JP2785361B2 - Non-aqueous resin dispersion - Google Patents

Description

The present invention relates to a new and useful non-aqueous dispersion.
More specifically, in the presence of certain polymeric azo initiators,
A specific reactive resin, and further obtained by dispersing a (co) polymer obtained by polymerizing an ethylenically unsaturated monomer copolymerizable with the reactive resin in a specific organic solvent, In particular, a non-aqueous dispersion having excellent dispersion stability and a uniform particle size, which is particularly useful for architectural exteriors or metal coatings, for bonding, or for sealing agents, that is, non-aqueous dispersion It relates to a dispersion of a mold resin.

[Conventional technology]

In recent years, this type of non-aqueous dispersion type resin has relatively little adverse effect on the environment due to the use of a non-polar weak solvent, exhibits a thixotropy in viscosity behavior due to its particle system, and has a thick coating. Because it has features such as simplicity and other features, it also offers better performance than conventional solvent-type resins and emulsion-type resins. Such as painting the outer panel,
It has begun to be used in various fields.

By the way, as a conventional method of preparing a non-aqueous dispersion type resin,
In a solvent in which a dispersing resin is dissolved, a monomer is soluble in the solvent, but a polymer obtained from the monomer is insoluble. Although the method of polymerizing and making particles is common,
As the form of the polymer in the case of following such a method, a polymerization active site is generated in a part of the molecule of the dispersion resin incorporated in the polymer, that is, the dispersion stabilizer, and the organic solvent is The polymer becomes an insoluble new polymer (hereinafter, referred to as an insoluble polymer), and a very small portion of the vinyl monomer reacts with the polymerization active site to form a polymer based on the dispersion stabilizer. A block copolymer or a graft copolymer consisting of a so-called soluble polymer portion and an insoluble polymer portion based on the vinyl monomer will be formed, and at the same time, most of the polymer is subjected to the polymerization reaction. Amount of the vinyl monomer does not participate in such block copolymerization or graft copolymerization, and homopolymerization occurs to form an insoluble polymer. Take That.

Such conventional non-aqueous polymer dispersions, first,
The content of the above-mentioned block copolymer or graft copolymer having good dispersion stability is low, and the content of the insoluble polymer obtained by the above-mentioned homopolymerization is high. The polymer is merely dispersed in an organic solvent or a so-called organic liquid containing the solvent by a physical secondary bond with a block copolymer or a graft copolymer. The dispersion has a problem that dispersion stability is poor.

In particular, when the non-aqueous polymer dispersion obtained as described above is used as a coating film-forming component, there is a more serious problem.

In addition, such a non-aqueous polymer dispersion, due to the high shearing force applied during the pigment dispersion, insoluble polymer coagulates and precipitates, a polar solvent having strong dissolving power for polymer particles, a plasticizer, etc. When added, the dispersion stability during storage becomes extremely poor, and there is a danger of eventually gelling or coagulating and sedimenting.

In order to solve this problem, the dispersion stabilizer is used to increase the concentration of the polymerization active site of the dispersing resin. According to such a method, a block copolymer or a graft copolymer is contained in a large amount, so that as an insoluble polymer portion, a soft, lower-polarity polymer portion is formed. The effect is that the substances are stably dispersed, but on the other hand, the control of the polymerization reaction becomes extremely difficult, and the reaction proceeds smoothly even if it gels during the reaction or it does not go to that point. There were manufacturing problems such as not progressing.

Apart from that, recently, a technique of stabilizing dispersion by performing block copolymerization or graft copolymerization using a special peroxide catalyst called polymeric peroxide has been proposed, but such polymeric peroxide has been proposed. There remains a problem with its own manufacturing peculiarities and dangers.

[Problems to be solved by the invention]

As described above, all of the non-aqueous polymer dispersions that have been practically used so far have problems in terms of synthesis means, dispersion stability, and the like. Satisfactory film-forming polymers have not been obtained, and at present there is a great demand for technical improvements.

Therefore, the present inventors, based on the recognition of the current situation, drastic solution of various unresolved problems in the prior art, and earnest demands in the art, this type of non-aqueous dispersion In order to realize the practical application of the true meaning of this, we started research earnestly.

Accordingly, an object of the present invention is to provide a dispersion of a non-aqueous dispersion resin, which has excellent dispersion stability, has a uniform particle diameter, and is extremely useful. It is in.

[Means for solving the problem]

Thus, the present inventors focused on the problems to be solved by the present invention as described above, and as a result of intensive studies to obtain the intended useful non-aqueous dispersion, as a result, a specific polymer azo In the presence of an initiator, a (co) polymer obtained by polymerizing a specific reactive resin and further an ethylenically unsaturated monomer copolymerizable with the reactive resin is converted into a specific organic solvent. By dispersing the non-aqueous dispersion resin having excellent dispersion stability and uniform particle diameter, the present invention has been completed. Was.

That is, the present invention has one or more ethylenically unsaturated bonds in one molecule in the presence of 2 to 97 parts by weight of a polymeric azo initiator having both a urethane bond and a diazo bond in the molecular main chain. And a (co) polymer having a number average molecular weight of 500 to 100,000 and being soluble in an organic solvent containing an aliphatic and / or alicyclic hydrocarbon solvent. It is intended to provide a useful non-aqueous resin dispersion.

Here, if only a typical example of the above-mentioned high-molecular azo initiator is exemplified, the general formula And the general formula And one having at least one structural unit represented by the following formula in one molecule.
It is desirable to use 500 to 50,000 compounds (hereinafter also referred to as polyurethane polyazo initiator).

Each of these structural units represented by the general formulas (I) and (II) has at least one in a molecule,
Polyurethane polyazo initiator having a number average molecular weight of 1,500 to 50,000 is, for example, azobiscyanopropanol,
Azobiscyanoalkanol compounds such as azobiscyanobutanol or azobiscyanopentanol, or "VA-080", "VA-082" or "VA-086"
A compound having at least one diazo bond and at least two hydroxyl groups in one molecule, such as an azoamide polyol compound such as [product of Wako Pure Chemical Industries, Ltd.], isophorone diisocyanate, methylcyclohexane-2 , 4-diisocyanate, methylcyclohexane-
Alicyclic diisocyanates such as 2,6-diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate) or 1,3-di (isocyanatomethyl) cyclohexane; aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate or trimethylhexane diisocyanate Or a diisocyanate compound such as tolylene diisocyanate, xylene diisocyanate or aromatic diisocyanate such as 4,4'-diphenylmethane-diisocyanate as an essential component.

That is, the polyurethane polyazo initiator is the diisocyanate compound itself as described above, or the diisocyanate compound and trimethylolethane, trimethylolpropane, pentaerythritol,
Adducts with polyhydric alcohols such as glycerin or dipentaerythritol, or polyester compounds having a functional group capable of reacting with an isocyanate group and having, for example, a number average molecular weight of about 500 to 2,000 and a very low molecular weight. And polyisocyanate compounds such as ethylene glycol, propylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,3-
Butylene glycol, neopentyl glycol, 1,6-
Diols such as hexanediol, 3-methyl-1,5-pentanediol, cyclohexanediol, polyethylene glycol, polypropylene glycol, polyhexamethylene glycol, hydrogenated bisphenol or bisphenol, and various polyhydric alcohols as described above And a compound having at least one diazo bond and at least two hydroxyl groups in one molecule as described above, and at least one of each of the three components is subjected to an addition condensation reaction.

At that time, a method of simultaneously charging and reacting the above three-component compounds, or first synthesizing an isocyanate group-containing polyurethane intermediate, that is, a so-called urethane prepolymer, is added to at least one diazo compound in one molecule. There is a method of reacting a compound having both a bond and at least two hydroxyl groups, but any of these methods may be used, and the method is not limited to only these methods.

In addition, these diisocyanate compounds and / or polyisocyanate compounds, a polyol compound,
At least one diazo bond and at least 2
When reacting with a compound having both hydroxyl groups, ethylenediamine, hexamethylenediamine, as a chain extender,
Polyamine compounds such as triethylenetetramine, bisaminopropylamine or 4-aminomethyl-1,8-diaminooctane may be used.

Examples of the polyurethane polyazo initiator include various polyurethane polyazo initiators depending on R ₃ in the general formula [II] described above.

That is, such a polyol residue of R ₃ is, respectively, a polyurethane polyol residue, a polyester polyol residue, a polyester polyurethane polyol residue,
Corresponding to the representation of polyether polyol residue, polyether polyester polyol residue, polyether polyurethane polyol residue and / or polyether polyurethane polyester residue, etc., respectively, polyurethane polyazo initiator, polyester polyurethane polyazo initiator , A polyether polyurethane polyazo initiator or a polyether polyester polyurethane polyazo initiator.

Among the polyurethane polyazo initiators, first, a more specific method for preparing a polyester polyurethane polyazo initiator will be described. Various polyol compounds as described above, isophthalic acid, terephthalic acid, and (tetrahydrophthalic anhydride) -Dehydration condensation reaction with polyhydric carboxylic acids such as hexahydrophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, maleic acid, fumaric acid, succinic acid or adipic acid; ε-caprolactone or valero Ring-opening polymerization of various lactones such as lactones; or a hydroxyl group-containing polyester resin (including an oil-modified type) obtained by an addition reaction of the above-mentioned polyol compound with the above-mentioned lactones includes one in one molecule. A compound having at least two diazo bonds and at least two hydroxyl groups, The method can be mentioned that allowed to addition reaction between supra was diisocyanate compound and / or polyisocyanate compound.

At this time, a polyamine compound as described above may be used as the chain extender, or a polyol compound may be used.

Next, as a more specific method for preparing a polyether polyurethane polyazo initiator, polyether diols such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol, and ethylene oxide or propylene oxide to the polyol compound described above are used. A polyether polyol such as an addition polymer of various alkylene oxides, a diisocyanate compound and / or a polyisocyanate compound, and a compound having one or more diazo bonds and two or more hydroxyl groups in one molecule described above. A method of subjecting at least one of the three components to an addition condensation reaction.

Also in this case, the above-mentioned polyamine compound and / or polyol compound are used as a chain extender.

Further, as a more specific method for preparing the polyether polyester polyurethane polyazo initiator, a polyester polyether polyol is first synthesized by a dehydration condensation reaction between the above-mentioned polyvalent carboxylic acid and the above-mentioned polyether polyol. And then addition condensation of at least one of each of the three components of the above-mentioned diisocyanate compound and / or polyisocyanate compound and the above-mentioned compound having one or more diazo bonds and two or more hydroxyl groups in one molecule. A method of causing the reaction to occur.

Also in this case, the aforementioned polyamine compound and / or polyol compound may be used as a chain extender.

The compound thus obtained having at least one of the structural units represented by the aforementioned general formulas (I) and (II) in one molecule is in the range of 1,500 to 50,000, preferably 2,000 to 20,000. Those having a number average molecular weight within the range are appropriate because the solubility in organic solvents and various monomers is particularly good, and when it is less than 1,500, the introduction rate of diazo bonds is low. As a result, it becomes difficult to obtain a coating resin composition having a characteristic coating film characteristic of the present invention, while if it exceeds 50,000, the solubility in a solvent is poor, so that a uniform block copolymerization is obtained. Cannot be carried out, so neither is preferable.

Thus, the polymer to be polymerized in the presence of the obtained high molecular weight polyazo initiator compound has one or more ethylenically unsaturated bonds in one molecule, and has a number average molecular weight of 500 to 1
In 00,000, and aliphatic and / or alicyclic hydrocarbon solvent-soluble polymer comprising (A), to name only a particularly typical as the reactive resin, the C ₄ or higher alkyl groups alkyl (meth) having an ethylenically unsaturated bond as a main component an acrylate comprising monomer (co) polymers having, having an ethylenically unsaturated bond as a main component C ₄ or more vinyl monomers (co A) Alkyd resin having an ethylenically unsaturated bond, or an alkyd resin having an ethylenically unsaturated bond obtained by grafting a vinyl monomer using such an alkyd resin as a trunk polymer.

That is, for example, a vinyl copolymer containing a thiol group is obtained by polymerizing a vinyl monomer in the presence of mercaptans, and then glycidyl (meth)
Glycidyl (meth) acrylate is added to a vinyl polymer having a terminal carboxyl group obtained by reacting an epoxy group-containing unsaturated monomer such as acrylate or by polymerizing a vinyl polymer in the presence of an initiator having a carboxyl group. (Co) polymerized resins in which a double bond is introduced by various methods such as reacting an epoxy group-containing unsaturated monomer such as glycidyl (meth) acrylate with a carboxyl group-containing alkyd resin. Alkyd resins into which a double bond has been introduced by, for example, reacting an epoxy group-containing unsaturated monomer as described above.

Of course, the method for preparing the reactive resin is not limited to the method described above.

In addition, as the reactive resin, a resin containing one or more ethylenically unsaturated double bonds is used.
If the number of functional groups is three or more, special attention is required because the system becomes gelled.

Rather, it is recommended that you stop it by two.

Further, the number average molecular weight of the polymer (A) as the reactive resin is suitably in the range of 500 to 100,000, preferably in the range of 2,500 to 20,000. The stability of the particles of the dispersion after phase inversion tends to be insufficient, while if it exceeds 100,000, the reactivity of the functional group capable of reacting with a double bond or a carboxyl group is inferior, and sufficient particles are not obtained. In this case, it is difficult to obtain a target resin having the above stability, and the viscosity of the system becomes too high, resulting in poor coating workability.

The amount of the polymer (A) used is suitably in the range of 3 to 93 parts by weight, preferably 5 to 50 parts by weight. When the amount is less than 3 parts by weight, the stability of the particles and the uniformization of the particle diameter are reduced. When the amount exceeds 93 parts by weight, the viscosity of the system becomes high, and the coating workability is remarkably reduced.

If only typical representative examples of the above-mentioned ethylenically unsaturated monomer (B) are given, methyl (meth)
Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t- Various types such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate or diethylaminoethyl (meth) acrylate (Meth) acrylic acid esters; dialkyl (C ₁ -C ₄ ) of unsaturated dibasic acids such as dimethyl malate, dimethyl fumarate, dibutyl malate, dibucil fumarate or dibutyl itaconate
Esters; Cyano group-containing monomers such as acrylonitrile; Vinyl acetate, vinyl benzoate or "Veoba"
Various vinyl esters such as (branched aliphatic carboxylic acid vinyl esters manufactured by Ciel, The Netherlands); "Biscoat 8F, 8FM, 3F or 3FM" [Osaka Organic Chemicals Co., Ltd. ) Acrylic esters] (par)
Fluoroalkyl group-containing monomers; halogenated olefins such as vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride or chlorotrifluoroethylene; or styrene, α-methylstyrene, pt-
Aromatic vinyl monomers such as butylstyrene or vinyltoluene; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate or 4-
Hydroxyl-containing vinyl monomers such as hydroxy (meth) acrylate; carboxyl-containing vinyl monomers such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid; or epoxy such as glycidyl (meth) acrylate And group-containing vinyl monomers.

Various organic polyazo initiators such as those listed above, the organic solvent used in performing the solution radical polymerization using a reaction resin and an ethylenically unsaturated monomer, methyl acetate, ethyl acetate Acetic acid-n-
Representatives are butyl or esters such as amyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; or alcohols such as methanol, ethanol, i-propyl alcohol or n-butanol. However, it is needless to say that an aromatic hydrocarbon solvent such as toluene or xylene and an alcohol solvent such as those described above can be used in combination, and an aliphatic and / or alicyclic Of course, a hydrocarbon solvent of the formula can also be used in combination as the solvent for polymerization.

If only typical examples of such aliphatic hydrocarbon solvents are given, n-heptane, “loose” may be mentioned.
(Ciel, Netherlands), Isopar E or G (Exxon Chemical, USA), Naphtha 5 or 6 (Products of the same company), IP Solvent
1620 "(product of Idemitsu Petrochemical Co., Ltd.) or" White Zole "(product of Kyodo Petroleum Co., Ltd.), and in the form of a mixed solvent of an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent. Those are also included in the present invention. In that case, the amount of the aliphatic solvent used should be 50% by weight or more.

On the other hand, typical examples of the alicyclic hydrocarbon solvent include cyclohexane, methylcyclohexane and ethylcyclohexane, and the alicyclic hydrocarbon solvent and the aliphatic hydrocarbon solvent as described above. The present invention also encompasses the combined use of the alicyclic hydrocarbon-based solvent and the aromatic hydrocarbon-based solvent as well as the combined use of the alicyclic hydrocarbon-based solvent and the aromatic hydrocarbon-based solvent. When such an alicyclic solvent is used in combination with an aromatic solvent, the amount of the alicyclic solvent should be 50% by weight or more.

In order to carry out such solution radical polymerization, an organic solvent such as those listed above, and an azo type represented by azobisisobutyronitrile, or a peroxide type represented by benzoyl peroxide are also used. Various radical polymerization initiators may be used in combination, and further, if necessary, various chain transfer agents such as lauryl mercaptan, octyl mercaptan, or α-methylstyrene dimer may be used as a molecular weight regulator. Of course.

Thus, in the polymerization solution obtained using the above-listed raw materials, the polymerization reaction is carried out in the case where the polymerization reaction is carried out in an organic solvent not containing an aliphatic and / or alicyclic hydrocarbon solvent. While removing the solvent,
In parallel with such a solvent removing operation, it is necessary to replace the solvent while dropping the aliphatic and / or alicyclic hydrocarbon-based solvent as described above.

By the way, the viscosity of the system is such that the ratio of the alcohol, ketone or ester solvent which is a good solvent and the aliphatic and / or alicyclic hydrocarbon solvent which is a poor solvent is a fixed value (the type of the solvent and the resin). When the amount of the aliphatic and / or alicyclic hydrocarbon-based solvent increases, the viscosity of the system becomes the most severe when the amount of the aliphatic and / or alicyclic hydrocarbon-based solvent increases. Has a decreasing viscosity.

And, needless to say, the polymerization solvent used in performing such solvent substitution, that is, the organic solvent, and the dispersing solvent, that is, the aliphatic and / or alicyclic hydrocarbon-based solvent are used. The greater the difference in boiling points,
In the production process, the merit that the target dispersion can be obtained in a short time can be expected.

By the way, when "Loose" or "Isoper E" is combined with i-propyl alcohol or methyl ketone, such an advantage in the production process can be expected, but conversely, when the difference in boiling point is less than 20 ° C. In the case of combinations that are close to each other, it takes a long time to replace the solvent. Therefore, it is desirable to select a combination of solvents so that the difference in boiling point is 20 ° C. or more.

To the dispersion of the non-aqueous dispersion resin thus obtained, various additives such as other polymers, pigments or fillers can be added as necessary. Melamine resin, butyl etherified benzoguanamine resin, butyl etherified urea resin, blocked polyisocyanate compound, aromatic, aliphatic or alicyclic polyepoxide, polyamide resin, or glycidyl group, carboxyl group, hydroxyl group, isocyanate group, alkoxy group or A typical example is a vinyl resin containing an N-methylolated amide group, and each of these polymers is cured with a functional group complementary to the functional group present in the non-aqueous dispersion type resin of the present invention. It is a thermosetting film-forming component as an agent.

〔The invention's effect〕

As described above, in the non-aqueous dispersion type resin for paint of the present invention, most of the produced polymer is composed of a polymer portion soluble in an organic liquid (soluble polymer portion) and an insoluble polymer portion ( (Insoluble polymer portion), it has a special feature that it is a dispersion of a non-aqueous dispersion resin having excellent dispersion stability and a uniform particle size because it is a block copolymer. Things.

Furthermore, the non-aqueous resin dispersion of the present invention is useful for metal coating, especially for coating of automobile outer panels and architectural outer panels, and is used not only for coating but also for bonding. Alternatively, it can also be used as a sealing agent.

〔Example〕

Next, the present invention will be described more specifically with reference examples, examples and comparative examples. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 [Preparation Example of Unsaturated Bond-Containing Polymer (A)] In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet, 66.7 parts of "Loose" and di-t were added. After charging 0.2 parts of -butyl peroxide, the temperature was raised to 120 ° C, and when the temperature reached the temperature, 97 parts of n-butyl methacrylate, 7 parts of t-butyl peroctoate, and 2 parts of thioglycolic acid were used. The resulting mixture was added dropwise over 5 hours, and after completion of the addition, the temperature was maintained at the same temperature for 5 hours to continue the reaction. Next, 13 parts of glycidyl methacrylate was added and the reaction was carried out at 125 ° C. for 4 hours.
A high molecular weight polymeric monomer having a viscosity (Gardner viscosity at 25 ° C .; the same applies hereinafter) of UV and a number average molecular weight of 3,500 was obtained. Hereinafter, this is abbreviated as (A-1).

Reference Example 2 [Preparation Example of Unsaturated Bond-Containing Polymer (A)] In the same flask as Reference Example 1, 10
0 parts and 0.2 parts of di-t-butyl peroxide were charged and heated to 120 ° C., and at that temperature, 98 parts of i-butyl methacrylate, 2 parts of 2-hydroxyethyl methacrylate and t-butyl A mixture consisting of 8 parts of peroxyoctoate was added dropwise over 6 hours. After completion of the addition, the mixture was maintained at the same temperature for 5 hours, and 2 parts of dimethacrylic anhydride and 0.01 part of t-butylcatechol were added. The reaction was continued for 2 hours to obtain a target polymer monomer having a nonvolatile content of 50%, a viscosity of BC and a number average molecular weight of 5,000. Hereinafter, this is abbreviated as (A-2).

REFERENCE EXAMPLE 3 [Preparation Example of Unsaturated Bond-Containing Polymer (A)] In the same manner as in Reference Example 1, "Naphtha No. 5"
0 parts and "Beccosol P-470-70" [a polyester polyol containing unsaturated bonds containing a soybean oil-modified alkyd resin having a solid content of 70%, a soybean oil content of solids of 65%, manufactured by Dainippon Ink and Chemicals, Inc. )]], I
A mixture consisting of 50 parts of -butyl methacrylate, 45 parts of n-butyl acrylate and 1.0 part of t-butyl peroctoate was added dropwise over 4 hours. A target polymerizable monomer having a content of 50%, a viscosity of XY and a number average molecular weight of 15,000 was obtained. Hereinafter, this is abbreviated as (A-3).

Reference Example 4 [Preparation Example of Unsaturated Bond-Containing Polymer (A)] As in Reference Example 1, 49
The mixture was heated to 80 ° C., and “Beccosol P-470-7” was added.
0 ", 77.5 parts of i-butyl methacrylate, n-
A mixture of 18 parts of butyl acrylate, 2 parts of isocyanate ethyl methacrylate and 8 parts of t-butyl peroctoate was added dropwise over 8 hours. After the completion of the dropwise addition, the temperature was maintained at the same temperature for 8 hours to continue the reaction.
1.7 parts of 2-hydroxyethyl methacrylate and 0.01 parts of t-butyl catechol are added, and the reaction is continued for 2 hours. The target weight is 50% in non-volatile content, BC in viscosity and 5,200 in number average molecular weight. A united monomer was obtained. Less than,
This is abbreviated as (A-4).

Reference Example 5 [Preparation Example of Polyurethane Polyazo Initiator Compound] In a four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, 250 parts of N-methylpyrrolidone, 73 parts of neopentyl glycol, azobiscyanopropanol Was charged and 135 parts of hexamethylene diisocyanate was added dropwise thereto over 2 hours while stirring and cooling with ice.

After the completion of the dropwise addition, the reaction was maintained at 25 ° C. for 20 hours to continue the reaction, whereupon it was washed with ion-exchanged water, passed, and then dried under reduced pressure with a vacuum pump to obtain the target compound.

This had a number average molecular weight in terms of polystyrene of 9,800 as determined by gel permeation chromatography (the same applies hereinafter), and contained an average of 4.9 diazo bonds in one molecule.

Reference Example 6 (same as above) In a reaction vessel similar to that of Reference Example 1, methyl ethyl ketone was added.
672 parts, 65 parts of neopentyl glycol, 9 parts of trimethylolpropane and 0.01 parts of di-n-butyltin dilaurate were charged, and 130 parts of hexamethylene diisocyanate was added dropwise with stirring over 2 hours, and the addition was completed. After
The reaction was continued at 40 ° C. for 2 hours to cool to room temperature.

Next, 26 parts of azobiscyanopentanol was added with stirring under ice cooling to uniformly disperse the mixture.
0.07 parts of butyltin dilaurate was added, and the mixture was kept at 25 ° C. for 10 hours to continue the reaction, whereby the number average molecular weight was 10,2.
As a result, a 25% solution of the target compound having an average number of diazo bonds in one molecule of 5.1 was obtained.

Reference Example 7 (same as above) In a reaction vessel similar to Reference Example 1, methyl ethyl ketone was added.
212 parts, 160 parts of polypropylene glycol having an average molecular weight of 400 and 0.06 parts of di-n-butyltin dilaurate were charged, and 32.4 parts of hexamethylene diisocyanate and 1 part of xylene diisocyanate were stirred at room temperature under stirring.
8.8 parts were added dropwise over 2 hours, and after completion of the addition, the mixture was kept at 50 ° C. for 2 hours to continue the reaction, and the average molecular weight was 3,200.
And, of the polyurethane polyol having a hydroxyl value of 26
A 50% solution was obtained.

Then, 216 parts of this solution, 19.6 parts of azobiscyanopropanol, 375.6 parts of methyl ethyl ketone and 0.08 parts of di-n-butyltin dilaurate were added to Reference Example 1
In a similar manner as described above, 33.6 parts of hexamethylene diisocyanate was added dropwise under ice-cooling, and after completion of the addition, the reaction was maintained at 25 ° C. for 20 hours to continue the reaction.The number average molecular weight was 12,300. A 25% solution of the target compound having an average number of diazo bonds in one molecule of 5.7 was obtained.

Reference Example 8 (same as above) “Placcel 208” was placed in the same reaction vessel as in Reference Example 1.
[Lactone diol manufactured by Daicel Industries Ltd.] 164
Parts, 715 parts of methyl ethyl ketone, 20 parts of azobiscyanopropanol and 20 parts of di-n-butyltin dilaurate.
After charging 0.07 part, 50 parts of hexamethylene diisocyanate was added dropwise over 1 hour under ice cooling. After completion of the dropwise addition, the reaction was continued at 25 ° C. for 20 hours to obtain a 25% solution of the target compound having a number average molecular weight of 10,500 and an average number of diazo bonds in one molecule of 5.3.

Reference Example 9 (same as above) In a four-necked flask equipped with a thermometer, a stirrer and an air condenser, 50 parts of adipic acid, 50 parts of neopentyl glycol, 88.5 parts of polypropylene glycol having an average molecular weight of 400, and isophthalic acid , And reacted at 140 ° C for 1 hour.
C. and kept at the same temperature for 6 hours to continue the reaction. The acid value is 2, the hydroxyl value is 32, and the number average molecular weight is
2,500 polyester polyether resins were obtained.

Next, 240 parts of this polyester polyether resin, 20 parts of azobiscyanopropanol, 0.07 part of di-n-butyltin dilaurate and 700 parts of methyl ethyl ketone were charged into the same reaction vessel as in Reference Example 1, and cooled with ice. Below, 32 parts of hexamethylene diisocyanate was added dropwise over 2 hours.

After the completion of the dropwise addition, the reaction was continued at 25 ° C. for 20 hours to obtain a 25% solution of the target compound having a number average molecular weight of 9,500 and an average number of diazo bonds in one molecule of 5.4.

Reference Example 10 (same as above) In the same reaction vessel as in Reference Example 1, methyl ethyl ketone was added.
518 parts, 100 parts of N-methylpyrrolidone, 10 parts of azobiscyanopropanol, 10 parts of "VA-086", 60 parts of neopentyl glycol, 6 parts of trimethylolpropane and 6 parts of di-n-butyltin dilaurate 0.06 parts were charged, and 120 parts of hexamethylene diisocyanate was added dropwise with stirring over 2 hours under ice cooling.

After completion of the dropwise addition, the mixture was kept under ice-cooling for 2 hours, then heated to 25 ° C. and allowed to continue the reaction at the same temperature for 20 hours. The number average molecular weight was 11,800 and the average number of diazo bonds in one molecule. Is 4.
Nine 25% solutions of the target compound were obtained.

Reference Example 11 The same reaction vessel as in Reference Example 1 was charged with methyl ethyl ketone.
738 parts, 10 parts of azobiscyanopropanol, `` VA-08
6 '' of 10 parts, 150 parts of polypropylene glycol having an average molecular weight of 400 and 0.0 parts of di-n-butyltin dilaurate.
After charging 7 parts, 76 parts of hexamethylene diisocyanate was added dropwise over 2 hours while stirring under ice cooling, and the mixture was further kept under ice cooling for 2 hours. Hold the reaction for a long time to continue the reaction,
A 25% solution of the target compound was obtained at 10,400 and the average number of diazo bonds in one molecule was 3.6.

Example 1 In a reaction vessel similar to that of Reference Example 1, methyl ethyl ketone was added.
900 parts, 200 parts of the polymer azo initiator obtained in Reference Example 5,
Of the unsaturated bond-containing polymer (A-1) obtained in Reference Example 1.
250 parts, 162.5 parts of methyl methacrylate and 162.5 parts of ethyl acrylate were charged and heated to 80 ° C., and a mixture consisting of 162.5 parts of methyl methacrylate and 162.5 parts of ethyl acrylate was added dropwise over 3 hours.
After completion of the dropwise addition be maintained during the 15 hours at the same temperature, nonvolatile content of 50% and a viscosity to obtain a solution of Z ₁ becomes resins.

Next, 700 parts of "Loose" was added, and then 1,000 parts of the solvent was removed by vacuum distillation at 40 ° C.

After that, add 300 parts of "Loose" at 40 ℃
For 2 hours.

Thus, the desired non-aqueous resin dispersion was obtained,
This was a milky white non-aqueous dispersion type resin dispersion having a nonvolatile content of 50% and a viscosity of UV.

Examples 2 to 7 Resin solutions were obtained in the same manner as in Example 1 except that the organic solvents, monomers and initiators shown in Table 1 were used.

The characteristic values (nonvolatile content, viscosity and number average molecular weight) of each resin solution are shown in the same table.

Thereafter, except for changing to use an aliphatic and / or alicyclic hydrocarbon solvent as shown in the same table,
A milky white non-aqueous dispersion was obtained in the same manner as in Example 1.

The property values (nonvolatile content, viscosity and average particle size) of each non-aqueous dispersion are shown in the same table.

As is clear from Table 1, the non-aqueous resin dispersion of the present invention is known to be a dispersion having excellent dispersion stability. That is, this non-aqueous dispersion type resin is known to provide an excellent non-aqueous polymer dispersion.

Continuation of the front page (51) Int.Cl. ⁶ identification symbol FI C09D 155/00 C09D 155/00 C09J 155/00 C09J 155/00 (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 290 / 00 C08F 299/00 C08F 2/08 C08F 4/04 C09D 5/00 B C09D 155/00

Claims (2)

(57) [Claims] 1. A polymer having one or more ethylenically unsaturated bonds in one molecule in the presence of 2 to 97 parts by weight of a polymeric azo initiator having both a urethane bond and a diazo bond in the main chain of the molecule. And 98 to 3 parts by weight of a polymer (A) having a number average molecular weight of 500 to 100,000 and soluble in an aliphatic and / or alicyclic hydrocarbon solvent, and the polymer (A). A polymer or copolymer obtained by polymerizing 0 to 95 parts by weight of the polymerizable ethylenically unsaturated monomer (B) contains the aliphatic and / or alicyclic hydrocarbon-based solvent. A non-aqueous resin dispersion liquid dispersed in an organic solvent. 2. The polymer azo initiator described above has a general formula: And the general formula The non-aqueous resin dispersion according to claim 1, which is a compound having at least one structural unit represented by the following formula in one molecule and having a number average molecular weight of 1,500 to 50,000.