JP2000191743A - Self-emulsifying polyisocyanate, aqueous coating material and aqueous adhesive using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a self-emulsifying polyisocyanate having excellent antifoaming property and water dispersing stability, sufficient pot life in a water dispersing state and having excellent physical properties after curing, and an aqueous coating material and an aqueous adhesive using the polyisocyanate. SOLUTION: This self-emulsifying polyisocyanate is obtained by reacting (A) an active hydrogen group-containing ionic surfactant obtained by bonding (a1) a compound containing an ethylenic unsaturated bonding and an active hydrogen group with (a2) in ethylenically unsaturated bonding-containing ionic surfactant by radical polymerization, (B) an active hydrogen group-containing nonionic surfactant, and (D) another active hydrogen group-containing compound, and occasionally, with (C) an organic polyisocyanate. The aqueous coating material or the aqueous adhesive is obtained by using the resultant self- emulsifying polyisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a self-emulsifiable polyisocyanate in which isocyanate groups can exist in water for a long time, and to a water-based paint and a water-based adhesive using the same.

[0002]

2. Description of the Related Art Paints, adhesives, coatings and the like containing a large amount of organic solvents have adverse effects on the human body, safety and health problems such as explosions and fires, and pollution problems such as air pollution. Therefore, in order to improve these problems,
Development of water system is being actively conducted. Traditionally,
Although a water-soluble polymer solution or an aqueous emulsion is used, an aqueous one-liquid system often cannot exhibit the performance required in the market. For this reason, a curing agent and a cross-linking agent are used for improving durability and adhesiveness. Various methods have been proposed for the curing / crosslinking system, one of which is to use a hydrophilic group-containing polyisocyanate as a curing agent / crosslinking agent.

[0003] Conventional self-emulsifying polyisocyanates are disclosed in JP-A-62-50373 and JP-A-61-29.
There are those described in, for example, JP-A No. 1613 and the like, in which a hydrophilic surfactant-like structure is introduced into polyisocyanate. Japanese Patent Application Laid-Open No. 8-85716 describes a self-emulsifying polyisocyanate having a hydrophilic surfactant and a hydrophobic chain introduced therein.

[0004] However, the conventional self-emulsifiable polyisocyanate has the disadvantage that, when dispersed in water, the isocyanate group cannot exist for a long time due to the reaction between the isocyanate group and water, and the pot life is short. Had.

Therefore, various improvements have been attempted to improve the pot life of a self-emulsifying polyisocyanate dispersed in water. For example, Japanese Patent Application Laid-Open No. 9-7172
0, JP-A-9-302309, JP-A-9-302309
In 328654 and the like, an attempt is made to improve the pot life by mixing an ionic surfactant.

However, according to the methods disclosed in these publications,
Since the ionic surfactant is present in a free state, the appearance, strength and durability of the cured product are uneasy. In addition, the "foam disappearance" (defoaming property) generated upon mixing with water is poor, and it is inconvenient to use it as it is. In order to solve this problem, an antifoaming agent is added. However, a self-emulsifiable polyisocyanate to which a large amount of an antifoaming agent is added tends to cause a decrease in the adhesion and the adhesion strength of the coating film.

[0007]

SUMMARY OF THE INVENTION The present invention provides a self-emulsifying polyisocyanate having excellent defoaming properties and aqueous dispersion stability, sufficient pot life in an aqueous dispersion state, and good physical properties after curing. An object of the present invention is to provide a water-based paint and a water-based adhesive using the same.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve such conventional problems, and as a result, they have obtained by introducing a nonionic hydrophilic group and an ionic hydrophilic group into polyisocyanate. The present inventors have found that the self-emulsifying polyisocyanate obtained can solve the above-mentioned problems, and have completed the present invention.

That is, the present invention provides the following (1) to (4)
It is. (1) An active hydrogen group-containing ionic surfactant obtained by bonding a compound (a1) containing an ethylenically unsaturated bond and an active hydrogen group with an ethylenically unsaturated bond-containing ionic surfactant (a2) by radical polymerization A self-emulsifying polyisocyanate obtained by reacting (A), a nonionic surfactant containing an active hydrogen group (B), and an organic polyisocyanate (C).

(2) An active hydrogen group-containing ionic compound in which a compound (a1) containing an ethylenically unsaturated bond and an active hydrogen group and an ionic surfactant (a2) containing an ethylenically unsaturated bond are bonded by radical polymerization. A surfactant (A);
A self-emulsifying polyisocyanate obtained by reacting an active hydrogen group-containing nonionic surfactant (B), an active hydrogen group-containing compound (D) other than these, and an organic polyisocyanate (C).

(3) An aqueous paint comprising water, a water-soluble resin and / or an aqueous emulsion and the self-emulsifiable polyisocyanate (1) or (2).

(4) An aqueous adhesive characterized by containing water, a water-soluble resin and / or an aqueous emulsion, and the self-emulsifying polyisocyanate of (1) or (2).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The isocyanate content of the self-emulsifying polyisocyanate of the present invention is preferably from 5 to 45% by mass, more preferably from 7 to 43% by mass. If the isocyanate content is too small, the crosslinking point will be too small,
The cured product tends to have poor mechanical strength and durability. If it is too large, the crosslink density of the cured product becomes unnecessarily large, so that the flexibility of the coating film or the adhesive layer tends to be insufficient.

The viscosity at 25 ° C. of the self-emulsifying polyisocyanate of the present invention is preferably 10,000 mPa · s or less, more preferably 7,000 mPa · s or less. If the viscosity is too high, workability will deteriorate.

The average number of functional groups of the self-emulsifying polyisocyanate of the present invention is preferably from 2.0 to 5.0, more preferably from 2.0 to 4.0. If the average number of functional groups is too small, the crosslink density will be low, so that the coating strength and the adhesive strength tend to be insufficient. On the other hand, if it is too large, the crosslinking density of the cured product becomes unnecessarily large, so that the flexibility of the coating film or the adhesive layer tends to be insufficient.

The compound (a1) containing an ethylenically unsaturated bond and an active hydrogen group used in the present invention is a compound containing at least one ethylenically unsaturated bond and at least one active hydrogen group in a molecule. The active hydrogen group in (a1) is a group that reacts with an isocyanate group such as a hydroxyl group, an amino group, and an imino group.

The ethylenically unsaturated bond of (a1)
By subjecting the ethylenically unsaturated bond of the ethylenically unsaturated bond-containing ionic surfactant (a2) described below to a radical polymerization reaction, an active hydrogen group-containing ionic surfactant (A) is obtained.

Japanese Patent Application Laid-Open No. 7-48429 discloses that
There is a description that a self-emulsifiable polyisocyanate can be obtained by using an active hydrogen group-containing ionic surfactant. However, Japanese Patent Application Laid-Open No. 7-48429 does not specifically disclose a means or method for introducing an ionic surfactant into a polyisocyanate. The point of the present invention is to obtain a self-emulsifiable polyisocyanate which has no site to react with isocyanate, improves the pot life by using industrially available raw materials, and does not generate bleed in the cured product. is there.

Examples of the compound (a1) containing an ethylenically unsaturated bond and an active hydrogen group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, and ε-caprolactone thereof. Active hydrogen group-containing acrylates such as adducts and γ-valerolactone adducts;
Hydroxy methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid esters such as ε-caprolactone adducts and γ-valerolactone adducts, hydroxy unsaturated fatty acids such as ricinoleic acid, methyl ricinoleate, etc. And unsaturated aliphatic alcohols such as allyl alcohol, geraniol, nerol, and hexenol, and aromatic ring-containing unsaturated alcohols such as cinnamyl alcohol. These may be used alone or in combination of two or more. The compound (a1) having an ethylenically unsaturated bond and an active hydrogen group which is preferable in the present invention is a compound having one ethylenically unsaturated bond and an active hydrogen group in each molecule, and more preferably an active hydrogen group. The group is a hydroxyl group. When there are two or more ethylenically unsaturated bonds, gelation tends to occur during a radical reaction. When there are two or more active hydrogen groups, gelation is likely to occur during the reaction with the organic polyisocyanate. When the active hydrogen group is other than a hydroxyl group, for example, an amino group, a urea group is generated after the reaction with the organic polyisocyanate. This urea group is likely to cause an increase in viscosity and turbidity. Also, active hydrogen groups other than hydroxyl groups and amino groups have a slow reaction with isocyanate groups.

The ethylenically unsaturated bond-containing ionic surfactant (a2) used in the present invention includes an anionic type and a cationic type. Examples of the anion type include a carboxylate type, a sulfate type, a sulfonate type, and a phosphate type, and examples of the cation type include those into which a quaternary ammonium salt or the like is introduced. In the present invention, an anion type is preferable, and a sulfonate type is particularly preferable. Specific examples include compounds represented by the following general formulas (1) to (3). Further, a liquid at room temperature is preferred because it is easy to handle in preparation and the like. Furthermore, 1
A single ethylenically unsaturated bond present in the molecule is preferred because it does not cause gelation in the reaction between the reactant (A) and the organic polyisocyanate (C) after the radical polymerization reaction.

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

In the general formulas (1) and (2), R represents an alkyl group having 1 to 20 carbon atoms. R ′ in general formula (3)
Represents a hydrogen atom or a methyl group. General formula (1)-
M in (3) represents an alkali metal or N (R ″) ₄ (R ″ is a hydrogen atom or an alkyl group). In the general formulas (1) and (2), n represents an integer of 1 to 20.

Specific examples of the cation type include:
A compound represented by the following general formula (4) is exemplified.

[0026]

Embedded image

R ^{a in the} general formula (4) represents a hydrogen atom or a methyl group. R ^{b to} R ^d each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may be the same or different. X ^- represents a monovalent anion.

The amount of the ionic polar group introduced into the self-emulsifying polyisocyanate of the present invention is preferably 0.001 to 0.2 mmol in the self-emulsifying polyisocyanate.
/ G, more preferably 0.005 to 0.15 mmol /
g.

If the amount of the ionic polar group introduced is less than the lower limit, the water dispersibility of the self-emulsifiable polyisocyanate deteriorates, and, for example, sedimentation is not preferred.
On the other hand, when the ratio exceeds the upper limit, the affinity between the self-emulsifying polyisocyanate and water becomes too strong, so that the stability of the isocyanate group in water deteriorates.

The active hydrogen group-containing nonionic surfactant (B) used in the present invention is a nonionic surfactant containing at least one active hydrogen group, and is preferably a polyoxyalkylene ether, a polyoxyalkylene ether or a polyoxyalkylene ether. Examples include alkylene ether fatty acid esters.

Initiators in the production of this polyoxyalkylene ether include methanol, ethanol, n
-Propanol, iso-propanol, n-butanol, iso-butanol, t-butanol, cyclohexanol, phenol, ethylene glycol, propylene glycol, aniline, trimethylolpropane, glycerin and the like. Of these, compounds having 5 or less carbon atoms, such as methanol, ethanol, ethylene glycol and propylene glycol, are preferred because the self-emulsifiable polyisocyanate has higher hydrophilicity and good water dispersibility.

The fatty acids used in the production of polyoxyalkylene ether fatty acid esters include acetic acid,
Propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid,
iso-valeric acid, caproic acid, glycolic acid, lactic acid, methoxyacetic acid and the like. Among these, acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, i
Compounds having 5 or less carbon atoms such as so-valeric acid make the self-emulsifying polyisocyanate more hydrophilic,
It is preferable because of good water dispersibility.

The polyether unit present in polyoxyalkylene ether, polyoxyalkylene ether fatty acid ester and the like is preferably 50 mol%
Above, particularly preferably at least 70 mol% are ethylene oxide units, and the (repeated) number of polyether units is preferably 3 to 90, particularly preferably 5 to 5.
There are 50.

The amount of the active hydrogen group-containing nonionic surfactant (B) to be introduced is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, based on the whole self-emulsifying polyisocyanate. Most preferably 1 to 30% by mass
It is.

When the amount of (B) introduced is less than the lower limit, the pot life after dispersion of the obtained self-emulsifiable polyisocyanate in water is too short, resulting in poor workability. On the other hand, if it exceeds the upper limit, the isocyanate content of the obtained self-emulsifiable polyisocyanate will decrease, and the weather resistance of the coating film will not be improved.

The organic polyisocyanate (C) used in the present invention includes, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
4'-diphenylmethane diisocyanate, 2,4'-
Diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate,
p-phenylene diisocyanate, m-phenylene diisocyanate, o-xylylene diisocyanate, m-
Xylylene diisocyanate, p-xylylene diisocyanate, tetramethyl xylylene diisocyanate,
4,4'-diphenyl ether diisocyanate, 2-
Nitrodiphenyl-4,4'-diisocyanate, 2,
2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-
Diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,
Aromatic diisocyanates such as 4'-diisocyanate,
Also, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2
Aliphatic diisocyanates such as -methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate;
Examples include alicyclic diisocyanates such as hydrogenated xylylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, and cyclohexyl diisocyanate, and mixtures of two or more of these. Further, a urethane-modified diisocyanate, an allophanate-modified product,
A single product or a mixture of a modified buret, a modified carbodiimide, a modified uretonimine, a modified uretdione, a modified isocyanurate, and the like can also be used. Further, polymeric isocyanates such as polyphenylene polymethylene polyisocyanate and crude tolylene diisocyanate can also be used. The organic polyisocyanate (C) used in the present invention is preferably an aliphatic and / or alicyclic diisocyanate or a modified product thereof, particularly a modified aliphatic diisocyanate, in consideration of the reactivity with water and weather resistance.

The self-emulsifying polyisocyanate of the present invention is obtained by reacting, if necessary, an active hydrogen group-containing compound (D) other than (a1), (A) and (B). There may be. This active hydrogen group-containing compound (D)
As methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-
Low molecular weight monols such as butanol, t-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, benzyl alcohol, cyclohexanol and alkylene glycol monoalkyl ether, and low molecular weight first grades such as ethylamine, butylamine and aniline Low molecular weight secondary monoamines such as monoamines, diethylamine, dibutylamine, and methylaniline;
An active hydrogen group-containing polyester, an active hydrogen group-containing polyether having less than 50 mol% of ethylene oxide units,
Examples include active hydrogen group-containing polycarbonates, active hydrogen group-containing polyolefins, hydroxy higher fatty acids having 6 or more carbon atoms and esters thereof. The number average molecular weight of (D) is preferably 1,000 or less, and more preferably 800 or less. The amount of (D) to be introduced is preferably not more than twice as much as that of (B). When the number average molecular weight of (D) is too large or the amount introduced is too large, it tends to be difficult to disperse in water.

Next, a method for producing the self-emulsifying polyisocyanate of the present invention will be described. The self-emulsifying polyisocyanate of the present invention can be suitably produced by the following two methods. In any method, the first step may be omitted, but it is preferable to provide the first step because the self-emulsifiable polyisocyanate can have various properties. Production method A First step (isocyanate modification step): a step of modifying an organic polyisocyanate. It is preferable that an isocyanuration reaction is included. Second step (radical polymerization reaction step): ethylenically unsaturated bond of compound (a1) containing an ethylenically unsaturated bond and an active hydrogen group, and ethylene of ethylenically unsaturated bond-containing ionic surfactant (a2) A step of radically polymerizing the unsaturated unsaturated bond. By this step, an active hydrogen group is introduced into the ionic surfactant. Third step (urethane-forming step): (obtained in the first step)
An organic polyisocyanate (C), an active hydrogen group-containing ionic surfactant (A) obtained in the second step, and an active hydrogen group-containing nonionic surfactant (B);
(A1) a step of subjecting an active hydrogen group-containing compound (D) other than (A) and (B) to a urethanation reaction. Production method B First step (isocyanate modification step): a step of modifying an organic polyisocyanate. It is preferable that an isocyanuration reaction is included. Second step (urethane-forming step): (obtained in the first step)
An organic polyisocyanate (C), a compound (a1) containing an ethylenically unsaturated bond and an active hydrogen group, and a nonionic surfactant (B) containing an active hydrogen group;
(A1) A step of subjecting an active hydrogen group-containing compound (D) other than (A) and (B) to a urethanation reaction. Third step (radical polymerization reaction step): a step of radically polymerizing the reaction product obtained in the second step and the ethylenically unsaturated bond of the ethylenically unsaturated bond-containing ionic surfactant (a2). By this step, the ionic surfactant is introduced into the molecule of the self-emulsifying polyisocyanate.

The first step in both production methods A and B is a step of modifying an organic polyisocyanate. Specific reactions in this step include a urethanation reaction, a ureation reaction, an allophanation reaction, a biuretation reaction, a carbodiimidation reaction, a uretonimination reaction, a uretdionation reaction, an isocyanuration reaction, a combination thereof, and the like. . In addition, a well-known method is used for these reaction methods.

In the second step of the production method A and the third step (radical polymerization reaction step) of the production method B, a radical polymerization initiator is generally used. 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, azobiscyanovaleric acid, 1,1'-azobis- (cyclohexane- 1-carbonitrile), 2,2'-azobis- (2,
4-dimethylvaleronitrile), 2,2'-azobis-
Azo compounds such as (4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1
-Bis (t-hexylperoxy) cyclohexane,
1,1-bis (t-hexylperoxy) -3,3,5
-Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, n-butyl-4,4
-Bis (t-butylperoxy) valerate, 2,2-
Bis (t-butylperoxy) butane, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, t-hexyl peroxide, 1,1,3,3-tetramethylbutyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, di-t-butyl peroxide, isobutyroyl peroxide,
3,5,5-trimethylhexanoyl peroxide,
Octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoyl peroxide, toluylbenzoyl peroxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, bis (4-t-butyl (Cyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di (3-methyl-3-methoxybutyl) Peroxydicarbonate, α, α'-bis (neodecanylperoxy) diisopropylbenzene, cumylperoxyneodecanate, 1,1,3,3-tetramethylbutylperoxyneodecane 1-cyclohexyl-1-methylethyl peroxyneodecanate, t-hexylperoxyneodecanate, t-butylperoxyneodecanate, t-hexylperoxypivalate, t-butylperoxypivalate , 2,5-dimethyl-2,5
-Bis (2-ethylhexylperoxy) hexane,
1,1,3,3-tetramethylbutylperoxy-2-
Ethyl hexanate, 1-cyclohexyl-1-methylethyl peroxy-2-ethyl hexanate, t-hexyl peroxy-2-ethyl hexanate, t-butyl peroxy-2-ethyl hexanate, t-butyl peroxy Isobutylate, t-butyl peroxy laurate, t-butyl peroxy-3,5,5-trimethyl hexanate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy Oxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butyl Peroxyacetate, t-hexylperoxybenzoe DOO, t- butyl peroxy -m- toluoyl benzoate, t- butyl peroxybenzoate, and a bis (t-butylperoxy) organic peroxides such as isophthalate.

The amount of the polymerization initiator to be charged in the radical polymerization is preferably from 0.1 to 50 mol%, particularly preferably from 0.5 to 40 mol%, of the total number of moles of the ethylenically unsaturated bonds present before the reaction. When the charged amount of the radical polymerization initiator is too small or too large, the radical polymerization reaction does not easily proceed well. The reaction temperature during radical polymerization is 30 to 120.
° C, particularly preferably 50 to 100 ° C.

In the second step of the production method A and the third step of the production method B, the ethylenically unsaturated double bond (a) of the compound (a1) containing an ethylenically unsaturated bond and an active hydrogen group, The molar ratio of the ethylenically unsaturated double bond (b) of the ethylenically unsaturated bond-containing ionic surfactant (a2) is preferably (a) / (b) = 1/20 to 20/1, more preferably. Is (a) / (b) = 1/15 to 15 /
It is one. When the amount of (a) is too large, the amount of the introduced ionic surfactant often does not reach the required amount, so that the pot life of the obtained self-emulsifying polyisocyanate after water dispersion is short. Many. If the amount of (a) is too small, the proportion of the (ionic polymer) present in a free state increases, so that the self-emulsifiable polyisocyanate obtained tends to have poor defoaming properties.

The third step of the above-mentioned production method A and the second step (urethane-forming step) of the production method B may be carried out in a molten state or, if necessary, a solvent commonly used in the polyurethane industry, for example,
Aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene; ester solvents such as methyl acetate and ethyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethylene glycol monomethyl ether acetate; propylene glycol monoethyl Glycol ether ester solvents such as ether acetate, ether solvents such as tetrahydrofuran and dioxane, methanol, ethanol,
It can be carried out using one or a mixture of two or more of alcoholic solvents such as isopropanol and polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Further, at the time of the urethanization reaction, an urethanization catalyst such as an organic metal compound such as dibutyltin dilaurate or dioctyltin dilaurate, an organic amine such as triethylenediamine or triethylamine, or a salt thereof can be used as necessary. The reaction temperature at this time is preferably from 30 to 120C, more preferably from 50 to 100C.

The reaction apparatus is not particularly limited as long as the reaction can be performed uniformly. For example, a mixing and kneading apparatus such as a reaction vessel equipped with a stirrer, a kneader, a single-screw or multi-screw extrusion reactor, and the like can be used. No. Second step and third step
As a reactor in the process, a reactor with a stirrer is preferable.

In the self-emulsifying polyisocyanate of the present invention, if necessary, additives and auxiliaries commonly used in aqueous two-component systems can be used. For example, pigments, dyes, dispersion stabilizers, viscosity modifiers, leveling agents, gelling inhibitors, light stabilizers, antioxidants, ultraviolet absorbers, heat resistance improvers, inorganic and organic fillers, plasticizers, lubricants, Antistatic agents, reinforcing materials, catalysts, thixotropic agents, surfactants, emulsifiers and the like can be added. In addition, if necessary, an antifoaming agent can be added. However, the self-emulsifiable polyisocyanate of the present invention has good defoaming properties, and is therefore preferably not added or less than usual.

The application fields of the self-emulsifying polyisocyanate of the present invention include coating materials, adhesives, sealing materials, inks, fiber / glass fiber treating agents, sizing agents,
It can be used as a filler, a primer, a binder, an anchor coat agent, various binders and the like.

The water-based paint and water-based adhesive of the present invention use the above-mentioned self-emulsifying polyisocyanate as a curing agent. A preferred embodiment of the water-based paint and water-based adhesive of the present invention is a mixture of the above-mentioned self-emulsifiable polyisocyanate, a water-soluble resin and / or a water-based emulsion. Applications include paints (including coatings) and adhesives for metals, woodwork, plastics, inorganic materials and the like. By mixing the two components, the isocyanate groups present in the self-emulsifying polyisocyanate can improve the adhesion and the strength, hardness, and durability by crosslinking, and the like.

The water-soluble resin used in the water-based paint and water-based adhesive of the present invention is preferably polyvinyl alcohol, polyethylene oxide, water-soluble ethylene-vinyl acetate copolymer, water-soluble acrylic resin, water-soluble epoxy resin. Resin, water-soluble cellulose derivative, water-soluble polyester,
Water-soluble lignin derivatives, water-soluble fluororesins, water-soluble silicone resins, and the like.

The water-based emulsion used in the water-based paint and water-based adhesive of the present invention includes all of what is called latex and emulsion. Preferably, styrene butadiene copolymer latex, acrylonitrile butadiene copolymer latex, methyl methacrylate butadiene copolymer latex, chloroprene latex, rubber latex such as polybutadiene latex, polyacrylate latex, polyvinylidene chloride latex, polybutadiene Latex, or those obtained by carboxyl-modifying these latexes, and polyvinyl chloride emulsion, urethane acrylic emulsion, silicone acrylic emulsion, vinyl acetate acrylic emulsion, polyurethane emulsion, acrylic emulsion, and the like are exemplified. In addition, the fluorine emulsion having excellent weather resistance and stain resistance is poor in solvent resistance because of non-crosslinking, but by using the self-emulsifying polyisocyanate of the present invention as a curing agent, weather resistance, stain resistance and Solvent resistance and the like can be further improved.

The water-soluble resin and / or the water-based emulsion used in the present invention, even if they do not contain active hydrogen groups capable of reacting with isocyanate groups or contain only a small amount thereof, are finally self-emulsified. The reactive polyisocyanate reacts with water in a water-soluble resin and / or an aqueous emulsion to form a polyurea compound, and forms a hard and tough coating film, thereby improving weather resistance. Further, since the isocyanate group reacts with an active hydrogen group existing on the surface of the adherend, the adhesion is also improved. However, when a water-soluble resin and / or an aqueous emulsion containing a large amount of active hydrogen groups that can react with isocyanate groups at room temperature is used, the active hydrogen groups in the polymer react with the isocyanate groups in the self-emulsifiable polyisocyanate. However, since a crosslinked structure is formed, weather resistance, solvent resistance, and the like are further improved. In addition, when baking is performed at a high temperature, in the uretdione group-containing type, the uretdione group is dissociated and an isocyanate group is generated. Therefore, it is more preferable that the water-soluble resin and / or the water-based emulsion contain an active hydrogen group capable of reacting with an isocyanate group.

In the water-based paint and water-based adhesive of the present invention, the method of compounding the self-emulsifying polyisocyanate with the water-soluble resin and / or water-based emulsion is as follows. Alternatively, a method of dissolving in a solvent commonly used in urethane industry may be used. A preferred method is to disperse the self-emulsifying polyisocyanate in water and then blend it with a water-soluble resin and / or an aqueous emulsion.

In the water-based paint and water-based adhesive of the present invention, the amount of the self-emulsifying polyisocyanate added to the water-soluble resin and / or water-based emulsion is 100 parts by mass of the solid content of the water-soluble resin and / or water-based emulsion. On the other hand, the resin component of the self-emulsifying polyisocyanate is preferably 0.5 to 100 parts by mass, more preferably 1 to 8 parts by mass.
0 parts by weight, most preferably 3 to 60 parts by weight.

Since the water-based paint and water-based adhesive of the present invention use the above-mentioned self-emulsifying polyisocyanate, even if only the self-emulsifying polyisocyanate and water are blended, they are sufficiently practical. Can withstand. Applications include paints (including coatings) and adhesives for metals, woodwork, plastics, inorganic materials and the like.

In this case, the mixing ratio of the water and the self-emulsifying polyisocyanate is preferably 1 to 100 parts by mass with respect to 100 parts by mass of water.
More preferably 10 to 100 parts by mass, most preferably 2 to 100 parts by mass.
0 to 100 parts by mass. This dispersion becomes a paint (coating agent) or adhesive with very good adhesion because the isocyanate groups which are present relatively stably even after being dispersed in water react with the active hydrogen present on the surface of the substrate. .
In addition, a considerable time has elapsed after the aqueous dispersion, and the aqueous dispersion after the isocyanate groups have disappeared also has a particle size of 0.05 to 0.5.
It exists stably as an emulsion state of about μm, and a coating mainly composed of a urea compound obtained by drying it at room temperature or by heating is hard and tough, so that it is in the form of a film or sheet or of various substrates. It can be used as a coating agent or the like. When importance is attached to the adhesion to the base material, it is desirable to use in a state where the isocyanate group is present.

Paints (including coating agents) and adhesives using the self-emulsifying polyisocyanate of the present invention include:
If necessary, additives and auxiliaries commonly used in the aqueous two-component systems described above can be used.

[0056]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, “parts” were used.
Means “parts by mass”, and “%” means “% by mass”.

[Synthesis of Self-Emulsifying Polyisocyanate] Example 1 In a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube, and a cooler, 0.10 parts of A-1 and 1.15 parts of B-1. Department,
15.00 parts of C-1 and 0.02 parts of AIBN were charged.
The reaction was performed at 90 ° C. for 6 hours. Thereafter, the mixture was cooled to 50 ° C., 100.00 parts of D-1 was charged, and reacted at 80 ° C. for 3 hours to obtain a self-emulsifying polyisocyanate F-1. Isocyanate content 18.8%, viscosity 3,200
mPa · s (25 ° C.) and the average number of functional groups was 3.0.

Example 2 In the same reactor as in Example 1, 100.00 parts of D-1 was added.
5.00 parts of A-2 and 15.00 parts of C-1 were charged, and 8
The reaction was performed at 0 ° C. for 3 hours. Then, B-2 is set to 1.20.
Parts and 0.12 parts of AIBN, and reacted at 90 ° C. for 6 hours to obtain a self-emulsifying polyisocyanate F-2. Isocyanate content is 17.5%, viscosity is 2,800
mPa · s (25 ° C.) and the average number of functional groups was 2.9.

Examples 3 and 5 In the same manner as in Example 1, self-emulsifying polyisocyanates F-3 and F-5 were obtained using the raw materials shown in Table 1.

Examples 4 and 6 In the same manner as in Example 2, using the raw materials shown in Table 1, self-emulsifiable polyisocyanates F-4 and 6 were obtained.

Comparative Example 1 In a reactor similar to that in Example 1, 100.00 parts of D-2 was added.
20.00 parts of C-1 was charged and reacted at 80 ° C. for 3 hours. Thereafter, 1.10 parts of B-3 were charged and uniformly mixed to obtain a self-emulsifiable polyisocyanate F-7. Isocyanate content is 15.8%, viscosity is 2,800 mPa.
s (25 ° C.), the average number of functional groups was 3.3.

Comparative Example 2 In a reactor similar to that in Example 1, 100.00 parts of D-2 was added.
10.00 parts of A-2 and 20.00 parts of C-1 are charged.
The reaction was carried out at 80 ° C. for 3 hours to obtain a self-emulsifying polyisocyanate F-8. Isocyanate content is 13.7
%, The viscosity was 2,600 mPa · s (25 ° C.), and the average number of functional groups was 3.1.

Comparative Examples 3 and 4 Self-emulsifying polyisocyanates F-9 and 10 were obtained in the same manner as in Example 2 using the raw materials shown in Table 2. Examples 1 to 6 are shown in Table 1, and Comparative Examples 1 to 4 are shown in Table 2.

[0064]

[Table 1]

[0065]

[Table 2]

In Examples 1 to 6, Comparative Examples 1 to 4 and Tables 1 and 2, A-1: 2-hydroxyethyl methacrylate A-2: methyl ricinoleate A-3: ε-caprolactone addition of 2-hydroxyethyl acrylate Product (molecular weight = 244) B-1: Formula 1 type surfactant (number average molecular weight = 870) B-2: Formula 1 type surfactant (number average molecular weight = 560) B-3: Formula 2 type Surfactant (number-average molecular weight = 800) C-1: methoxypolyethylene glycol (number-average molecular weight = 400) D-1: Isocyanurate-modified hexamethylene diisocyanate (trade name: duranate TPA-100, manufactured by Asahi Kasei Corporation) Isocyanate Content = 23.5% Average number of functional groups = 3.2 Viscosity (25 ° C.) = 1,500 mPa · s D-2: Hexamethyle Isocyanurate modified product of diisocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry) Isocyanate content = 21.2% Average number of functional groups = 3.7 Viscosity (25 ° C.) = 2,000 mPa · s D-3: isophorone diisocyanate Isocyanurate modified product (trade name: Vestnut T-1890, manufactured by Huls AG) Isocyanate content = 17.3% Average functional group number = 3.6 Room temperature white solid AIBN: 2,2′-azobis-2-isobutyro Nitrile TBPOEH: t-butyl peroxy-2-ethylhexanoate E-1: acrylate of poly (oxyethylene) nonylphenol ether (number average molecular weight = 980)

[Method of Calculating Average Number of Functional Groups of Polyisocyanate of Examples and Comparative Examples] The modifier used to react with the raw material organic polyisocyanate (modified) used in Examples and Comparative Examples resulted in one molecule. 1 active hydrogen group (= hydroxyl group)
Therefore, the average number of functional groups of the modified organic polyisocyanate can be calculated by the following formula. fB = fA × (1-X / Y) where X = a / Ma + b / Mb + c / Mc + d / Md Y = exf / 4200 fB: average number of isocyanate functional groups after modification fA: average number of functional groups of raw material organic polyisocyanate a : Number of charged parts of A-1 Ma: Molecular weight of A-1 b: Number of charged parts of A-2 Mb: Number average molecular weight of A-2 c: Number of charged parts of A-3 Mc: Number average molecular weight of A-3 d: Number of charged parts of C-1 Md: Number average molecular weight of C-1 e: Number of charged parts of raw material organic polyisocyanate f: Isocyanate content (%)

[Performance of Self-Emulsifying Polyisocyanate]
Application Examples 1 to 6, Application Comparative Examples 1 to 5 [Defoaming Test] 400 parts of self-emulsifying polyisocyanate obtained in Examples 1 to 6 and Comparative Examples 1 to 4, and 600 parts of ion-exchanged water 2,000r with a homomixer
The mixture was foamed by high-speed stirring at pm for 30 seconds, and left standing in this state to measure the time until the bubbles disappeared. In Application Comparative Example 5, after dispersing F-7 in water, an antifoaming agent (FS
(Antifoam 013B, manufactured by Dow Corning) is added at 0.1% based on the solid content. Table 3 shows the results. Evaluation standard of defoaming property A: Foam disappears within 30 minutes. (B: The foam disappears in 30 minutes to 2 hours.) C: The foam disappears in 2 to 5 hours. (D: Foam does not disappear within 5 hours.)

[Water dispersibility test] Examples 1 to 6, Comparative Example 1
Self-emulsifiable polyisocyanate obtained in
Parts, and 900 parts of ion-exchanged water were charged in a container, dispersed by high-speed stirring at 2000 rpm for 30 seconds with a homomixer, and allowed to stand still in this state to observe the appearance. In Application Comparative Example 5, F-7 was dispersed in water, and then 0.1% of a solid content of an antifoaming agent (FS Antifoam 013B) was added. Table 3 shows the results. Evaluation criteria for water dispersibility ：: Disperses uniformly in water. (×: does not disperse in water.)

[Measurement of pot life] The self-emulsifying polyisocyanate obtained in Examples 1 to 6 and Comparative Examples 1 to 4 was
00 parts and 900 parts of ion-exchanged water are charged into a container, and stirred at a high speed of 2000 rpm for 30 seconds with a homomixer to disperse in water, and sampled every hour to measure the isocyanate content. Was measured. In Application Comparative Example 5, F-7 was dispersed in water, and then 0.1% of a solid content of an antifoaming agent (FS Antifoam 013B) was added. Table 3 shows the results.

[0071]

[Table 3]

Application Comparative Example 3 did not disperse in water and could not be measured.

[Evaluation of Paint] Application Example 7 The following paint components were charged into a sand grind mill and dispersed for 1 hour to prepare an aqueous paint. A self-emulsifiable polyisocyanate F-1 previously dispersed in water (solid content = 10%) was blended in an amount equivalent to the hydroxyl groups contained in the water-based paint, and the paint AP-1 was evaluated.
Was prepared. The mixing ratio of each paint component is as follows. <Blending ratio of water-based paint before blending polyisocyanate> Makrinal VSM2521 (manufactured by Hoechst Synthetic Co., Ltd., acrylic emulsion, solid content = 42%, hydroxyl value = 140 mgKOH / g, acid value = 40 mgKOH / g) 640 parts Titanium oxide paste * 335 parts Kyowanol M (manufactured by Kyowa Hakko) 25 parts * Titanium oxide paste compounding ratio Titanium oxide (manufactured by Ishihara Sangyo, Taipaque R-630) 709 parts Water 179 parts Surfactant (manufactured by Nippon Emulsifier, 25% Newcol 723aq) 85 parts Dispersant ( Arco Chemical, SMA-1440H) 20 parts Ammonia water 6 parts Preservatives (Zeneca, Broxel BDN) 1 part

This AP-1 was applied to a bond steel plate with a dry film thickness of 30.
It was applied to a thickness of ４０40 μm and cured at 25 ° C. for 2 weeks. The properties of each coating film of this coating sample were measured. The measurement items are as follows. Table 4 shows the results.・ Gloss: 60 ° according to JIS K5660-1995
Measure specular gloss. -Water resistance: measured according to JIS K5400-1995. -Adhesion: Measured according to JIS K5400-1995 (cross-cut peeling test method). -Solvent resistance: The painted surface was rubbed with absorbent cotton impregnated with xylene, and the number of times the appearance of the coating film was destroyed was measured (xylene rubbing test).

Application Examples 8 to 12 and Application Comparative Examples 6 to 10 Aqueous paint AP was prepared by using F-2 to 10 instead of F-1.
-2 to 11 were prepared and tested in the same manner as in Application Example 7. In application comparative example 10, after dispersing F-7 in water, an antifoaming agent (FS Antifoam 013B) to which 0.1% was added to the solid content was used as a curing agent. . The results are shown in Tables 4 and 5.

[0076]

[Table 4]

[0077]

[Table 5]

In Tables 4 and 5, evaluation of gloss: The larger the value of 60 ° specular gloss, the better. Evaluation criteria of water resistance ：: Almost no change in the appearance of the coating film was observed. ×: A change in the appearance of the coating film can be confirmed. Evaluation of adhesion In a cross-cut peel test, the larger the area ratio of the remaining portion, the better. Evaluation of solvent resistance In a xylene rubbing test, the larger the value, the better.

[Evaluation of Adhesive] Application Example 13 Polyurethane emulsion (content of carboxylate = 0.
3 mmol / g, non-yellowing polyester, solid content = 30
%) Previously dispersed in water (solid content = 10%)
A self-emulsifiable polyisocyanate F-1 was blended (blending mass ratio: polyurethane resin / F-1 = 10 in terms of solid content).
0/10) to obtain an aqueous adhesive AD-1. AD-1
Bar coater-N on treated surface of PET film and aluminum foil
o. 6 was applied. After the application of the adhesive, the substrate was placed in an oven at 80 ° C. for 30 seconds to remove moisture, and the adhesive applied surfaces were overlapped with each other, and then bonded by a bonding roll of 80 ° C. × 0.3 MPa. After passing through the roll, the laminate was cured at 40 ° C. for 3 days to obtain a laminate film A. The laminated film A is cut into a width of 1 cm, and a tensile speed: 300 mm
/ Min, measurement atmosphere: T-type peel test was performed at 25 ° C. × 50% RH. Similarly, a laminate film B of an aluminum foil / CPP film was prepared, and T-peel strength was measured. The laminate film B was also subjected to a peel test after boiling at 85 ° C. for 1 hour. Tables 6 and 7 show the results of the peel test.

Application Examples 14 to 18 and Application Comparative Examples 11 to
15 F-2 to 10 in place of F-1 to form an aqueous adhesive A
D-2 to D-11 were prepared and tested in the same manner as in Application Example 13. In Application Comparative Example 15, F-7 was dispersed in water, and then a defoaming agent (FS Antifoam 013B) added at 0.1% based on the solid content was used as a curing agent. . The results are shown in Tables 6 and 7.

[0081]

[Table 6]

[0082]

[Table 7]

Application Examples 13 to 18, Application Comparative Examples 11 to
15. In Tables 6 and 7, PET (film): E-5100 (manufactured by Toyobo) Aluminum (foil): Aluminum Hacks C (manufactured by Toyo Aluminum) CPP (film): RXC-11 (manufactured by Tosero) Delami: Delamination occurred

[0084]

The self-emulsifying polyisocyanate of the present invention has a longer pot life after water dispersion than conventional ones.
Further, since the defoaming property after dispersion in water is good, the workability is good even without using an antifoaming agent. A water-based paint and a water-based adhesive using the self-emulsifiable polyisocyanate also have good physical properties after curing.

Continued on the front page F term (reference) 4J034 BA03 BA07 BA08 CA02 CA13 CC01 CC12 CC23 DA01 DA03 DA05 DB03 DC02 DC50 DE02 DE04 DG02 DP03 DP18 HA01 HA07 HA11 HC03 HC12 HC22 HC71 JA03 JA13 QB12 QC05 RA07 RA08 4J038 BA021 CA011 CA071 CA071 CB051 CC041 CD021 CD081 CD091 CF021 CF031 CG141 CG161 CH191 CL001 DB001 DD001 DF021 DG262 DG272 DL031 GA02 GA06 GA08 GA13 GA14 KA03 MA08 MA10 NA26 NA27 4J040 BA021 BA231 DA051 DC091 DD021 DE031 DF04 EA01 001 001 001 001 001

Claims (4)

[Claims] 1. An active hydrogen group-containing ionic interface in which a compound (a1) containing an ethylenically unsaturated bond and an active hydrogen group and an ionic surfactant containing an ethylenically unsaturated bond (a2) are bonded by radical polymerization. A self-emulsifying polyisocyanate obtained by reacting an activator (A), a nonionic surfactant containing an active hydrogen group (B), and an organic polyisocyanate (C). 2. An active hydrogen group-containing ionic interface in which a compound (a1) containing an ethylenically unsaturated bond and an active hydrogen group and an ionic surfactant containing an ethylenically unsaturated bond (a2) are bonded by radical polymerization. Self-emulsifying properties obtained by reacting an activator (A), an active hydrogen group-containing nonionic surfactant (B), an active hydrogen group-containing compound (D) other than these, and an organic polyisocyanate (C) Polyisocyanate. 3. An aqueous paint comprising water, a water-soluble resin and / or an aqueous emulsion and the self-emulsifying polyisocyanate according to claim 1 or 2. 4. A water-based adhesive comprising water, a water-soluble resin and / or a water-based emulsion, and the self-emulsifying polyisocyanate according to claim 1 or 2.