JPH02120311A - Blocked polyisocyanate dispersion - Google Patents

Abstract

PURPOSE:To obtain the title dispersion stable for a long time and useful for paints, adhesives, varnishes, etc., by dispersing a reaction product of a specified compd. with an isocyanate compd., a specified compd. different from said compd. and a blocked isocyanate in an aq. medium. CONSTITUTION:A reaction product (A) of a compd. of the formula (wherein x is 10-60; y is 0-60; n is 1-3) with an isocyanate compd. contg. one or more NCO groups in its molecule, one or more compd. (B) selected from an alkali metal alkylnaphthalenesulfonate (a), an alkali metal dialkylsulfosuccinate (b), an alkylphenol-ethylene oxide adduct (c) and a higher alcohol-ethylene oxide adduct (d) and a polyisocyanate compd. (C) blocked with an active hydrogen compd. which is different from the formula of the compd. A are dispersed in a medium wherein water is a main component. The title dispersion exhibition no phase separation after storage for a long time and useful for paints, adhesives, varnishes, etc., is thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a blocked polyisocyanate dispersion that is useful as paints, adhesives, festivals, and the like.

Prior Art] Various blocked polyisocyanate dispersions have been used in the past. These blocked polyisocyanate dispersions are produced by processing blocked polyisocyanate compounds in which the incyanate groups of various polyisocyanate compounds are blocked with a compound having active hydrogen in the presence of a surfactant using a ball mill, various media dispersers, or homogenizers. For example, in Example 1 of JP-A No. 57-56584, 4
, a method of dispersing a phenol block of 4"-diphenylmethane diisocyanate in water using a ball mill in the presence of dioctyl sulfosuccinate Na salt as a surfactant, and also in Example 1 of JP-A-55-152815. The ε-caprolactam block of polymethylene polyphenylisocyanate is converted into methylcellulose,
A method is disclosed in which sodium alkyl sulfonate and polyethylene glycol monolaurylate are dispersed in water using a ball mill.

[Problem to be solved by the invention] When these blocked polyisocyanate dispersions are left for a long period of time, the blocked polyisocyanate compound separates from the water and settles and sticks to the bottom of the container, making it difficult to use. There was a problem. In addition, when the blocked polyisocyanate dispersion is diluted with water or mixed with other aqueous liquids such as epoxy compound aqueous solution, polyester aqueous solution, rubber latex, resorcinol/formaldehyde resin aqueous solution, etc. during stirring, Since foaming occurs violently during the squeezing process after being applied to woven or knitted fabrics, there are problems with operability and the need to use an antifoaming agent.

[Means for Solving the Problems] The object of the present invention described above is to provide A. a compound represented by the following general formula [I] (provided that the above [
I] in the formula, X is an integer of 10 to 6o, y is an integer of 0 to 60, and n is an integer of 1 to 3) and - an incyanate compound having one or more active isocyanate groups in the molecule. and at least one selected from the following (a) to (d):
Species compound (a) Alkali metal salt of alkylnaphthalene sulfonic acid (b) Alkali metal salt of dialkyl sulfosuccinic acid (C) Ethylene oxide adduct of alkylphenol (d) Ethylene oxide addition of higher alcohol and active hydrogen other than C1 above [Formula 11] This can be achieved by a blocked polyisocyanate dispersion in which each component consisting of a blocked polyisocyanate compound (hereinafter abbreviated as blocked polyisocyanate compound) blocked with a compound having .

The compound represented by the general formula [I] of the present invention includes:
For example, di(polyoxyethylene monostyrylphenyl)methane (X in formula [I] = 10 to 60), di(polyoxyethylene distyrylphenyl)methane (formula [I]
X=10-60), di(polyoxyethylene tristyrylphenyl)methane (X10-60 in formula [I]
), di(polyoxyethylene, polyoxypropylene,
monostyrylphenyl)methane (x=10 in formula [I]
~60. y=o~60), di(polyoxyethylene polyoxypropylene distyrylphenyl)methane (X in formula [I]=10~60. y=o~60), di(polyoxyethylene polyoxy Propylene tristyrylphenyl> methane (x in formula [I] = 10 to 60.y
=o~60), etc. These compounds alone,
Alternatively, X-13 to 40. in formula [I] can be used in combination. y=0
~10 compounds are preferred. The incyanate compound having one or more active incyanate groups in one molecule that is reacting with the compound represented by the above formula [I] is, for example, methyl isocyanate, ethyl isocyanate,
Monoisocyanate compounds such as propyl isocyanate, isobutyl isocyanate, hexamethylene monoisocyanate, phenyl isocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate,
Examples include diisocyanate compounds such as 4,4'-diphenylmethane diisocyanate, triisocyanate compounds such as triphenylmethane triisocyanate, and trimethylolpropane/hexamethylolpropane adducts. The reaction product of the above formula [I] compound and these isocyanate compounds is preferably a compound in which the isocyanate group of the isocyanate compound has almost completely reacted with the above formula [I] compound, and unreacted Above [I]
may include compounds of the formula. A reaction product (hereinafter referred to as the reaction product) of the compound represented by the above formula [I] and the above incyanate compound having one or more active incyanate groups in one molecule, which has water as the main component. The concentration in the medium is usually adjusted to a range of 0.2 to 10% by weight. To dissolve the reactant in water, the reactant may be added to water and stirred, but in some cases, the reactant may be dissolved in a small amount of a water-soluble organic solvent such as acetone, alcohol, dioxane, etc. After that, it may be added to water and stirred and dissolved. In addition, when the reactant is dissolved in a small amount of water-soluble organic solvent as described above, the concentration of the reactant is 15 to 60%.
It may also be dissolved in water to give a weighted amount of %. The reactant may be added at any step of emulsification.

Examples of the compounds (a) to (d) of the present invention include sodium propylnaphthalenesulfonate, sodium ethylnaphthalenesulfonate, sodium dimethylsulfosuccinate, sodium diethylsulfosuccinate, and ethylene oxide of octylphenol (hereinafter referred to as EO).
Examples include adducts (E○=3 to 30 moles added), EO adducts of lauryl alcohol (E○=3 to 30 moles added), and the like. These compounds can be used alone or in combination. The concentration of these compounds in a medium mainly composed of water is usually 0.1 to 3% by weight.
is adjusted to the range of These compounds are added to water, stirred and dissolved.

The blocked polyisocyanate compound of the present invention is -
It is a reaction product of a polyisocyanate compound having two or more incyanate groups in the molecule and a compound having an active hydrogen atom in the molecule, and specific examples include hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2.4-Chlorphenylene diisocyanate, 4.4
Diisocyanates such as “-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, ω,ω°-(ditrimethylenethioether) diisocyanate, S-triazine triisocyanate, thiophosphoric acid tris(p-isocyanate phenyl) ester, triphenylmethane Triisocyanates such as triisocyanate, diphenylmethane triisocyanate, butane-1,2,2-triisocyanate, trimethylolpropane tolylene diisocyanate triadduct, 2,4,4-diphenyl ether triisocyanate, polymethylene polyphenylisocyanate Polyisocyanate compounds such as (including crude diphenylmethane diisocyanate), phenols such as phenol, cresol, and thiophenol, lactams such as ε-caprolactam and valerolactam, oximes such as acetoxime and methyl ethyl ketoxime, and ethyleneimine. The concentration of the blocked polyisocyanate compound in the emulsion may be normally adjusted to 10 to 50% by weight.The blocked polyisocyanate compound may be powdered as necessary, and then mixed with water. The blocked polyisocyanate dispersion of the present invention is obtained by adding the polyisocyanate into a medium containing as a main component and emulsifying it using a known fine dispersion method, for example, a ball mill, a homogenizer, various media dispersers, etc. The particle size of the fine particles made of the blocked polyisocyanate compound in the blocked polyisocyanate dispersion of the present invention is mostly 10 μm.
It is preferable that the average particle diameter is in the range of 0.1 to 5.0 μm.

The blocked polyisocyanate dispersion of the present invention may contain partially hydrolyzed ammonium of polyacrylic acid alkyl ester, hydroxyalkyl cellulose, etc., if necessary.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, each evaluation in Examples was performed by the following method.

(1) Phase separation after standing The niblocked polyisocyanate dispersion was placed in a test tube with an inner diameter of 16 mm and a length of 15 cm so that the liquid depth was 10 cm, the liquid was sealed with a silicone rubber stopper, and after being left for 2 months, the liquid The liquid depth of the transparent portion wE layer formed on the top of the phase is expressed in mm, and the smaller the value, the better the storage stability.

(2) Thickness of fixed sediment after standing: Gently remove the blocked polyisocyanate dispersion liquid from the test tube after evaluating the phase separation after standing in the previous section (1), and deposit/fixed sediment layer at the bottom of the test tube. This is the deposition thickness expressed in mm, and the smaller the value, the better the storage stability.

(3) Foaming amount Niblocked polyisocyanate dispersion 4
Put 5 ml into a 100 ml graduated cylinder, and introduce air from the bottom of the graduated cylinder through a bubble-generating glass tube (inner diameter 6 mm, outer diameter 8 mm, with a glass filter at the tip) at 40 ml/min for 3 minutes. Check the amount of bubbles. Volume (m
! ＞, and the smaller the value, the less bubbles are generated and the better.

Example 1. Comparative Example 1.2 Di(polyoxyethylene polyoxypropylene tritristyrylphenyl)methane (formula [x in eco = 18
．． 17 parts by weight of the reaction product of y=3>1 mole and 2 moles of isopropyl isocyanate, 3 parts by weight of sodium dimethylsulfosuccinate, 20 parts by weight of the methyl ethyl ketoxime block of 4.4-1 diphenylmethane diisocyanate.
0 parts by weight and 780 parts by weight of water were charged into a ball mill,
Table 1 shows the storage stability (phase separation after standing and thickness of fixed sediment after standing) and foam height of the blocked polyisocyanate dispersion obtained by treatment with Orpm for 36 hours. For comparison, di(polyoxyethylene/polyoxypropylene/tristyrylphenyl)methane (formula [x in eco
=18. y=3>1 mole and isopropyl isocyanate 2
The same blocked polyisocyanate dispersion as in Example 1 (Comparative Example 1) and sodium dimethylsulfosuccinate were used, except that the reactant with mole was not added and the amount of sodium dimethylsulfosuccinate added was changed to 20 parts by weight. Table 1 shows the evaluation results of the same blocked polyisocyanate dispersion as in Example 1 (Comparative Example 2) except that no additive was added.

Table 1 shows that the blocked polyisocyanate dispersion of the present invention has excellent storage stability and little foaming.

Example 2 Substitute for the reaction product of 1 mole of di(polyoxyethylene polyoxypropylene tristyrylphenyl)methane (formula [x=18.y=3 in eco) and 2 moles of isopropyl isocyanate in Example 1 , di(polyoxyethylene distyrylphenyl)methane (x= in formula [I]
Evaluation of the same blocked polyisocyanate dispersion as in Example 1 except that a reaction product of 20>1 mol and 2 mol of isopropyl isocyanate was used, and sodium propylnaphthalene sulfonate was used instead of sodium dimethylsulfosuccinate. The results are shown in Table 1. Table 1 shows that the blocked polyisocyanate dispersion of the present invention has excellent storage stability and little foaming.

Example 3 Di(polyoxyethylene polyoxypropylene tristyrylphenyl)methane (formula [Il
Inside x=18. y=3>, x=18. Table 1 shows the evaluation results of the same blocked polyisocyanate dispersion as in Example 1 except that y=3> was used. Table 1 shows that the blocked polyisocyanate dispersion of the present invention has excellent storage stability and little foaming.

Example 4.5 An EO adduct of octylphenol (EO = 15 mol addition) was used in place of sodium dimethylsulfosuccinate in Example 1 (Example 4), an EO adduct of octyl alcohol (EO = 15 mol addition) was used. ) was used (
Table 1 shows the evaluation results of the same blocked polyisocyanate dispersion as in Example 1 except for Example 5).

Table 1 shows that the blocked polyisocyanate dispersion of the present invention has excellent storage stability and little foaming.

Example 6.7 The methyl ethyl ketoxime block of 4,4"-diphenylmethane diisocyanate in Example 1 was converted into 4.
Replacement of 4-1 diphenylmethane diisocyanate with ε-caprolactam block (Example 6), 4.4
Table 1 shows the evaluation results of the same blocked polyisocyanate dispersion as in Example 1, except that diphenylmethane diisocyanate was used instead of tyreneimine block (Example 7). Table 1 shows that the blocked polyisocyanate dispersion of the present invention has excellent storage stability and little foaming.

Example 8 Di(polyoxyethylene polyoxypropylene tristyrylphenyl)methane (formula [I]
Inside x=18. Table 1 shows the evaluation results of the same blocked polyisocyanate dispersion as in Example 1, except that 1 mole of y=3) was replaced with 2 moles, and 1 mole of isopropyl isocyanate was replaced with 1 mole of hexamethylene diisocyanate. Table 1 shows that the blocked polyisocyanate dispersion of the present invention has excellent storage stability and little foaming.

Table 1 (blank below) [Effects of the invention] The blocked polyisocyanate dispersion of the present invention has excellent storage stability, such as less separation, less sticking to the bottom of the container, and less sedimentation even when stored for a long period of time. . In addition, foaming is suppressed when mixed and stirred with water or other aqueous liquids, and during the squeezing process after being applied to woven or knitted fabrics, eliminating the need for antifoaming agents, making it excellent for use in paints, adhesives, festivals, etc. It is something that

Claims (1)

[Claims] A. A compound represented by the following general formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼...[I] (However, X in the above formula [I] is an integer of 10 to 60. ,y
is an integer of 0 to 60, n is an integer of 1 to 3) and an isocyanate compound having one or more active isocyanate groups in one molecule, B. The following (a) to (d) ) at least one selected from
Species compounds (a) Alkali metal salts of alkylnaphthalene sulfonic acids (b) Alkali metal salts of dialkyl sulfosuccinic acids (c) Ethylene oxide adducts of alkylphenols (d) Ethylene oxide adducts of higher alcohols and C, other than the above [I] formula A blocked polyisocyanate dispersion obtained by dispersing each component consisting of a blocked polyisocyanate compound blocked with a compound having an active hydrogen in a medium containing water as a main component.