JPH0841153A - Polyisocyanate particles - Google Patents

Abstract

PURPOSE:To obtain polyisocyanate particles which have a high isocyanate group content and are water-dispersible by using a nonaq. dispersion polymn. using a specific dispersion stabilizer and a specific polyethylene oxide deriv. CONSTITUTION:This particles are obtd. by mixing 100 pts.wt. polyisocyanate, a solvent, and a reaction product of 100 pts.wt. unsatd. polyol with 20-400 pts.wt. ethylenically unsatd. monomer having a 2C or higher alkyl group as the side chain and reacting the resulting mixture with 0-100 pts.wt. active hydrogen compd. and 1-20 pts.wt. polyethylene oxide deriv. of the general formula: RO(CH2 CH2O)n(R'O)mH (wherein R is 1-4C alkyl; R' is 3-4C alkylene; n is an integer of 3-120; and m is an integer of 0-10).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyisocyanate particle having a water-dispersible isocyanate group.

[0002]

2. Description of the Related Art A conventional polyisocyanate particle (isocyanate microcapsule) is disclosed in JP-A-3-109937.
As disclosed in the publication, it was produced by a non-aqueous dispersion polymerization method. That is, it was obtained by dispersing polyisocyanate, a polyol and a special dispersion stabilizer in a non-polar solvent and reacting them.

[0003]

However, the polyisocyanate particles produced by the non-aqueous dispersion polymerization method are basically not dispersible in water. If a highly hydrophilic polyol such as polyethylene glycol is used as the polyol used in this production method, the obtained polyisocyanate particles can be dispersed in water, but since it is necessary to use a large amount of polyethylene glycol, polyisocyanate is used. There was a problem that the concentration of the isocyanate group in the particles was reduced and the particles could not be used as a curing agent. Further, since the molecular weight of polyethylene glycol needs to be made relatively large, there is a problem that the melting point of the obtained polyisocyanate particles is lowered and it cannot be obtained as a powder at room temperature.
An object of the present invention is to provide a polyisocyanate particle body having a high isocyanate group concentration and dispersible in water.

[0004]

The present inventor has conducted extensive studies in order to solve such conventional problems, and as a result, has found that a non-aqueous dispersion polymerization method using a special dispersion stabilizer and a special polyethylene oxide derivative is used. It has been found that a polyisocyanate particle dispersible in water can be obtained by using it, and the present invention has been completed. That is, according to the present invention, as 100 parts by weight of polyisocyanate, a solvent and a dispersion stabilizer,
A compound obtained by reacting 100 parts by weight of a polyol having an unsaturated bond in the molecule with 20 to 400 parts by weight of an ethylenically unsaturated monomer having a side chain composed of a hydrocarbon group having 2 or more carbon atoms The mixture contains 0 active hydrogen compounds.
100 parts by weight, and the general formula _{RO (CH 2 CH 2 O)} n (R'O) mH ( wherein, R 1-4 alkyl carbon atoms, R'is 3
An alkylene group having 4 carbon atoms, n is 3 to 120, and m is 0.
Indicates an integer of 10. The present invention provides a polyisocyanate particle obtained by reacting 1 to 20 parts by weight of the polyethylene oxide derivative represented by the formula (1).

As the polyisocyanate of the present invention, all the commonly used polyisocyanate compounds can be used. For example, tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate and the like and their isomers, and or aromatic polyisocyanate consisting of polynuclear, hexamethylene diisocyanate, aliphatic polyisocyanate such as dodecane diisocyanate, cyclohexane Examples thereof include alicyclic polyisocyanates such as diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate. In addition, an isocyanate group terminal compound by a reaction of these compounds with an active hydrogen group-containing compound, an isocyanate modified product by an isocyanurate-forming reaction or a dimerization reaction, and the like are also included.

As the solvent used in the present invention, any solvent used in a usual urethanization reaction can be used. In particular, nonpolar solvents such as hexane, heptane, octane, normal paraffin, isoparaffin and naphthene are preferable. These non-polar solvents are butyl acetate,
A polar solvent such as methyl isobutyl ketone can be used together. The amount of solvent added is 2 for the resin content of the reaction solution.
The amount is preferably 0 to 80% by weight.

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 polyester polyol, an unsaturated group-containing glycol or an unsaturated group-containing glycol or an unsaturated group is partially contained in the starting glycols or dibasic acids. Examples thereof include those produced using a saturated group-containing dicarboxylic acid. Further, a polyol obtained by esterification of a hydroxyl group-terminated polyester, polyether, polycarbonate or the like having a molecular weight of 2000 or less with an unsaturated group-containing dicarboxylic acid can also be mentioned. Examples of the unsaturated group-containing glycol described here include 2-butene-1,4-diol and glycerin monoallyl ether. Examples of the unsaturated group-containing dicarboxylic acid include maleic acid and itaconic acid. The molecular weight and unsaturated group 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 5000 or less, preferably 500 to 4000.
The unsaturated group concentration is preferably 5 or less per one molecule of polyol, and particularly preferably 0.2 to 3 per one molecule of polyol.
The method for producing the polyol having an unsaturated bond in the molecule of the present invention can be carried out by an ordinary method for producing polyester, polyether and the like.

2 carbon atoms used in the dispersion stabilizer of the present invention
As the ethylenically unsaturated monomer having a side chain composed of the above hydrocarbon group, 1-octene, vinyl such as 2-methyl-1-decene, propenyl, or isopropenyl group-containing aliphatic linear unsaturated Examples thereof include esterification products of hydrocarbons, acrylic acid or methacrylic acid with aliphatic or alicyclic alcohols having 2 or more carbon atoms such as 2-ethylhexyl alcohol, butyl alcohol, ethyl alcohol, cyclohexanol and norbornanol. These can be used alone or as a mixture of two or more kinds. The dispersion stabilizer used in the present invention is obtained by reacting a polyol having an unsaturated bond with an ethylenically unsaturated monomer. These reaction methods are not particularly limited, and a general polymerization method of an ethylenic monomer using a radical initiator 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 the polymerization of ordinary ethylenic monomers such as butyl acetate and dioctyl phthalate can be used.

The amount ratio of the polyol having an unsaturated bond and the ethylenically unsaturated monomer constituting the dispersion stabilizer of the present invention is preferably 100/20 to 100/400 (weight ratio).
When the amount of the ethylenically unsaturated monomer is less than 20 parts by weight with respect to 100 parts by weight of the polyol, the performance as a dispersion stabilizer is deteriorated, and when the polyisocyanate particles are produced, a large amount of the dispersion stabilizer is charged. Need to do so, which is economically disadvantageous. When 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 polar and non-polar is lost, and the performance as a dispersion stabilizer deteriorates. The amount of the dispersion stabilizer used in the present invention is preferably 1 to 30% by weight based on the polyisocyanate. If it is less than 1% by weight, there is no dispersibility and the resulting polyisocyanate complex separates from the solvent to form a lump, which is not preferable. If it exceeds 30% by weight, the particle size becomes too small and filtration during separation from the solvent becomes difficult, which is not preferable.

As the active hydrogen compound used in the present invention, any one which is usually used as a reaction partner of polyisocyanate can be used. Examples include polyester polyols, polyalkylene ether polyols, polycarbonate polyols, and the like, and mixtures thereof. It also contains at least two active hydrogen groups per molecule, which are usually used as chain extenders, and have a molecular weight of 62-
About 300 can be used alone or in combination. When the polyisocyanate particles of the present invention are used in a powder state, they must be solid at room temperature. In this case, it is preferable to use a linear alkylene glycol as the chain extender. In particular, 1,4-butylene glycol, 1,6-hexamethylene glycol, 1,9-nonanediol and the like are preferable. The active hydrogen compound used in the present invention is 0 per 100 parts by weight of polyisocyanate.
It is preferable to blend in 100 to 100 parts by weight. Especially 5 to 50
It is preferred to blend in parts by weight. If it exceeds 100 parts by weight, the isocyanate content of the polyisocyanate particles is reduced, which is not preferable.

The polyethylene oxide derivative used in the present invention has a structure represented by the following general formula. _{RO (CH 2 CH 2 O)} n (R'O) mH In the formula, R is 1-4 alkyl carbon atoms, R'3-4
An alkylene group having a carbon number of, n is 3 to 120, and m is 0 to 1.
It is an integer of 0. R is a methyl or ethyl group, R'is an isopropyl group, n is 4 to 50, m is 0 to 5, and the n / m ratio is preferably 60/40 or more. Particularly preferred is methoxypolyethylene glycol having a methyl or ethyl group for R and n of 4 to 50, for example, a molecular weight of 200 to 2000. The polyethylene oxide derivative is preferably added in an amount of 1 to 20 parts by weight based on 100 parts by weight of polyisocyanate. Particularly, 1 to 10 parts by weight is preferable. When the amount is less than 1 part by weight, the polyisocyanate particles obtained have poor water dispersibility, and when the amount is more than 20 parts by weight, the hydrophilicity of the polyisocyanate particles becomes strong and the storage stability deteriorates, which is not preferable.

The polyisocyanate particles of the present invention are produced by adding an active hydrogen compound and a polyethylene oxide derivative to a dispersion mixture consisting of polyisocyanate, a dispersion stabilizer and a solvent, and heating at 2 to 10 at 40 to 120 ° C.
After reacting for a time and returning to room temperature, the solvent can be separated if necessary. The molecular weight of the polyisocyanate particles thus obtained varies depending on the type of polyisocyanate, polyol, etc. used and the compounding ratio, but is 400 to 3000, preferably 400.
~ 2000. If the molecular weight is 3000 or more, the isocyanate content of the particles becomes small, and the effect of addition such as improvement of physical properties becomes small, which is not preferable. As the apparatus used for the reaction of the present invention, all apparatuses used for ordinary urethanization reaction can be used. After the completion of the reaction, the solvent is removed by a method such as pressure filtration, reduced pressure filtration, centrifugal filtration, centrifugation or evaporation, if necessary. The obtained polyisocyanate particles are dried under reduced pressure and classified by a sieve. The size of the obtained particles depends on the amount of the dispersion stabilizer and the like, but is 1 to 1000 microns. When used in a state of being dispersed in a solvent, the solvent separation step is not performed.

The polyisocyanate particles obtained by the present invention include other substances, if necessary, such as an antioxidant, a heat resistance improver, an electron donating colorless color former, a dye, a liquid crystal, a filler, a modifier, Other resins and the like can be added. These substances can be added at any stage of the manufacturing process.

[0014]

The polyisocyanate particles of the present invention are
As it is, or after polyisocyanate particles are previously dispersed in water and added to an aqueous emulsion polymer or a polymer aqueous solution, mechanical properties, adhesiveness, heat resistance, moist heat resistance, water resistance, oil resistance, chemical resistance, It is possible to improve weather resistance and the like. Examples of aqueous emulsion polymers and polymers of aqueous polymer solutions include polyvinyl alcohol, cellulose compounds, formalin resins, vinyl acetate resins, olefin resins and the like. Further, the polyisocyanate particles of the present invention, as a modifier as it is, vinyl chloride resin, nylon resin, acetal resin,
Polyester resin, silicone resin, olefin resin,
It can be added to formalin resin, epoxy resin, urethane resin, etc. to improve mechanical properties, adhesiveness, antistatic property, heat resistance, moist heat resistance, water resistance, oil resistance, chemical resistance, weather resistance, etc. , Can be used for all conventional resin applications. Further, the polyisocyanate particles of the present invention can be blended with an active hydrogen group-containing compound to cause a reaction such as urethanization to form a resin.

[0015]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 (1) Synthesis of Polyol Having Unsaturated Bond in Molecule A 2000 ml 4-necked flask was equipped with a stirrer, a thermometer, a distillation column and a nitrogen gas inlet tube, and a polybutylene adipate having a molecular weight of 1000 was attached. (Nipporan 4009, manufactured by Nippon Polyurethane Industry, hydroxyl value 110 mgKOH / g) 1000
g and 40 g of maleic anhydride are weighed and mixed by heating while flowing nitrogen gas. After the condensed water was discharged from the system at 140 to 160 ° C., the reaction was continued while gradually reducing the pressure in the system, and finally the reaction was performed at 190 ° C. and 30 mmHg for 4 hours to obtain the target polyol. (2) Synthesis of dispersion stabilizer A 500 ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a condenser, and the polyol synthesized in (1) was added to
g and 99 g of butyl acetate are weighed out. The mixture is heated and mixed while flowing nitrogen gas into the system. At 100 ° C., a dissolution mixture of 102 g of lauryl methacrylate and 2 g of benzoyl peroxide was added dropwise from a dropping funnel over one and a half hours. Then, the mixture was reacted at 120 ° C. for 3 hours to obtain a dispersion stabilizer. (3) Synthesis of Polyisocyanate Particles A 500 ml 4-necked flask was equipped with a stirrer, a thermometer, a cooler, etc., and hexamethylene diisocyanate 88.5 was added.
g, 10 g of the above dispersion stabilizer, and 131 g of Isopar G (manufactured by Exxon Chemical Co., isoparaffin solvent),
The mixture was heated and mixed at 60 ° C. for 1 hour in a nitrogen gas atmosphere. 1,
6-Hexamethylene glycol (15.5 g) and methoxypolyethylene glycol (molecular weight 300) (10 g) were added and reacted at 90 ° C. for 6 hours. The mixture was cooled to 25 ° C., and the solvent was removed by filtration with filter paper to obtain 131 g of powdery polyisocyanate particles. Isocyanate content is 1
The powder was 1.2% and the particle size was about 50 microns or less. When 20 g of the particles were added to 60 g of water and stirred, the particles were uniformly dispersed.

Comparative Example 1 (1) Synthesis of Polyisocyanate Particles A 500 ml 4-necked flask was equipped with a stirrer, thermometer, condenser, etc., and hexamethylene diisocyanate 88.5.
g, 10 g of the same dispersion stabilizer as in Example 1 and 121 g of Isopar G were charged, and the mixture was kept under a nitrogen gas atmosphere for 1 hour.
Heated and mixed to 0 ° C. 15.5 g of 1,6-hexamethylene glycol was added, and the mixture was reacted at 90 ° C. for 6 hours. 25
The solvent was removed by cooling with a filter paper to obtain 134 g of powdery polyisocyanate particles. The powder had an isocyanate content of 12.3% and a particle size of about 100 microns or less. When 20 g of the particles were added to 60 g of water and stirred, they were separated and were not dispersed.

Example 2 (1) Synthesis of Polyisocyanate Particles A 500 ml four-necked flask was equipped with a stirrer, a thermometer, a cooler, etc., and Coronate 2365 (Nippon Polyurethane Industry Co., Ltd., a uretdione prepolymer of hexamethylene diisocyanate). , Isocyanate content 22%) 82.4
g, 8.2 g of the dispersion stabilizer of Example 1 and Isopar G
(The same as in Example 1) 124 g was charged, and the mixture was heated and mixed at 60 ° C. for 1 hour in a nitrogen gas atmosphere, 1,9-nonanediol 11.5 g and methoxypolyethylene glycol (molecular weight 600) 5 g were charged, and 90 ° C., 6 Reacted for hours. The mixture was cooled to 25 ° C., and the solvent was removed by filtration with filter paper to obtain 124 g of powdery polyisocyanate particles. The powder had an isocyanate content of 9.0% and a particle size of about 20 microns or less. When 20 g of the particles were added to 60 g of water and stirred, the particles were uniformly dispersed.

Comparative Example 2 (1) Synthesis of Polyisocyanate Particles A 500 ml four-necked flask was equipped with a stirrer, a thermometer, a cooler and the like, and the same coronate 2368 as in Example 2 was used.
2.4 g, the dispersion stabilizer of Example 1 (8.2 g) and Isopar G (119 g) were charged, and the mixture was kept under a nitrogen gas atmosphere for 1 hour.
Heat mixed to 0 ° C., 11.5 g of 1,9-nonanediol
Was charged and reacted at 90 ° C. for 6 hours. The mixture was cooled to 25 ° C. and the solvent was removed by filtration with filter paper to obtain 126 g of powdery polyisocyanate particles. The powder had an isocyanate content of 9.3% and a particle size of about 20 microns or less.
When 20 g of the particles were added to 60 g of water and stirred, they were separated and were not dispersed.

Example 3 (1) Synthesis of Polyol Having Unsaturated Bond in Molecule Polyethylene butylene adipate having a molecular weight of 1000, equipped with a stirrer, a thermometer, a distillation column and a nitrogen gas introduction tube in a 2000 ml four-necked flask. (Nipporan 141, manufactured by Nippon Polyurethane Industry Co., Ltd., hydroxyl value 115 mgKOH / g) 1
000 g and 40 g of maleic anhydride are weighed and mixed by heating while flowing nitrogen gas. After the condensed water was discharged from the system at 140 to 160 ° C., the reaction was continued while gradually reducing the pressure in the system, and finally the reaction was performed at 190 ° C. and 30 mmHg for 4 hours to obtain the target polyol. (2) Synthesis of dispersion stabilizer A 500 ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a condenser, and 100 g of the polyol synthesized in Example 3 (1) and 133 g of butyl acetate were weighed. The mixture is heated and mixed while flowing nitrogen gas into the system. At 100 ° C,
2-Ethylhexyl methacrylate 1 from dropping funnel
A dissolution mixture of 00 parts and 2 parts of benzoyl peroxide was added dropwise over one and a half hours. Then, the mixture was reacted at 120 ° C. for 3 hours to obtain a dispersion stabilizer. (3) Synthesis of Polyisocyanate Particles A 500 ml 4-necked flask was equipped with a stirrer, a thermometer, a cooler, etc., and diphenylmethane diisocyanate 100 was added.
g, 10 g of the above dispersion stabilizer and 121 g of Isopar G (same as in Example 1) were charged and mixed by heating at 60 ° C. for 1 hour in a nitrogen gas atmosphere. 9 g of 1,6-hexamethylene glycol and 10 g of methoxypolyethylene glycol (molecular weight 400) were added and reacted at 70 ° C. for 3 hours. The mixture was cooled to 25 ° C. and the solvent was removed by filtration with filter paper to obtain 105 g of powdery polyisocyanate particles. The powder had an isocyanate content of 14.6% and a particle size of about 100 microns or less. This particle body 20g 60g
When added to water and stirred, it was dispersed uniformly. (4) Addition effect to polyvinyl alcohol adhesive To 10 g of a 10% aqueous solution of polyvinyl alcohol (PVA, polymerization degree 1700, saponification degree 98.5 mol%), 10 g of the above polyisocyanate particles is added and dispersed in a cloudy state. did. 1.0 + 1.0 + with this adhesive
Plywood with 1.0 mm veneer composition, coating amount: 30 g / 30 c
m ² , cold press; pressure 10 Kg / cm ² , 15 minutes ×
25 ° C, hot press; pressure 10 Kg / cm ² , 40 seconds ×
It was produced under the condition of 100 ° C., and after 3 days of curing, the adhesive strength was measured by the JAS (single plate laminated material) method. As a result, the normal adhesive strength was 16 Kg / cm ² and the wood breaking rate was 85%.

Comparative Example 3 (1) Synthesis of Polyisocyanate Particles A 500 ml four-necked flask was equipped with a stirrer, a thermometer, a condenser, etc., and diphenylmethane diisocyanate 100 was added.
g, 10 g of the dispersion stabilizer of Example 3 and Isopar G
111 g was charged, and the mixture was heated and mixed at 60 ° C. for 1 hour in a nitrogen gas atmosphere. 1,6-hexamethylene glycol 9g
Was added and reacted at 70 ° C. for 3 hours. The mixture was cooled to 25 ° C., and the solvent was removed by filtration with filter paper to obtain 102 g of powdery polyisocyanate particles. The powder had an isocyanate content of 14.3% and a particle size of about 100 microns or less. When 20 g of the particles were added to 60 g of water and stirred, they were separated and were not dispersed. (2) Effect of addition to polyvinyl alcohol adhesive 10% aqueous solution of polyvinyl alcohol 1 as in Example 3
When 100 g of the above polyisocyanate particles was added to 00 g and mixed, a non-uniform dispersion state was obtained. Using this adhesive, an adhesive test was conducted in the same manner as in Example 3 to measure the adhesive force. As a result, the normal adhesive force was 12 Kg / cm ² , and the wood breaking rate was 5.
It was 0%.

Example 4 (1) Synthesis of Polyisocyanate Particles A 500 ml 4-necked flask was equipped with a stirrer, a thermometer, a condenser, etc., and diphenylmethane diisocyanate 100 was added.
g, 18 g of the dispersion stabilizer of Example 3 and Isopar G
119 g (same as in Example 1) was charged and heated and mixed at 60 ° C. for 1 hour in a nitrogen gas atmosphere. 1,6-hexamethylene glycol 10 g and methoxypolyethylene-propylene glycol (molecular weight 700, oxyethylene /
6 g of oxypropylene (molar ratio of 80/20) was added and reacted at 70 ° C. for 3 hours. The mixture was cooled to 25 ° C., the solvent was removed by filtration with filter paper, and 92 g of powdery polyisocyanate particles were obtained. Isocyanate content is 14.0
%, And the particle size was about 100 microns or less. When 20 g of the particles were added to 60 g of water and stirred, the particles were uniformly dispersed.

Comparative Example 4 (1) Synthesis of Polyisocyanate Particles A 500 ml four-necked flask was equipped with a stirrer, a thermometer, a condenser, etc., and diphenylmethane diisocyanate 100 was added.
g, 18 g of the dispersion stabilizer of Example 3 and Isopar G
114 g (the same as in Example 1) was charged and heated and mixed at 60 ° C. for 1 hour in a nitrogen gas atmosphere. 10 g of 1,6-hexamethylene glycol was added and reacted at 70 ° C. for 3 hours. The mixture was cooled to 25 ° C. and the solvent was removed by filtration through filter paper to obtain 87 g of powdery polyisocyanate particles.
The powder had an isocyanate content of 14.7% and a particle size of about 100 microns or less. When 20 g of the particles were added to 60 g of water and stirred, they were separated and were not dispersed.

Claims (1)

[Claims] 1. An ethylenic monomer having 100 parts by weight of polyisocyanate, 100 parts by weight of a polyol having an unsaturated bond in the molecule as a solvent and a dispersion stabilizer, and a side chain having a hydrocarbon group having 2 or more carbon atoms. Saturated monomer 20
To 400 parts by weight of a compound obtained by reacting the resulting compound with 0 to 100 parts by weight of an active hydrogen compound and a general formula RO (CH ₂ CH ₂ O) n (R'O) mH (wherein R is 1 ~ 4 carbon number alkyl group, R'is 3 ~
An alkylene group having 4 carbon atoms, n is 3 to 120, and m is 0.
Indicates an integer of 10. ) Polyisocyanate particles obtained by reacting 1 to 20 parts by weight of the polyethylene oxide derivative represented by the formula (1).