JPS6249282B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a non-aqueous polymer dispersion having extremely excellent dispersion stability in which a block copolymer is uniformly dispersed in an organic liquid. Generally, non-aqueous polymer dispersions are used as coating compositions, which are characterized by low viscosity and high solids content, in paints, inks, etc.
It is useful in fields such as adhesives. Particularly in the field of paints, such non-aqueous polymer dispersions can be used to reduce the amount of solvent used or to switch to photochemically inactive solvents, and are expected to be greatly developed in the future as low-pollution paints. By the way, most of the non-aqueous polymer dispersions that have been put to practical use use a polymer soluble in an organic liquid as a dispersion stabilizer, and a vinyl monomer that becomes a polymer insoluble in the organic liquid is used as a dispersion stabilizer. The dispersion stabilizer and the polymer were uniformly dispersed in the organic liquid obtained by polymerization in the organic liquid. In this case, the form of the polymer is a vinyl-type monomer in which polymerization active sites are generated in some of the molecules of the dispersion stabilizer during polymerization, resulting in a polymer that is insoluble in the organic liquid (hereinafter referred to as an insoluble polymer). A block or graft copolymer in which a small portion of the copolymer reacts with the polymerization active site and consists of a soluble polymer portion based on the dispersion stabilizer and an insoluble polymer portion based on the vinyl monomer. However, at the same time, most of the vinyl monomers subjected to the polymerization reaction undergo monopolymerization to form an insoluble polymer without participating in block or graft copolymerization. Such conventional non-aqueous polymer dispersions have a low content of the above-mentioned block or graft copolymer having good dispersion stability and a large content of the above-mentioned homopolymerized insoluble polymer. , the insoluble polymer is simply dispersed in the organic liquid by physical secondary bonding with the block or graft copolymer; therefore, such a non-aqueous polymer dispersion is There was a problem with poor stability. Particularly when the non-aqueous polymer dispersion obtained in this manner is used as a coating film-forming component, a major problem arises. In other words, the above-mentioned block or graft copolymer and insoluble polymer cannot maintain dispersion stability unless they are strongly secondary bonded by physical intermolecular forces. The types of monomers that can be used as such are limited, and it is necessary to use a large number of vinyl monomers that can form rigid polymers with large secondary bonding strength and high polarity. Therefore, the coating film obtained from such a non-aqueous polymer dispersion not only lacks flexibility, moisture resistance, acid resistance, and adhesion to the object being coated, but also the insoluble polymer particles are hard and cannot be used during coating film formation. The resulting coating film was not sufficiently melted and flowed, and the resulting coating film was formed in the form of particles, which caused a decrease in coating film strength. In addition, the above-mentioned non-aqueous polymer dispersions have poor mechanical dispersion stability; for example, when high shear stress is applied for pigment dispersion, insoluble polymers coagulate and settle.
Furthermore, when polar solvents or plasticizers that have a strong ability to dissolve insoluble polymers are added, the dispersion stability during storage is extremely poor, and there is a risk that the insoluble polymers will gel or coagulate and settle. The essence of the above problem is to maintain the dispersion stability of the insoluble polymer by secondary bonding between a small amount of block or graft copolymer having dispersion stability and a large amount of the insoluble polymer using physical intermolecular force. The reason lies in the fact that Therefore, in order to solve these problems, we developed a reaction system that increases the amount of block or graft copolymers with good dispersion stability in the reaction between the dispersion stabilizer and the vinyl monomer as described above. A method of using . For example, introducing a polymerizable vinyl group into the dispersion stabilizer molecule (U.S. Pat. No. 3,607,821, Japanese Patent Publication No. 40-23350, Japanese Patent Application Publication No. 11397-1982, Japanese Patent Application Laid-open No. 126093-1983). , a functional group other than a vinyl group is provided in the vinyl monomer molecule, and a complementary functional group to that functional group is introduced into the dispersion stabilizer molecule (U.S. Pat. No. 3,365,414). Vinyl type monomers with soluble polymeric parts are used as dispersion stabilizers (UK Patent No. 1096912)
Specification of British Patent No. 1206442, JP-A-Sho
49-30434) to obtain a nonaqueous polymer dispersion containing a large amount of a block or graft copolymer of a dispersion stabilizer and a vinyl monomer. Since these methods contain a large amount of block or graft copolymer, they have the effect of stably dispersing the insoluble polymer portion as a soft, low polarity polymer portion, but on the other hand, it is extremely difficult to control the polymerization reaction, and the reaction There were manufacturing problems, such as gelation or the reaction not proceeding properly. Furthermore, in JP-A-49-5194, a peroxyester type organic peroxide having two peroxy bonds with different decomposition temperatures is used, and as a first stage polymerization in an organic liquid, a soluble compound in the organic liquid is produced at a low decomposition temperature. A vinyl monomer that will become the resulting polymer is polymerized, and as a second stage polymerization, a vinyl monomer that will become the resulting polymer that is insoluble in the organic liquid is graft-polymerized at a high temperature decomposition temperature to form a non-aqueous polymer. A method for producing polymer dispersions has been proposed. Since the organic peroxide used in this method is bifunctional, due to its polymerization mechanism, approximately half of the polymers produced in the first stage polymerization become homopolymers that do not participate in graft polymerization in the second stage polymerization. Moreover, in the second stage polymerization, about half of the polymer produced becomes a homopolymer, resulting in a substantially very low grafting efficiency, resulting in an unfavorable method. As mentioned above, the non-aqueous polymer dispersions that have been practically used have an extremely narrow selection range of vinyl monomers that form insoluble polymers, and also have problems with dispersion stability. No satisfactory polymer has yet been obtained, and technical improvements are highly desired. An object of the present invention is to provide a new method for producing a non-aqueous polymer dispersion that eliminates the drawbacks of conventional non-aqueous polymer dispersions as described above. That is, the first manufacturing method of the present invention is based on (a) general formula () [In the formula, R ₁ represents an alkylene group or substituted alkylene group having 1 to 18 carbon atoms, a cycloalkylene group or substituted cycloalkylene group having 3 to 15 carbon atoms, or a phenylene group or substituted phenylene group, and R ₂ represents an alkylene group having 2 to 18 carbon atoms or a substituted cycloalkylene group, ~10 alkylene groups or substituted alkylene groups,

[Formula] (In the formula, R ₃ is a hydrogen atom or a methyl group, R ₄ is an alkylene group or substituted alkylene group having 2 to 10 carbon atoms, and m is an integer of 1 to 13.)

[expression] or

[Formula] represents. Moreover, n is 2-20. ] or two or more of the following and the general formula () [In the formula, R ₁ and n are the same as in the above general formula (). ] One or more polymeric peroxides selected from the group consisting of one or more of the following and one or more vinyl monomers defined in (a) below. a step of copolymerizing in an organic liquid to obtain the organic liquid solution of the peroxy bond-containing copolymer;
A liquid mixture of one or more types of vinyl monomers and one or more types of other vinyl monomers having different compositions, or the other vinyl type monomers and an organic liquid defined in (a) below. (c) performing block copolymerization of the peroxy bond-containing copolymer and the other vinyl monomer to obtain the organic liquid solution of the block copolymer; The block copolymer is characterized by a step of mixing an organic liquid defined in (b) below with the combined solution, wherein the block copolymer is mixed with an organic liquid defined in (a) below and an organic liquid defined in (b) below. This is a method for producing a non-aqueous polymer dispersion dispersed in a mixed liquid with an organic liquid. (b) A polymer of one or more vinyl monomers to be copolymerized with the polymeric peroxide and one or more vinyl monomers to be block copolymerized with the peroxy bond-containing copolymer. An organic liquid that exhibits solubility in any polymer of one or more vinyl monomers different from the vinyl monomer. (b) The above-mentioned 1 shows insolubility in the polymer of one or more vinyl monomers to be copolymerized with the polymeric peroxide, and is block copolymerized with the peroxy bond-containing copolymer.
An organic liquid that exhibits solubility in a polymer of one or more vinyl type monomers different from the species or two or more vinyl type monomers. Further, the second production method of the present invention provides a block copolymer as defined in (a) above obtained by the same steps as steps (a) and (b) of the first production method. For the organic liquid solution, instead of the step (c) above, as the step (d), the organic liquid defined in (a) is separated and removed by a conventional method to obtain only the block copolymer,
By performing the step of mixing the organic liquid defined in (b) above with the block copolymer, the block copolymer is mixed with the organic liquid defined in (b) above. This method is characterized by obtaining an aqueous polymer dispersion. In the production method of the present invention, since the peroxy bond-containing copolymer serves as a polymerization initiator in the step (b), a large amount of block copolymer with good dispersion stability is produced, and the block copolymer is The copolymerization reaction is also very stable, and there is no risk of polymer particles agglomerating due to gelation or the like, or of sudden increases in viscosity during the reaction. The non-aqueous polymer dispersion obtained by the production method of the present invention as described above is based on (i) the peroxy bond-containing copolymer that is insoluble in the organic liquid defined in (b) above. The polymer portion and (ii) the above (b)
A block copolymer consisting of a polymer portion based on a vinyl monomer block copolymerized in the step (b) above, which is soluble in an organic liquid defined by
It is dispersed and contained at a high concentration in the mixture of organic liquids (a) and (b) or in the organic liquid of (b) above,
Moreover, it has a low viscosity and extremely excellent dispersion stability. The general formula () used in the production method of the present invention
Examples of polymeric peroxides include: (n=2 to 20 in each formula). Further, as the polymeric peroxide represented by the general formula (), for example, (In each formula, n=2 to 20.) etc. The polymerization mechanism of vinyl monomers by these polymeric peroxides can be explained as follows. First, in step (a) above, when one or more vinyl monomers are polymerized using polymeric peroxide, a so-called peroxy bond-containing copolymer in which peroxy bonds are introduced into the chain is obtained. Then, in the step (b), one or more other vinyl monomers having a different composition from the one or more vinyl monomers are added to the specific organic liquid. When the peroxy bond-containing copolymer is added and polymerized, the peroxy bond-containing copolymer is cleaved at the peroxy bond contained therein, and a block copolymer can be efficiently obtained. This block copolymer consists of an insoluble polymer portion based on the above-mentioned peroxy bond-containing copolymer and a soluble polymer portion based on the above-mentioned other vinyl monomer, ) By carrying out the process, the insoluble polymer part aggregates into particles, and the soluble polymer part extends into the organic liquid, and as a whole, particles are dispersed in the organic liquid. state. The organic liquid defined in the above (a) and the organic liquid defined in the above (b) used in the present invention are the organic liquid defined in the above (a).
The vinyl monomer used in the step and the above (b)
An organic liquid exhibiting solubility or insolubility as defined in (a) and (b) above must be selected and used depending on the type of vinyl monomer used in the step. The type of organic liquid selected according to the type of vinyl monomer has the relationship shown in Table 1, for example.

[Table] The organic liquids in Table 1 are specifically shown below. Examples of aliphatic or alicyclic hydrocarbons include n-hexane, n-heptane, n-octane, petroleum benzine, ligroin, mineral spirits, petroleum naphtha, kerosene, cyclohexane,
Aromatic hydrocarbons such as methylcyclohexane include toluene and xylene; esters include ethyl acetate and butyl acetate; ketones include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; lower alcohols include methyl alcohol and ethyl alcohol. , n-propyl alcohol, isopropyl alcohol, etc. Higher alcohols include butyl alcohol, pentyl alcohol,
Hexyl alcohol, heptyl alcohol, octyl alcohol, etc., and examples of ether alcohols include methyl cellosolve, ethyl cellosolve, and butyl cellosolve. These organic liquids are used with one or more types selected as the main component meeting the definitions of (a) and (b) above, but with respect to the organic liquid as the main component, a block copolymer is used. Organic liquids other than the main components can be added to an extent that does not impair the insolubility of the insoluble polymer portion of the combination and to an extent that does not impair the solubility of the soluble polymer portion. The vinyl type monomer used in the present invention is the above-mentioned (a)
There are some vinyl monomers used in step (a) and (b), and the selection of each vinyl monomer used in steps (a) and (b) depends on the selection of the vinyl monomers used in step (a) and (b). In relation to the type of organic liquid, for example, the first
It is appropriately selected in consideration of the solubility and insolubility relationship between the vinyl monomer and the organic liquid as shown in the table. Examples of vinyl monomers to be selected include methyl (meth)acrylate [(meth)acrylic acid refers to acrylic acid or methacrylic acid. Same below. ], lower alkyl (meth)acrylates such as ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and glycidyl (meth)acrylate; n-(meth)acrylate
Butyl, (meth)isobutyl acrylate, (meth)
tert-butyl acrylate, (meth)acrylic acid n
- Higher alkyl (meth)acrylates such as hexyl, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; vinyl acetate ,
Lower fatty acid vinyl esters such as vinyl propionate; higher fatty acid vinyl esters such as vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, and vinyl stearate;
Aromatic vinyl monomers such as styrene, vinyltoluene, and vinylpyrrolidone; Vinyl monomers containing amide groups such as (meth)acrylamide, N-methylol(meth)acrylamide, and N-methoxymethyl(meth)acrylamide; Hydroxyl group-containing vinyl monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and allyl alcohol; (meth)acrylic acid,
Carboxylic acid group-containing vinyl monomers such as itaconic acid, crotonic acid, fumaric acid, and maleic acid; butadiene; vinyl chloride; vinylidene chloride; (meth)acrylonitrile; dibutyl fumarate; maleic anhydride; dodecynyl succinic anhydride; Examples include meta)allyl glycidyl ether. One or more of these vinyl monomers are used as the main component of the vinyl monomer in the step (a) or the step (b) above, but the vinyl monomer as the main component A vinyl type monomer other than the main component may be added to the vinyl type monomer of the main component to the extent that the solubility or insolubility of the polymer portion of the block copolymer based on the polymer is not impaired in the organic liquid. can. The peroxy bond-containing copolymer used in the present invention can be produced by a conventional solution polymerization method using a polymer peroxide represented by the above general formula () and/or a polymer peroxide represented by the above general formula (). It can be easily obtained by polymerizing the polymer. In this case, the amount of polymer peroxide used is 0.5 to 10 parts by weight per 100 parts by weight of the vinyl monomer.
Parts by weight, polymerization temperature 60~130℃, polymerization time 2~
5 hours is a suitable range for each. In this case, the polymer peroxides used in the present invention can be used alone or in combination of two or more. In addition, the polymerization temperature of block copolymerization reaction is 60~
A temperature of 140°C and a polymerization time of 3 to 6 hours are suitable. The amount of organic liquid to be used is preferably in a range such that the solid content of the non-aqueous polymer dispersion is 30 to 70% by weight, that is, 70 to 30% by weight. Further, the ratio of the soluble polymer part to the insoluble polymer part in the block copolymer is not particularly limited, but from the viewpoint of the stability of the dispersion liquid of the present invention and the physical properties of the coating film, the amount of the soluble polymer part is determined by the amount of the insoluble polymer part. 5 to 70 relative to the total amount of polymer part and soluble polymer part
Weight % is suitable, particularly 10 to 50 weight %. Various additives such as other polymers, pigments, fillers, etc. can be added to the non-aqueous polymer dispersion of the present invention, if necessary. For example, butylated melamine formaldehyde resin, butylated benzoguanamine formaldehyde resin, butylated urea formaldehyde resin, blocked isocyanate resin, aromatic, aliphatic or alicyclic compound-based polyepoxide, polyamide resin, glycidyl group,
Adding a curing agent having a functional group complementary to the functional group of the polymer in the non-aqueous polymer dispersion of the present invention, such as a vinyl resin containing carboxyl groups, hydroxyl groups, isocyanate groups or alkoxymethylolated amide groups. It can also be used as a thermosetting film-forming polymer composition. As described above, the method for producing a non-aqueous polymer dispersion of the present invention has the following advantages over conventional methods, and its industrial value is extremely high. (1) The manufacturing process is extremely simple and industrially advantageous. (2) Since most of the produced polymers are block copolymers consisting of a polymer part soluble in organic liquids and a polymer part insoluble, excellent dispersion stability is achieved by containing a high concentration of block copolymers. A non-aqueous polymer dispersion liquid is obtained. (3) The copolymerization reaction step (a) in the present invention and
Since the block copolymerization reaction step (b) is both carried out by the solution polymerization method, the average molecular weight of the resulting block copolymer is relatively small, and therefore the resulting non-aqueous polymer dispersion is This produces the effect that the viscosity of
Furthermore, due to the low average molecular weight, the coating composition prepared from the non-aqueous polymer dispersion according to the present invention has good hot melt fluidity when formed into a coating film, and the cured coating film has good properties. A continuous coating layer with excellent smoothness and high gloss can be formed. Next, the manufacturing method of the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. In addition, all "parts" and "%" in each example are based on weight. Example 1 (A) Production of peroxy bond-containing copolymer solution In a reactor equipped with a thermometer, a stirrer and a reflux condenser, was heated to 70°C while blowing nitrogen gas, and a polymerization reaction was carried out for 3 hours. the result,
Contains 59.5% peroxy bond-containing copolymer, 25
A clear solution was obtained with a viscosity of 4.5 poise at °C. (B) Production of block copolymer solution 190 parts of the peroxy bond-containing copolymer solution of (A) above was charged into the same reactor as above (A), and methacrylate was added thereto at 75°C while blowing nitrogen gas. A mixture of 61.1 parts of ethyl acid, 6.4 parts of hydroxypropyl methacrylate, and 2.5 parts of methacrylic acid was added dropwise over 1.5 hours, and the polymerization reaction was further carried out at 80°C for 4 hours to obtain a transparent solution of the block copolymer. (C) Production of non-aqueous polymer dispersion By adding 100 parts of ethyl alcohol to the total amount of the block copolymer solution obtained in (B) above and mixing, a milky white non-aqueous polymer dispersion is produced. Obtained. This dispersion contains a block copolymer.
The content was 50.8%, and the viscosity at 25°C was 1.7 poise, and the dispersion state remained stable with no particle sedimentation, phase separation, or viscosity change observed even after being left at 25°C for 6 months. When this dispersion was applied to a steel plate to a dry film thickness of 30 to 40 μm and force-dried at 140°C for 30 minutes, the film was smooth and glossy, and no foaming or sagging was observed. Nakatsuta. Example 2 (A) Production of peroxy bond-containing copolymer solution In a reactor equipped with a thermometer, a stirrer and a reflux condenser, was heated to 70°C while blowing nitrogen gas, and a polymerization reaction was carried out for 3 hours. the result,
Contains 59.9% peroxy bond-containing copolymer, 25
A clear solution was obtained with a viscosity of 4.3 poise at °C. (B) Production of block copolymer solution 170 parts of the peroxy bond-containing copolymer solution of (A) above was charged into the same reactor as above (A), and methacrylic acid was added thereto at 75°C while blowing nitrogen gas. A mixture consisting of 69.8 parts of ethyl acid, 7.3 parts of hydroxypropyl methacrylate, 2.9 parts of methacrylic acid, and 20 parts of ethyl acetate was added dropwise over 1.5 hours.
The polymerization reaction was carried out at 80°C for 4 hours to obtain a transparent solution of the block copolymer. (C) Production of non-aqueous polymer dispersion By adding 100 parts of ethyl alcohol to the total amount of the block copolymer solution obtained in (B) above and mixing, a milky white non-aqueous polymer dispersion is produced. Obtained. This dispersion contained 49.2% block copolymer, had a viscosity of 1.6 poise at 25°C, and
The dispersion state remained stable even after being left for 6 months at 0.degree. C., and no particle sedimentation, phase separation, or viscosity change was observed. When this dispersion was subjected to a coating test in the same manner as in Example 1, the coating film was smooth and glossy, and no phenomena of foaming or sagging were observed. Example 3 (A) Production of peroxy bond-containing copolymer solution According to the method of Example 2 (A), A peroxy bond-containing copolymer solution was produced using the following method. This solution contained 59.6% of the peroxy bond-containing copolymer and was a clear solution with a viscosity of 5.8 poise at 25°C. (B) Production of block copolymer solution Peroxy bond-containing copolymer solution of (A) above
A block copolymer solution was prepared according to the method of Example 2(B) using a mixed solution consisting of 170 parts of n-butyl methacrylate, 80 parts of methyl isobutyl ketone, and 20 parts of methyl isobutyl ketone. (C) Production of non-aqueous polymer dispersion By adding and mixing 100 parts of mineral spirits to the total amount of the block copolymer solution obtained in (B) above, a milky white non-aqueous polymer dispersion is prepared. I got it. This dispersion contains 49.0% block copolymer and has a viscosity of 2.0 poise at 25°C.
The dispersion state remained stable even after being left for 6 months at 0.degree. C., and no particle sedimentation, phase separation, or viscosity change was observed. When this dispersion was subjected to a coating test in the same manner as in Example 1, the coating film was smooth and glossy, and no phenomena of foaming or sagging were observed. Examples 4 to 7 (A) Production of peroxy bond-containing copolymer solution The method of Example 1 (A) was followed using the charging composition shown in each column (A) of Examples 4 to 7 in Table 2. Each peroxy bond-containing copolymer solution was produced. Each of the solutions contained a peroxy bond-containing copolymer at a content as shown in Table 2, and a second
It was a clear solution with a viscosity as shown in the table. (B) Production of block copolymer solution Using the peroxy bond-containing copolymer solution obtained in (A) above, the method of Example 1 (B) was carried out with the charging composition shown in column (B) of Table 2. A block copolymer solution was prepared according to the method described in . (C) Production of non-aqueous polymer dispersion By adding and mixing an organic liquid as shown in column (C) of Table 2 to the total amount of the block copolymer solution obtained in (B) above, A milky white non-aqueous polymer dispersion was obtained. The content of the block copolymer in this dispersion and the viscosity of the dispersion are as shown in Table 2.
Even after being left at 25°C for 6 months, the dispersion state remained stable, with no particle sedimentation, phase separation, or viscosity change observed. When this dispersion was subjected to a coating test in the same manner as in Example 1, the coating film was smooth and glossy, and no phenomena of foaming or sagging were observed.

【table】

[Table] Examples 8 and 9 (A) Production of peroxy bond-containing copolymer solution Copolymerization reaction of Example 8 with the charging composition shown in column (A) of Examples 8 and 9 in Table 3. Each peroxy bond-containing copolymer solution was produced according to the method of Example 1(A), with the polymerization temperature of 90° C. and the polymerization temperature of the copolymerization reaction of Example 9 of 100° C.
Each of the solutions contained the peroxy bond-containing copolymer at the content shown in Table 3, and was a transparent solution having a viscosity shown in Table 3. (B) Production of block copolymer solution Using the peroxy bond-containing copolymer solution obtained in (A) above, the block copolymerization of Example 8 was carried out with the charging composition shown in column (B) of Table 3. A block copolymer solution was prepared according to the method of Example 1(B), with the polymerization temperature of the reaction being 95°C and the polymerization temperature of the block copolymerization reaction of Example 9 being 105°C. (C) Production of non-aqueous polymer dispersion The entire amount of the block copolymer solution obtained in (B) above is subjected to a freeze-drying method to contain the amount of the non-aqueous polymer dispersion added in the step (A) above. The organic liquid was frozen and released and separated and removed from the system by suction under reduced pressure to obtain a block copolymer. Next, by adding and mixing the organic liquid shown in column (C) of Table 3 (the organic liquid defined in (b) above) to the block copolymer, the desired milky white non-aqueous polymer dispersion is obtained. I got it. The content of the block copolymer in this dispersion and the viscosity of the dispersion are as shown in Table 3.
Even after being left for 6 months, the dispersion state remained stable, with no particle sedimentation, phase separation, or viscosity change observed. When this dispersion was subjected to a coating test in the same manner as in Example 1, the coating film was smooth and glossy, and no phenomena of foaming or sagging were observed.

【table】

【table】

Claims (1)

[Claims] 1 General formula () [In the formula, R ₁ represents an alkylene group or substituted alkylene group having 1 to 18 carbon atoms, a cycloalkylene group or substituted cycloalkylene group having 3 to 15 carbon atoms, or a phenylene group or substituted phenylene group, and R ₂ represents an alkylene group having 2 to 18 carbon atoms or a substituted cycloalkylene group, ~10 alkylene groups or substituted alkylene groups, [Formula] (wherein R ₃ is a hydrogen atom or a methyl group, R ₄ is an alkylene group or substituted alkylene group having 2 to 10 carbon atoms, and m is 1 ~13 integers),
Represents [formula] or [formula]. Moreover, n is 2-20. ] and the general formula () [In the formula, R ₁ and n are the same as in the above general formula (). ] and one or more polymeric peroxides selected from the group consisting of polymeric peroxides shown in
The peroxy bond-containing copolymer is copolymerized with at least one vinyl type monomer in an organic liquid defined in (a) below to obtain the organic liquid solution of the peroxy bond-containing copolymer, and then the peroxy bond-containing copolymer is copolymerized with In the polymer solution, one or more vinyl monomers different from the one or more vinyl monomers mentioned above or the other vinyl monomers and the following (a) are added. Adding a mixture with a defined organic liquid to perform block copolymerization of the peroxy bond-containing copolymer and the other vinyl monomer to obtain a solution of the block copolymer in the organic liquid; A method for producing a non-aqueous polymer dispersion, which comprises mixing the block copolymer solution with an organic liquid defined in (b) below. (b) A polymer of one or more vinyl monomers to be copolymerized with the polymeric peroxide and one or more vinyl monomers to be block copolymerized with the peroxy bond-containing copolymer. An organic liquid that exhibits solubility in any polymer of one or more vinyl monomers different from the vinyl monomer. (b) The above-mentioned 1 shows insolubility in the polymer of one or more vinyl monomers to be copolymerized with the polymeric peroxide, and is block copolymerized with the peroxy bond-containing copolymer.
An organic liquid that exhibits solubility in a polymer of one or more vinyl type monomers different from the species or two or more vinyl type monomers. 2 General formula () [In the formula, R ₁ represents an alkylene group or substituted alkylene group having 1 to 18 carbon atoms, a cycloalkylene group or substituted cycloalkylene group having 3 to 15 carbon atoms, or a phenylene group or substituted phenylene group, and R ₂ represents an alkylene group having 2 to 18 carbon atoms or a substituted cycloalkylene group, ~10 alkylene groups or substituted alkylene groups, [Formula] (wherein R ₃ is a hydrogen atom or a methyl group, R ₄ is an alkylene group or substituted alkylene group having 2 to 10 carbon atoms, and m is 1 ~13 integers),
Represents [formula] or [formula]. Moreover, n is 2-20. ] and the general formula () [In the formula, R ₁ and n are the same as in the above general formula (). ] and one or more polymeric peroxides selected from the group consisting of polymeric peroxides shown in
The peroxy bond-containing copolymer is copolymerized with at least one vinyl type monomer in an organic liquid defined in (a) below to obtain the organic liquid solution of the peroxy bond-containing copolymer, and then the peroxy bond-containing copolymer is copolymerized with In the polymer solution, one or more vinyl monomers different from the one or more vinyl monomers mentioned above or the other vinyl monomers and the following (a) are added. Adding a mixture with a defined organic liquid to perform block copolymerization of the peroxy bond-containing copolymer and the other vinyl monomer to obtain a solution of the block copolymer in the organic liquid; The organic liquid defined in (a) below contained in the block copolymer solution is separated and removed by a conventional method, and the organic liquid defined in (b) below is mixed therein. A method for producing a non-aqueous polymer dispersion. (b) A polymer of one or more vinyl monomers to be copolymerized with the polymeric peroxide and one or more vinyl monomers to be block copolymerized with the peroxy bond-containing copolymer. An organic liquid that exhibits solubility in any polymer of one or more vinyl monomers different from the vinyl monomer. (b) The above-mentioned 1 shows insolubility in the polymer of one or more vinyl monomers to be copolymerized with the polymeric peroxide, and is block copolymerized with the peroxy bond-containing copolymer.
An organic liquid that exhibits solubility in a polymer of one or more vinyl type monomers different from the species or two or more vinyl type monomers.