JPH0699629B2 - Polyurethane composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyurethane composition used for forming a breathable porous polyurethane resin layer and the like.

[Conventional technology]

Organic solvent composition of polyurethane resin, that is, 20% by weight or less of polyvinyl acetate, polyvinyl chloride, based on an organic solvent solution of polyurethane resin or polyurethane resin which does not impair the physical properties of polyurethane resin and polyurethane resin,
In the organic solvent solution with a polymer such as polyacrylic acid ester, polyamide, polyester or the like, or a composition in which an additive such as a colorant, an antistatic agent, a stabilizer against light or heat is added to these solutions Water-in-oil type (W / O type) hydrous polyurethane dispersion mixed and dispersed with the aid of an activator is applied or impregnated with it, then the organic solvent is evaporated first, and then water is added. It is used to form a breathable porous polyurethane resin layer and the like by evaporation. Generally, such W / O polyurethane dispersions
If the standing time from the production to the use becomes a little longer, there is a problem that dispersed particles of water associate with each other to become coarse and unevenly distributed, or a film is easily formed on the surface. However, when the polyurethane-based surfactant previously invented by the present inventors, which is known from JP-B-57-27232, is used as the surfactant, the surfactant has the flexibility and antistatic property of artificial leather. The purpose is to improve the antifouling property, but it is possible to obtain a W / O type polyurethane dispersion having relatively good stability.

[Problems to be Solved by the Invention]

The W / O type polyurethane dispersion liquid using a polyurethane-based surfactant described in JP-B-57-27232 is also capable of forming a film on the surface when left in a relatively high temperature atmosphere for a long time. There is also a problem that the dispersed particles of water become coarse and unevenly distributed.

The present invention is a polyurethane composition capable of producing a W / O type polyurethane dispersion liquid which can achieve its original purpose by using the polyurethane surfactant disclosed in JP-B-57-27232 and which also solves the above problems. The purpose is to provide goods.

[Means for Solving the Problems]

The present inventors have studied a surfactant that can stably disperse a relatively large amount of water with fine particles, does not deteriorate the physical properties of the polyurethane resin layer, and does not exude from the polyurethane resin layer. As a result, a surfactant comprising a polyalkylene oxide-modified polysiloxane in which a polysiloxane component and an alkylene oxide component are bonded together with the above-mentioned polyurethane-based surfactant,
When a surfactant in which the amount of polyethylene oxide chains in the polyalkylene oxide component accounts for 20 to 80% by weight of the surfactant is used in the polyurethane composition, a film may be formed on the surface even when left in a high temperature atmosphere for a long time. It was found that a W / O type polyurethane dispersion liquid can be prepared in which coarsening and uneven distribution of dispersed particles of water do not occur.

The present invention has been made based on this finding, a polyurethane composition comprising an organic solvent having a solubility of water of 1 to 50 g / 100 g of an organic solvent and a boiling point of 120 ° C. or less, and a polyurethane resin. In a polyurethane composition forming a W / O type polyurethane dispersion by mixing and dispersing, a hydrophobic component mainly containing a compound selected from the group consisting of hydrophobic polyalkylene oxide, aliphatic polyester and a mixture thereof. A polyurethane-based surfactant in which a hydrophilic component mainly composed of polyethylene oxide reacts with an organic polyisocyanate and is bonded, and the hydrophilic component accounts for 20 to 80% by weight of the surfactant (A ), And a polyalkylene oxide-modified polysiloxane in which a polysiloxane component and a polyalkylene oxide component are combined. Thus, 0.1 to 10% by weight of the polyurethane resin and the surfactant (B) in which the amount of polyethylene oxide chain in the polyalkylene oxide component accounts for 20 to 80% by weight of the surfactant are added respectively. In a polyurethane composition.

[Work]

The polyurethane composition of the present invention improves the flexibility, antistatic property, antifouling property, etc. of the polyurethane resin layer formed by containing the surfactant (A) in an amount of 0.1 to 10% by weight of the polyurethane resin. The W / O type polyurethane dispersion prepared by adding water by adding 0.1 to 10% by weight of the activator (B) to the polyurethane resin forms a film on the surface or disperses the water in a relatively high temperature atmosphere for a long time. There is an effect that the particles are not coarsened and unevenly distributed, and the surfactant does not exude from the formed polyurethane resin layer or the like. Further, for example, when the hydrophilicity of the surfactant (A) is low (when the polyethylene oxide (PEO) in the surfactant (A) is 20 to 35% by weight), the hydrophilicity of the surfactant (B) is low. When the composition has a large composition (PEO in the surfactant (B) is 61 to 80% by weight), conversely when the surfactant (A) has a large hydrophilicity (PEO in the surfactant (A)) Is 61-80%)
Is a surfactant (B) having a small hydrophilicity (using 20 to 35% by weight of PEO in the surfactant (B), and 36 to 60% by weight of PEO in the surfactant (A). In the case where it is said that PEO of about 36 to 60% by weight is also used for the surfactant (B) if the same amount of both surfactants (A),
By selecting (B), both surfactants (A)
As the synergistic action of (B), the above-mentioned effects can be further increased.

〔Example〕

The polyurethane resin in the present invention has, for example, a molecular weight
Polyalkylene ether diols such as 1000-4000 polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, etc., and polyester diols such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate having a molecular weight of 1000-4000 are used as long-chain diols. Diphenylmethane-4,4'-diisocyanate, Tolylene-2.4
-Diisocyanate, phenylene diisocyanate, xylene diisocyanate, dicyclohexylmethane-4
.4'-diisocyanate, hexamethylene diisocyanate, etc. as diisocyanates, ethylene glycol, 1,4-butanediol, cyclohexane-1,4-
Diol, α ・ α'-p-xylene diol, 1.4-bis (β-hydroxyethoxy) benzene, 2.2-bis [4- (β-hydroxyethoxy) phenyl] propane, propylenediamine, hexamethylenediamine, etc. As the low molecular weight chain extender, a conventionally known polyurethane resin obtained by melt polymerization, solution polymerization or slurry polymerization can be used. As the organic solvent for solution polymerization in this case, a good solvent for the polyurethane resin such as tetrahydrofuran can be used, but a non-water-soluble solvent such as toluene, benzene, or xylene is mixed after or during the polymerization. Water solubility of 1-50g / organic solvent 10
It can be 0g. Organic solvents for slurry polymerization include methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, etc. or mixtures of these with tetrahydrofuran, acetone, dioxane, etc. Are used.

The organic solvent composition of the polyurethane resin, in addition to the polyurethane resin, within the range that does not impair the physical properties of the polyurethane resin,
20% or less of the weight of polyurethane resin, polyvinyl acetate,
It may contain polymers such as polyvinyl chloride, polyacrylic acid ester, polyamide and polyester. Further, additives such as colorants, antistatic agents, flame retardants, stabilizers against heat and light may be added. As the organic solvent for this composition, the solubility of water in the above-mentioned organic solvent for slurry polymerization or solution polymerization is 1 to 50 g / 100 g of organic solvent.
The boiling point is 120 ° C. or lower, preferably 100 ° C. or lower. When the composition contains a polymer other than the polyurethane resin, a polymer in which the polymer is dissolved is also used. Therefore, in the case of a slurry or solution-polymerized polyurethane resin, the polyurethane composition may be prepared without separating the polyurethane resin. The composition has a concentration of polyurethane resin or, if it also contains other polymers, a concentration of 5 to 30% by weight to obtain a W / O type polyurethane dispersion which is widely used for coating and impregnation. It is preferable above.

The polyalkylene oxide as the hydrophobic component of the surfactant (A) may contain a polyethylene oxide chain in the molecule as long as it is substantially hydrophobic. Examples of preferred hydrophobic polyalkylene oxides have a molecular weight of 1500-
6000 polypropylene ether glycol, polytetramethylene ether glycol, propylene oxide adduct of bisphenol A, propylene oxide adduct of trimethylolpropane, propylene oxide adduct of trimethylolpropane, propylene oxide adduct of pentaerythritol, pluronic type polypropylene Examples thereof include oxide and polyethylene oxide. In addition, one end of the glycol may be blocked with an alkoxide group or phenylisocyanate.

The aliphatic polyester as the hydrophobic component has 20 in the molecule.
It may be a substantially aliphatic polyester containing less than or equal to wt% aromatic or alicyclic rings. Preferred examples of the aliphatic polyester include polyethylene adipate having a molecular weight of 1500 to 6000, polybutylene diadipate, and polyhexamethylene adipate. As a preferable example of the substantially aliphatic polyester containing an aromatic ring, polybutylene isophthalate / butylene adipate having a molecular weight of 1500 to 6000 can be mentioned.

The hydrophilic component polyethylene oxide may contain a polypropylene oxide chain in the molecule as long as it is substantially hydrophilic. Preferable examples of polyethylene oxide include polyethylene glycol having a molecular weight of 800 to 9,000. One end of this glycol may be blocked with an alkoxy group or phenylisocyanate.

As a preferred example of the organic polyvalent isocyanate for urethane-bonding the hydrophobic component and the hydrophilic component, the same diisocyanate as in the polyurethane resin can be mentioned.

The surfactant (A) is a compound obtained by reacting a hydrophobic polyalkylene oxide, an aliphatic polyester or a hydrophilic polyethylene oxide with an organic polyvalent isocyanate, and converting the resulting compound having at least one isocyanate group into a hydrophilic polyamine. It can be obtained by a conventionally known method of reacting with ethylene oxide or a hydrophobic polyalkylene oxide or an aliphatic polyester. These reactions are carried out in a molten state or in a solution of an organic solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl formate, ethyl acetate, toluene, etc., if necessary, with a catalyst such as triethylenediamine, trimethylamine, dibutyltin dilaurate. Is performed using. In the case of solution reaction, the reaction may be carried out at 40 to 80 ° C. under normal pressure for 60 to 180 minutes.

With respect to the surfactant (A), when the hydrophilic component is less than 20% by weight, the effect of improving the flexibility and antistatic property of the polyurethane resin layer formed cannot be recognized, and when the hydrophilic component exceeds 80% by weight, the interface is improved. The activator comes to seep to the surface of the polyurethane resin layer or the like. The surfactant (A) has a molecular weight of 25.
It is preferably in the range of 00 to 5000. If the molecular weight is less than 2500, the surfactant is likely to exude to the surface of the polyurethane resin layer or the like, and if the molecular weight exceeds 50,000, the crystallization separation precipitation of the surfactant is likely to occur in the polyurethane resin layer or the like. Therefore, the effect of improving the flexibility, antistatic property, and antifouling property by the surfactant (A) decreases.

The surfactant (B) includes an isocyanate, a polysiloxane having a reactive group and a polyalkylene oxide containing a polyethylene oxide such as polyethylene glycol, at the terminal or in the molecular chain, in the same manner as the surfactant (A). From a polyurethane resin layer or the like that is obtained by a conventionally known method such as a method of urethane- or urea-bonding using an organic polyvalent isocyanate, or a method of directly bonding with a catalyst or the like, and has a high affinity with a polyurethane resin. From the viewpoint that the surfactant (B) is less likely to exude, it is preferable to use a method of urethane or urea bonding.

If the weight ratio of the polyethylene oxide chain in the polyalkylene oxide component to the surfactant (B) is less than 20%, the stability of the water dispersion will decrease and the storage temperature of the polyurethane dispersion will decrease. When the value becomes higher, the water-dispersed particles become associated and unevenly distributed. When it exceeds 80%, water is likely to remain in the formed polyurethane resin layer, etc., and it is formed when the temperature is raised to sufficiently evaporate the water. The polyurethane resin layer, etc. will not become porous. In the surfactant (B), the polysiloxane component in the surfactant (B) preferably has a molecular weight of 740 or more, and the surfactant (B) preferably has a molecular weight of 1200 to 120,000. When the molecular weight of the polysiloxane component is less than 740 or the molecular weight of the surfactant (B) is less than 1200, the surfactant (B) easily exudes from the formed polyurethane resin layer or the like, and the interface When the molecular weight of the activator (B) exceeds 120,000, it becomes difficult to disperse enough water finely and stably with an amount of the surfactant that does not deteriorate the physical properties of the polyurethane resin layer and the like.

If the addition amount of each of the surfactants (A) and (B) is less than 0.1% of the weight of the polyurethane resin, the effect of each addition cannot be obtained, and each of the addition amount exceeds 10% of the weight of the urethane resin. If so, the polyurethane resin layer or the like on which they are formed is likely to seep out, it is not easy to evaporate water from the polyurethane resin layer or the like, or the mechanical properties of the polyurethane resin layer or the like are deteriorated.

The amount of water dispersed to prepare a W / O type polyurethane dispersion using the polyurethane composition of the present invention to which the surfactants (A) and (B) have been added is such that the amount of water dispersed when water is added to the composition It is preferable that the amount of added water is 50% or more and 90% or less. If it is less than 50%, a breathable porous polyurethane resin layer or the like cannot be obtained, and if it exceeds 90%, coarse water-dispersed particles are mixed and the polyurethane resin is gelated, resulting in a dense A breathable porous polyurethane resin layer or the like having a structure cannot be obtained, or the mechanical properties of the polyurethane resin layer or the like are deteriorated.

Hereinafter, the present invention will be further described with reference to specific examples and comparative examples.

Example 1.1 1) Polymerization of polyurethane slurry 300 parts of polytetramethylene glycol (molecular weight 2190),
Dissolve 296 parts of polycaprolactone diol (molecular weight 1810), 30 parts of diethylene diglycol, 315 parts of diphenyl 4.4'diisocyanate in 235 parts of methyl ethyl ketone,
After adding 0.2 parts of triethylenediamine to it and reacting at 60 ° C for 90 minutes, 710 parts of a mixed solvent having a methylethylethylketone / toluene mixing ratio of 9/1 was further added, and then 60 parts of tetramethylene glycol was added, and When the viscosity rises with stirring while controlling at 65-70 ℃, methyl ethyl ketone /
A mixed solvent with a toluene mixing ratio of 9/1 was poured for about 4 hours to cause a reaction, and a polyurethane slurry having a viscosity of 1800 cps / 70 ° C./20% polyurethane was obtained.

2) Synthesis of surfactant (A) 90 parts of 404 parts of polypropylene oxide glycol having a molecular weight of 2020 and 75 parts of diphenylmethane 4.4 'diisocyanate are added.
What was reacted at 60 ° C. for 60 minutes was separately prepared in four sets of reactors. And the following a), b), which have different molecular weights,
The polyoxyethylene glycols of c) and d) were added to the reactors prepared above in the amounts of a), b), c), and d), and the reaction was carried out at 90 ° C for 60 minutes. A surfactant (A) was obtained.

Polyethylene glycol Addition amount (part) a) Molecular weight 750 150 b) 〃 1540 308 c) 〃 3020 604 d) 〃 5200 1040 3) Synthesis of surfactant (B) Dimethyl poly- mer with two hydroxyl groups at the end and an average molecular weight of 3400 After the addition reaction of polypropylene oxide with siloxane under a caustic catalyst, the addition reaction of polyethylene oxide was performed to obtain the surfactant (B) shown in Table 1.

4) Preparation of polyurethane dispersion Table-1 against 100 parts of the polyurethane slurry obtained in 1)
After adding the surfactants (A) and (B) obtained in 2) and 3) in the proportions shown in 1), water was added little by little to 28 parts while stirring with a homomixer, and W / O A mold aqueous dispersion was prepared.

After adjustment, put the dispersion in an Erlenmeyer flask and seal it,
Immerse and store in a constant temperature bath adjusted to 40 ℃, and after 3 hours
The size of dispersed water particles in the W / O type aqueous dispersion was examined by a light transmission optical microscope, and the results are shown in Table 1.

5) Formation of porous polyurethane resin layer After storing the W / O type aqueous dispersion prepared in 4) at 40 ° C for 30 minutes, the twill fabric of nylon filament yarn has a solid content of about 30 g / m ²
Coated so that the temperature is 70 ℃, relative humidity is 30
It was dried at% RH for 1 minute and then at 100 ° C. for 5 minutes.
The physical properties of the obtained porous sheet are also shown in Table 1.

Comparative Example 1. 2) In Example 1, the reaction was conducted under the same conditions except that polyoxyethylene glycol having a molecular weight of 423 was added in the synthesis of the surfactant (A) and the addition amount was 85 parts. 15 wt% of surfactant (A) was synthesized. In addition, in the same manner as in 3) Synthesis of surfactant (B) in Example 1, polypropylene oxide (PPO) estimated molecular weight 1200, polyethylene oxide (PEO) estimated addition to dimethylsiloxane diol having an average molecular weight of 3400. A surfactant (B) having a molecular weight of 820 and a PEO content of 15% by weight in the surfactant was synthesized. Polyurethane slurry 10 obtained in 1) of Example 1 with 4 parts of each of these surfactants (A) and (B).
After adding to 0 and mixing uniformly, 28 parts of water was added by the same method as 4) of Example 1 to prepare a polyurethane dispersion. When this dispersion was left to stand at 40 ° C., the dispersed water particles tended to associate with each other to form coarse particles, and the dispersion stability of water was insufficient. The porous sheet prepared from this dispersion liquid has coarse pores and pinholes on the surface, which is not preferable.

Comparative Example 2. Surfactants (A) and (B) each having a PEO content of 90% by weight were synthesized, and were synthesized in Example 1 respectively.
After adding 2 parts each to 100 parts of the polyurethane slurry obtained in 1), 28 parts of water was added in the same manner as in 4) of Example 1 to obtain W /
An O type dispersion was prepared. This dispersion had good water dispersion stability at 40 ° C., but the porous sheet prepared under the same conditions as in Example 1 did not meet the purpose of the present invention because the polyurethane resin layer was likely to be filled. there were.

Comparative Example 3. A dispersion was prepared in the same manner as in Example 1 except that the amounts of the surfactants (A) and (B) used in Example 1- (3) in Table 1 were changed to 0.05 parts each. Fabrication and formation of a porous sheet were performed. In this case, the W / O type dispersion had insufficient water dispersion stability, and the obtained porous sheet had coarse pores, which was not preferable. On the contrary, when the amount of each of the surfactants (A) and (B) added is 15 parts, the water dispersibility of the dispersion is stabilized, but the evaporation of the solvent during the formation of the porous sheet is suppressed. Within the same drying time, the residual solvent increased and the polyurethane resin layer became full.

〔The invention's effect〕

The polyurethane composition of the present invention can disperse water in a relatively large amount in the form of fine particles, and the resulting W / O type polyurethane dispersion is stable. By using the polyurethane dispersion, a dense breathable porous material can be obtained. It is possible to form a polyurethane resin layer, etc., which has excellent mechanical properties and is capable of forming a polyurethane resin layer, etc. without the surfactant leaching from the formed polyurethane resin layer, etc. The obtained artificial leather has the effect of being excellent in flexibility, antistatic property, and stain prevention.

Claims (1)

[Claims] 1. A polyurethane composition comprising an organic solvent having a water solubility of 1 to 50 g / 100 g of an organic solvent and a boiling point of 120 ° C. or less and a polyurethane resin, wherein water-in-oil polyurethane is prepared by mixing and dispersing water. In a polyurethane composition forming a dispersion, a hydrophobic component mainly containing a compound selected from the group consisting of hydrophobic polyalkylene oxides, aliphatic polyesters and mixtures thereof, and a hydrophilic component mainly containing polyethylene oxide. Is a polyurethane-based surfactant bonded by reacting with an organic polyisocyanate, wherein a hydrophilic component accounts for 20 to 80% by weight of the surfactant (A), a polysiloxane component and a polyalkylene oxide. A surfactant comprising a polyalkylene oxide-modified polysiloxane bonded to a component,
The amount of polyethylene oxide chains in the polyalkylene oxide component accounts for 20 to 80% by weight of the surfactant, and the surfactant (B) and 0.1 to 10% by weight of the polyurethane resin, respectively.
A polyurethane composition characterized by being added.