JP2622774B2 - Method for producing liquid organic filler - Google Patents

Description

The present invention relates to a method for producing a liquid organic filler, and more specifically, to a foam, a paint, an adhesive, an elastomer,
The present invention relates to a method for producing a liquid organic filler in which a powdered polyurethane resin mainly used in a field such as a lubricant is dispersed.

[Conventional technology]

As the conventional organic filler, a polymer obtained by dehydrating a polymer polymerized in an aqueous solvent was used. When this type of organic filler is actually used, it must be mixed with a polyol or the like and then redispersed using a disperser such as a pole mill.

Further, there is a drawback that a typical vinyl polymer among conventional organic fillers dissolves or swells in a polar solvent used in a coating material.

[Problems to be solved by the invention]

The present inventors have made intensive studies to improve the redispersion process which has been regarded as a problem, and produced a powdered polyurethane resin dispersion by a non-aqueous solvent dispersion polymerization method using a specific dispersion stabilizer, By mixing and dispersing a liquid compound such as a polyol, a method for producing a liquid organic filler having excellent workability was found, and the present invention was completed.

[Means for solving the problem]

That is, the present invention provides a polyisocyanate, an active hydrogen compound, a dispersion stabilizer,
And 10 to 80 parts by weight of a resin component of the powdered polyurethane resin dispersion comprising an organic medium, a plasticizer, a lubricant, a polyol, a polyamine and a polyamine and a polyisocyanate compound containing a mixture of two or more kinds of room temperature liquid compounds 90 to 90.
This is a method for producing a liquid organic filler, characterized by being dispersed in 20 parts by weight.

The liquid organic filler obtained by the present invention has an excellent property that a powdered polyurethane resin is uniformly dispersed in a liquid compound in a spherical shape having a small particle size, and the spherical resin is not attacked by a polar solvent.

The polyisocyanate that can be used in the present invention is a compound having at least two isocyanate groups. Examples thereof include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate and the like, and aromatic diisocyanates composed of these isomers, aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate and 1,12-dodecane diisocyanate, cyclohexane-1 And alicyclic diisocyanates such as 4,4-diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. Further, an isocyanate group-terminated compound obtained by the reaction of these compounds with an active hydrogen group-containing compound, and an isocyanate-modified compound obtained by a carbodiimidization reaction and the like are also included. Also, methanol, n
-It is also possible to use a polyisocyanate partially or wholly stabilized with a blocking agent having one active hydrogen in the molecule, such as butanol, benzyl alcohol, ethyl acetoacetate, ε-cabrolactam, methyl ethyl ketone oxime, phenol and cresol. I can do it.

As the active hydrogen compound that can be used in the present invention, all compounds that are usually used as a reaction partner of a polyisocyanate can be used. Examples include polyester polyols, polyalkylene ether polyols, polyalkylene ether polyamines, polycarbonate polyols and mixtures thereof. Also, active hydrogen compounds having a relatively low molecular weight, for example, ethylene glycol, 1,4-butanediol, trimethylolpropane, triethanolamine, tolylenediamine, isophoronediamine, trimellitic anhydride and the like can be used.

As the polyol having an unsaturated bond in the molecule used in the dispersion stabilizer of the present invention, for example, in the case of a polyester polyol, a raw material glycol, a dibasic acid or the like, an unsaturated group-containing glycol or unsaturated group-containing glycol is partially contained. And those produced using dicarboxylic acids.
In the case of a polyether polyol, there may be mentioned those produced using an unsaturated group-containing glycol as a starting material. Further, polyols obtained by esterification of a hydroxyl group-terminated polyester, polyether, polycarbonate or the like having a molecular weight of 2,000 or less with an unsaturated group-containing dicarboxylic acid are also included. Examples of the unsaturated group-containing glycol described herein include 2-butene-1,4-diol,
Glycerin monoallyl ether and the like can be mentioned. Examples of the unsaturated group-containing dicarboxylic acid include maleic acid and itaconic acid. The molecular weight and unsaturated bond concentration of the polyol having an unsaturated bond in the molecule that can be used in the present invention are not particularly limited, but the molecular weight is 4000 or less, and the unsaturated bond concentration is 10 unsaturated groups per polyol molecule. It is preferable to use the following, and in particular, one in the range of 1 to 3 per polyol molecule is preferable.

The production of the polyol having an unsaturated bond in the molecule of the present invention can be carried out by a usual production method of polyester, polyether and the like.

Examples of the ethylenically unsaturated monomer having a side chain composed of a hydrocarbon group having 6 or more carbon atoms used in the dispersion stabilizer of the present invention include, for example, 1-octene, 1 or 2-nonene,
1- or 2-decene, 1- or 2-heptadecene,
2-methyl-1-nonene, 2-methyl-decene, 2-methyl-1-dodecene, 2-methyl-1-hexadecene,
Vinyl, propenyl or isopropenyl group-containing aliphatic linear unsaturated hydrocarbons such as 2-methyl-1-heptadecene, and aliphatic alcohols having 6 or more carbon atoms such as acrylic acid or methacrylic acid and 2-ethylhexyl alcohol and hexyl alcohol Alternatively, an ester with an alicyclic alcohol having 6 or more carbon atoms such as cyclohexanol, norbornanol, and adamantanol can be used. These can be used alone or in combination of two or more.

The dispersion stabilizer used in the present invention is obtained by reacting a polyol having an unsaturated bond with an ethylenically unsaturated monomer. The reaction method is not particularly limited, and a usual polymerization method of an ethylenic monomer using a radical initiator or the like as a reaction initiator can be used. In this reaction,
A solvent can be used if necessary. As the solvent, for example, all solvents used for polymerization of ordinary ethylenic monomers such as butyl acetate, cyclohexane, and n-heptane can be used.

Further, the amount ratio of the polyol having an unsaturated bond to the ethylenically unsaturated monomer of the present invention is desirably 100/20 to 100/400 (weight ratio). When the amount of the ethylenically unsaturated monomer is less than 20 parts by weight relative to 100 parts by weight of the polyol, the performance as a dispersion stabilizer is reduced, and when producing a polyurethane resin,
It is necessary to increase the amount of the dispersion stabilizer, which is economically disadvantageous. If the amount of the ethylenically unsaturated monomer exceeds 400 parts by weight with respect to 100 parts by weight of the polyol, the balance between polarity and non-polarity is lost, and the performance as a dispersion stabilizer deteriorates.

The powdered polyurethane resin dispersion used in the present invention can be produced by a non-aqueous dispersion polymerization method. This is a method in which a monomer is polymerized using an organic medium other than water as a medium, and a polymer is produced in a discontinuous particle form using the organic medium as a continuous phase. In this case, a technique for generating a polymer in a stable state by adding a dispersion stabilizer is used, and selection of the dispersion stabilizer is extremely important.

The amount of the dispersion stabilizer used in the present invention is 1 to 30% by weight based on the total amount of the polyisocyanate and the active hydrogen compound.
Is preferred. When the amount is less than 1% by weight, there is no dispersing ability, and the organic medium and the reactant are separated, so that dispersion polymerization cannot be performed. 30
If the content is more than 10% by weight, the particle size of the dispersed phase (reactant) may be too small to be in an unstable state.

The organic medium used in the non-aqueous dispersion polymerization method of the present invention is insoluble in the resulting powdery polyurethane resin and has an inert property that does not inhibit the polymerization reaction. As the organic medium, for example, aliphatic such as n-hexane, octane, dodecane, liquid paraffin, or alicyclic hydrocarbon such as cyclohexane is used. Considering the reaction temperature, those having a boiling point of 50 ° C. or higher are preferred. These can be used alone or in a mixture of two or more.

Further, as a means for reducing the particle size of the resulting powdered polyurethane-based resin, a polar solvent such as ethyl acetate, methyl ethyl ketone, or tetrahydrofuran may be used as a part of the organic medium. These polar solvents are preferably used in a proportion of not more than 40% of the organic medium.

The amount ratio of the organic medium to be a continuous phase and the reactant to be a dispersed phase (polyisocyanate, active hydrogen compound and dispersion stabilizer) is preferably in a range where the reactant is 10 to 80% by weight based on the total amount. In terms of production efficiency and cost, the reactant is particularly preferably 40% by weight or more.

The content of the polyisocyanate, the active hydrogen compound and the dispersion stabilizer for producing the powdered polyurethane resin dispersion can not be limited because it varies depending on the performance of the powdered polyurethane resin, but the isocyanate group of the polyisocyanate and the active hydrogen compound and The molar ratio of active hydrogen groups in the dispersion stabilizer is usually preferably in the range of 1.5 to 0.5.

In order to disperse the reactant comprising the polyisocyanate, active hydrogen compound and dispersion stabilizer in the present invention in an organic medium, any known type of emulsifying apparatus may be used. As for the charging method, all the raw materials may be charged at the same time or may be charged stepwise according to the purpose. As a stepwise charging method, (1) an organic medium is added to and dispersed in a mixture of a dispersion stabilizer and an active hydrogen compound, and a polyisocyanate is charged.

(2) An organic medium is added to and dispersed in a mixture of the dispersion stabilizer, a part of the active hydrogen compound, and the polyisocyanate, and the remaining active hydrogen compound (for example, a low-molecular-weight polyol) is charged immediately or after the reaction is allowed to proceed. .

(3) reacting in advance a dispersion stabilizer, a part of the active hydrogen compound and polyisocyanate dissolved in a solvent such as ethyl acetate if necessary, to form a prepolymer;
After adding and dispersing the organic medium, the remaining active hydrogen compound (for example, low molecular weight polyol) is charged.

And so on.

In the production of the powdered polyurethane resin dispersion, it is desirable to use a catalyst to increase the reaction rate and complete the reaction. Examples of this catalyst include dibutyltin dilaurate, stannous octoate, N-methylmorpholine, and tertiary amines such as triethylamine, lead naphthenate, zinc octoate, and the like.
These catalysts are used in an amount necessary for providing a catalytic action, and the amount is usually preferably about 0.01 to 1% by weight based on the reactants. The catalyst may be charged at any time, but it is preferable that the catalyst be charged after the entire amount has been charged.

In the production of powdered polyurethane resin dispersion, a suitable blocking agent having one active hydrogen in the molecule such as methanol, ε-caprolactam, methyl ethyl ketone oxime, or phenol is added during or before or after the reaction, if necessary. You can let me know.

As the plasticizer, lubricant, polyol, polyamine, and polyisocyanate compound as the room temperature liquid compound used in the present invention, for example, as the plasticizer, dioctyl phthalate, dibutyl phthalate, dioctyl adipate is a liquid at room temperature. Everything can be used. Lubricants must be room temperature liquids such as machine oil, petrolatum, mineral oil, castor oil, dibasic acid diester, phosphate ester, silicone oil, animal and vegetable oil-based lubricants, petroleum-based lubricants, and synthetic lubricants. Can be done. The polyol is
Polyester polyols such as Nipporan 800, Nipporan 141 (Nippon Polyurethane Industry, trade name), polyether polyols such as Sanix GP600, Sanix FA909 (Sanyo Chemical Industry, trade name), etc. Two or more hydroxyl groups in the molecule Compounds that have a room temperature liquid can be used. Polyamine has two amino groups in the molecule.
Compounds that have at least one and are liquids at room temperature can be used. The polyisocyanate compound is a compound which has two or more isocyanate groups in a molecule such as Coronate L, Coronate HX, Millionate MTL (Nippon Polyurethane Industry, trade name) and is a liquid at normal temperature or Coronate 2507 (Nippon Polyurethane Industry, product ) Is blocked with a blocking agent, and
Compounds that are liquids at room temperature can be used. These compounds can be used alone or as a mixture of two or more as required. However, a compound having two or more isocyanate groups in the molecule and being a liquid at room temperature is used alone.

A liquid organic filler is produced by dispersing 10 to 80 parts by weight of the resin component of the powdery polyurethane resin dispersion thus obtained in 90 to 20 parts by weight of a liquid compound. When the amount of the polyurethane resin powder is less than 10 parts by weight and the amount of the liquid compound exceeds 90 parts by weight, the amount to be charged for manufacturing the powdery polyurethane resin dispersion is less than the required capacity of the kettle, so it is difficult and difficult to manufacture. Absent. On the other hand, when the amount of the powdered polyurethane resin exceeds 80 parts by weight and the amount of the liquid compound is less than 20 parts by weight, the viscosity of the obtained liquid organic filler is increased, and the dispersion of the powdered polyurethane resin is not preferable.

The liquid compound such as the polyol of the present invention is mixed after the production of the powdered polyurethane resin dispersion is completed. Also,
If the liquid compound is liquid at room temperature and does not contain an active hydrogen group, it can be used in advance when preparing the powdered polyurethane resin dispersion or used as a substitute for an organic medium. . The mixing method and the mixing conditions are carried out in a usual manner, but it is necessary at 60 to 100 ° C. for about 1 hour. After mixing the liquid compound, the organic medium is removed out of the system as necessary. It is preferable to remove the organic medium by heating or heating under reduced pressure.

The liquid organic filler obtained by the present invention may contain other substances as required, for example, an antioxidant, an ultraviolet absorber, a heat resistance improver, a dye, a pigment, an inorganic and organic filler, a plasticizer, a lubricant, an antistatic agent, A reinforcing agent or the like can be added.

〔Application areas〕

The liquid organic filler obtained by the present invention is used in the fields of foams, paints, adhesives, elastomers, lubricants and the like. The addition amount of the liquid organic filler is about 1 to 50% in terms of the powdered polyurethane resin, and the addition amount varies depending on the use and purpose.

Mechanical strength, heat resistance, cold resistance, chemical resistance, weather resistance, abrasion resistance, bending resistance, molding shrinkage, mold release, flame resistance, friction resistance by using the liquid organic filler obtained by the present invention Improvements in performance, such as properties, sound-absorbing properties, and matting properties, can be given to products such as molded articles.

〔Example〕

Next, the present invention will be described in detail with reference to examples and comparative examples.

Example 1. (1) Synthesis of polyol having unsaturated bond in molecule In a 2 l four-necked flask, a stirrer, a thermometer, a distillation column, N ₂
Attach a gas inlet tube and make a polybutylene adipate with a molecular weight of 1,000 (trade name: Nipporan 4009, manufactured by Nippon Polyurethane Industry,
1000 g of hydroxyl value (110 mgKOH / g) and 49 g of maleic anhydride are weighed, and heated and mixed while flowing N ₂ gas. 140-160
After the condensed water was taken out of the system at ℃, the reaction was continued while gradually reducing the pressure in the system. Finally, the reaction was carried out at 190 ° C. and 30 mmHg for 4 hours, and the reaction was completed. Polyester has a hydroxyl value of 53
mgKOH / g and acid value 4.1 mgKOH / g. This polyester has a molecular weight of 2,100 and has an average of one double bond in one molecule.

(2) Synthesis of dispersion stabilizer A 500 ml four-necked flask was equipped with a stirrer, thermometer, dropping funnel and cooler, and 44 g of the polyol synthesized in (1) was added.
And weigh 99 g of butyl acetate. Heat and mix while flowing N ₂ gas into the system from the top of the dropping funnel. When the temperature reaches 110 ° C, lauryl methacrylate 10
A drop mixture of 2 g and 2 g of benzoyl peroxide is started dropwise. Dropping was completed in 1.5 hours and then at 130 ° C for 2 hours.
The reaction was allowed to proceed for a period of time to complete the reaction. The hydroxyl value of this dispersion stabilizer was 11 mgKOH / g.

(3) Synthesis of liquid organic filler in which powdered polyurethane resin was dispersed A 500 ml four-necked separable flask was equipped with a stirring blade, a thermometer, and a cooler, and 7.7 g of the dispersion stabilizer obtained in (2) was obtained.
48.4 g of SANNIX PP-1000 (trade name of Sanyo Chemical Industries, polyether diol with hydroxyl value of 112 mgKOH / g), 8.7 g of 1,4 butanediol, 70.0 g of cyclohexane, 30.0 g of acetone
And uniformly mixed. After charging 35.2 g of diphenylmethane diisocyanate, 0.02 g of dibutyltin dilaurate was added, and the mixture was mixed at 30 to 40 ° C for 1 hour.
Let react for 4 hours and reduce the isocyanate group concentration in the system to 0.1%
The reaction was completed as follows. 100 g of SANNIX FA909 (trade name, Sanyo Kasei Kogyo Co., Ltd., a polyether polyol having a hydroxyl value of 28 and liquid at room temperature) was charged, and the mixture was mixed for 1 hour. A liquid organic filler in which powdered polyurethane resin having a particle size of 10 to 40 μ was uniformly dispersed in Sanix FA909 was obtained.

Example 2. (1) Synthesis of liquid organic filler in which powdered polyurethane resin was dispersed Example 1 (2) was added to the flask used in Example 1. (3).
21.4 g of the dispersion stabilizer obtained above, 91.0 g of Nipporan 800 (a polyester polyol having a hydroxyl value of 290 mgKOH / g, manufactured by Nippon Polyurethane Industry), 37.6 g of hexamethylene diisocyanate
g, cyclohexane 105 g, methyl ethyl ketone 45.0 g dibutyltin dilaurate 0.08 g, and uniformly mixed. 7
The reaction was carried out at 0 ° C. for 4 hours, and it was confirmed that the isocyanate group concentration in the system was 0.1% or less, and the reaction was terminated. 94.3 g of Nipporan 800 (liquid at room temperature) was added and mixed at 60 ° C. for 1 hour. A liquid organic filler in which a powdered polyurethane resin having a particle size of 10 to 50 μ was uniformly dispersed in cyclohexane and Nipporan 800 was obtained.

Example 3. (1) Synthesis of liquid organic filler in which powdered polyurethane resin was dispersed Example 1 (2) was added to the flask used in Example 1. (3).
18.4 g of the dispersion stabilizer obtained in Nipporan 800 67.5 g,
Charge 121.3 g of dioctyl azelaate and mix uniformly. Add 42.8 g of diphenylmethane diisocyanate,
After mixing at room temperature for 1 hour, the mixture was reacted at 80 to 90 ° C. for 4 hours to confirm that the isocyanate group concentration in the system was 0.1% or less, and the reaction was terminated. A liquid organic filler in which a powdered polyurethane resin having a particle size of 5 to 30 μm was uniformly dispersed in dioctyl azelate was obtained.

Example 4 (1) Synthesis of Dispersion Stabilizer Example 1 was added to the flask of the apparatus used in Example 1. (2).
74.6 g of the polyol synthesized in (1) and 99.4 g of butyl acetate are weighed. Heat and mix while flowing N ₂ gas into the system from the top of the dropping funnel. When the temperature reached 110 ° C, 2-ethylhexyl methacrylate 74.6 was added from a dropping funnel.
g and 1.5 g of benzoyl peroxide dissolved mixture are started dropwise. Dropping was completed in one and a half hours, and then 130 ° C
For 2 hours to complete the reaction. The hydroxyl value of this dispersion stabilizer was 15 mgKOH / g.

(2) Synthesis of liquid organic filler in which powdered polyurethane resin was dispersed In the flask used in Example 1. (3), 14.3 g of the dispersion stabilizer obtained in (1), 53.2 g of Sanix P-1000, 2,4
6.5 g of tolylenediamine, 70.0 g of cyclohexane and 30.0 g of acetone were charged and mixed at 50 ° C. for 30 minutes. Liquid temperature 25 ℃
Then, 26.1 g of diphenylmethane diisocyanate was added, and after 30 minutes, 0.02 g of dibutyltin dilaurate was added. The reaction was completed at 50 ° C. for 4 hours. After adding 200 g of Sanniex FA909 and mixing for 1 hour, the solvent in the system was distilled off by heating under reduced pressure. A liquid organic filler in which a powdered polyurethane resin having a particle size of 1 to 30 μm was uniformly dispersed in Sanix FA909 was obtained.

Example 5. (1) Synthesis of a liquid organic filler in which a powdered polyurethane resin was dispersed Example 4 (1) was added to the flask used in Example 1. (3).
8.2 g of the dispersion stabilizer obtained in the above, 67.0 g of Nipporan 1100 (trade name, manufactured by Nippon Polyurethane Industry, polyester polyol having a hydroxyl value of 213 mgKOH / g), 80.8 g of cyclohexane, and 20.2 g of ethyl acetate are charged and uniformly mixed. 31.8 g of diphenylmethane diisocyanate was charged and mixed at room temperature for 1 hour. The reaction was completed at 70 ° C. for 5 hours. After 242 g of Millionate MTL (trade name, liquid diphenylmethane diisocyanate, manufactured by Nippon Polyurethane Industry Co., Ltd.) was charged and mixed for 1 hour, the solvent in the system was distilled off by heating under reduced pressure. Particle size 3 ~
A liquid organic filler in which 50 μm powdered polyurethane resin was uniformly dispersed in millionate MTL was obtained.

Example 6. (1) Synthesis of liquid organic filler in which powdered polyurethane resin was dispersed Example 4 (1) was added to the flask used in Example 1. (3).
10.7 g of the dispersion stabilizer obtained in 2,4-tolylenediamine 2
Charge 1.1g, mineral oil 175g, methyl ethyl ketone 25.0g, 6
Mix for 1 hour at 0 ° C. After cooling to room temperature, 43.2 g of diphenylmethane diisocyanate are charged in portions. 35-45
After mixing for 1 hour at 70 ° C., the reaction was completed by reacting at 70 ° C. for 2 hours. The solvent in the system was distilled off by heating under reduced pressure. Length 5-50μ diameter
A liquid organic filler obtained by uniformly dispersing 0.5 to 20 μm rod-shaped or egg-shaped powdered polyurethane resin in mineral oil was obtained.

Comparative Example 1 An aqueous urethane emulsion was synthesized by the following method.
The flask used in Example 1. (3) was filled with Sanix PP-
1000 44.4 g, diphenylmethane diisocyanate 33.3
g, and 80 g of acetone, and reacted at 50 ° C. for 3 hours.
4.0 g of 4-butanediol and 5.4 g of N-methyldiethanolamine were added to continue the reaction, and when the solution became highly viscous, 80 g of acetone was added. After reacting at 50 ° C for 16 hours,
160 g containing 1.5 g of hydrochloric acid was added with vigorous stirring to obtain a white aqueous urethane emulsion.

Decompression treatment was performed to distill off acetone and water in the aqueous urethane emulsion. However, the particles became continuous during the process, and powdering was not possible.

Also, 250 g of this aqueous urethane emulsion was placed in another flask, and 88 g of Sanix FA909 used in Example 1 was used.
Were mixed and separated. Acetone and water were distilled off by heating under reduced pressure in the separated state.
The granular urethane aggregated, and a uniform liquid organic filler could not be obtained.

Claims (2)

(57) [Claims] 1. A polyurethane resin dispersion comprising a polyisocyanate, an active hydrogen compound, a dispersion stabilizer, and an organic medium, comprising 10 to 80 parts by weight of a resin component, a plasticizer, a lubricant,
A process for producing a liquid organic filler, characterized by dispersing in 90 to 20 parts by weight of a room temperature liquid compound comprising a polyol, a polyamine and a polyisocyanate compound alone or as a mixture of two or more. 2. An ethylenically unsaturated monomer having a side chain comprising a hydrocarbon group having 6 or more carbon atoms per 100 parts by weight of a polyol having an unsaturated bond in a molecule as a dispersion stabilizer.
The method for producing a liquid organic filler according to claim 1, wherein the compound is a compound obtained by reacting 20 to 400 parts by weight.