0 parts n-Methyl-2pyrrolidone: 4.0 parts M-3: 3.0 parts 100 after spray-painting the compounded liquid on the coating material (iron plate)
After drying at ℃ for 3 minutes, it was further heat-treated at 180 ℃ for 10 minutes. The surface of this coated article was scratched with a pencil (hardness 5H) and then immersed in warm water at 80 ° C. for 2 minutes, and the surface state was restored to a scratch-free state.

Example 5 PC-2000: 15 was placed in a reaction can which had been replaced with dry nitrogen gas.
5.7 parts, BPEO: 214.4 parts, n-MDA: 2
9.8 parts,: MDI-H: 308.4 parts, DMK: 30
Charge 3 parts and carry out a prepolymerization reaction under pressure at a reaction system temperature of 50 ° C to 130 ° C for about 15 hours to obtain NCO%.
A 1.46% prepolymer solution was obtained. After cooling this to 40 ° C., 30.0 parts of DMS was charged and stirred for 3 hours to carry out a quaternization reaction. Next, under high speed stirring, deionized water: 1
A 20% aqueous solution containing 821 parts and 17.6 parts of CDH was sequentially charged and stirred at about 40 ° C. for about 5 hours to carry out emulsification and chain extension reaction. Next, attach a distiller, raise the temperature to 80 ° C, and gradually reduce the pressure to remove DMK by distillation to obtain a resin concentration of 2
An O / W type aqueous dispersion of a polyurethane resin having a viscosity of 9.8% and a viscosity of 23.5 cps / 20 ° C. (containing 20.8% by weight of the group represented by Formula 4 derived from the b1 component) was obtained. The O / W type aqueous dispersion of the polyurethane resin was used to prepare a mixed solution having the following formulation. O / W type aqueous dispersion of polyurethane resin: 90.0 parts Water: 4.0 parts Isopropyl alcohol: 3.0 parts n-Methyl-2pyrrolidone: 3.0 parts The above-mentioned compounded solution is cast on a glass plate 60 1 hour at ℃ and 1
After drying at 20 ° C. for 1 hour, heat treatment was performed at 150 ° C. for 15 minutes to obtain a film having a thickness of about 0.2 mm. This film (1 cm wide and 10 cm long) was cut at 70 ° C
The deformed shape, which was cooled to about 25 ° C. while being bent by 180 °, was fixed. Soaking this in warm water of about 70 ℃ 2
Within a second, it was almost completely restored to its original shape. Another piece left bent at about 25 ° C. was still bent even after one month, but when immersed in warm water at about 70 ° C., it was almost completely restored to its original shape within 2 seconds.

Comparative Example 1 PC-2000: 29 was added to a reaction can which was replaced with dry nitrogen gas.
5.4 parts, EG: 17.84 parts, DMPA: 14.89
Parts, MDI-H: 171.0 parts, MEK: 214 parts were charged and prepolymerization reaction was performed at a reaction system internal temperature of 50 ° C. to 130 ° C. for about 15 hours to obtain a prepolymer solution of NCO% 1.29%. .. After cooling this to 40 ° C, TEA: 1
After charging 1.5 parts and stirring for 30 minutes, ion-exchanged water: 1283 parts was charged under high speed stirring. Next, a distiller was attached and the temperature was raised to 80 ° C. to gradually reduce the pressure to remove MEK by distillation to obtain an O / W type aqueous dispersion of polyurethane resin having a resin concentration of 19.9% and a viscosity of 12.8 cps / 20 ° C. .. The O / W type aqueous dispersion of the polyurethane resin was used to prepare a mixed solution having the following formulation. O / W type aqueous dispersion of polyurethane resin: 90.0 parts Water: 4.0 parts Isopropyl alcohol: 3.0 parts n-Methyl-2pyrrolidone: 3.0 parts The above-mentioned compounded solution is cast on a glass plate at room temperature. 8 after drying for 24 hours
The water was completely dried at 0 to 120 ° C. Then 150
After heat treatment at 15 ° C. for 15 minutes, a film-shaped compact having a thickness of about 0.2 mm was obtained. This molded product (width 1 cm, length 10 cm
When it was tried to fix the deformed shape, which was cooled to about 25 ° C. while being bent 180 ° at 65 ° C., the original shape was immediately recovered and the deformed shape could not be fixed.

Comparative Example 2 The mixed solution prepared in Comparative Example 1 was dipped in a polyester non-woven fabric having a thickness of about 1.2 mm and an apparent density of about 0.3 to give about 80
It was completely dried at 120 ° C to obtain a molded product having a thickness of 1.1 mm and an apparent density of about 0.5. This molded body (width 1c
m, 10 cm long) was heated to 80 ° C., bent to 180 ° and cooled to about 25 ° C. However, the original shape was immediately recovered and the deformed shape could not be fixed.

Comparative Example 3 Using the O / W type aqueous dispersion of the polyurethane resin obtained in Comparative Example 1, a compounding solution having the following formulation was prepared. O / W type aqueous dispersion of polyurethane resin: 85.0 parts Titanium oxide fine powder: 5.0 parts Isopropyl alcohol: 3.0 parts n-Methyl-2pyrrolidone: 4.0 parts Sumitex Resin M-3: 3. 0 parts 100 parts after spray-painting this compounded liquid on the coating material (iron plate)
After drying at ℃ for 3 minutes, it was further heat-treated at 180 ℃ for 10 minutes. The surface of this coated article was scratched with a pencil (hardness 5H) and then immersed in warm water of 80 ° C. for 10 minutes, but the flaw was not recovered.

[0048]

EFFECT OF THE INVENTION Since the polyurethane resin type O / W type aqueous dispersion of the present invention is an aqueous type, it solves the problems of handling dangerous substances such as the conventional solvent type and pellet type and the problems of molding equipment. It is a thing. Further, it is characterized in that it has good adhesion to fibers, metals, glass and the like, and has a lower viscosity than that of solvent solution type polyurethane resin. Furthermore, the polyurethane resin-based molded product of various shapes obtained from the water-based dispersion of the present invention can be made to have excellent transparency, and has high elasticity and also has shape memory property and scratch recovery property. Since the aqueous dispersion of the present invention has such characteristics, the fiber treatment agent (texture modifier, color developer, impact resilience imparting agent, shaping agent, paste agent, washing fastness improver, etc.) It is useful for applications such as coatings, synthetic leather, natural leather, and other coating agents.

Claims (2)

[Claims] 1. An organic polyisocyanate (a) and a polyol (b) represented by any one of the following general formulas 1 to 3
1) At least 10% by weight of one or more groups derived from the active hydrogen component (b) consisting of one or more and derived from the polyol (b1) in the molecule, represented by any one of the following general formulas 4 to 6. % Polyurethane resin O / W characterized by containing dispersed polyurethane resin
Type aqueous dispersion. [Chemical 1] [Chemical 2] [Chemical 3] An alkyl group having 1 to 3 carbon atoms, fluorine or chlorine), A ₁ and A ₂ are alkylene groups having 2 to 4 carbon atoms, m and n
Is a positive integer satisfying 2 ≦ m + n ≦ 10, o and p
Is 0 or a positive integer that satisfies 0 ≦ o + p ≦ 10, q
And r are 0 or a positive integer satisfying 0 ≦ q + r ≦ 10, and X represents hydrogen or a methyl group. ] [Chemical 4] [Chemical 5] [Chemical 6] [In the above formulas, A ₃ , R ₁ and R ₂ , A ₁ and A ₂ , m
And n, o and p, q, r, and X are the same as in general formulas 1 to 3, respectively. ] 2. The aqueous dispersion according to claim 1, wherein the polyurethane resin is a polyurethane resin having a cation group or an anion group in the molecule.