JPH061846A - Production of dispersion of crosslinked resin particles - Google Patents

Abstract

PURPOSE:To obtain a dispersion of crosslinked condensation resin particles which can form a film excelling in water resistance, chemical resistance and toughness and suffering no or little coloration or emission of odor during baking. CONSTITUTION:A self-water-dispersible resin containing functional groups capable of addition reaction or a mixture thereof with a hydrophobic resin containing functional groups capable of addition reaction and a monomer containing a functional group reactive with the functional group capable of addition reaction and a hydrolyzable silyl group are subjected to an addition reaction, and the obtained addition product is polycondensed in an aqueous medium.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful method for producing a crosslinked resin particle dispersion. More specifically, in the present invention, a self-water-dispersible resin having an addition-reactive functional group is subjected to an addition reaction with a monomer having both a functional group capable of reacting with the addition-reactive functional group and a hydrolyzable silyl group. , Followed by polycondensation in an aqueous medium, or with a self-water-dispersible resin having an addition-reactive functional group,
A hydrophobic resin having an addition-reactive functional group is subjected to an addition reaction with a monomer having both a functional group capable of reacting with the addition-reactive functional group and a hydrolyzable silyl group, and then polycondensed in an aqueous medium. The present invention also relates to a method for producing an aqueous dispersion of condensed crosslinked resin particles and an organic solvent dispersion.

The dispersion of the crosslinked resin particles obtained by the present invention has stable dispersibility because it is fine particles having an average particle size of 1 micron (μm) or less, and moreover, it has water resistance. A film excellent in chemical resistance and toughness can be formed.

Further, the dispersion of the crosslinked resin particles obtained in the present invention is used as a film-forming resin component alone or in the form of containing a curing agent, or in combination with other film-forming resin. In this way, it can be used for a wide range of applications such as paints, inks, adhesives, paper fiber processing agents, etc.

It can also be used as an anti-sagging agent, a flow control agent, a thixotropic agent or a matting agent.

[0005]

2. Description of the Related Art Dispersions of crosslinked resin particles used in paints, inks, adhesives, paper fiber processing agents, etc. are mostly vinyl type, and most of them are
The fact is that they are manufactured by the emulsion polymerization method.

However, in the emulsion polymerization method, the water resistance and chemical resistance are remarkably deteriorated due to the emulsifier, which limits the use and the amount used. Although there is a method of using a reactive emulsifier in order to improve such a defect, water resistance and chemical resistance are not so different from those using an emulsifier.

As a method for producing a dispersion of vinyl-based crosslinked resin particles which does not use an emulsifier, there is a method by non-aqueous dispersion, but it is difficult to control the particle size and the dispersion stability is not good.

On the other hand, the dispersion of the condensation type crosslinked resin particles has good film-forming property, good adhesion to the material, easy balance between hardness and flexibility, and good compatibility with the condensation type resin. Although it has various features such as good compatibility, due to manufacturing difficulties and some performance defects,
At present, it has hardly been put to practical use industrially.

For example, a method in which a mixture of an aqueous resin and a crosslinking agent such as a melamine resin or a phenol resin is dispersed in water and heated to produce crosslinked resin particles (JP-A-63-137745). 63-170
No. 465), it is necessary to apply a temperature of 100 ° C. or higher under pressure in order to achieve substantial cross-linking, and yet a cross-linking degree of sufficient cannot be obtained. .

A mixed resin of a polyester resin having a hydroxyl group and a carboxyl group and a polyisocyanate resin,
The method of obtaining crosslinked resin particles by dispersing them in water (Japanese Patent Publication No. 1-501869) is a process in which the reaction of the isocyanate group is a competitive reaction between the hydroxyl group and water, and thus sufficient crosslinking is achieved. It is difficult to manufacture the one of the degree,
It is also difficult to control the degree of crosslinking.

As a method for producing a dispersion of urethane urea crosslinked resin, a method of dispersing an isocyanate-terminated prepolymer having a carboxyl group in water and crosslinking with a polyamine (US Pat. No. 4,203,
No. 883), or a mixture of a self-water-dispersible resin having an isocyanate group and a polyisocyanate compound is microencapsulated in water and then crosslinked with a polyamine (Japanese Patent Application No. -279257).

[0012] In any of the methods, a film excellent in water resistance and chemical resistance can be obtained, but since polyamine is used as a cross-linking agent, the odor during heating and drying is particularly serious, which causes problems in occupational health. Many. The baked film is also markedly colored.

Further, the toughness of the film is insufficient, and it is not possible to meet even higher requirements.
Also, there are many difficulties in its manufacturability. Good dispersion stability,
In order to obtain a dispersion of fine particles having an average particle size of 1 μm or less, preferably 0.1 μm or less, it is necessary to dilute the polyamine to a considerable extent. , It ends up being an inefficient manufacturing method.

Furthermore, since the isocyanate group itself reacts with water, after the resin having an isocyanate group is dispersed in water, the polyamine must be added promptly, which is a problem in production. The allowable range is narrow.

That is, in the prior art, the dispersion of vinyl-based crosslinked resin particles does not have sufficient film performance, and the dispersion of condensed crosslinked resin resin particles also
The degree of crosslinking is not sufficient, it is difficult to manufacture, it is not efficient, or
There are no satisfactory ones because of defects such as coloring and odor of the film, and further, the toughness of the film is insufficient.

[0016]

However, the present inventors have earnestly started research in view of the various drawbacks or the existence of such defects in the prior art.

Therefore, the problem to be solved by the present invention is that the average particle size is 1 μm or less, the dispersion stability is good, and there is little or no odor at the time of coloring or baking of the film. Moreover, it is possible to form a tough film having excellent water resistance, chemical resistance, etc., which is a highly practical dispersion of crosslinked resin particles, which can be easily and efficiently prepared by crosslinking. Another object of the present invention is to provide a novel and useful method for producing a resin particle dispersion.

[0018]

Therefore, the present inventors have
As a result of earnest and repeated studies to solve such a difficult problem, a monomer having both a functional group capable of reacting with the addition-reactive functional group and a hydrolyzable silyl group in a resin having the addition-reactive functional group. (Hereinafter, abbreviated as silane coupling agent.) Addition reaction, and then polycondensation in an aqueous medium are carried out to find out that such problems can be solved and solved. Came to complete.

That is, according to one aspect of the present invention, a self-water-dispersible resin having an addition-reactive functional group and a monomer having both a functional group capable of reacting with the addition-reactive functional group and a hydrolyzable silyl group. The present invention is intended to provide a method for producing a crosslinked resin particle dispersion, which comprises subjecting and addition-reacting and then polycondensing in an aqueous medium, and secondly, self-water containing an addition-reactive functional group. A dispersible resin and a hydrophobic resin having an addition-reactive functional group are subjected to an addition reaction with a monomer having both a functional group capable of reacting with the addition-reactive functional group and a hydrolyzable silyl group, and then an aqueous medium. It is intended to provide a method for producing a crosslinked resin particle dispersion, which comprises polycondensation in the resin.

That is, the present invention basically comprises the following two. 1. 1. A method in which a self-water-dispersible resin having an addition-reactive functional group is subjected to an addition reaction with a silane coupling agent and then polycondensed in an aqueous medium. A self-water-dispersible resin having an addition-reactive functional group and a hydrophobic resin having an addition-reactive functional group are subjected to an addition reaction with a silane coupling agent, and then microencapsulated in an aqueous medium. , Polycondensation method.

The structure of the present invention will be described in detail below. First, as the addition-reactive functional group in the present invention, an isocyanate group and a glycidyl group are preferable because of the ease of the addition reaction, but a carboxyl group can also be used.

The silane coupling agent has
When the addition-reactive functional group is an isocyanate group, a mercapto group, a primary or secondary amino group or a hydroxyl group is suitable as the functional group capable of reacting with the addition-reactive functional group. When the group is a glycidyl group,
A mercapto group or a 1, 2, 3 or quaternary amino group is suitable, and a glycidyl group is suitable when the addition-reactive functional group is a carboxyl group.

Further, the hydrolyzable silyl group is preferably an alkoxysilyl group, and further, mono-, di- or trimethoxysilyl, or mono-,
Typical examples include di- or triethoxysilyl groups.

As the silane coupling agent, only typical ones will be exemplified. Γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyrimethyldiethoxysilane, β- (3,4-glycidoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-dibutylamino Examples include propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane.

Among these, when a silane coupling agent having two amino groups in one molecule is used, it is contained in the self-water-dispersible resin having an addition-reactive functional group, or in the addition-reactive functional group. The average number of the addition-reactive functional groups in the hydrophobic resin having is preferably 1 to 2 per molecule. If the number exceeds two, gelation may occur during the addition reaction.

When the addition-reactive functional group is a glycidyl group and the functional group of the silane coupling agent is a primary amino group, the number of glycidyl groups is 1 for the same reason. It is desirable that the average number is 1 to 2 in the molecule.

The amount of the silane coupling agent used with respect to the self-water-dispersible resin having an addition-reactive functional group or the hydrophobic resin is the amount of the self-water-dispersible resin having an addition-reactive functional group or the hydrophobic resin. The amount is such that at least one molecule of the silane coupling agent is added to one molecule, and the ratio is not more than one molecule with respect to one addition-reactive functional group. It is desirable to use a silane coupling agent.

If the amount is less than the above range of use,
The silane coupling agent does not react, and the resin having the addition-reactive functional group remains unreacted. On the other hand, if the amount exceeds the range of use, it does not react with the resin having the addition-reactive functional group. Since the silane coupling agent remains unreacted, it is not preferable in any case.

The self-water-dispersible resin having an addition-reactive functional group is a hydrophilic group such as a carboxyl group, a sulfonate group or a quaternary amino group or a tertiary amino group neutralized with an acid, or polyethylene glycol. It has an ether group based on the above. Especially, from the viewpoint of easy production of the resin, or from the viewpoint of easily obtaining a film excellent in water resistance, chemical resistance, etc., a sulfonate group and a carboxyl group are preferable, and further, a carboxyl group is It can be said that it is more preferable.

Here, the self-water-dispersible resin is itself stable because it has a hydrophilic group in its molecule, without using any emulsifier or dispersion stabilizer. A resin having the property of forming an aqueous dispersion of

Microencapsulation refers to a method in which a resin having no self-water dispersibility is mixed with a resin having self-water dispersibility to co-disperse it in water. .

No special method is required to introduce a carboxyl group into the resin,
A known and commonly used method may be exclusively used. For example, when synthesizing a polyester resin, leaving a carboxyl group; adding acid anhydrides to hydroxyl groups in the resin; using dimethylolpropionic acid during the urethanization reaction; There is a method in which a tetracarboxylic dianhydride is reacted with the resin-like resin; or an acid monomer having an ethylenically unsaturated bond is graft-copolymerized.

As the base for imparting hydrophilicity by neutralizing the carboxyl group, it is preferable to use so-called volatile tertiary amines such as triethylamine, tributylamine, dimethylethanolamine, etc. Basic substances or alkalis can also be used depending on the case. As the amount of the carboxyl group, an acid value in the resin solid content of 10 to 100 is preferable, and 20 to 80 is preferable. The proportion of carboxyl groups to be neutralized is preferably in the range of 20 to 120%, preferably 30 to 120%.
The range of 100% is suitable.

The acid value of the resin and the ratio of its neutralization are appropriately determined in view of particle size, dispersibility, film performance and the like.

In order to introduce a sulfonic acid group neutralized with a base, there is a method of using 5-sodium sulfoisophthalic acid in the synthesis of a polyester resin. In order to introduce an ether group based on polyethylene glycol, polyethylene glycol or its one-terminal methoxylated product may be used in the synthesis of polyester resin or polyurethane resin.

The self-water-dispersible resin having the addition-reactive functional group is a hydrophilic group, preferably a carboxyl group, and the addition-reactive functional group is preferably an isocyanate group and / or a glycidyl group. It is preferable to use a polyester resin, a polyurethane resin, or an epoxy resin having both of the above and more preferable to use a resin which is substantially linear in order to avoid gelation during synthesis.

As a method for producing a self-water-dispersible resin having an isocyanate group, a diol resin (polymer diol) having a hydrophilic group and a diisocyanate compound are used in an organic solvent that does not react with an isocyanate group, or A method of reacting a diol resin (polymer diols), a diol compound having a carboxyl group, and a diisocyanate compound at a ratio of a hydroxyl group having a larger amount of an isocyanate group is easier and simpler to operate. is there.

In this case, if necessary, a low molecular weight diol compound may be used, or if the amount is in a range such that gelling or gelation does not significantly increase the viscosity of the resin, a hydroxyl group or an isocyanate group is added. Bifunctional or higher polyfunctional compounds can also be used.

Here, only representative ones of the various raw materials used in the preparation of the above-mentioned isocyanate group-containing self-water-dispersible resin will be exemplified. a) diol resin (polymer diol): polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyester diol, polyether diol, polycaprolactone diol, polycarbonate diol, silicone diol, polybutadiene diol, polyisoprene diol, polyolefin resin diol (Polymer diols) or fatty acid monoglyceride.

Such diol resin (polymer diols)
The number average molecular weight of is preferably in the range of 500 to 4,000.

B) Low molecular weight diol compound: ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol , 2-methyl-1,3-propanediol, 1,5-pentanediol, 2,2-diethyl-1,3-propanediol,
2,2,4-trimethyl-1,3-pentanediol,
1,4-butene diol, monoester of hydroxypivalenic acid and neopentyl glycol, hydrogenated bisphenol A, alkylene oxide adduct of bisphenol A, alkylene oxide adduct of hydrogenated bisphenol A, and the like.

C) A diol compound having a carboxyl group: dimethylolpropionic acid, a trivalent polyol to which an acid anhydride is added, and the like. d) A diol resin having a hydrophilic group: 5-sodium sulfoisophthalic acid is used as a raw material for polyester diol; diol resin (polymer diol) and / or low-molecular diol compound and tetracarboxylic dianhydride A form obtained by reacting with; a diol resin (polymer diol) and / or a low molecular diol compound,
A form in which a diol compound having a carboxyl group and a diisocyanate compound are reacted in such a manner that the proportion of hydroxyl groups is large with respect to the isocyanate groups.

Further, it is desirable to use those having a number average molecular weight within the range of 500 to 4,000.

E) Diisocyanate compound: toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) benzene, 1,3-bis (isocyanatomethyl)
Cyclohexane, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, etc.

A method for producing a self-water-dispersible resin having a glycidyl group is a method in which an isocyanate group-containing self-water-dispersible resin as described above is subjected to an addition reaction with a compound having both a hydroxyl group and a glycidyl group; There are various methods such as a method of adding a diglycidyl compound to a terminal carboxyl group-containing linear resin having a polyethylene glycol or a sodium sulfonate group. Any resin can be used as long as it is a resin having both a hydrophilic group such as a group and a glycidyl group.

As a compound having both a hydroxyl group and a glycidyl group, a diglycidyl ether of glycerin or glycidol, or an epoxy resin having a repeating unit of bisphenol A of 2 to 3 is particularly representative.

As the diglycidyl compound, a bifunctional compound is particularly representative among the epoxy resins described below, but as for the other compounds, all difunctional compounds can be used.

The self-water-dispersible resin having a carboxyl group as an addition-reactive functional group is not special and if it is a resin having a carboxyl group,
Everything can be used. Part of the carboxyl group,
Water dispersibility may be imparted by addition-reacting with a silane coupling agent and neutralizing the remaining carboxyl groups.

Next, a hydrophobic resin having an addition-reactive functional group but having no self-water dispersibility will be described.
As a typical example of such resins, polyisocyanate resins having an average of 2 or more isocyanate groups in one molecule, or an average of 2 or more in one molecule, may be mentioned. An epoxy resin having a glycidyl group may be used.

The polyisocyanate resin is, for example,
It refers to various polyisocyanate prepolymers, which are generally called by the name of a curing agent for a moisture-curable urethane resin or a two-component curable urethane resin.

As the polyisocyanate resin, only typical ones are exemplified, and trimethylolpropane, trimethylolethane, glycerin,
Various polyols such as trishydroxyethyl isocyanurate or ntaerythritol; or
Using the above-mentioned low-molecular diols and diol resins (polymer diols) and the above-mentioned diisocyanate compounds as the basic raw materials, the isocyanate group is made to have a ratio higher than that of the hydroxyl group, and the urethanization reaction is carried out. The average number of functional groups of the isocyanate groups obtained as a result is within the range of about 2 to 6.

Further, there are also polymers of diisocyanate compounds and alohanates having water molecules intervening in the reaction.

The above-mentioned epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins or hydrogenated bisphenol A type epoxy resins; triglycidyl isocyanurate, neopentyl glycol diglycidyl. Diglycidyl ethers represented by various diols such as ethers; polyglycidyl ethers of various polyols such as trimethylolpropane triglycidyl ether; diglycidyl ethers of various dibasic acids such as sebacic acid diglycidyl ester. Glycidyl esters; glycidyl ethers of novolac phenol; or glycidyl amines are particularly representative.

Further, in the present invention, a dispersant or a surfactant is used for the purpose of assisting water dispersion or micro-encapsulation, improving dispersion stability, or improving film performance. It is also possible to use resins or aqueous resins. Further, it is needless to say that any resin having no hydrophilicity can be used as long as it is within the range that does not hinder the dispersibility and the micro-encapsulation.

Furthermore, in the present invention, in addition to the polycondensation reaction between silanol groups produced by hydrolysis of alkoxysilyl groups, a polycondensation reaction between silanol groups and hydroxyl groups can be utilized. . For this purpose, a method of introducing a hydroxyl group into a self-water-dispersible resin having an addition-reactive functional group and / or a hydrophobic resin having an addition-reactive functional group, or a self-water-dispersing property having a hydroxyl group Various methods such as a method of using a resin together or a method of using a hydrophobic resin having a hydroxyl group together and dispersing them in water by microencapsulation can be used.

Up to this point, the raw materials constituting the present invention have been described, but next, the manufacturing process thereof will be described. The manufacturing process mainly includes the following three or four steps.

1. 1. A step of adding a silane coupling agent to the addition-reactive functional group. 2. Dispersion or microencapsulation in an aqueous medium, A process of causing a polycondensation reaction of a hydrolyzable silyl group. 4. If necessary, a step of converting the aqueous dispersion into an organic solvent dispersion.

First, a resin having an addition-reactive functional group is added to
The step of subjecting the silane coupling agent to the addition reaction is particularly recommended because it is easy to perform the step in an organic solvent at room temperature or by heating, if necessary.

At this time, it is also preferable to use a urethane-forming catalyst or a glycidyl group ring-opening catalyst. As the organic solvent to be used, when an isocyanate compound is used, it is necessary to use an alcohol-based solvent with caution, but in other cases, there is no particular limitation.

Of course, there is no problem in using the alcohol solvent after the addition reaction of the isocyanate group and the silane coupling agent. Considering the concentration in the final step, it is preferable to use methanol, ethanol, isopropanol, n-propanol, acetone, methyl ethyl ketone, ethyl acetate or n-hexane, which has a lower boiling point than water, as the organic solvent. Then, when an organic solvent having a boiling point lower than that of water is used, a dispersion containing substantially only water as a medium can be obtained by concentration.

Of course, the use of an organic solvent having a boiling point higher than that of water does not pose any problem as long as the dispersion stability is not impaired.

Dispersed or micro-dispersed in the second aqueous medium
In the encapsulation step, the self-water-dispersible resin in the form of the addition reaction of the silane coupling agent or the self-water-dispersible resin in the form of the addition reaction of the silane coupling agent was added to the silane coupling agent. There is a method in which water is gradually added to a mixed resin with a hydrophobic resin in the shape, or conversely, a method in which the resin is added in an aqueous medium.

When the hydrophilic group is a carboxyl group, it must be neutralized with a base before being dispersed in water or microencapsulated.

In the case of the method by microencapsulation, the amount of the hydrophobic resin per 100 parts by weight of the self-water-dispersible resin is appropriately 100 parts by weight or less, and more preferably 70 parts by weight or less. Appropriate. If the amount of the hydrophobic resin is excessively larger than 100 parts by weight, the particle size of the dispersed particles becomes large and the particles end up, which is not preferable in terms of dispersion stability and film smoothness.

The third polycondensation step may be carried out by heating the dispersion dispersed in water or microencapsulated to about 60 to 80 ° C., and may be carried out at the same temperature in parallel with the concentration.

It is also preferable to use a hydrolysis catalyst of an alkoxysilyl group or a polycondensation catalyst of a silanol group. When such a catalyst is used, a higher catalytic effect can be obtained by adding it before dispersing it in water.

Fourth, the aqueous dispersion of crosslinked resin particles according to the present invention can be converted into a dispersion of an organic solvent by a known and commonly used method. For example, add an organic solvent,
There is a method in which water is removed by azeotropic distillation; a method in which an organic solvent is added, followed by reverse neutralization and phase inversion to an organic solvent system.

If necessary, it can be used after being pulverized.

As described above, although the process up to this point has been described with respect to the method for producing the condensation type crosslinked resin particle dispersion, the present invention is characterized by being never obtained according to the prior art. have.

First, the physical properties of the formed film are excellent in toughness as compared with the most excellent urethane urea crosslinked resin particles in the existing technology, and the water resistance and the chemical resistance are equal or better. Is.

In addition, yellowing of the film when printed,
There is little or no odor. Moreover, in the production itself, particles having a sufficient degree of crosslinking can be produced easily and efficiently.

The crosslinked resin particle dispersion obtained according to the method of the present invention can be used alone to form a film. If necessary, a curing agent such as an amino resin or a block isocyanate resin may be added. Alternatively, it may be blended with another film-forming resin to form a film.

Thus, the crosslinked resin particle dispersion obtained by the method of the present invention is particularly useful in the paint industry, but can also be used as an adhesive, an ink or a paper fiber processing agent.

It can also be used as various additives such as anti-sagging agents, flow control agents, thixotropic agents and matting agents.

[0075]

EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples.
More specifically, in the following, parts and%
Unless otherwise specified, all are based on weight.

Example 1 A four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas inlet pipe and a rectification pipe (a device for removing condensed water outside the system and returning glycols into the flask). , 336 parts of adipic acid, 191 parts of terephthalic acid, 191 parts of isophthalic acid, 280 parts of neopentyl glycol, 172 parts of ethylene glycol and 0.3 parts of dibutyltin dioxide, from 150 ° C to 230 ° C , 6
Temperature rises while dehydrating over time, and at 230 ° C
After allowing the reaction to continue for 5 hours, the polycondensation reaction was terminated by removing the condensed water for 30 minutes under a reduced pressure of about 20 mmHg.

Next, with ethyl acetate, the nonvolatile content was 50%.
And the acid value per resin solid content (hereinafter, the acid value is also represented by the value per resin solid content) is 1.
A resin solution having a characteristic value of 89 and a hydroxyl value per resin solid content (hereinafter, the hydroxyl value is also represented by a value per resin solid content) was obtained.

2,000 parts of this resin solution (composed of 1,000 parts of resin solids and 1,000 parts of ethyl acetate), 533 parts of isophorone diisocyanate, 107 parts of dimethylolpropionic acid, Dibutyltin dilaurate (0.08 parts) and ethyl acetate (640 parts) were charged and subjected to a urethanization reaction at 78 ° C for 3 hours to give a nonvolatile content of 50%, an acid value of 28, and a number average molecular weight of A self-water dispersible polyurethane resin having a terminal isocyanate group of 2,050 was obtained. Hereinafter, this is abbreviated as pre-polymer A.

First, to 200 parts of pre-polymer A, 80 parts of methyl ethyl ketone and then 19 parts of γ-mercaptopropyltrimethoxysilane were added, and the reaction was carried out at room temperature for 30 minutes. ．
1 part and 0.6 part of dibutyltin dilaurate were added. Then, 620 parts of ion-exchanged water was added dropwise at room temperature over 30 minutes to disperse the resin in water, and further 60 ° C.
At 60 ° C. under reduced pressure until the nonvolatile content becomes 35% to obtain an aqueous dispersion of crosslinked resin particles having an average particle diameter of about 0.05 μm. . Hereinafter, this is abbreviated as G-1.

Example 2 To 200 parts of Prepolymer A, 21 parts of γ-aminopropyltriethoxylane and 40 parts of methyl ethyl ketone are added.
Parts diluted with 42 parts of isopropyl alcohol and reacted at room temperature for 30 minutes, then 5.1 parts of triethylamine and 0.6 parts of dibutyltin dilaurate were added. It was

Next, at room temperature, 500 parts of ion-exchanged water was added dropwise over 30 minutes to disperse the resin in water, and the reaction and concentration were carried out in the same manner as in Example 1 to give a nonvolatile. An aqueous dispersion of crosslinked resin particles having a content of 35% and an average particle size of about 0.05 μm was obtained. Hereinafter, this is abbreviated as G-2.

Example 3 200 parts of Pre-Polymer A and "Bernock DN-
To a mixture of 15 parts of "980", 110 parts of ethyl acetate and then 30 parts of γ-mercaptopropyltrimethoxysilane were added, and the reaction was carried out at room temperature for 30 minutes, and then 5.1 parts of triethylamine was added. Parts and 0.6 parts of dibutyltin dilaurate were added.

Then, at room temperature, 525 parts of ion-exchanged water was added dropwise over 30 minutes to disperse the resin in water by microencapsulation, and the reaction and reaction were carried out in the same manner as in Example 1. Concentration was carried out to obtain a nonvolatile content of 35
%, And an average particle diameter of about 0.07 μm was obtained to obtain an aqueous dispersion of crosslinked tree particles. Hereinafter, this is abbreviated as G-3.

The "Bernock DN" used here is used.
-980 "is a polymerization type polyisocyanate prepolymer of hexamethylene diisocyanate manufactured by Dainippon Ink and Chemicals, Inc., having a nonvolatile content of 75% and an isocyanate content per resin solid content of 20. ．
It has a characteristic value of 5%.

Example 4 To 100 parts of the crosslinked resin particles (G-3) obtained in Example 3, 300 parts of ion-exchanged water and 400 parts of n-butanol were added.
And then neutralized with hydrochloric acid until the pH reached 6.8, and allowed to stand in a separating funnel to remove the water in the lower layer, and further 300 parts of ion-exchanged water. So 2
After repeatedly washing with water, 50 parts of butyl cellosolve was added, and then the mixture was concentrated at a temperature of 60 ° C. until the nonvolatile content became 20%, and the average particle diameter of the crosslinked resin particles was about 0.08 μm. An organic solvent dispersion was obtained. Hereinafter, this is abbreviated as G-4.

Example 5 200 parts of prepolymer A and "Epiclon 85
0 ”(a bisphenol A type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc .; epoxy equivalent = 190) in a mixture with 11 parts, 34 parts of γ-aminopropyltriethoxysilane and 60 parts of methyl ethyl ketone. Then, what was diluted with 60 parts of isopropyl alcohol was added, and the reaction was carried out at room temperature for 30 minutes, and then 5.1 parts of triethylamine and 0.6 part of dibutyltin dilaurate were added.

Then, 600 parts of ion-exchanged water was added dropwise at room temperature over 30 minutes to disperse the resin in water by microencapsulation, and the reaction and concentration were carried out in the same manner as in Example 1. And the nonvolatile content is 30%,
Further, an aqueous dispersion of crosslinked resin particles having an average particle diameter of about 0.06 μm was obtained. Hereinafter, this is abbreviated as G-5.

Example 6 346 parts of adipic acid, 197 parts of isophthalic acid, 138 parts of terephthalic acid, 145 parts of ethylene glycol,
The isocyanate was reacted in the prepolymer A prepared in Example 1 except that 236 parts of neopentyl glycol, 94 parts of 5-sodium sulfoisophthalic acid and 0.3 parts of dibutyltin dilaurate were used. The reaction was carried out in the same manner as in the case of the resin before denaturation to obtain a resin solution diluted with xylene, having a nonvolatile content of 80%, an acid value of 25, and a hydroxyl value of 2.5. .

1,250 parts of this resin solution (consisting of 1,000 parts of resin solid content and 250 parts of xylene).
In addition, 125 parts of "Denacol EX-211" (diglycidyl ether of neopentyl glycol manufactured by Nagase & Co., Ltd .; epoxy equivalent = 140) (glycidyl group / carboxyl group = 2.0). And 2-
0.5 parts of methylimidazole was added and the reaction was carried out at 130 ° C. for 5 hours, and then diluted with ethyl acetate to a non-volatile content of 50% to have a glycidyl group at the molecular end. A self-water dispersible resin was obtained. Hereinafter, this is abbreviated as pre-polymer B.

Then, to 200 parts of this prepolymer B, 60 parts of ethyl acetate was added, and further, 2.2 parts of γ-aminopropyltriethoxysilane and 3.8 parts of γ-mercaptotrimethoxysilane were added. 60 ℃
Then, 0.6 part of dibutyltin dilaurate was added, and 500 parts of ion-exchanged water was added dropwise at room temperature over 30 minutes to disperse the resin in water. Reaction and concentration were carried out in the same manner as in Example 1 to obtain an aqueous dispersion of crosslinked resin particles having a nonvolatile content of 30% and an average particle diameter of about 0.06 μm. Hereinafter, this is abbreviated as G-6.

Example 7 To 2,000 parts of Prepolymer B was added 62% of ethyl acetate.
0 part was added, then 78 parts of γ-mercaptotrimethoxysilane was added, and the reaction was carried out at 60 ° C. for 60 minutes to obtain a resin solution (a).

In a separate flask, place the "Bernock DN-9
To 148 parts of "80", 300 parts of ethyl acetate was added, then 109 parts of γ-mercaptotrimethoxysilane was added, and the reaction was carried out at 60 ° C for 30 minutes to obtain a resin solution (b). To a mixture of 270 parts of the resin solution (a) and 55 parts of the resin solution (b) was added 0.6 part of dibutyltin dilaurate, and then 700 parts of ion-exchanged water was added for 30 minutes at room temperature. The resin was dispersed in water by microencapsulation by dropwise addition, and the reaction and concentration were carried out in the same manner as in Example 1 to obtain a nonvolatile content of 3
An aqueous dispersion of crosslinked resin particles having an average particle size of 0% and an average particle size of about 0.06 μm was obtained. Hereinafter, this is abbreviated as G-7.

Example 8 382 parts of isophthalic acid, 336 parts of adipic acid, 132 parts of ethylene glycol, 216 parts of neopentyl glycol, 48 parts of trimethylolpropane and 0.3 parts of dibutyltin dioxide are used. Then, using the same reactor as in Example 1, the temperature was raised from 150 ° C. to 220 ° C., dehydration was performed for 5 hours, and further 2
After continuing the reaction at 20 ° C. for 5 hours and then terminating the reaction, the reaction mixture was diluted with a solvent of xylene / butyl cellosolve = 80/20 (weight ratio) so that the nonvolatile content was 80%, and the acid value was 40%. And a resin solution having a hydroxyl value of 45 was obtained.

1,250 parts of this resin solution (composed of 1,000 parts of solid resin part and 250 parts of organic solvent)
Was added to 89 parts of γ-glycidoxypropylmethyldiethoxysilane and 0.5 part of 2-methylimidazole, and the reaction was carried out at 125 ° C. for 2 hours. Diluted to give a resin solution having an acid value of 20.

To 200 parts of this resin solution was added 50 parts of methyl ethyl ketone, 4 parts of triethylamine and 0.5 parts of dibutyltin dilaurate, and then at room temperature,
460 parts of ion-exchanged water was added dropwise over 30 minutes to disperse the resin in water, and the reaction and concentration were carried out in the same manner as in Example 1 to obtain a nonvolatile content of 35%.
And an aqueous dispersion of crosslinked resin particles having an average particle diameter of about 0.05 μm was obtained. Hereinafter, this is abbreviated as G-8.

Comparative Example 1 To 200 parts of Prepolymer A, 60 parts of methyl ethyl ketone and 5.1 parts of triethylamine were added, and 800 parts of ion-exchanged water was added dropwise at room temperature over 30 minutes to give a resin. It was dispersed in water, then 3.3 parts of diethylenetriamine dissolved in 200 parts of ion-exchanged water was added, and the reaction and concentration were carried out in the same manner as in Example 1 to obtain a nonvolatile content of 30%. And a control aqueous dispersion of crosslinked resin particles having an average particle diameter of about 0.09 μm was obtained. Hereinafter, this is abbreviated as G-9.

Comparative Example 2 200 parts of Prepolymer A and "Bernock DN-
To a mixture of 15 parts with "980", 75 parts of methyl ethyl ketone and 5.1 parts of triethylamine were added, and 1,000 parts of ion-exchanged water was added dropwise at room temperature over 30 minutes to obtain a resin containing micro resin. Disperse in water by encapsulation, and then add 5.2 parts of diethylenetriamine dissolved in 200 parts of ion-exchanged water,
Further, the reaction and concentration were carried out in the same manner as in Example 1 to obtain a nonvolatile content of 30% and an average particle size of about 0.1.
A control aqueous dispersion of crosslinked resin particles having a size of μm was obtained.
Hereinafter, this is abbreviated as G-10.

Then, the constitutions of the respective crosslinked resin particles (G-1) to (G-8) obtained in Examples 1 to 8 and the crosslinked resin particles for both controls obtained in Comparative Examples 1 and 2 were used. The configurations of (G-9) and (G-10) are shown collectively in Tables 1 and 2.

[0099]

[Table 1]

[0100]

[Table 2]

Application Examples 1-8 and Comparative Application Examples 1 and 2 The respective crosslinked resin particles (G
-1) to (G-8) and both crosslinked resin particles (G-9) and (G-10) obtained in Comparative Example 1 and Comparative Example 2 were used to evaluate and examine various performances. went.

First, the test conditions of the clear film will be described. (1) Conditions for producing a clear film A dispersion of each crosslinked resin particle was coated on a tin plate to a dry film thickness of about 20 μm, and preheated for 5 minutes at 100 ° C. Baking was performed at 5 ° C. for 5 minutes, and the film was peeled off to prepare a test piece.

(2) Conditions for forming clear coating film: A zinc phosphate-treated steel sheet "Bondelite 144 #" was coated to a dry film thickness of about 20 μm, and preheated at 100 ° C. for 5 minutes. A test piece was prepared by baking at 180 ° C. for 5 minutes.

(3) Test items Tensile strength and elongation at break: 5 cm × 1 c in Tensilon
A test piece having a size of m was measured at a test temperature of 20 ° C. and a tensile speed of 1 cm / min.

Water resistance: The surface of the film after being immersed in boiling water for 2 hours was visually evaluated. Acid resistance: The surface of the film after being immersed in a 35% sulfuric acid aqueous solution for 100 hours was visually evaluated.

<< Judgment Criteria for Water Resistance and Acid Resistance >> ◎: No abnormalities ○: Very slight gloss loss Δ: Complete gloss loss ×: Partially Light damage is found XX ... Significant damage is found

<Yellowing of Baking Coating: Visual Judgment> Odor during baking: Baking was performed at 180 ° C. for 5 minutes, and the odor immediately after being taken out from the dryer was judged by the sense of smell.

The respective test results are collectively shown in Tables 3 and 4.

[0109]

[Table 3]

[0110] "in Table 3 footnote""tensilestrength" ......... unit is "kg / cm ^2". “Growth” ………… The unit is “%”.

[0111]

[Table 4]

[0112]

INDUSTRIAL APPLICABILITY The dispersion of the condensation type crosslinked resin particles obtained by the present invention has a higher water resistance and a higher resistance than the dispersion of the urethane urea crosslinked resin particles, which has the most excellent film physical properties among the conventional crosslinked resin particles. The chemical properties are equivalent or higher, and the toughness of the film is considerably excellent as shown in the physical properties of the film in Table 3.

Moreover, there is little or no coloration or odor of the film at the time of baking. The present invention provides a method for easily producing such a dispersion of crosslinked resin particles having extremely excellent performance.

The dispersion of the crosslinked resin particles may be used alone or in combination with a curing agent, or in another film-forming resin to prepare a coating, ink, adhesive or paper fiber processing agent. Can be used as

Claims (13)

[Claims] 1. A self-water-dispersible resin having an addition-reactive functional group is subjected to an addition reaction with a monomer having both a functional group capable of reacting with the addition-reactive functional group and a hydrolyzable silyl group, and then an aqueous solution. A method for producing a crosslinked resin particle dispersion, which comprises polycondensation in a medium. 2. A self-water-dispersible resin having an addition-reactive functional group, a hydrophobic resin having an addition-reactive functional group, a functional group capable of reacting with the addition-reactive functional group, and a hydrolyzable silyl group. Characterized in that it is subjected to an addition reaction with a monomer having both, and then polycondensed in an aqueous medium.
Method for producing crosslinked resin particle dispersion. 3. The self-water-dispersible resin having an addition-reactive functional group is at least one condensation resin selected from the group consisting of polyester resins, polyurethane resins and epoxy resins. 2. The manufacturing method according to 2. 4. The hydrophobic resin having an addition-reactive functional group is at least one condensation resin selected from the group consisting of polyester resins, polyurethane resins and epoxy resins. Production method. 5. The above-mentioned addition-reactive functional group is an isocyanate group and / or a glycidyl group.
Or the manufacturing method according to 4. 6. The production method according to claim 3, wherein the addition-reactive functional group is a carboxyl group. 7. The production method according to claim 5, wherein the functional group capable of reacting with the addition-reactive functional group is a mercapto group and / or an amino group. 8. The production method according to claim 6, wherein the functional group capable of reacting with the addition-reactive functional group is a glycidyl group. 9. The method according to claim 5, wherein the functional group capable of reacting with the addition-reactive functional group is a hydroxyl group. 10. The production method according to claim 3, wherein the self-water-dispersible resin having an addition-reactive functional group has a carboxyl group as a hydrophilic group. 11. The production method according to claim 3, wherein the self-water-dispersible resin having an addition-reactive functional group has a sulfonate group as a hydrophilic group. 12. A crosslinked resin particle dispersion, wherein an aqueous dispersion of crosslinked resin particles obtained by the production method according to any one of claims 1 to 11 is dispersed in an organic solvent. Production method. 13. The dispersion in the organic solvent is such that the organic solvent is first added to the aqueous dispersion of the crosslinked resin particles, and then water is removed.
The manufacturing method described in.