JPH0269560A - Polyurethane composition - Google Patents

Abstract

PURPOSE:To provide the subject composition capable of giving a stabilized W/O type polyurethane dispersion to form an air-permeable porous polyurethane resin layer by simultaneously using a polyurethane surfactant and a surfactant comprising a polyalkylene oxide-modified polysiloxane. CONSTITUTION:In a composition comprising an organic solvent having a water solubility of 1-50g/the organic solvent and a boiling point of <=120 deg.C and a polyurethane resin, (A) a polyurethane surfactant prepared by reacting an organic polyvalent isocyanate with a hydrophobic component comprising a compound selected from a hydrophobic polyalkylene oxide, etc., and with a hydrophilic component comprising mainly polyethylene oxide and (B) a surfactant comprising a polyalkylene oxide-modified polysiloxane containing 20-80wt.% of polyethylene oxide chains are added in amounts of 0.1-10wt.%, respectively, based on the polyurethane resin as surfactants.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyurethane composition used to form a breathable porous polyurethane resin layer.

[Conventional technology]

Organic solvent composition of polyurethane resin, that is, polyvinyl acetate or polyvinyl chloride 5 polyacrylic acid ester in an amount of 20% by weight or less based on organic solvent solution of polyurethane resin or polyurethane resin that does not impair the physical properties of polyurethane resin and polyurethane resin. , polyamide, polyester, and other polymers in organic solvents, or in compositions in which additives such as colorants, antistatic agents, and stabilizers against light and heat are added to these solutions, water is added with the help of surfactants. A water-in-oil type (W2O type) hydrous polyurethane dispersion prepared by mixing and dispersing the water-in-oil type (W2O type) can be applied or impregnated, and then the organic solvent is evaporated first, and then the water is evaporated. It is used to form porous polyurethane resin layers, etc. In general, when such a W10 type polyurethane dispersion is left for a little longer after being prepared until it is used, the water dispersed particles may aggregate and become coarse and unevenly distributed, or a film may be formed on the surface. The problem is that it is easy to However, in surfactants,
When the polyurethane surfactant previously invented by the present inventors and known from the above publication is used, the surfactant is intended to improve the flexibility, antistatic property, and stain resistance of artificial leather. However, a type 0 polyurethane dispersion with relatively good stability can be obtained.

[Problem to be solved by the invention]

The type 0 polyurethane dispersion using a polyurethane surfactant described in Japanese Patent Publication No. 57-27232 may also form a film on the surface if left in a relatively high temperature atmosphere for a long time. , coarsening of water dispersed particles,
There is a problem that uneven distribution may occur.

The present invention uses the polyurethane surfactant disclosed in Japanese Patent Publication No. 57-27232 to produce a polyurethane composition that can achieve the original purpose and also solve the above-mentioned problems. For the purpose of providing.

[Means for Solving the Problems] The present inventors have discovered that it is possible to stably disperse a relatively large amount of water in the form of fine particles, without deteriorating the physical properties of the polyurethane resin layer, etc. As a result of repeated research on surfactants that do not cause oxidation, we have developed a surfactant consisting of a polyalkylene oxide-modified polysiloxane in which a polysiloxane component and an alkylene oxide component are combined together with the above-mentioned polyurethane surfactant.
If a surfactant in which the polyethylene oxide chain in the polyalkylene oxide component accounts for 20 to 80% by weight of the surfactant is used in a polyurethane composition, a film may form on the surface even if left in a high temperature atmosphere for a long time. It has been found that it is possible to produce a type 110 polyurethane dispersion in which the dispersed particles of water do not become coarse or unevenly distributed.

The present invention was made based on this knowledge, and the boiling point is 120 g when the solubility of water is 1 to 50 g/100 g of organic solvent.
A polyurethane composition consisting of an organic solvent and a polyurethane resin at a temperature of 0.degree. A polyurethane surfactant in which a hydrophobic component mainly consisting of a compound selected from the group consisting of a mixture of A surfactant consisting of a surfactant (^) that accounts for 20 to 80% by weight of the surfactant, and a polyalkylene oxide-modified polysiloxane in which a polysiloxane component and a polyalkylene oxide component are combined, surfactant (B) in which the amount of polyethylene oxide chains in the oxide component accounts for 20 to 80% by weight of the surfactant;
There is a polyurethane composition characterized in that it is added in an amount of % by weight.

[For production]

The polyurethane composition of the present invention contains a surfactant (A) in an amount of 0.1 to 10% by weight of the polyurethane resin, thereby improving the flexibility of the polyurethane resin layer and the like.

A type 110 polyurethane dispersion prepared by adding water and having improved antistatic properties and antifouling properties and further containing 0.1 to 10% by weight of a surfactant (B) based on the polyurethane resin is placed in a relatively high temperature atmosphere. Even if left for a long time, a film may form on the surface or the water-dispersed particles may become coarse.

The effect is that uneven distribution does not occur, and the surfactant does not ooze out from the formed polyurethane resin layer or the like.

For example, when the hydrophilicity of the surfactant (A) is small (
Polyethylene oxide (PEO) in surfactant (A)
20-35% by weight), use a surfactant (B) with a highly hydrophilic composition (surfactant (B) containing 61-80% PEG); Agent (＾
) is highly hydrophilic (PEO in surfactant (A)
When PEO is 61 to 80%), a surfactant (B) with a low hydrophilic composition (surfactant (B) containing 20 to 35% by weight of PEO) is used; ) to P
Both surfactants (A) and (B) can be used in polymerization in which 36 to 60% by weight of EO is used, and 36 to 60% by weight of PEO is also used for surfactant (B). By selecting these surfactants, the above-mentioned effects can be further enhanced as a synergistic effect of both surfactants (A) and (B).

〔Example〕

The polyurethane resin in the present invention includes, for example, molecule 1
1000-4000 polyethylene ether glycol,
Polypropylene ether glycol 1 A polyalkylene ether diol such as polytetramethylene ether glycol or a polyester diol such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, etc. having a molecular weight of 100 to 4000 is used as a long one-ring diol,
Diisocyanates include diphenylmethane-4,4'-diisocyanate, tolylene-2,4-diisocyanate, phenylene diisocyanate, xylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, etc., ethylene glycol, l,4-butanediol, cyclohexane-
1,4-diol.

α・α-P-xylene diol, 1,4-bis(β-hydroxyethoxy)benzene, 2,2bis(4-(β-
Conventionally known polyurethane resins obtained by melt polymerization, solution or slurry polymerization using hydroxyethoxy)phenyl]propane, propylene diamine, hexamethylene diamine, etc. as a low molecular weight chain extender can be used. In this case, there is 8! for solution polymerization! As a solvent, a good solvent for polyurethane resin such as tetrahydrofuran can be used, but after or during polymerization, a water-insoluble solvent such as toluene, benzene, xylene, etc. may be mixed to reduce the solubility of water to 1 to 50 g. /100g of organic solvent. Organic solvents for slurry polymerization include methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, ethyl formate, and propyl formate.

Butyl formate, methyl acetate, ethyl acetate, etc., or mixtures thereof with tetrahydrofuran, acetone, dioxane, etc. are used.

The organic solvent composition for the polyurethane resin includes, in addition to the polyurethane resin, as long as it does not impair the physical properties of the polyurethane resin.
The polyurethane resin may contain a polymer such as polyvinyl acetate, polyvinyl chloride, polyacrylic acid ester, polyamide, polyester, etc. in an amount of 20% or less of the weight of the polyurethane resin, and may also contain a coloring agent, an antistatic agent, a flame retardant, a heat resistant agent, etc. The solvent for this composition, to which additives such as light stabilizers may be added, is one of the aforementioned organic solvents for slurry polymerization or solution polymerization that has a water solubility of 1 to 50 g/organic solvent. 10
0 g, and a boiling point of 120° C. or lower, preferably 100° C. or lower, is used. If the composition also contains a polymer other than the polyurethane resin, one that can also dissolve that polymer is used. Therefore, in the case of slurry or solution polymerized polyurethane resins, the polyurethane composition may be prepared without separating the polyurethane resin. In order to obtain a W10 type polyurethane dispersion, which is widely used for coating and impregnating, the composition should have a concentration of polyurethane resin or, if it contains other polymers, a concentration of 5 to 30% by weight. It is preferable.

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 include molecular weight is 150
0 to 6000 polypropylene ether glycol, polytetramethylene ether glycol, propylene oxide adduct to bisphenol, propylene oxide adduct of trimethylolpropane, propylene oxide adduct of trimethylolpropane, propylene oxide adduct of pentaerythritol, Pluronic type Examples include polypropylene oxide and polyethylene oxide. Note that one end of the glycol may be blocked with an alkoxide group, phenyl isocyanate, or the like.

Aliphatic polyester as a hydrophobic component has 2
Preferred examples of aliphatic polyesters, which may be substantially aliphatic polyesters containing 0% by weight or less of aromatic rings or alicyclic rings, have a molecular weight of 1500 to 600.
0 polyethylene adipate, polybutylene adipate, and polyhexamethylene adipate. Preferred examples of the substantially aliphatic polyester containing an aromatic ring include polybutylene isophthalate/butylene adipate having a molecular weight of 1,500 to 6,000.

The hydrophilic component polyethylene oxide may contain a polypropylene oxide chain in its molecule as long as it is substantially hydrophilic. A preferred example of polyethylene oxide is polyethylene glycol having a molecular weight of 800 to 9,000. This glycol may also be blocked at one end with an alkoxy group or phenyl isocyanate.

Preferred examples of organic polyvalent isocyanates that form a urethane bond between a hydrophobic component and a hydrophilic component include diisocyanates similar to those used in polyurethane resins.

The surfactant (A) is made by reacting hydrophobic polyalkylene oxide, aliphatic polyester, or hydrophilic polyethylene oxide with an organic polyvalent isocyanate, and converting the resulting compound having a small number (in each case, one isocyanate group) into a hydrophilic compound. Polyethylene oxide or hydrophobic polyalkylene oxide or aliphatic polyester is reacted with polyethylene oxide or hydrophobic polyalkylene oxide or aliphatic polyester. The reaction is carried out in the form of a solution in an organic solvent such as toluene, using a catalyst such as triethylenediamine, trimethylamine, dibutyltin dilaurate, etc., if necessary.In the case of a solution reaction, the reaction is carried out at 40 to 80'C under normal pressure for 60 to 180 minutes. Just let it happen.

If the surfactant (A) contains less than 20% by weight of the hydrophilic component, it will reduce the flexibility of the polyurethane resin layer formed.

The effect of improving antistatic properties is no longer observed, and when the hydrophilic component exceeds 80% by weight, the surfactant begins to ooze out onto the surface of the polyurethane resin layer, etc. In addition, surfactant (A
) preferably has a molecular weight in the range of 2,500 to 5,000. If the molecular weight is less than 2,500, the surfactant will easily ooze out onto the surface of the polyurethane resin layer, etc.
If it exceeds oooo, the surfactant tends to crystallize and separate and precipitate in the polyurethane resin layer, etc., which reduces the effect of the surfactant (A) on improving flexibility, antistatic property, and antifouling property. I come to do it.

Similar to surfactant (A), surfactant (B) contains isocyanate at the terminal or in the molecular chain, polysiloxane having a reactive group, and polyalkylene oxide containing polyethylene oxide such as polyethylene glycol. From polyurethane resin layers, etc., which are obtained by conventionally known methods such as urethane or urea bonding using organic polyvalent isocyanates, or direct bonding with catalysts, etc., and are formed due to their high affinity with polyurethane resins. The method of bonding urethane or urea is preferable in that the surfactant (B) is difficult to ooze out.

When the weight ratio of the polyethylene oxide chain in the polyalkylene oxide component to the surfactant (B) is less than 20%, the stability of water dispersion decreases.
As the storage temperature of the polyurethane dispersion increases, association and uneven distribution of water-dispersed particles will occur, and when the storage temperature exceeds 80%,
Water tends to remain in the formed polyurethane resin layer, etc., and if the temperature is raised to sufficiently evaporate the water, the formed polyurethane resin layer etc. will not become porous. Also,
The surfactant (B) is a polysiloxane in which the molecular weight of the polysiloxane component in the surfactant (B) is preferably 740 or more, and the molecular weight of the surfactant (B) is preferably in the range of 1,200 to 120,000. If the molecular weight of the component is less than 740 or the molecular weight of the surfactant (B) is less than 1200, the surfactant (B) will easily ooze out from the formed polyurethane resin layer, etc. (B
) If the molecular weight exceeds 120,000, it becomes difficult to finely and stably disperse sufficient water with an amount of surfactant that does not deteriorate the physical properties of the polyurethane resin layer, etc.

If the amount of surfactants (A) and (B) added is less than 0.1% of the weight of the polyurethane resin, the effect of each addition will not be obtained (also, each will be less than 0.1% of the weight of the urethane resin). If it exceeds 10%, each of them may easily ooze out from the formed polyurethane resin layer, etc., it may not be easy to evaporate water from the polyurethane resin layer, etc., or the mechanical properties of the polyurethane resin layer, etc. may deteriorate. do.

The amount of water to be dispersed in preparing a type 10 polyurethane dispersion using the polyurethane composition of the present invention to which surfactants (A) and (B) have been added is determined so that when water is added to the composition and mixed, gelation occurs. 50% or more of the maximum amount of water added
% or less; if it is less than 50%, it will not be possible to obtain a breathable porous polyurethane resin layer, and if it exceeds 90%, coarse water-dispersed particles will be mixed in, or the polyurethane resin will be As a result of gelation, it becomes impossible to obtain a porous polyurethane resin layer with a dense structure, and the mechanical properties of the polyurethane resin layer deteriorate.

Hereinafter, the present invention will be further explained by specific examples and comparative examples.

Example 1゜l) Polymerization of polyurethane slurry polytetramethylene glycol (molecules 12190) 30
0 parts, polycaprolactone diol (molecular weight 1810)
296 parts of diethylene glycol, 30 parts of diethylene glycol, and 315 parts of diphenyl 4,4' diisocyanate were dissolved in 235 parts of methyl ethyl ketone, and 0.2 parts of triethylene diamine was dissolved therein.
After adding 2 parts and reacting at 60'C for 90 minutes, a mixed solvent 7 of methyl ethyl ketone/toluene with a mixing ratio of 9/1 was added.
Add 10 parts of tetramethylene glycol and 60 parts of tetramethylene glycol, and stir while controlling the temperature at 65-70°C. When the viscosity increases, the methyl ethyl ketone/toluene mixing ratio is 9.
/1 mixed solvent was poured for about 4 hours to react and the viscosity was 1800 cps /70'C/polyurethane 20
A polyurethane slurry of % weight was obtained.

2) Polypropylene oxide glycol 4 with a synthetic molecular weight of 2020 as surfactant (A)
04 parts and diphenylmethane 4,4' diisocyanate 7
Five parts were reacted at 90° C. for 60 minutes and each was prepared separately in a 4×1 reactor. Then, the following polyoxyethylene glycols with different molecular weights (a) 1 mouth), c), and 2) were placed in the reactors previously prepared.
, 2) and reacted at 90°C for 60 minutes Table 1
The surfactants (A) shown in , respectively, were obtained.

Polyethylene glycol Addition amount (parts) a) Molecular weight
750 150 mouths) 1540 308 ha)
3020 604 2) 5
200 10403) Synthesis of surfactant (B) After adding polypropylene oxide to dimethylpolysiloxane having two hydroxyl groups at the terminals and having an average molecular weight t of 3400 under a caustic alkali catalyst, polyethylene oxide was added to the dimethylpolysiloxane having two hydroxyl groups at the terminals. The surfactants (B) shown in -1 were obtained.

4) Preparation of polyurethane dispersion For 100 parts of the polyurethane slurry obtained in l),
After adding the surfactants (A) and (B) obtained in 2) and 3) in the proportions shown in 1, respectively, add water little by little while stirring with a homomixer until the volume reaches 28 parts.W1
A type 0 aqueous dispersion was prepared.

After adjustment, put the dispersion into an Erlenmeyer flask and seal it.
The size of the dispersed water particles in the type 110 aqueous dispersion after 3 hours of storage by immersion in a constant temperature bath controlled at 40°C was examined using a light transmission optical microscope. The results are shown in Table 1. It was shown.

5) Formation of porous polyurethane resin layer After storing the -10 type aqueous dispersion prepared in 4) at 40°C for 30 minutes, coat it on a twill workpiece made of nylon filament yarn so that the solid content is about 30 g/IIIt. After drying for 1 minute at a temperature of 70°C and a relative humidity of 30% R11,
It was dried at 100°C for 5 minutes. The physical properties of the obtained porous sheet are shown in Table 1.

Comparative Example 1゜Example 1-2) In the synthesis of surfactant (A), the reaction was carried out under the same conditions except that the polyoxyethylene glycol in the synthesis of molecule @423 was changed to 85 parts, and the content of PEO was reduced. A 15% by weight surfactant (A) was synthesized. In addition, in the same manner as in Example 1 3) Synthesis of surfactant (B), an estimated additional molecule of polypropylene oxide (PPO) of 1t1200. Polyethylene oxide (PEO)
) Estimated added molecular weight 820. PEO content in surfactant [1
A 15% by weight surfactant (B) was synthesized. 4 parts each of these surfactants (A) and (B) were added to 10'o of the polyurethane slurry obtained in 1) of Example 1, and after uniformly mixing, 28 parts of water was added to 4 parts of the polyurethane slurry obtained in 1) of Example 1. ) to prepare a polyurethane dispersion. When this dispersion was allowed to stand still at 40''C, the dispersed water particles tended to aggregate and form coarse particles, resulting in insufficient water dispersion stability.

The porous sheet prepared from this dispersion had large pores and pinholes on the surface, which was not desirable.

Comparative Example 2 Surfactants (A) and (B) with a PEO content of 90% by weight were synthesized, and 2 parts of each was added to 100 parts of the polyurethane slurry obtained in Example 1, 1). After that, 28 parts of water was added in the same manner as in 4) of Example 1 to prepare a -10 type dispersion. This dispersion has 40
Although the water dispersion stability at 0.degree. C. was good, the porous sheet prepared under the same conditions as in Example 1 had a rather substantial polyurethane resin layer, which did not meet the purpose of the present invention.

Comparative Example 3゜Surfactant used in Example 1-(3) in Table-1 (＾
).

A dispersion liquid and a porous sheet were formed in the same manner as in Example 1, except that the amount of (B) added was changed to 0.05 part each. In this case, the W10 type dispersion had insufficient water dispersion stability, and the resulting porous sheet had large pores, which was not preferable.

Conversely, when the amount of surfactant (^) and (B) added is 15 parts each, the water dispersibility of the dispersion is stabilized, but the evaporation of the solvent during porous sheet molding is suppressed. Therefore, within the same drying time, the amount of residual solvent increased, and the polyurethane resin layer became more complete.

〔Effect of the invention〕

The polyurethane composition of the present invention can disperse a relatively large amount of water as fine particles, and the resulting Type 110 polyurethane dispersion is stable. It is possible to form a polyurethane resin layer with excellent structural mechanical properties, and the surfactant does not ooze out from the formed polyurethane resin layer. The artificial leather is flexible and antistatic.

It has the effect of being excellent in stain prevention.

Claims (1)

[Claims] The solubility of water is 1 to 50 g/100 g of organic solvent and the boiling point is 1.
A polyurethane composition comprising an organic solvent at 20° C. or lower and a polyurethane resin, which forms a water-in-oil polyurethane dispersion by mixing and dispersing water, wherein a hydrophobic polyalkylene oxide, an aliphatic A polyurethane surfactant in which a hydrophobic component mainly consisting of a compound selected from the group consisting of polyesters and mixtures thereof and a hydrophilic component mainly consisting of polyethylene oxide are combined by reacting with an organic polyvalent isocyanate. , a surfactant comprising a surfactant (A) in which the hydrophilic component accounts for 20 to 80% by weight of the surfactant, and a polyalkylene oxide modified polysiloxane in which a polysiloxane component and a polyalkylene oxide component are combined, , a surfactant (B) in which the amount of polyethylene oxide chains in the polyalkylene oxide component accounts for 20 to 80% by weight of the surfactant, and 0.1 to 80% by weight of the polyurethane resin, respectively.
A polyurethane composition characterized in that 10% by weight of the polyurethane composition is added.