JPH06239957A - Aqueous emulsion composition of isocyanate - Google Patents

Abstract

PURPOSE:To obtain the subject composition providing an aqueous coating compound having excellent weather resistance, durability, etc., because of exhibition of high weather resistance, a high solid content concentration, low viscosity, readily water diluting properties and a long pot life by adding a specific compound to a specific copolymer solution. CONSTITUTION:(D) A compound of formula III (R3 is 1-4C alkyl; (m) is 5-120; X is di- or polyisocyanate residue and contains free NCO) is added to a copolymer solution obtained from (A) 1-80wt.% of meta-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate of formula I, (B) 10-80wt.% monomer of formula II (R1 is H or CH3; R2 is 1-4C alkyl; (n) is 5-100)[e.g. methoxypolyethylene glycol (meth) acrylate] and (C) 10-80wt.% of an alpha,beta-ethylenic unsaturated monomer copolymerizable with the components A and B in such a way that the amount of the copolymer solution is 5-95wt.% based on the total amount of the composition and the ratio of NCO in the copolymer solution to NCO in the component D is 0.1/9.9 to 9.9/0.1 to give the objective composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel isocyanate aqueous emulsion composition, which can be used in the field of paints for construction finish coating materials or waterproof materials, flooring materials, sports facility materials.

[0002]

2. Description of the Related Art In recent years, as the problems of global environmental pollution, global warming, and depletion of petroleum resources have become more serious, social demands such as pollution-free, environmental conservation, and resource saving have rapidly increased for the paint and waterproof industries. ing. In order to meet these demands, one-component acrylic emulsion water-based paints and two-component epoxy water-based paints have been developed as paints used for building finish coating materials or waterproof materials, flooring materials, sports facility materials,
Compared with the oil-based acrylic urethane paints that have been used in the past, they have drawbacks such as poor adhesion to substrates, durability, and weather resistance. Furthermore, due to its toxicity, there are many requirements that must be taken into consideration in practice, and the emergence of a water-based paint that is safe and has excellent performance is desired.

[0003]

An object of the present invention is to obtain a material which is excellent in weather resistance, durability and adhesiveness to a substrate and which can be easily diluted with water. The idea of the present invention is to select an acrylic resin system which is widely recognized as having excellent weather resistance, and in this system, (1) a monomer having an NCO group showing low reactivity is used as a copolymer. By utilizing it as a component, NCO groups are introduced into the polymer chains that make up the emulsion particles to enhance the physical properties of the produced film (2)
By adopting a monomer having a surfactant function capable of exhibiting the self-emulsifying power of the copolymer by introducing it as one component of the copolymer, it is possible to obtain a high solid content concentration which has hitherto been unattainable. By preparing a copolymer solution that has low viscosity, can be easily diluted with water and can exhibit high physical properties, and is used in combination with a highly reactive polyisocyanate derivative containing a surfactant, Weather resistance, high physical properties, high solid content concentration, low viscosity, easy water dilution,
The point is to obtain an isocyanate aqueous emulsion composition capable of exhibiting a long pot life.

Further, by using the present isocyanate aqueous emulsion composition in combination with a conventionally used acrylic emulsion coating composition, it is water-based but has weather resistance, durability and base properties equivalent to those of the conventionally used oil-based acrylic urethane coating composition. A water-based acrylic urethane paint having adhesiveness with a material is obtained.

By the completion of the invention according to the present idea, it is possible to overcome the drawbacks of the water-based epoxy resin system, which is excellent in the conventional physical properties, but is hard to expect weather resistance, and has a problem in the toxicity of the amine derivative used as the curing agent. Further, it becomes possible to overcome the technical limitation of the adhesiveness with the base material of the one-pack acrylic emulsion system. The inventors of the present invention have paid attention to this point and have conducted intensive studies to complete the present invention.

[0006]

The present invention provides (A) meta-isopropenyl-α, α-dimethylbenzyl isocyanate.

[Chemical 4] 1-80% by weight, (B) general formula (I)

[Chemical 5] (Wherein R ₁ is H or CH ₃ group, R ₂ is C _{1 to} C ₄ alkyl group, n is an integer of 5 to 100), and 10 to 80% by weight of one or more of the monomers represented by (C) 10 to 80% by weight of at least one α, β ethylenically unsaturated monomer copolymerizable with the component (A) and the component (B)
To the copolymer solution obtained by using (D)
I)

[Chemical 6] (Here, R ₃ is a C ₁ -C ₄ alkyl group, and m is 5-12.
An integer of 0, X is the residue of a di- or polyisocyanate and contains at least one isocyanate group),
The amount of the copolymer solution relative to the whole is in the range of 5 to 95% by weight, and the amount of NCO groups in the copolymer solution to the N in the component (D).
The present invention relates to an isocyanate aqueous emulsion composition which is adjusted and contained so that the ratio of the amount of CO groups is 0.1: 9.9 to 9.9: 0.1. A particularly preferred embodiment is an isocyanate aqueous emulsion composition using an isocyanurate body or burette body of the general formula (II) where X is hexamethylene diisocyanate.

The meta-isopropenyl-α, α-dimethylbenzylisocyanate monomer, which is one of the essential components of the copolymer solution of the present invention, is a monomer containing an NCO group, but it is generally used as a curing material. Compared to the reactivity of the NCO group in the polyisocyanate derivative used, it is relatively mild, and when considering the mixing of water, alcohol, etc. during polymerization, monomers are introduced to the copolymer in a considerable proportion. The monomer of the general formula (I), which is another essential component, is a surfactant-containing monomer capable of expressing water dilutability, and is mixed with other monomers. An acrylic polyisocyanate containing a high NCO group and having excellent weather resistance and water dilutability can be prepared by combining them, and a general formula having good weather resistance, water dilutability and reactivity can be prepared. (II) By combining a surfactant-containing polyisocyanate represented by, high physical properties with excellent weather resistance,
It is possible to provide an isocyanate aqueous emulsion composition having a high potability for diluting with water.

Further, by using the present isocyanate aqueous emulsion composition in combination with a conventionally used acrylic emulsion coating composition, the isocyanate aqueous emulsion composition has excellent weather resistance, high physical properties, high water dilutability,
It is possible to provide a water-based acrylic urethane coating composition which has appropriate pot life performance and is water-based and has various performances equivalent to those of conventionally used oil-based acrylic urethane coatings.

The present invention will be described in more detail as follows. That is, 1 to 80% by weight, preferably 5 to 60% by weight, of meta-isopropenyl-α, α-dimethylbenzyl isocyanate (A component), and 10 to 10% of the monomer (B component) represented by the general formula (I). 80% by weight, preferably 15 to 60% by weight, at least one or more α, β ethylenically unsaturated monomer (C component) copolymerizable with A component and B component, 10 to 80% by weight, preferably Is 15-60% by weight
With respect to the copolymer solution obtained by using
I) one or more polyisocyanates represented by (I) (component D) in the copolymer solution in an amount of 5 to 95% by weight, preferably 10 to 90% by weight, based on the whole. The ratio of the amount of NCO groups to the amount of NCO groups in the D component is 0.1.
9.9 to 9.9 to 0.1, preferably 0.3 to 9.7.
It is sufficient that the content is adjusted so as to be up to 9.0 to 1.0.

The copolymerization method is not particularly limited, and the copolymerization may be carried out according to a general method. However, the point to be noted when carrying out the polymerization should be carried out in a water-free manner. For example, a urethane grade solvent may be used or a water removing agent may be used. As a moisture remover,
For example, Aditive T1 (Sumitomo Bayer product), Aditive OF (Sumitomo Bayer product), Moreshler sieve, etc. can be used.

Further, any solvent may be used as long as it has a solubility to such an extent that the produced polymer can be dissolved during the polymerization, and consideration is given to isocyanate, and the solvent is relatively hydrophilic. For example, propylene glycol monomethyl ether acetate, cellosolve acetate, ethyl acetate, methyl ethyl ketone, etc. can be used. Before the polymerization, the surfactant-containing polyisocyanate represented by the general formula (II) (D component) may be synthesized and then copolymerized in the presence of the D component.

The usable polymerization initiators are t-butylperoxyisopropyl carbonate, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4).
Azo initiators such as dimethyl valeronitrile), 1,1 ′ azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, t-butylperoxy (2-ethylhexanoate), cumene hydroperoxide, No. 3 Peroxides such as primary butyl hydroperoxide, ditertiary butyl peroxide, and lauryl peroxide can be used alone or as a mixture, and as a polymerization degree regulator, NOFMER MSD (manufactured by NOF Corporation), With general chain transfer agents such as 2-ethylhexyl mercaptan and n-octyl mercaptan,
It can be used alone or in a mixed system.

In the monomer (component B) represented by the general formula (I) that can be used in the present invention, R ₁ is hydrogen or a methyl group, and R ₂ is an ethyl group, a propyl group or a butyl group. A methyl group is particularly preferable. Further, in order to obtain good water dilutability, the presence of sufficient oxyethylene groups (C ₂ H ₄ O) is necessary, n is required to be 5 to 100 on average, and particularly n is 7 on average. The case of up to 60 is excellent.

Examples of the monomer include methoxy polyethylene glycol (meth) acrylate, (n = 9), methoxy polyethylene glycol (meth) acrylate (n
= 30), ethoxy polyethylene glycol (meth) acrylate, propoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate and the like may be used in combination of one or more.

As the α, β ethylenically unsaturated monomer (component C) which can be used in the present invention, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) Isopropyl acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, (meth) acrylic acid t
ert-butyl, isopentyl (meth) acrylate,
Neopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, Undecyl (meth) acrylate, palmityl (meth) acrylate, cetyl (meth) acrylate, (meth)
Stearyl acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate,
Examples thereof include ethoxyethyl acrylate, styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, vinylidene chloride, vinyl acetate and vinyl ester of saturated monocarboxylic acid. These can be used alone or in combination of two or more.

In the surfactant-containing polyisocyanate represented by the general formula (II) (component D) which can be used in the present invention, R ₃ is a methyl group, an ethyl group, a propyl group or a butyl group, and a methyl group is particularly preferable. . Further, sufficient oxyethylene groups (C ₂ H ₄ O) must be present to obtain good water dilutability, and m must be 5 to 100 on average. In particular, the case where m is 7 to 60 on average is excellent.

X is the residue of a di- or polyisocyanate and contains at least one free isocyanate group. Examples of isocyanates that can be used are hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), lysine isocyanate methyl ester, xylylene diisocyanate (XD).
I), metaxylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, cyclohexylmethane diisocyanate, and other non-yellowing isocyanates, m- and p-phenylene diisocyanates, tolylene-2-4- and -2,6- Diisocyanate (TDI), diphenylmethane-4,4 '
-Yellow-type isocyanates such as diisocyanate, chlorophenylene-2,4-diisocyanate, naphthylene-1,5-diisocyanate and diphenylene-4,4'-diisocyanate, as well as their isocyanurates, burettes and trimethylolpropane Adducts, compounds with active hydrogen, such as amines,
Adducts with carboxylic acids, alcohols and their derivatives can be used.

In the present invention, it is preferable to use hexamethylene diisocyanate isocyanurate and burette in order to obtain particularly excellent weather resistance and high physical properties. The method for synthesizing the surfactant-containing polyisocyanate represented by the general formula (II) (D component) is such that an alcohol component of R ₃ —O— (C ₂ H ₄ O) _m H and at least two isocyanate groups are used. It can be synthesized by reacting with the isocyanate that it has, and at that time, at least 1 mol of isocyanate is used with respect to 1 mol of the alcohol component. In this case, it is advantageous to use an excess of isocyanate. The reaction can be carried out by adding an alcohol component to isocyanate and heating the reaction mixture at a temperature of 50 to 150 ° C.

If desired, an inorganic or organic pigment, an extender pigment, a powder pigment of aluminum flakes, etc. may be added to the isocyanate aqueous emulsion composition of the present invention. Further, as a curing accelerator, stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, organometallic catalysts such as formate K (manufactured by Takeda Pharmaceutical Co., Ltd.), 1,4-diazabicyclo (2,2,2)
Octane, triethylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N ",
N ″ -pentamethyldiethylenetriamine, triethylenediamine, dimethylaminoethanol, amine catalysts such as bis (2-dimethylaminoethyl) ether, dibutyltin dilaurate and 1,4-diazabicyclo (2,2)
2,2) A mixed catalyst of an amine catalyst such as octane and an organometallic catalyst can be used. Further, a non-slip agent such as silica sand, rubber powder, or silicon oxide can be added and used. Further, an anti-sagging agent such as calcium carbonate, organic bentonite, or silicon oxide may be added and used. In addition, various solvents, antifoaming agents, leveling agents, ultraviolet absorbers, silane coupling agents, adhesion improvers for resins, etc.,
It is also possible to use commonly used paint additives such as antioxidants.

The isocyanate water-based emulsion composition of the present invention comprises a finishing coating material for construction, a waterproof material, a floor material, a sports facility material, a plastic molding material, which are particularly required to have weather resistance, durability, and adhesion to a substrate. It can be applied to all fields where conventional organic solvent-based paints such as stone paints, woodwork paints, metal paints, inks, adhesives, binders, and primers were used.

[0021]

EXAMPLES The present invention will now be described in more detail with reference to examples. Parts and% in the text are based on weight unless otherwise noted. Example 1 Production Example of Copolymer Solution (1) In a 2 liter flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introducing tube, an isocyanurate body of hexamethylene diisocyanate (solid content 100 %, NCO group content 23%, viscosity 2300c
ps) 35 parts, methoxy polyethylene glycol (m =
22) After charging 15 parts and 67 parts of propylene glycol monomethyl ether acetate, the temperature was raised to 110 ° C. with stirring while blowing nitrogen gas, and then reacted for 3 hours. A dehydrating agent (Additive T1; manufactured by Sumitomo Bayer Urethane Co., Ltd.) (0.5 part) was added, and the temperature was raised to 130 ° C. Thereafter, 5 parts of styrene, 5 parts of methyl methacrylate, 10 parts of butyl acrylate, 15 parts of metaisopropynyl α, α dimethylbenzyl isocyanate as a dropping component,
Methoxy polyglycol methacrylate (n = 22) 1
5 parts, chain transfer agent (Nofmer MSD; NOF Corporation)
(Manufactured by Nippon Oil & Fat Co., Ltd.) and 0.25 parts by weight of a polymerization catalyst (Perbutyl I; manufactured by NOF CORPORATION) were uniformly added dropwise over 3 hours. After completion of dropping, the mixture was aged for 3 hours and then cooled to room temperature. The copolymer solution (1) thus obtained had a ratio of NCO groups in the copolymer solution to NCO groups in the component (D) of 3.0: 7.0, a nonvolatile content of 60% and a viscosity of 682 cp.
s (BM viscometer NO3 rotor, 60 rpm, 25
℃), the characteristic value of the isocyanate group content 6.3% was shown.

Example 2 Production Example (2) of Copolymer Solution The copolymer composition of Production Example (1) of the copolymer of Example 1 is shown in Table 1.
The ratio was changed to the following ratio, and the same polymerization operation as in Example 1 was performed to obtain a copolymer solution (copolymer solution numbers 2 to 13). Comparative Example 1 Preparation of Comparative Copolymer Solution Preparation of copolymer solution of Example 1 The copolymerization composition of Example (1) was changed to the ratio shown in Table 2, and the same polymerization operation as in Example 1 was performed. The comparative copolymer solutions (Comparative Copolymer Solution Nos. 1 to 7) are shown in Table 2.

Example 3 Production Example of Isocyanate Aqueous Emulsion 100 parts of the copolymer solutions obtained in Examples 1 and 2 and 200 parts of water were mixed and mixed with a stirrer for 20 minutes to produce an isocyanate aqueous emulsion. did. The stability of the isocyanate aqueous emulsion is shown in Table 3.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4] A stable isocyanate aqueous emulsion was obtained with each of the copolymer solutions of Example 1, and in the case of the comparative copolymer solution of Comparative Example 1, resin separation, gelation, thickening, etc. occurred, and usable isocyanates were used. No nate aqueous emulsion was obtained.

Example 4 Clear Paint for Woodworking Paint 100 parts of the copolymer solution obtained in Example 1, 0.008 part of a curing accelerator (formate K), 100 parts of water, an antifoaming agent (FZ-336). 0.1 part of Nippon Unicar Co., Ltd. was mixed and mixed for 20 minutes with a stirrer to produce a clear coating. The clear paint was brush-painted on a white wood so that the applied amount would be 100 g / m ^2, and cured at room temperature for 1 week. This coated product was excellent in weather resistance, yellowing resistance, water resistance, chemical resistance, crack resistance and adhesiveness, and could be sufficiently used as a clear paint for woodwork paints.

Example 5 Stone clear coating material Example 2 Copolymer solution No. 4 (100 parts), curing accelerator (formate K) 0.008 parts, water 200 parts, defoaming agent (FZ-336) 0. 1 part was mixed and mixed for 20 minutes with a stirrer to produce a clear coating. The clear paint was spray-painted on the marble so that the applied amount was 150 g / m ² and cured at room temperature for 1 week. This coated material has weather resistance, yellowing resistance, stain resistance, acid resistance, water resistance, crack resistance,
A product having excellent adhesiveness, which can be sufficiently used as a clear coating for stone, was obtained.

Example 6 One-part moisture-curable enamel paint Example 2 100 parts of copolymer solution No. 2; 20 parts of dehydrated white pigment (R-820; manufactured by Ishihara Sangyo Co., Ltd.); Additive T1 (Sumitomo) Bayer Co., Ltd. 1 part, curing accelerator (formate K) 0.008 part, leveling agent (L-
7607N; manufactured by Nippon Unicar Co., Ltd., 0.5 part was mixed, and the pigment was dispersed in a super mill to produce an enamel coating. 100 parts of this enamel coating was diluted with 200 parts of water, spray-coated on a slate plate and a tin plate so that the coating thickness was 30 μ, and cured at room temperature for 1 week. This coated product is excellent in weather resistance, water resistance, chemical resistance, and adhesion resistance, and is used as a finishing coating material for construction, waterproofing material, floor material, sports facility material, plastic molding material, stone paint and woodworking paint, metal paint. A product that can be sufficiently used for applications such as inks and inks was obtained.

Example 7 Two-component curing type curing agent for water-based coating materials The following main ingredients were mixed in the following formulation and stirred with a disper for 1 hour to produce an emulsion coating material. (Blending agent) Acrylic emulsion (E-1) ^{* 1} 45 Antifoaming agent 0.2 Dispersing agent 0.5 Preservative 0.1 Leveling agent 1 Calcium carbonate 10 Silica powder 10 Chromium oxide green 10 Thickener 3 Ethylene glycol 2 Butyl cellosolve 3 Water 15 ² Total 100 ^{* 1} Hydroxyl number 10 manufactured by Taisei Kako Co., Ltd., solid content 50, viscosity 125 cps (25 ° C) hydroxyl group-containing acrylic emulsion Example 2 Copolymer solution 13 was used as a curing agent 1
After mixing with 00 parts curing agent 20 parts and water 100 parts, coating amount on floor urethane sheet and floor polyester sheet 250 g / m
Roller brush coating was applied so that the number became ^2, and curing was carried out at room temperature for 1 week. This coated material has weather resistance, water resistance, chemical resistance,
It was excellent in abrasion resistance, pot life, especially elongation and adhesiveness. This coated product was obtained by greatly improving the adhesiveness and abrasion resistance of the one-pack type acrylic emulsion paint, and greatly improving the weather resistance, elongation and toxicity of the two-pack type epoxy paint. From this point of view, it can be applied to all fields of use of oil-based two-component acrylic urethane coatings that have been conventionally used.

Example 8 Primer Example 2 Copolymer solution No. 11 (100 parts), a curing accelerator (0.001 part), and water (200 parts) were mixed and mixed for 20 minutes with a stirrer. m ²
Was applied with a roller brush. After standing at room temperature for 1 day, the two-component curable emulsion coating composition of Example 7 was applied at a coating amount of 250.
It was coated with a roller brush at a rate of g / m ² and cured at room temperature for 1 week. The adhesive strength of this coated product was 18 kg / cm ² , which was a sufficient performance as a primer.

[0033]

INDUSTRIAL APPLICABILITY As is clear from the examples and comparative examples, the isocyanate aqueous emulsion composition of the present invention can be easily obtained by simply adding water and stirring, and the aqueous dispersion is an aqueous system. Nevertheless, it has a pot life that does not interfere with actual work. Further, by using the present isocyanate aqueous emulsion composition together as a curing agent for conventionally used acrylic emulsion paints, excellent weather resistance, water resistance, chemical resistance, elongation, adhesiveness, physical properties, and water dilutability pot life are obtained. A composition is obtained, which is water-based and has various performances equivalent to those of an oil-based acrylic urethane coating that has been conventionally used, therefore, a finishing coating material for construction, a waterproof material, a floor material, a sports facility material, a plastic molding material, a stone material, It can be applied to all fields such as woodwork, paints and primers for metals, adhesives, etc.

Claims (2)

[Claims] 1. (A) Meta-isopropenyl-α, α
-Dimethylbenzyl isocyanate 1-80% by weight, (B) General formula (I) (Wherein R ₁ is H or CH ₃ group, R ₂ is C _{1 to} C ₄ alkyl group, n is an integer of 5 to 100), and 10 to 80% by weight of one or more of the monomers represented by (C) 10 to 80% by weight of at least one α, β ethylenically unsaturated monomer copolymerizable with the component (A) and the component (B)
To the copolymer solution obtained by using (D)
I) [Chemical Formula 3] (Here, R ₃ is a C ₁ -C ₄ alkyl group, and m is 5-12.
An integer of 0, X is the residue of a di- or polyisocyanate and contains at least one free isocyanate group)
In the range of 5 to 95% by weight of the copolymer solution and the ratio of the amount of NCO groups in the copolymer solution to the amount of NCO groups in the component (D) is 0.1 to 9. An isocyanate aqueous emulsion composition, which is adjusted to 9 to 9.9 to 0.1 and contained. 2. The isocyanate aqueous emulsion composition according to claim 1, wherein X in the general formula (II) is selected from an isocyanurate body and a burette body of hexamethylene diisocyanate.