JPS6315816A - Production of aqueous dispersion of modified polyurethane - Google Patents

Abstract

PURPOSE:To obtain the title aqueous dispersion excellent in film forming property, mechanical strength, water resistance and solvent resistance, by modifying a carboxyl group-containing polyurethane dispersion with a specified polyepoxy compound or polyaziridine compound. CONSTITUTION:0.5-20wt%, based on solid matter, carboxyl groups are introduced into a polyurethane resin obtained from a polyol of an MW of 200-10,000, an aromatic, aliphatic or alicyclic diisocyanate and, optionally, a chain extender, and the obtained resin is dispersed or dissolved in the absence of any emulsifier to obtain a carboxyl group-containing polyurethane dispersion (A). Component (A) is mixed with a polyepoxy compound or polyaziridine compound (B) having at least two oxirane or aziridine rings the the molecule in an amount to provide at most one equivalent of epoxy groups or aziridinyl groups per equivalent of the carboxyl groups of component A and, if necessary, heated to 100 deg.C or below, preferably, 20-80 deg.C.

Description

[Detailed description of the invention]

[Industry-1- usage! )1 The present invention is a new modification of stable aqueous dispersions based on polyurethane. ), which has a particularly good film-forming ability, as well as excellent mechanical strength, water resistance, solvent resistance, heat resistance, and adhesion to various substrates. Regarding the manufacturing method. [Prior Art] In recent years, water-based resins have been used instead of conventional organic solvent-based resins from the viewpoint of pollution and environmental issues. There has been increasing interest in water-based polyurethane resins due to their excellent mechanical properties.
19.38 publication or fiber, ■, 4 [11 (+97
In addition to its use as a treatment agent for artificial leather and fibers as mentioned in 5), it has been used in 11 wide fields as a vinyl chloride base material, glass welding agent, and Ti agent. However, in order for such polyurethane aqueous dispersions to be stably dispersed in water, a large amount of, for example, carboxyl), ':'S-hydrophilicity + 1 no, () is introduced into the polyurethane. The dry film obtained from the liquid is particularly lacking in long-term properties such as water resistance, solvent resistance, and heat resistance, as well as toughness and contact resistance, and it is difficult to obtain practical level materials f1. For this reason, crosslinking agents such as melamine resins, epoxy resins, and acyridine compounds are generally blended for practical use. [Problems to be solved by the invention] However, conventionally,
4- When the crosslinking agent described above and, if necessary, a catalyst for promoting crosslinking are used in combination, the crosslinking agent reacts systematically, increasing the viscosity of the blended liquid, and ultimately causing gelation. Therefore, there is a constraint that the usable time (pot life) is limited. In addition, after processing and drying using a compounded solution containing the crosslinking agent, it is usually necessary to perform heat treatment to complete the crosslinking reaction between the crosslinking agent and the polyurethane resin, and when the crosslinking agent is blended in this way, When used, there are many restrictions on use such as pot life and heat treatment, and there is a problem that the applications are limited. [Means for solving the problems] From this point of view, the present inventors have overcome the disadvantages listed in L, and
Regarding a method for producing a modified polyurethane aqueous dispersion having film properties equivalent to those obtained when processed by blending the above-mentioned crosslinking agent,
As a result of α research, it was found that by reacting a polyepoxy compound or a polyacylidine compound with an amount less than the equivalent of the carboxyl group in polyurethane and a polyurethane water dispersion of 1tk in an aqueous medium, it is stable without gelation and has the ability to form a skin. They discovered that a modified polyurethane aqueous dispersion having excellent film properties could be obtained and completed the present invention. That is, the present invention provides a method for modifying a carboxyl group-containing polyurethane aqueous dispersion (A) with a polyepoxy compound or a polyaziridine compound (B) having at least two oxirane rings or aziridine rings in the molecule. , (containing polyurethane aqueous dispersion (
^) A polyepoxy compound or a boriasilidine compound (8) with the carboxyl group contained in the fil- or less
The present invention provides a method for producing a modified polyurethane aqueous dispersion, which is characterized in that it uses a modified polyurethane aqueous dispersion. The polyurethane aqueous dispersion used for unreleased IJ1 has a solid content of J, l is &/or approximately l;i 5-00φ, 111%
, more II (preferably lO ~ 50 East I11 111% (
1. < is a self-dispersion type aqueous dispersion containing no emulsifier, and is a polyurethane aqueous dispersion having a carboxyl group bonded to a polyurethane skeleton. The self-dispersing polyurethane aqueous dispersion suitable as the polyurethane aqueous dispersion used in the present invention is composed of a polyol such as a polyester polyol or a polyether polyol, an aromatic or aliphatic diisocyanate, and, if necessary, a chain extender. A polyurethane resin obtained by stably dispersing or dissolving in water without using an emulsifier. The following methods are known as methods for dispersing or dissolving. (1) A method in which ionic groups such as sulfos (and carboxyl groups) are introduced into the side chains or terminals of polyurethane polymers to impart wood-philic properties, and the polymers are dispersed or dissolved in water through self-emulsification. (2) Main raw materials for polyurethane A method of dispersing or dissolving in water a wood-philic polyurethane resin using a water-soluble polyol such as polyethylene glycol as the -part of the polyol. The method is not limited to dispersion or square RP, but mixtures obtained by each method can also be used.Any conventionally known method may be used to introduce carboxyl groups into the polyurethane resin. For example, (0 general formula 110C1b -C-C1b Oll
... (1) 000+1 E in the formula R represents an alkyl group having 1 to 3 carbon atoms r-] A pendant obtained by co-merging a compound represented by the following as a glycol component when synthesizing a polyester. Examples include a method using a polyester polyol containing polyester polyol, or a method using a pendant polyester polyol represented by the general formula (I) as a chain extender. Compounds represented by (I) include 2,2-dimethylolpropionic acid, 2,2
-dimethylolbutyric acid, 2,2-dimethylol-I-butyric acid, etc. Also, as a method for introducing a carboxyl group other than 1-,
Japanese Patent Publication No. 52-3438 c'F (method using aromatic diamine containing two carboxyl groups as a chain extender); How to use half ester as a chain extender :), Japanese Patent Publication No. 53-7479
No. 4067 (method of reacting excess polyalkylene polyamine with incyanate-terminated prepolymer to form polyurethane urea polyamine and then adding trimellitic anhydride), Japanese Patent Publication No. 52-4067 (method of reacting excess polyalkylene polyamine with incyanate-terminated prepolymer and adding trimellitic anhydride); Examples include a method in which a polyester intermediate with a high acid value is synthesized from an acid and reacted with a polyisocyanate as described in ``Hydroxyl.'' The content of carboxyl (() is within the necessary range to be able to exhibit a crosslinking effect while maintaining the stability and film-forming properties of the aqueous dispersion through reaction with the polyepoxy compound or polyaziridine compound. Preferably, 0.5 to 20 ton&j% (
solid content ratio) is preferred. In addition, there are also agents used to neutralize such carboxyl groups.
h JWk amines, alkali metals or alkaline earth metals, and the like. In addition, carboxyl J, (in addition to the sulfo group, polyethylene'A-1-1ξ), J'/J (which is made self-emulsifying by introducing it), and J'/J, which are conventionally known For example, ethylenediamine-2
-ethanesulfonic acid, 2-year-old he-ethiethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, 1,3-phenylenediamine-4,6-disulfonic acid, 4,6-diamitzhensen-1,3 Jl of -disulfonic acid, 2,4-diaminotoluene-5-sulfonic acid, etc. and 1 compound containing these sulfonic acids! , 1? and derivative; min(-j
i130 Q~10,000 polyethylene glycol, ethylene oxide/propylene oxide copolymer, monoal-1-l ether of these polyoxyalkylene glycols, etc. are copolymerized together with other raw materials during the urethanization reaction, and 1- Examples include a method in which a polyester polyol obtained by copolymerizing a compound containing a sulfo group and a polyethylene oxide group is used as lJ& of the polyol, and can be used in conjunction with the method for introducing a carboxyl group. Containing such sulfo group, polyethylene oxide group t4
is preferably in a range necessary to maintain the stability and film-forming properties of the aqueous dispersion during and after the reaction with the polyepoxy compound or polyaziridine compound, and the solid content ratio with respect to the polyurethane resin. 0.01~5
% by weight, preferably 0.1-20% by weight. The polyol used in the production of the aqueous polyurethane dispersion of the present invention preferably has a molecular weight of 200 to 0,000, preferably 300 to 5,000, and includes conventionally known polyesters and polyethers, as well as polycarbonates, polyesteramides, polyacetals, polythioethers,
Examples include polybutadiene glycol. Examples of polyesters include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-bentanediol, l,B-hexanesiol, neopentyl glycol, diethylene glycol, triethylene glycol, and tetraena I/N. Glycol, polyethylene glycol (molecule 1,130
0 to C1QOQ), cyfurohylene glycol, tripropylene glycol, 1,4-cyclohexanediol, l,4-cyclohexane dimetatool, bisphenol A, hydroquinone and their alkyl 1/one oxide derivatives, and other glycol components. Succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid,
Maleic anhydride, fumaric acid, 1,3-cyclopestanedicarponic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, 2.5-naphthalene dicarvone M,
2. B-Naphthalene dicarboxylic acid, naphthalic acid, Hif-
1-nyl dicarboxylic acid, 1,2-his(pheno-1-cy)ethane-p, ρ'-dicarboxylic acid and anhydrides or ester-forming derivatives of these dicarboxylic acids: p-hydroxybenzoic acid, p-(2-hydroxy Polyesters obtained by dehydration condensation reaction with acid components such as (ethoxy)benzoic acid and ester-forming derivatives of these hydroxycarboxylic acids, polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone, and these. Examples include copolymerized polyesters. Examples of polyether include ethylene glycol, diethylene glycol, triethylene glycol, 1.2-propylene glycol, trimethylene glycol, 1.3-
Butylene gelicol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, glycerin, sorbitol, sucrose, aconitic acid, trimellitic acid, hemimellitic acid, phosphoric acid, ethylene diamine, propylene diamine, diethylene triamine, triisopropazuramine, pyrogallol, One or two compounds having at least two active hydrogen atoms, such as dihydroxybenzoic acid, hydroxybenzoic acid, 1,2,3-propane I-richiol, etc., are used as an initiator to prepare ethylene oxide, propylene oxide, butylene. oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, etc.
Examples include those in which the seeds or two inserts are combined with one another. The chain extender used in the above polyol and
For example, glycols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, hexamethylene glycol, neopentyl glycol; ethylenediamine, propylene diamine, hexamethylene diamine, phenylenecyamine, tolylene diamine, diphenylcyamine, Diamines such as diaminodiphenylmethane, diaminocyclohegycylmethane, piperazine, and inphorondiamine 19; and hydrazine can be mentioned. The polyisocyanate compound used in the production of the polyurethane/tan wood dispersion of the present invention is, for example, 2.4%
-tolylene diisocyanate, 2.6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, inphorone diisocyanate, Trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate,
4.4'-dicyclohexylmethane diisocyanate,
3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4
'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate and the like. At least two scenes in the molecule used in the present invention-1
- As a polyepoxy compound having an oxirane ring, for example, epichlorohydrin bisphenol A5 represented by the structural formula [I]:
Epoxy tree 1ni, a chain epoxy resin represented by the structural formula [11]:% formula %], a structural formula [I[[]...
・ Novolak J (Ij epoxy resin, represented by [II[], structural formula [■]: Flame-retardant epoxy resin represented by, structural formula [V]: Examples include resins, dimer acid-based diglycidyl esters, etc., and solutions of these in organic solvents.Also, epoxy resin emulsicone or ethyl 1/ glycol, diethylene glycol, I-riethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycerin, trimethylolethane, I-listyrolpropane, diglycidyl, 3-methylpentanetriol, polyglycerin, sorbitol, Polyglycidyl ethers of polyhydroxy compounds such as glycerin ethylene oxide, co-/phosphoric acid, adipic acid,
Examples include water-soluble epoxy resins such as diglycidyl esters of dicarboxylic acids such as terephthalic acid. Among these, liquid or emulsion type polyepoxy compounds are preferred in the production method of the present invention. Molecules used in the present invention - at least two scenes 1
Examples of polyaziridine compounds having an aziridine ring of -butanol triester, 2,4.8-)lis(2-methyl-1-aziridinyl)-1,3,5-)riazine, 2,4.
6-) Lis(2-ethyl-1-aziridinyl) -1,
3,5-1=riazine, 4,4'-bis(ethyleneiminocarbonylaminone, bis(2-ethyl-1-aziridinyl)benzene-
1.3-Dicarboxylic acid amide, tris(2-ethyl-1
-aziridinyl)benzene-1.3.5-tricarboxylic acid amide, bis(2-ethyl-1-aziridinyl)sebacic acid amide, 1,8-bis(ethyleneiminocarbonylamino)hexane, 2,4-diethyleneureidotoluene, 1.1'-carbonyl-bis-ethyleneimine, polymethylene-bis-ethylene urea (C7-C4)
, N,N'-bis(4,8-diethyleneimino-1
, 3.5-triazin-2-yl)-hexamethylene diamine, and the like. The polyepoxy compound or polyaziridine compound used in the present invention is such that the epoxy (or aziridinyl group 1) in these compounds is less than 1 m of the carboxyl group, (() contained in the aqueous polyurethane dispersion, i.e. [Evot group or aziridinyl group (]
/carboxyl group≦l (j.j.It), preferably 0.01
~l (this 1+!: IL'). The ratio of epoxy group or aziridinyl group to carboxyl group is 0
．． Less than Ol equivalent ratio

[J Modification effect of polyurethane aqueous dispersion by polyepoxy compound or polyaziridine compound, such as ml heat resistance, ml water, solvent resistance, etc.-1;
The effect may be low. On the other hand, if the equivalent M-ratio is exceeded, an excess of the polyepoxy compound or polyaziridine compound will remain relative to the carboxyl group, resulting in formation of aggregates or complete gelation during the reaction.
Modified polyurethane moisture 11 & flk eave 1f obtained! This is unsuitable because it results in poor stability. B When carrying out the method according to the present invention, the polyepoxy compound or polyaziridine compound is added to the carboxyl group-containing polyurethane aqueous dispersion to be modified in the present invention, mixed and dispersed sufficiently with stirring, and then mixed as necessary. If necessary, heat to 100°C to complete the reaction. At this time, the reaction temperature can be arbitrarily selected, but is preferably 20 to 8
It is 0°C. It is preferable to stir until the reaction is completed. Furthermore, when carrying out the method of the present invention, a nonionic or anionic emulsifier may be used in combination to maintain the stability of the aqueous polyurethane dispersion during or after the reaction. [Effect of the invention] The modified polyurethane aqueous dispersion obtained by the method of the present invention, like the unmodified polyurethane aqueous dispersion, can be used for various plastics such as vinyl chloride, nylon, polyester, and polyurethane; textile products, synthetic leather products, and aluminum. ,copper,
Not only does it have excellent adhesion to metals such as iron, paper, wood, glass, etc., stability of the aqueous dispersion, and film-forming properties, but it also does not require the use of a crosslinking agent unlike conventional polyurethane aqueous dispersions. It has excellent mechanical strength, TM wood properties, solvent resistance, heat resistance, and other durability. Therefore, it is possible to apply it to all kinds of applications without being subject to restrictions such as pot life and high temperature heat treatment, which were problems when using conventional crosslinking agents.1 For example, it can be used as a treatment agent for textiles and synthetic leather products. , each insertion, (
Adhesives, coatings, water-based paints, wood P1 ink,
Alternatively, it can be widely used as a sizing agent. The excellent effect that is the basis of its application to such a wide range of applications is that it can be uniformly toughened at a much lower temperature than the softening temperature of the film (warm temperature at which it begins to flow using a Koka type flow tester). This is an unpredictable effect, as it can form a strong film. The present invention will be further explained below with reference to Examples. The present invention is not limited to this. In the present invention, unless otherwise specified, parts and percentages are based on weight. Reference Example 1 In a reactor equipped with a thermometer, a nitrogen gas inlet tube, and an IW stirrer, 1680 parts of isophthalic acid, 3304 parts of hexamethylene glycol, 1352 parts of neopentyl glycol, and 0 parts of dibutyltin oxide were introduced while introducing nitrogen gas. After charging .5 parts and esterifying at 180 to 220°C for 5 hours,
A polycondensation reaction was carried out at 23.0° C. for 6 hours until the acid value reached 0.5. It was cooled to 120°C, 5840 parts of adipic acid and 2010 parts of 2,2-dimethylolpropionic acid were added, and the temperature was raised to 170°C again and reacted at this temperature for 200 hours to obtain a hydroxyl value of 54.2 and an acid value of 68. A pendant carboxyl group-containing polyester polyol of No. 6 was obtained. J- 1035 parts of polyester polyol was added under reduced pressure to 10
After dehydration at 0°C and then cooling to 70°C, 397 parts of ethyl acetate was added, and the mixture was thoroughly stirred and mixed. Then, 157 parts of tolylene diisocyanate was added and reacted at 70°C for 4 hours to obtain a terminal isocyanate. A prepolymer solution obtained by diluting the base prepolymer with 785 parts of methyl ethyl ketone was dissolved in 2560 parts of water.
．． After reacting with 8 parts of ethylenediamine and 127.8 parts of triethylamine, the solvent was further removed under reduced pressure to reduce the nonvolatile content to 30%. A transparent colloidal Shusui dispersion of pne,o was obtained. Reference Example 2 In the same manner as Reference Example 1, 1,11000 polypropylene glycol, 2,2-dimethylolpropionic acid and tolylene diasocyanate were mixed at 1/1/3.2 (1/1/3.2).
After reaction with an aqueous solution of anhydrous piperazine and triethylamine, the solvent was removed under reduced pressure to obtain a milky white aqueous dispersion with a nonvolatile content of 30% and a pH of 7.8. Reference example 3 Terephthalic acid/Isophthalic acid/Adipic acid/Ethylene glycol/Neopentyl glycol 30/30/401
50150 (mole ratio) copolymerized polyester polyol (acid value 0.2, wood acid) 1 (value 93.0) and 2.2-dimethylolpropionic acid and hexamethylene diisocyanate 1/1/2 (mole ratio) The mixture was reacted in methyl ethyl ketone to form a urethane, and then neutralized with aqueous ammonia to obtain a transparent colloidal aqueous dispersion with a non-volatile content of 20%. Examples 1-3. Comparative Example 1 In Reference Example 1, (
Prepare 1000 parts of aqueous polyurethane dispersion,
While stirring, apply Ebicuron 850 (11 large ink ink chemistry 1)
Manufactured by Kogyo, 11-yen epoxy! fl: 189), Bunacol EX-320 (manufactured by Nagashio Sangyo Co., Ltd., epoxy equivalent: 130), Chemitai) PZ-33 (manufactured by 1'1 Hon Shokubai Kagaku ■, 1.j per aziridine, +42) in the proportions shown in Table 1. and reacted at 60° C. for 12 hours to obtain a modified polyurethane aqueous dispersion. The resulting aqueous dispersion was spread into a film on a polypropylene sheet and dried at 80°C. The following tests were conducted on the resulting film, and the results shown in Table 1 were obtained. (1) Film strength and elongation Punch out the film with a No. 2 dumbbell.
(2) The flow start temperature was measured using a high-performance flow tester (1 m diameter x l mm).
From room temperature with a load of 10 kgF at A, 3 deg#+i
The samples were washed at a speed of 1.0 mm and measured. (3) A 5 cm x 5 am solvent-based film was cut out and soaked in each solvent for 24 hours. Surface swelling was measured in Table 1. Examples 4 to 6. Comparative Example 2 Reference Example 2 The modified polyurethane aqueous dispersion was prepared in the same manner as in Examples 1 to 3 except that the aqueous polyurethane dispersion of
1. The physical properties of the film were measured. The results are shown in Table 2. 152 Table Examples 7, 8. Comparative Example 3.4 A modified polyurethane aqueous dispersion was obtained by repeating Examples 1 to 3 except for using the polyurethane aqueous dispersion of Reference Example 3,
The physical properties of the film were measured. The resulting fiS3 table shows 1<zu. The results shown in Table 3 and above show that all the modified polyurethane aqueous dispersions of the present invention have hard physical properties. Agent Patent Attorney Chieko Tateno Proceedings Nerl] JlE Book January 29, 1988 Director General of the Patent Office Akio Kurokawa 1, Indication of Case Patent Application No. 3085 No. 3085 2, Title of Invention Modified Polyurethane Water Dispersion manufacturing method 3, relationship with the case of the person making the amendment Patent applicant address: 35-58 Sakashita, Itabashi-ku, Tokyo Name:
(288) Person Nippon Ink Chemical Industry Co., Ltd. Representative Shigeru Kuni Kawatori 4, Agent 158 Address 4-12-16-5 Tamagawa, Setagaya-ku, Tokyo Date of amendment order Vol. 7 Details of amendment (1) ) Insert the following sentence next to "Obtained aqueous dispersion" on page 23, line 10 of the specification. ``After standing for 6 months, we observed whether there were any changes in appearance.The results are shown in Table 1 under the heading ``Stability of aqueous dispersions''.

Claims (1)

[Claims] (1) Carboxyl group-containing polyurethane aqueous dispersion (A)
When modifying with a polyepoxy compound or polyaziridine compound (B) having at least two or more oxirane rings or aziridine rings in the molecule, the carboxyl group contained in the aqueous carboxyl group-containing polyurethane dispersion (A) A method for producing a modified polyurethane aqueous dispersion, which comprises using an equivalent amount or less of a polyepoxy compound or polyaziridine compound (B).