JPH0359080A - Nonaqueous resin dispersion - Google Patents

Abstract

PURPOSE:To obtain the title dispersion excellent in dispersion stability by (co) polymerizing a polymer containing ethylenically unsaturated bonds and soluble in an aliphatic and/or alicyclic hydrocarbon solvent in the presence of a specified high-molecular azo initiator, and dispersing the (co)polymer in an organic solvent containing the above-mentioned solvent. CONSTITUTION:98-3 pts.wt. polymer (e.g. a reaction product of n-butyl methacrylate, thioglycolic acid, and glycidyl methacrylate) of a number-average molecular weight of 500 to 100,000, having at least one ethylenically unsaturated bond in the molecule and soluble in an aliphatic and/or alicyclic hydrocarbon solvent (e.g. n-heptane), is (co)polymerized with 0-95 pts.wt. ethylenically unsaturated monomer copolymerizable therewith (e.g. methyl methacrylate) in the presence of 2-97 pts.wt. high-molecular azo initiator of a prescribed molecular weight, having both a urethane linkage and a diazo linkage in the principal molecular chain and preferably having one or more structural units of formula I [wherein R1 and R2 are each alkylene (containing specified substituents)] and formula II (wherein R3 is a polyol residue) in the molecule. The (co)polymer thus obtained is dispersed in an organic solvent containing the above-mentioned solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel and useful non-aqueous dispersion. More specifically, it is obtained by polymerizing a specific reactive resin and furthermore an ethylenically unsaturated monomer copolymerizable with the reactive resin in the presence of a specific polymeric azo initiator. (
A co)polymer dispersed in a specific organic solvent, which has particularly excellent dispersion stability and uniform particle size, and is used for building exteriors or metal coatings, adhesives, or sealants. The present invention relates to a non-aqueous dispersion, that is, a dispersion of a non-aqueous resin, which is particularly useful for applications.

[Conventional technology]

In recent years, this type of non-aqueous dispersion resin has been developed because of the fact that it has relatively little negative impact on the environment due to the use of non-polar weak solvents, that it exhibits chicken-like viscosity behavior because it is a particle system, and that it cannot be applied thickly. Because it has characteristics such as being easy to use, it also has superior performance than conventional solvent-based resins and emulsion-based resins, so it is suitable for metal coating,
In particular, it is beginning to be used in a wide variety of applications, including painting the exterior panels of automobiles and buildings.

By the way, in the conventional method for preparing a non-aqueous dispersion type resin, the monomer is soluble in the solvent in which the dispersing resin is dissolved, but the polymer obtained from the monomer is A common method is to polymerize a mixture of monomers in which the monomers are insoluble to form particles, but when such a method is followed, the form of the polymer is Polymerization active sites are generated in some of the molecules of the dispersion resin, that is, the dispersion stabilizer, and a new polymer that is insoluble in the above organic solvents (hereinafter referred to as an insoluble polymer) is formed. As a result, a very small portion of the vinyl monomer reacts with such polymerization active sites, resulting in a so-called soluble polymer portion based on the dispersion stabilizer and an insoluble polymer portion based on the above-mentioned vinyl monomer. A block copolymer or graft copolymer is formed, but at the same time, most of the vinyl monomers subjected to the polymerization reaction do not participate in the block copolymerization or graft copolymerization. Instead, homopolymerization occurs to form an insoluble polymer, which is in the form of a mixture of these polymers.

Such a conventional non-aqueous polymer dispersion has a low content of the above-mentioned block copolymer or graft copolymer, which has good dispersion stability, and is obtained by the above-mentioned homopolymerization. Because it has a high content of insoluble polymers,
Moreover, this insoluble polymer is simply dispersed in an organic solvent or a so-called organic liquid containing the solvent through physical secondary bonding with the block copolymer or graft copolymer, and therefore Non-aqueous polymer dispersions have a problem of poor dispersion stability.

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

In addition, such non-aqueous polymer dispersions may cause insoluble polymers to coagulate and precipitate due to the high shear force applied during pigment dispersion, or polar solvents with strong dissolving power for polymer particles, plasticizers, etc. If it is added, the dispersion stability during storage becomes extremely poor, and there is a risk of gelation or agglomeration and sedimentation.

In order to solve these problems, the concentration of polymerization active sites in the dispersion resin used as a dispersion stabilizer is increased, and the dispersion stabilizer and the vinyl monomer are reacted more actively, thereby improving dispersion stability. However, if such a method is followed, since a large amount of block copolymer or graft copolymer is contained, the insoluble polymer portion is in the form of a soft and less polar polymer portion. This has the effect of stably dispersing the substance, but on the other hand, it becomes extremely difficult to control the polymerization reaction, and the reaction may gel during the reaction, or even if it does not go that far, the reaction may not proceed smoothly. There were manufacturing problems such as failure to progress.

Apart from that, a technique has recently been proposed in which block copolymerization or graft copolymerization is performed using a special peroxide catalyst called polymeric peroxide to stabilize dispersion. Problems remain regarding its manufacturing peculiarities and risks.

[Problem to be solved by the invention]

As described above, all of the well water polymer dispersions that have been practically used to date have problems in terms of synthesis methods and dispersion stability, and in the end, they are still difficult to apply. A film-forming polymer that is satisfactory has not yet been obtained, and technical improvements are currently highly desired.

Therefore, the present inventors investigated the current situation! ! Based on this knowledge, fundamental solutions to various unresolved issues in conventional technology, and the earnest needs of this industry, we aim to put this type of well water type dispersion into practical use in the true sense of the word. , began earnest research.

Therefore, the problem to be solved by the present invention is to provide an extremely useful non-aqueous dispersion resin dispersion having excellent dispersion stability and uniform particle size. There is a particular thing.

[Means to solve the problem]

Therefore, the present inventors set their sights on the above-mentioned problems to be solved by the present invention, and as a result of intensive studies to obtain a useful well water type dispersion, A (co)polymer obtained by polymerizing a specific reactive resin and also an ethylenically unsaturated monomer copolymerizable with this reactive resin in the presence of an initiator is prepared using a specific organic solvent. The present invention has been completed by discovering an extremely useful dispersion of a non-aqueous dispersion type resin that has excellent dispersion stability and a uniform particle size. Ta.

That is, the present invention provides a polymeric azo initiator 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 a number average molecular weight of 500 to 100.00
To provide an extremely useful well water type resin dispersion, which is made by dispersing a (co)polymer which is soluble in an organic solvent containing 0 and an aliphatic and/or alicyclic hydrocarbon solvent. This is what I am trying to do.

Here, to exemplify only particularly representative polymeric azo initiators, the structural unit represented by -membrane (1) and the structural unit represented by -membrane are combined into one molecule. Among them, compounds having at least one polyurethane polyazo initiator are mentioned, and among them, it is preferable to use a compound having an average molecular weight of 1,500 to 50,000 (hereinafter also referred to as a polyurethane polyazo initiator).

Each molecule has at least one of both structural units represented by membrane-like (I) and (II),
The polyurethane polyazo initiator having a number average molecular weight of 1,500 to 50,000 is, for example, an azobiscyanoalkanol compound such as azobiscyanopropanol, azobiscyanobutanol or azobiscyanopentanol, or rVA-080J, rVA −
Azoamide polyol compounds such as 082J or rVA-086J (products of Wako Pure Chemical Industries, Ltd.) contain a small number of diazo bonds (one diazo bond and at least two
hydroxyl groups, isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate) or 1,3-di(isocyanatomethyl) ) alicyclic diisocyanates such as cyclohexane; aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate or trimethylhexane diisocyanate; or tolylene diisocyanate, xylene diisocyanate or 4.)
It is obtained by using a diisocyanate compound such as an aromatic diisocyanate such as 4'-diphenylmethane diisocyanate as an essential component.

That is, the polyurethane polyazo initiator is a combination of the diisocyanate compound itself as described above, or the diisocyanate compound and trimethylolethane,
A polymer having a functional group capable of reacting with a polyhydric alcohol such as trimethylolpropane, pentaerythritol, glycerin or dipentaerythritol, or an isocyanate group, and having a number average molecular weight of, for example, about 500 to 2.000. Polyisocyanate compounds such as adducts with low molecular weight polyester compounds, ethylene glycol, propylene glycol, dipropylene glycol, 1,4-phthylene gelicol,
1,3-butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-bentanediol, cyclohexanediol, polyethylene glycol, polypropylene glycol, polyhexamethylene glycol, hydrogenated bisphenol or bistuunol A three-component compound consisting of a polyol compound such as diols and various polyhydric alcohols listed above, and a compound having at least one diazo bond and at least two hydroxyl groups in one molecule as described above. can be obtained by subjecting at least one of each to an addition condensation reaction.

In that case, there is a method in which the above three-component compounds are simultaneously charged and reacted, or a polyurethane intermediate containing an isocyanate group, that is, a so-called urethane prepolymer is first prepared as a base, and at least one compound in each molecule is added to the base. There is a method of reacting a compound having both a diazo bond and at least two hydroxyl groups, but any of these methods may be used, and the method is not limited to these methods.

In addition, when reacting these diisocyanate compounds and/or polyisocyanate compounds, a polyol compound, and a compound having at least one diazo bond and at least two hydroxyl groups in one molecule, ethylene is used as a chain extender. Polyamine compounds such as shea fruit, hexamethylenecyamine, triethylenetetramine, bisaξnobrobylamine or 4-aminomethyl-1,8-cyaminooctane may be used.

Examples of the polyurethane polyazo initiator include various polyurethane polyazo initiators depending on R1 in the above-mentioned general formula [II].

That is, the polyol residues R1 are polyurethane polyol residues, polyester polyol residues, polyester polyurethane polyol residues, polyether polyol residues, polyether polyester polyol residues, polyether polyurethane polyol residues, and/or Polyurethane polyazo initiators, polyester polyurethane polyazo initiators, polyether polyurethane polyazo initiators, or polyether polyester polyurethane polyazo initiators may be mentioned, respectively, corresponding to polyether polyurethane polyester residues and the like. .

Among the polyurethane polyazo initiators, a more specific method for preparing the polyester polyurethane polyazo initiator will be described. First, the various polyol compounds listed above, isophthalic acid, terephthalic acid, and (anhydrous) tetrahydrophthalic acid are used. , (anhydrous) hexahydrophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, maleic acid, fumaric acid, succinic acid or adipic acid. A hydroxyl group-containing polyester resin (including oil-modified type) obtained by ring-opening polymerization of various lactones such as valerolactone; or an addition reaction between the above-mentioned polyol compound and the above-mentioned lactones is added to the above-mentioned polyester resin in one molecule. A method may be mentioned in which a compound having one or more diazo bonds and two or more hydroxyl groups is subjected to an addition reaction with the above-mentioned diisocyanate compound and/or polyisocyanate compound.

In this case, the above-mentioned polyamine compounds may be used as chain extenders, and furthermore, polyol compounds may be used.

Next, as a more specific method for preparing the polyether polyurethane polyazo initiator, polyethylene glycol,
Polyether diols such as polypropylene glycol or polytetramethylene glycol, polyether polyols such as addition polymers of various alkylene oxides such as ethylene oxide or propylene oxide to the above-mentioned polyol compounds, and diisocyanate compounds and/or polyether polyols. A method may be mentioned in which at least I type of each of the three components of an isocyanate compound and the aforementioned compound having one or more diazo bonds and two or more hydroxyl groups in one molecule are subjected to an addition condensation reaction.

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

Furthermore, as a more specific method for preparing the polyether polyester polyurethane polyazo initiator, first, a polyester polyether polyol is synthesized by a dehydration condensation reaction between the above-mentioned polyhydric carboxylic acids and the above-mentioned polyether polyols. This is combined with the diisocyanate compound and/or polyisocyanate compound mentioned above, and one or more diazo bonds and two
A method may be mentioned in which at least one of each of the three components is subjected to an addition condensation reaction with a compound having at least one hydroxyl group.

In this case as well, the above-mentioned boria phosphorous compound and/or
Alternatively, a polyol compound may be used as a chain extender.

In one molecule obtained in this way, the general formula CI
) and (ff), compounds having at least one structural unit of 1.500-50,
000, preferably from 2.000 to 20,000
Those having a number average molecular weight within this range are suitable because they have particularly good solubility in organic solvents and various monomers; As a result, it becomes difficult to obtain a coating resin composition having the characteristic coating film performance of the present invention, and
If it exceeds o or ooo, the solubility in the solvent will be poor, making it impossible to carry out uniform block copolymerization, and both are unfavorable.

The polymer polyazo initiator compound thus obtained has one or more ethylenically unsaturated bonds in one molecule and has a number average molecular weight of 500 to 500.
100.000 and is soluble in aliphatic and/or alicyclic hydrocarbon solvents. Typical examples of the reactive resin include alkyl groups of 04 or more. A (co)polymer having an ethylenically unsaturated bond whose main component is an alkyl (meth)acrylate monomer having ) polymers, alkyd resins having ethylenically unsaturated bonds, or alkyd resins having ethylenically unsaturated bonds obtained by grafting vinyl monomers onto such alkyd resins as a backbone polymer.

That is, for example, a vinyl copolymer containing a thiol group is obtained by polymerizing a vinyl monomer in the presence of a mercaptan, and then an unsaturated monomer containing an epoxy group such as glycidyl (meth)acrylate is added to this copolymer. Glycidyl (
(co)polymer resins in which double bonds have been introduced by various methods such as reacting unsaturated monomers containing epoxy groups such as meth)acrylates; furthermore, alkyd resins containing carboxyl groups. Examples include alkyd resins in which double bonds are introduced by a method such as reacting an epoxy group-containing unsaturated monomer such as glycidyl (meth)acrylate.

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

In addition, as the reactive resin, one containing one or more ethylenically unsaturated double bonds is used, but at most
It is preferable that the number is up to 2, and if there are 3 or more, be it double bonds or functional groups, the system will gel, so special care must be taken.

Rather, it is recommended to limit the number to two.

Furthermore, the number average molecular weight of the polymer (A), which is the reactive resin, is suitably within the range of 500 to 100.000, preferably within the range of 2.500 to 20,000, and in the case of less than 500. In this case, the stability of the particles of the dispersion after phase inversion due to solvent substitution tends to be insufficient;
If it exceeds 100.000, the reactivity of functional groups that can react with double bonds or carboxyl groups will be poor, making it difficult to obtain the desired resin with sufficient particle stability, and furthermore, the system will deteriorate. Either case is unfavorable because the viscosity becomes too high and the coating workability becomes poor.

The appropriate amount of the polymer (A) to be used is 3 to 93 parts by weight, preferably 5 to 50 parts by weight, and if it is less than 3 parts by weight, the stability of the particles and the uniformity of the particle size may deteriorate. On the other hand, if it exceeds 93 parts by weight, the viscosity of the system will increase and the coating workability will be significantly reduced, which is not preferable.

Particularly representative examples of the ethylenically unsaturated monomer (B) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and i-propyl (meth)acrylate. meth)acrylate, n-butyl(meth)acrylate, i-butyl(meth)acrylate, 5eC-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate, Various (meth)acrylic acid esters such as cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate; dimethyl maleate, dimethyl fumarate, dibutyl maleate, dibutyl Dialkyl (at-ct) unsaturated dibasic acids such as silfumarate or dibutyl itaconate
) Esters; cyano group-containing monomers such as acrylonitrile; various vinyl esters such as vinyl acetate, vinyl benzoate or "Beoba" (branched resin group carboxylic acid vinyl esters manufactured by Shell, Netherlands) ;"
Bisco-) 8F, 8FM.

3F or 3FMJ (manufactured by Osaka Organic Chemical Co., Ltd., fluorine-containing (meth)acrylic acid esters) (bar)fluoroalkyl group-containing monomers; vinyl chloride, vinyl butonide, vinylidene chloride, vinylidene butonide, or chlorotrifluoro Halogenated olefins such as ethylene; or aromatic vinyl monomers such as styrene, α-methylstyrene, pt-butylstyrene or vinyltoluene;
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate or 4-hydroxy(
Hydroxyl group-containing vinyl monomers such as meth)acrylates;
Carboxyl group-containing vinyl monomers such as (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid; or epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate.

Various polymeric polyazo initiators such as those listed above,
The organic solvent used in solution radical polymerization using a reaction resin and an ethylenically unsaturated monomer includes esters such as methyl acetate, ethyl acetate, n-butyl acetate, or amyl acetate. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetone or cyclohexanone:
Typical examples include alcohols such as methanol, ethanol, i-propyl alcohol, and n-butanol, and aromatic hydrocarbon solvents such as toluene or xylene and alcohol solvents such as those listed above. Of course, they can be used together,
Moreover, it goes without saying that an aliphatic and/or alicyclic hydrocarbon solvent can also be used in combination as the polymerization solvent.

Typical examples of these aliphatic hydrocarbon solvents include n-hebutane, wax,
(Product from Shell, Netherlands), Isopar E or Cl (Product from Exxon Chemical, USA),
"Naphtha No. 5 or No. 6" (same company product), rlP Solvent 1620J (Idemitsu Petrochemical @ product) or "
"White Sol" (Kyodo Sekiyu Product), etc. Also included in the present invention are solvents in the form of mixed solvents of aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. 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, but the alicyclic hydrocarbon solvent and the aliphatic hydrocarbon solvents listed above are Of course, the present invention also includes the combined use of the alicyclic hydrocarbon solvent and the aromatic hydrocarbon solvent. When such an alicyclic solvent and an aromatic solvent are used in combination, the amount of the alicyclic solvent used should be 50% by weight or more.

In order to perform such solution radical polymerization, an organic solvent such as those listed above and an azo type such as azobisisobutyronitrile or a peroxide type such as benzoyl peroxide are used. It may be used in combination with various radical polymerization initiators, and 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 raw materials listed above, when the polymerization reaction is carried out in an organic solvent that does not contain an aliphatic and/or alicyclic hydrocarbon solvent, this organic While removing the solvent, it is necessary to replace the solvent by dropping an aliphatic and/or alicyclic hydrocarbon solvent as described above in parallel with the solvent removal operation.

By the way, the viscosity of the system is determined by the ratio of the alcohol, ketone or ester solvent that is a good solvent to the aliphatic and/or alicyclic hydrocarbon solvent that is a poor solvent (depending on the type of solvent and the resin). ), the viscosity of the system increases most rapidly, and
Beyond that point, the viscosity of the system decreases as the amount of aliphatic and/or alicyclic hydrocarbon solvent increases.

Needless to say, the polymerization solvent used in this solvent replacement, that is, the organic solvent, and the dispersion solvent, that is, the aliphatic and/or alicyclic hydrocarbon solvent, are of course used. The greater the difference in boiling point, the more advantageous it can be expected that the desired dispersion can be obtained in a shorter time in the manufacturing process.

Incidentally, when combining i-propyl alcohol or methyl ketone with "loose" or "isopar E," such advantages in the manufacturing process can be expected.
On the other hand, if the boiling point difference is less than 20°C and the combinations are close, it will take a long time to replace the solvent, so the combination of solvents should be selected at 20°C or higher. It is desirable to have a boiling point difference of .

For the non-aqueous dispersion resin dispersion thus obtained,
If necessary, various additives such as other polymers, pigments or fillers can be added, such as butyl etherified melamine resins, butyl etherified benzoguanamine resins, butyl etherified urea resins,
Blocked polyisocyanate compounds, aromatic, aliphatic or alicyclic polyepoxides, polyamide resins, or vinyl resins containing glycidyl groups, carboxyl groups, hydroxyl groups, isocyanate groups, alkoxy groups or N-methylolated amide groups, etc. is a typical one,
Each of these polymers serves as a thermosetting film-forming component as a curing agent having a functional group complementary to the functional group present in the non-aqueous dispersible resin of the present invention.

〔Effect of the invention〕

As described above, in the non-aqueous dispersion resin for paints of the present invention, most of the produced polymers are composed of a polymer part soluble in organic liquid (soluble polymer part) and an insoluble polymer part ( Because it is a block copolymer consisting of an insoluble polymer portion), it has excellent dispersion stability, and has the special feature of being a non-aqueous dispersion liquid with a uniform particle size. It is something that you have.

Furthermore, the non-aqueous resin dispersion of the present invention is useful for coating metals, particularly for painting exterior panels of automobiles and exterior panels of buildings, and is useful not only for such coatings but also for adhesives. It can also be used as a sealant.

〔Example〕

Next, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples. In the following, parts and percentages are all based on weight unless otherwise specified.

Reference Example 1 [Example of preparation of unsaturated bond-containing polymer (A)] 66.7 parts of "Wax" and Z-T were placed in a four-way flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas inlet. - Charge 0.2 part of butyl peroxide to 12
The temperature was raised to 0°C, and when the same temperature was reached, 97 parts of n-butyl methacrylate, 7 parts of t-butyl peroctoate,
A mixture consisting of 2 parts of 1 and 2 parts of thioglycolic acid was added dropwise over 5 hours, and the reaction was continued by maintaining the same temperature for 5 hours even after the addition was completed. Next, 13 parts of glycidyl methacrylate was added and the reaction was carried out at 125°C for 4 hours, so that the nonvolatile content was 60%, the viscosity (Gardner viscosity at 25°C; hereinafter the same) was U-V, and the number average molecular weight was 3. .5
A high molecular weight polymeric monomer 00 was obtained. Hereinafter, this will be abbreviated as (A-1).

Reference Example 2 [Example of Preparation of Epoxy Group-Containing Polymer (^)] Into the same flask as in Reference Example 1, 100 parts of "Isopar E" and 0.2 parts of di-t-butyl peroxide were charged and heated at 120°C. When the temperature reached that temperature, a mixture consisting of 98 parts of i-butyl methacrylate, 2 parts of 2-hydroxyethyl methacrylate, and 8 parts of t-butyl peroxyoctoate was added dropwise over 6 hours. After the dropwise addition was completed, the temperature was kept at the same temperature for 5 hours, and then 2 parts of dimethacrylic anhydride and 0% of t-butylcatechol were added.
．． 01 part was added and the reaction was continued for 2 hours until the non-volatile content was 5.
0%, viscosity is B-C, and number average molecular weight is 5.0
A desired polymeric monomer named 00 was obtained. Below, this (
It is abbreviated as A-2).

Reference Example 3C Preparation Example of Unsaturated Bonded Gold-Containing Polymer (A)] In the same manner as in Reference Example 1, 1. oo
o part and 7 of “Pesocozole P-470-70J [polyester polyol manufactured by Dainippon Ink & Chemicals @]
．． After charging 2 parts, 5 parts of i-butyl methacrylate
A mixture consisting of 0 parts of n-butyl acrylate, 45 parts of t-butyl peroctoate, and 1.0 parts of t-butyl peroctoate was added dropwise over 4 hours, and after the addition was completed, the same temperature was maintained for another 7 hours to remove non-volatile components. 50%, the desired polymeric heptadumer having a viscosity of XY and a number average molecular weight of 15,000 was obtained.

Hereinafter, this will be abbreviated as (A-3).

Reference Example 4 [Example of preparation of unsaturated bond-containing polymer (A)] In the same manner as in Reference Example 1, 49 parts of "Isopar E" was charged into a flask and the temperature was raised to 80"C.
-70J (7) 3.5 parts, 77.5 parts of j-butyl methacrylate, 18 parts of n-butyl acrylate, 2 parts of isocyanate ethyl methacrylate and 8 parts of t-butyl peroctoate for 8 hours. It dripped. After the dropwise addition was completed, the temperature was kept at the same temperature for 8 hours to continue the reaction, and then 1.7 parts of 2-hydroxyethyl methacrylate and 0.01 part of t-butylcatechol were added, and the reaction was continued for 2 hours. A desired polymeric monomer having a nonvolatile content of 50%, a viscosity of B-C, and a number average molecular weight of 5,200 was obtained. Hereinafter, this will be abbreviated as (A-4).

Reference Example 5 [Preparation example of polyurethane polyazo initiator compound] In a four-eye flask equipped with a thermometer, a stirrer, and a reflux condenser, 250 parts of N-methylpyrrolidone, 73 parts of neopentyl glycol, and azobiscyanopropanol were added. 20
135 parts of hexamethylene diisocyanate were added dropwise over 2 hours while stirring and cooling on ice.

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

This product has a polystyrene-equivalent number average molecular ff1 (hereinafter the same) of 9,800 as determined by gel permiesigon chromatography, and an average of 4.9 in one molecule.
It contained two different diazo bonds.

Reference Example 6 (same as above) Into the same reaction vessel as in Reference Example 1, 672 parts of methyl ethyl ketone, 5 parts of neopentyl glycol, 9 parts of trimethylolpropane, and 0.01 part of di-n-butyltin dilaurate were charged. Then, 130 parts of hexamethylene diisocyanate was added dropwise over 2 hours while stirring, and after the addition was completed, the reaction was continued at 40"C for 2 hours, and then cooled to room temperature.

Next, 26 parts of azobiscyanopentanol was added with stirring under water cooling, and dispersed uniformly.
- Add 0.07 part of butyltin dilaurate at 25°C.
The reaction was continued for 10 hours, and a 25% solution of the target compound having a number average molecular weight of 10,200 and an average number of diazo bonds in the molecule of 5.1 was obtained.

Reference Example 7 (same as above) In a reaction vessel similar to Reference Example 1, 2 of methyl ethyl ketone was added.
12 parts of hexamethylene diisocyanate and 160 parts of polypropylene glycol having an average molecular weight of 400 and 0.06 parts of di-n-butyltin dilaurate were charged, and while stirring at room temperature, 32.4 parts of hexamethylene diisocyanate and 18 parts of xylene diisocyanate were added. 8 parts were added dropwise over 2 hours, and after the addition was completed, the temperature was maintained at 50°C for 2 hours to continue the reaction.
A 50% solution of polyurethane polyol having an average molecular weight of 3.200 and a hydroxyl value of 26 was obtained.

Next, 216 parts of this solution, 19.6 parts of azobiscyanopropanol, and 375.6 parts of methyl ethyl ketone were added.
and 0.08 parts of di-n-butyltin dilaurate were placed in another reaction vessel in the same manner as in Reference Example 1, and 33.6 parts of hexamethylene diisocyanate was added dropwise while cooling with water. was maintained at 25° C. for 20 hours to continue the reaction, to obtain a 25% solution of the target compound having a number average molecular weight of 12,300 and an average number of diazo bonds in one molecule of 5.7.

Reference Example 8 (Same as above) In a reaction container similar to Reference Example 1, "Plaxel 208J"
164 parts of lactone diol (manufactured by Daicel Corporation), 715 parts of methyl ethyl ketone, 20 parts of azobiscyanopropanol and 0.07 parts of di-n-butyltin dilaurate were added, and under water cooling, hexamethylene diisocyanate was added. 50 parts were added dropwise over 1 hour. After completion of the dropwise addition, the reaction was continued at 25°C for 20 hours, resulting in a number average molecular weight of 10.500 and an average number of diazo bonds in one molecule of 5. A 25% solution of three target compounds was obtained.

Reference Example 9 (same as above) In a four-eye flask equipped with a thermometer, stirrer, and air condenser, 50 parts of adipic acid, 50 parts of neopentyl glycol, 88.5 parts of polypropylene glycol with an average molecular weight of 400, and isophthalic acid. After reacting at 140°C for 1 hour, the temperature was raised to 220°C over 2 hours, and the reaction was continued by keeping at the same temperature for 6 hours until the acid value was 2 and the hydroxyl value was 2. A polyester polyether resin having a number average molecular weight of 32 and a number average molecular weight of 2,500 was obtained.

Next, reference cold 1.1! : In a similar reaction vessel, 240 parts of this polyester polyether resin, 20 parts of azobiscyatbrobanol, 0.07 parts of di-n-butyltin dilaurate, and 700 parts of methyl ethyl ketone were charged, and the mixture was cooled with water. , 32 parts of hexamethylene diisocyanate were added dropwise over 2 hours.

After completion of the dropwise addition, the reaction was continued by keeping it at 25°C for 20 hours to obtain 25% of the target compound with a number average molecular weight of 9.500 and an average number of diazo bonds in one molecule of 5.4.
A solution was obtained.

Reference Example 10 (same as above) In a reaction vessel similar to Reference Example 1, methyl ethyl ketone
18 parts, 100 parts of N-methylpyrrolidone, 10 parts of azobiscyanopropanol, 10 parts of "V^086",
60 parts of neopentyl glycol, 6 parts of trimethylolpropane and 0.0 parts of di-n-butyltin dilaurate.
06 parts of hexamethylene diisocyanate was added dropwise to the mixture over 2 hours while cooling with water and stirring.

After the dropwise addition was completed, the temperature was kept under water cooling for 2 hours, and then the temperature was raised to 25°C and the reaction was continued at the same temperature for 20 hours to obtain a number average molecular weight of 11,800 and an average diazo bond in one molecule. A 25% solution of the target compound having 4.9 atoms was obtained.

Reference Example 11 In a reaction vessel similar to Reference Example 1, 7 of methyl ethyl ketone was added.
38 parts, 10 parts of azobiscyatuburobanol, rVA
10 parts of -086J, 150 parts of polypropylene glycol with an average molecular weight of 400, and 0.07 parts of di-n-butyltin dilaurate were charged, and 76 parts of hexamethylene diisocyanate was added for 2 hours while stirring under water cooling. After dripping and keeping it under water cooling for 2 hours,
The temperature was raised to 25°C and maintained at the same temperature for 20 hours to continue the reaction, producing 2 of the target compound with a number average molecular weight of 10,400 and an average number of diazo bonds in one molecule of 3.6.
A 5% solution was obtained.

Example 1 In a reaction vessel similar to Reference Example 1, methyl ethyl ketone was added.
00 parts, 200 parts of the polymeric azo initiator obtained in Reference Example 5
part, unsaturated bond-containing polymer obtained in Reference Example 1 (A-1
), 162.5 parts of methyl methacrylate, and 162.5 parts of ethyl acrylate, and
The temperature was raised to 0°C, and 162% of methyl methacrylate was added.
A mixture consisting of 5 parts of ethyl acrylate and 162.5 parts of ethyl acrylate was added dropwise over 3 hours.
After holding for a period of time, a resin solution with a non-volatile content of 50% and a viscosity of Z was obtained.

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

Afterwards, 300 copies of ``Lows'' were added, making 40 copies.
Stirring was continued for 2 hours at °C.

In this way, the desired non-aqueous resin dispersion was obtained, which was a milky white non-aqueous resin dispersion with a non-volatile content of 50% and a viscosity of UV.

Examples 2 to 7 Each resin solution was 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, a milky white non-aqueous dispersion was obtained in the same manner as in Example 1, except that an aliphatic and/or alicyclic hydrocarbon solvent as shown in the table was used.

The property values (nonvolatile content, viscosity, and average particle size) of each well water type 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 have excellent dispersion stability. In other words, it is known that this non-aqueous dispersion type resin provides an excellent non-aqueous polymer dispersion.

Claims (1)

[Claims] 1. 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, one or more ethylenic unsaturations in one molecule A polymer (
A polymer or copolymer obtained by polymerizing 98 to 3 parts by weight of A) and 0 to 95 parts by weight of an ethylenically unsaturated monomer (B) copolymerizable with the polymer (A) A non-aqueous resin dispersion prepared by dispersing the above-mentioned aliphatic and/or alicyclic hydrocarbon solvent in an organic solvent. 2. The polymeric azo initiator described above has the general formula ▲ mathematical formula, chemical formula, table, etc. In addition, R_2 represents an alkylene group, an alkylene group containing a cyano group, an alkylene group containing an amide bond, or an alkylene group containing an oxide bond and a hydroxyl group. ] There are structural units represented by the general formula ▲ mathematical formulas, chemical formulas, tables, etc. ▼... [II] [However, R_2 in the formula represents the residue of the polyol. ] The non-aqueous resin dispersion according to claim 1, which is a compound having at least one structural unit represented by the following in one molecule and having a number average molecular weight of 1,500 to 50,000.