JP2685527B2 - Water-dispersible composition and aqueous dispersion using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention provides a cured product which is widely used as a heat-resistant sizing agent such as glass fiber or carbon fiber as an aqueous dispersion or a varnish for impregnating these base materials. A high-performance bismaleimide resin-based water-dispersible composition and an aqueous dispersion using the same.

<Prior Art and Problems Thereof> Various proposals have been made so far regarding a water-dispersible composition of various thermoplastic resins and thermosetting resins and a production method thereof. These include JP-A-62-209109, JP-A-62-209110, JP-A-50-66549 and the like. However, each of these has a limit in heat resistance, and for example, when used as a sizing agent for glass fiber, carbon fiber or Kevlar fiber or a varnish for impregnating these base materials, they decompose at high temperature and generate gas. However, there was a problem that the heat resistance was insufficient.

<Problem to be Solved by the Invention> An object of the present invention is to solve the problems in the prior art,
To provide a water-dispersible composition having a high concentration of an aqueous dispersion, a low viscosity, a small particle size of a dispersion, good stability, and high heat resistance of a cured product, and an aqueous dispersion using the same. .

<Means for Solving the Problems> In view of the current state of the art, the present inventors have found that a mixture of a polyamino compound and an unsaturated bismaleimide compound and / or
Alternatively, a water-dispersible heat-resistant resin composition containing the pre-reacted product thereof, a surfactant, a vinyl compound containing an epoxy group and a vinyl compound containing an amino group as essential components has been developed.

That is, the first aspect of the present invention is a water-dispersible composition comprising the following components (a) and (b), and further containing the following components (c) and / or (d). It is provided.

(A) at least one polyamino compound selected from the group consisting of an amino compound represented by the following general formula (1) and a compound represented by the following general formula (2), and RNH ₂ ) _m (1) (1) In the formula, R is an alkylene group, a cycloalkylene group or an arylene group, or a group containing an organic group containing N, O, S or P, and these groups are directly or via another bonding group. They may be bonded to each other.m
Indicates an integer of 2 or more. ) (However, R ₁ is an organic group having 1 to 8 carbon atoms and may contain O or S. x is 1 or 2.) The following general formula (3): (In the formula, R ₂ is a group containing an alkylene group having 2 or more carbon atoms, a cycloalkylene group or an arylene group, or an organic group containing O, S or P, and these groups are directly or other Which may be bonded to each other via a bonding group of 1.) and / or a pre-reaction product of the polyamino compound and the unsaturated bismaleimide compound.

(B) at least one surfactant selected from sodium alkylbenzene sulfonate, polyoxyethylene alkyl sulfate soda salt and polyvinyl alcohol (c) epoxy group-containing vinyl compound which is glycidyl acrylate, glycidyl methacrylate or allyl glycidyl ether ( d) p-aminostyrene, m-aminostyrene, p-
Amino group-containing vinyl compound which is isopropenylaniline, m-isopropenylaniline, acrylamide or methacrylamide. The second aspect of the present invention is characterized in that the above water-dispersible composition is dispersed in water. The present invention provides a water dispersion liquid.

 Hereinafter, the present invention will be described in detail.

First, each component constituting the present invention will be described.

Component (a) Component (a) comprises a mixture of a polyamino compound and an unsaturated bismaleimide compound, and / or a pre-reacted product thereof.

Examples of the polyamino compound include the following general formula (1): RNH ₂ ) _m (1) where R is an alkylene group, a cycloalkylene group or an arylene group, or a group containing an organic group containing N, O, S or P. However, these groups may be bonded to each other directly or via another bonding group.

 m represents an integer of 2 or more.

The amino compound represented by is used.

 Specifically, for example, the following compounds are used.

4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, m-phenylenediamine, p-phenylenediamine, 4,4'-
Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2-bis (4-aminophenyl) propane, benzidine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, bis (4-aminophenyl) ) Methylphosphine, bis (4-
Aminophenyl) -p-diisopropenylbenzene, m
-Xylylenediamine, 1,5-diaminonaphthalene, p
-Xylylenediamine, hexamethylenediamine, 1,
4'-diaminobenzophenone, 2,5-bis (m-aminophenyl) -1,3,4-oxadithiazole, 2,5-bis (p-aminophenyl) -1,3,4-oxadithiazole, 4,4'-bis (p-aminophenyl) -2,2'-dithiazole, 3,4'-diaminobenzanilide, 2,2'-bis (m-aminophenyl) -5,5'-dibenzimidazole , N, N'-bis (p-aminobenzoyl) -4,4'-
Diamino compounds such as diaminodiphenylmethane.

1,2,4-triaminobenzene, 1,3,5-triaminobenzene, 2,4,6-triaminotoluene, 2,4,6-triamino-1,3,5-trimethylbenzene, 1,3 , 7-Triaminonaphthalene, 2,4,4'-triaminodiphenyl, 2,4,6-triaminopyridine, 2,4,4'-triaminodiphenylmethane, p-aminophenyl-4,4'-diphenylmethane ,
Tri (4-aminophenyl) methane, 2,4,4'-triaminobenzophenone, 3,5,4'-triaminobenzanilide, melamine-1,2,4,5-tetraaminobenzene, 2,
3,6,7-Tetraaminonaphthalene, 3,3 ', 4,4'-Tetraaminodiphenyl ether, 3,3', 4,4'-Tetraaminodiphenylmethane, 3,5-bis (3,4'-diamino Tri- or tetra-amino compounds such as phenyl) pyridine, general formula (Provided that R ₁ is an organic group having 1 to 8 carbon atoms and may contain O or S. x is 1 or 2) and the like has three or more amino groups. Compound.

Of these, preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenyl sulfone and bis (4-aminophenyl) -p-diisopropenylbenzene are preferable.

Examples of the unsaturated bismaleimide compound used together with the above polyamino compound include compounds represented by the following general formula (3).

(In the formula, R ₂ is a group containing an alkylene group having 2 or more carbon atoms, a cycloalkylene group or an arylene group, or an organic group containing O, S or P, and these groups are directly or other May be bonded to each other via a bonding group of). Specifically, for example, the following compounds are used.

N, N'-phenylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-methylene-di-p-phenylene bismaleimide, N, N'-oxy-di-p-phenylene bismaleimide, N , N'-4,4'-benzophenone-bismaleimide, N, N'-p-diphenylsulfone bismaleimide, N, N '-(3,3'-dimethyl) -methylene-p-phenylene bismaleimide, N, N'-4,4'-dicyclohexylmethane-bismaleimide, N, N'-m-
Xylylene-bismaleimide, N, N'-p-xylylene-bismaleimide, N, N '-(3,3'-diethyl) -methylene-di-p-phenylenebismaleimide, N, N'-m
-Toluylene-dimaleimide, reaction product of aniline-formalin reactant and maleic anhydride.

These unsaturated bismaleimide compounds are, for example, N-
A monomaleimide compound such as allylmaleimide, N-propylmaleimide, N-hexylmaleimide or N-phenylmaleimide may be used by substituting up to about 60% by weight.

Of these, N, N'-phenylene bismaleimide, N, N'-methylene-di-p-phenylene bismaleimide, N, N'-oxy-di-p-phenylene bismaleimide, N, N 'are preferable. -4,4'-benzophenone-bismaleimide, N, N'-p-diphenylsulfone bismaleimide, N, N '-(3,3'-dimethyl) -methylene-p-
Phenylene bismaleimide, N, N'-m-xylylene-
Bismaleimide, N, N'-p-xylylene-bismaleimide, N, N '-(3,3'-diethyl) -methylene-di-p
-Phenylene bismaleimide, N, N'-m-toluylene-dimaleimide, reaction product of aniline-formalin reaction product and maleic anhydride, more preferably N, N'-phenylene bismaleimide, N, N'-methylene -Di-p-
Phenylene bismaleimide, N, N'-oxy-di-p-
Phenylene bismaleimide and N, N'-p-diphenylsulfone bismaleimide are preferred.

These polyamino compounds and unsaturated bismaleimide compounds generally contain about 0.1 g of the former and about 0.1 g of the latter.
It is used in the form of a mixture and / or pre-reactant in a proportion of -10 g eq, preferably about 0.5-5 g eq. In order to prepare the preliminary reaction product, for example, both of them are kneaded by using a roll or the like while being heated to a temperature of about 70 to 170 ° C. to be in a prepolymer state. Both of these can form a polyamino bismaleimide by Michael addition of the amino group of the polyamino compound to the unsaturated bond of the bismaleimide compound.

In the present invention, the curing polymerization reaction of the above-mentioned component (a) is an addition reaction, so that a volatile component is not generated during curing, and an advantage that a dense cured product can be formed is achieved.

Component (b) As the surfactant used in the present invention, a well-known surfactant suitable for oil-in-water aqueous dispersion among cation type, anion type, nonionic type and zwitterionic type may be used. Examples of such surfactants are given below.

Examples of cationic surfactants include higher alkyl amines and polyoxyethylene alkyl amines, and examples of anionic surfactants include alkyl alcohol sulfate ammonium salts, sodium alkylbenzene sulfonates, sodium polyoxyethylene alkyl sulphates, and higher fatty acids. Nonionic surfactants such as salts such as polyoxyethylene alkyl ether sorbitan fatty acid ester, polyoxyethylene acyl ester, polyvinyl alcohol, polyvinyl acetate or partial hydrolysates thereof, and amphoteric surfactants such as glycine derivatives such as poly In addition to carboxylic acid types such as octyl polyaminoglycine and dodecylaminoethylglycine, various types such as imidazoline type, sulfuric acid ester type, sulfonic acid type, phosphoric acid ester type It can be mentioned.

Of these, alkylbenzene sulfonic acid sodium salt, polyoxyethylene alkyl sulfate sodium salt, and polyvinyl alcohol are preferable, and alkylbenzene sulfonic acid sodium salt and polyvinyl alcohol are more preferable.

It is also possible to use conventionally used additives such as casein, gelatin, betaine and starch as a dispersion stabilizer, if necessary.

The type of these surfactants can be appropriately selected according to the application, and one type thereof can be used, or two or more types can be used in combination.

Component (c) As the epoxy group-containing vinyl compound of component (c),
The following are preferably used:

Vinyl monomers such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and allyl oxide.

Glycidyl acrylate, glycidyl methacrylate, and more preferably glycidyl methacrylate are preferably used.

The epoxy group-containing vinyl compound used as the component (c) acts as a diluent for the component (a), that is, it dissolves the component (a) uniformly at room temperature.
As a result, the curable resin composition obtained without using a special solvent is formed as a low-viscosity solution, and the workability thereof is improved.

The component (c) may contain a styrene-based monomer such as styrene, α-methylstyrene, vinyltoluene and divinylbenzene in an amount within a range that does not substantially impair the room temperature solubility of the prepolymer. The upper limit is usually 0.1 to 10 times the molar amount of component (c),
It is preferably set to 0.1 to 3 times by mole.

 Thereby, the strength of the cured product is further improved.

(D) Component As the amino group-containing vinyl compound of the (d) component, the following are preferably used.

Vinyl monomers such as p-aminostyrene, m-aminostyrene, p-isopropenylaniline, m-isopropenylaniline, acrylamide and methacrylamide.

Preferably, p-aminostyrene, m-aminostyrene, p-isopropenylaniline and m-isopropenylaniline, more preferably p-aminostyrene and p-isopropenylaniline are used.

The amino group-containing vinyl compound used as the component (d) has the same action as that of the component (c),
Styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, and divinylbenzene may be contained in an amount that does not substantially impair the room temperature solubility.

The upper limit is usually 0.1 to 1 per 1 mol of the component (d).
The molar ratio is set to 0, preferably 0.1 to 3 times.

In addition to these components, epoxy curing agent, curing catalyst,
A curing accelerator and the like may be mixed if necessary.

Specific examples of the epoxy curing agent include fatty acid amines, acid anhydrides, dicyandiamide, hydrazines, imidazoles, and amine complex compounds of boron trifluoride.

As the curing catalyst, the following radical polymerization initiators are typically used.

(1) at a secondary or tertiary carbon atom such as isopropyl hydroperoxide, tert-butyl hydroperoxide, cumyl hydroperoxide, and perbenzoic acid;
A combination of O-O-H.

(2) A group in which —O—O— is bonded to two secondary or tertiary carbon atoms such as diisopropyl peroxide, ditertiary butyl peroxide and dicumyl peroxide.

(3) 2,5-Dimethyl-2,5-bis (tertiary butylperoxy) hexane, 2,5-dimethyl-2,5-bis (tertiary butylperoxy) hexene-3,2,5-dimethyl-2 Bisperoxide containing two peroxy groups in one molecule such as 5,5-bis (tertiary butylperoxy) hexyne-3 and 1,3-bis (tertiary butylperoxyisopropyl) benzene.

These bisperoxides are particularly advantageous in terms of peroxy number.

(4) An organic azo compound having at least one —O—N—N— bond in the molecular structure represented by azobisalkanonitrile such as azobisisobutyronitrile and azobiscarbonamide.

As the curing accelerator, epoxy curing accelerators such as imidazoles, boron trifluoride amine complex compounds, tertiary amines, quaternary ammonium salts and urea compounds can be used.

Next, the composition of the present invention and a method for producing an aqueous dispersion using the composition will be described.

In the water-dispersible composition, the component (b) is generally 0.1 to 10 parts by weight, preferably 0.2 to 7 parts by weight per 100 parts by weight of the component (a), and the component (c) and / or the component (d) is (a). Ingredient 100
0 to 200 parts by weight, preferably 0 to 100 parts by weight, and optionally an epoxy curing agent as component (c) 100
0 to 200 parts by weight, preferably 0 to 100 parts by weight, and 0 to 10 parts by weight, preferably 0 to 2 parts by weight of the radical curing agent per 100 parts by weight of the components (a) and (c) and / or (d). Each component is mixed in a ratio of parts by weight.

 The aqueous dispersion of the present invention is obtained as follows.

That is, while (a) component and (b) component are made into a 40 to 70% solution of a polar solvent such as methylene chloride, THF, MEK, and acetone, water is gradually added while stirring the system, and thereafter, polar water is added under reduced pressure. Method for removing solvent, or (a) component and (b) component and (c) component and or (d)
This is a method of gradually adding water while stirring the component-blended composition.

Component (a), component (a) + (c) in the aqueous dispersion,
The concentrations of the (a) + (d) component and the (a) + (c) + (d) component are preferably 20 to 80 wt%, and particularly preferably 40 to 60 wt%.

The thus-obtained aqueous dispersion of the present invention has a small dispersion particle size, usually 10 μm or less, for example 0.05 to 10 μm, preferably 5 μm, and most preferably 1 μm or less.

In addition, it has excellent storage stability (20 ° C, 1 month or longer), has film-forming properties at a temperature of 100 ° C or lower, and has excellent thermosetting properties and heat resistance. Further, since it has good adhesion to a glass substrate or the like, it is preferably used as a heat-resistant sizing agent such as glass fiber, carbon fiber, Kevlar fiber or a varnish for impregnating these substrates.

<Examples> Hereinafter, the present invention will be specifically described with reference to Examples.

(Reference example) N, N'-4,4'-diphenylmethane bismaleimide 71.2
Part (same as below for weight), bis (4 aminophenyl) -p-
28.7 parts diisopropenylbenzene and 5-cyano-2
-Ethyl-4-methyl imidazole 0.1 part on roll 130
Preliminary reaction was carried out by heating at ℃ for 15 minutes to obtain 100 parts of prepolymer. 6 parts of sodium dodecylbenzene sulfonate was mixed with this prepolymer, and after further cooling, 60 parts of methylene chloride was added to obtain a solution. The prepolymer solution was stirred with a homomixer at a high speed of 10,000 rpm, and water was gradually mixed with 100 parts of the prepolymer until the water content became 200 parts. After that, methylene chloride and water were removed by reducing the pressure at 150 Torr for 3 hours at 65 ° C. to obtain an aqueous dispersion having a prepolymer concentration of 40 wt%. Table 1 shows the average particle size, viscosity, storage stability, adhesion of the thermosetting product to a glass plate at 200 ° C. for 1 hour, and thermal decomposition temperature.

(Example 1) N, N'-4,4'-diphenylmethane bismaleimide 82 parts (weight, same hereafter) and 4,4'-diaminodiphenylmethane 18 parts were heated at 130 ° C. for 15 minutes on a roll to carry out a preliminary reaction. , 100 parts of prepolymer were obtained. This prepolymer 6
After mixing 0 part and 40 parts of glycidyl methacrylate in a glass reaction vessel at room temperature for 30 minutes to dissolve the prepolymer, 2-ethyl-4 as an epoxy curing accelerator was mixed.
-Methylimidazole 0.5 parts, dicumyl peroxide 1 part as a radical polymerization initiator and sodium dodecylbenzene sulfonate 3 parts as a surfactant are mixed,
While stirring at a high speed of 10,000 rpm with a homomixer, 150 parts of water was gradually added to obtain an aqueous dispersion. The obtained aqueous dispersion was evaluated in the same manner as in Reference Example.

(Example 2) N, N'-4,4'-diphenylmethane bismaleimide 82 parts (weight, the same below) and 4,4'-diaminodiphenylmethane 18 parts were heated at 130 ° C. for 15 minutes on a roll to carry out a preliminary reaction. To obtain 100 parts of prepolymer.

60 parts of this prepolymer and 40 parts of m-isopropenylaniline were mixed in a glass reaction vessel at room temperature for 30 minutes to dissolve the prepolymer, and then 1 part of dicumyl peroxide as a radical polymerization initiator and an interface. As an activator, 3 parts of sodium dodecylbenzene sulfonate was mixed, and 150 parts of water was gradually added while stirring at a high speed of 10,000 rpm with a homomixer to obtain an aqueous dispersion. The obtained aqueous dispersion was evaluated in the same manner as in Reference Example.

Comparative Example 1 96 parts of a bis-A type epoxy resin having an epoxy equivalent of 185 to 195, 4 parts of dicyandiamide and 3 parts of sodium dodecylbenzenesulfonate were dissolved in 60 parts of methylene chloride to prepare a solution.

Subsequent operations were the same as in Example 1 to obtain an aqueous dispersion. The obtained aqueous dispersion was evaluated in the same manner as in Reference Example.

<Effects of the Invention> The water-dispersible composition of the present invention can be an aqueous dispersion having the following characteristics.

When an aqueous dispersion is used, a dispersion having a high concentration is obtained, the viscosity is low, the particle size of the dispersion is small, the stability of the aqueous dispersion is high, and the heat resistance of the thermosetting product is high.

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Claims (2)

(57) [Claims] 1. A water-dispersible composition comprising the following components (a) and (b) and further containing the following components (c) and / or (d). (A) at least one polyamino compound selected from the group consisting of an amino compound represented by the following general formula (1) and a compound represented by the following general formula (2), and RNH ₂ ) _m (1) (1) In the formula, R is an alkylene group, a cycloalkylene group or an arylene group, or a group containing an organic group containing N, O, S or P, and these groups are directly or via another bonding group. They may be bonded to each other.m
Indicates an integer of 2 or more. ) (However, R ₁ is an organic group having 1 to 8 carbon atoms and may contain O or S. x is 1 or 2.) The following general formula (3): (In the formula, R ₂ is a group containing an alkylene group having 2 or more carbon atoms, a cycloalkylene group or an arylene group, or an organic group containing O, S or P, and these groups are directly or other Which may be bonded to each other via a bonding group of 1.) and / or a pre-reaction product of the polyamino compound and the unsaturated bismaleimide compound. (B) at least one surfactant selected from sodium alkylbenzene sulfonate, polyoxyethylene alkyl sulfate soda salt and polyvinyl alcohol (c) epoxy group-containing vinyl compound which is glycidyl acrylate, glycidyl methacrylate or allyl glycidyl ether ( d) p-aminostyrene, m-aminostyrene, p-
Amino group-containing vinyl compound which is isopropenylaniline, m-isopropenylaniline, acrylamide or methacrylamide 2. An aqueous dispersion obtained by dispersing the water-dispersible composition according to claim 1 in water.