JPS6248964B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention focuses on bonding (grafting) of vinyl polymers.
The present invention relates to a resin composition emulsion containing cellulose ester. A method for producing an emulsion containing a cellulose derivative is disclosed in JP-A-51-28188, and the coating film of the emulsion containing nitrified cotton obtained by this method has excellent gasoline resistance, abrasiveness, and gloss, and is resistant to It has properties not found in conventional emulsion coatings in terms of blocking properties. However, the strength of the coating film is low and it is prone to cracks and breaks, which limits the range of applications. Furthermore, emulsions obtained by this method using cellulose derivatives other than nitrified cotton, such as cellulose acetate butyrate and cellulose acetate propionate, are usually
A heterogeneous emulsion is formed in which only the cellulose derivative is released from the radically polymerizable unsaturated monomer that is added to the polymerization system together with these cellulose derivatives, or a polymer from the radically polymerizable unsaturated monomer and the cellulose derivative are combined. The mixing ratio of the radically polymerizable unsaturated monomer and the cellulose derivative is significantly different from the mixing ratio of the radically polymerizable unsaturated monomer and the cellulose derivative at the time of charging into the polymerization system, and the agglomerated particles in which the cellulose derivative accounts for the majority and the radically polymerizable unsaturated monomer The drawback is that it results in a non-uniform emulsion consisting mostly of polymer particles. At this time, if special consideration is given to improving the emulsification dispersibility, a seemingly uniform emulsion may be obtained; however,
The coating film has poor gloss, is opaque, and is brittle, so it cannot be put to practical use. Therefore, the present inventors improved the above drawbacks,
In order to obtain a cellulose derivative-containing emulsion that provides a transparent, glossy, and tough coating film, we conducted intensive research and bonded (grafted) a vinyl polymer to a cellulose ester through an intermolecular reaction.
The inventors have discovered that by using this graft type cellulose ester, it is possible to obtain a high-performance resin composition emulsion that does not have the above-mentioned drawbacks, and have completed the present invention. According to the present invention, epoxy groups, carboxyl groups, acid halides, acid anhydrides, isocyanate groups,
At least one selected from active halogen, N-methylol group and N-methylol ether group
At least one type of cellulose ester bonded (grafted) with a vinyl type polymer obtained by intermolecular reaction between a vinyl type polymer having various functional groups and a cellulose ester, and at least one type of radically polymerizable inorganic polymer. A mixture consisting of a saturated monomer,
A resin composition emulsion obtained by emulsion polymerization in an aqueous medium in the presence of a dispersion stabilizer is provided. In the resin composition emulsion of the present invention, since the vinyl polymer is bonded to the cellulose ester, the vinyl polymer is produced from the radically polymerizable unsaturated monomer used in the present invention. By selecting a vinyl polymer that has good compatibility with the polymer, it is possible to make a polymer made from a simple cellulose ester radically polymerizable unsaturated monomer without bonding such a vinyl polymer. This results in a much better compatibility compared to the compatibility. The vinyl polymer graft type cellulose ester used in the present invention has good compatibility with both the cellulose ester and the polymer made from the above-mentioned radically polymerizable unsaturated monomer. Even if a simple cellulose ester that is not grafted is mixed at the same time as a cellulose ester that is grafted with a vinyl polymer, the compatibility with the polymer from the radically polymerizable unsaturated monomer is improved through the mediation of the grafted cellulose ester. The mixing condition becomes better. The vinyl polymer graft type cellulose ester (hereinafter sometimes abbreviated as "grafted product") of the present invention is slightly different from ordinary cellulose ester grafted products. In ordinary graft polymers, radicals are generated in the main polymer (cellulose ester) by some method, and from these radicals (active sites) branch polymers made of polymerized monomers grow, but in the vinyl polymer of the present invention, Polymer-grafted cellulose esters undergo an intermolecular reaction between the cellulose ester and the functional groups in the vinyl polymer, so the functional groups of the vinyl polymer are rarely located at the ends, and the vinyl polymer chain is Since it often exists in the middle, it has the characteristic that the cellulose ester and the vinyl polymer are often bonded in the form of a cross. According to such a structure between the graft bodies of the present invention, it is easy to control the composition and molecular weight of the vinyl polymer, and since the reaction between the polymers is forced, reliable production of the graft body can be expected. In the present invention, by using this graft body, each polymer (cellulose ester, graft body, polymer from monomer)
The polymers are well compatible with each other, and the respective polymers are well mixed and dispersed with each other. Furthermore, the mixture of this grafted material and the radically polymerizable unsaturated monomer becomes finer than the mixture of the cellulose ester and the radically polymerizable unsaturated monomer that are not grafted by the dispersion stabilizer. It is dispersed and forms a good emulsion.
The resulting cellulose ester-containing emulsion therefore provides sufficient film strength and good film gloss compared to conventional emulsions of this type. Moreover, the resin composition emulsion of the present invention is
Emulsion containing cellulose ester does not have the sticky feeling on the coating surface of the coated object, has a good texture, and has excellent gasoline resistance and abrasiveness, and is suitable for use on wood, paper, metal, and leather. It is expected to be used as a paint for plastics, buildings, etc., as well as in printing inks, adhesives, molding materials, and resin additives. Vinyl polymer having at least one functional group selected from the group of epoxy group, carboxyl group, acid halide, acid anhydride, isocyanate group, active halogen, N-methylol group and N-methylol ether group of the present invention. A polymer is a polymer composed of one or more radically polymerizable unsaturated monomers, and at least one functional group selected from the above group of functional groups is present in the polymer chain. It is a polymer with Vinyl polymers having such functional groups include polymers produced from radically polymerizable unsaturated monomers and into which functional groups such as those described above are introduced by post-treatment such as hydrolysis. However, vinyl polymers having the desired functional groups are usually produced by introducing functional groups through homopolymerization or copolymerization of radically polymerizable unsaturated monomers having these functional groups. There are many cases. The radically polymerizable unsaturated monomers used in the production of vinyl polymers having the above-mentioned functional groups are particularly limited as long as they have a radically polymerizable ethylenically unsaturated bond (>C=C<). However, some typical examples are as follows. (i) General formula of esters of acrylic acid or methacrylic acid

[Formula], R is hydrogen or a methyl group, R ₁ is a C _1-20 alkyl group,
_C5-6 cycloalkyl group, methoxybutyl, ethoxybutyl, phenyl, benzyl, allyl,
_C2-8 hydroxyalkyl, dicyclopentynyl, polyethylene glycol, etc. (ii) Amides of acrylic acid or methacrylic acid, such as acrylamide, N-methylolacrylamide, etc. (iii) Vinyl aromatic compounds

[Formula] R ₂ is hydrogen or methyl group X is hydrogen, methyl group, halogen, nitro group, amino group, N (alkyl) ₂ group, etc. (iv) Others: vinyl acetate, ethylene, butadiene, chloroprene, isoprene, acrylonitrile , vinyl chloride, carboxylic acid vinyl ester, etc.(v) Vinyl monomers with functional groups Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, acrylic acid chloride, methacrylic acid bromide, acrylic acid, methacrylic acid, maleic anhydride, fumaric acid etc. These unsaturated monomers may be used alone or in combination of two or more. As an example of use alone, a carboxyl group may be introduced by partially hydrolyzing a homopolymer of acrylic esters or methacrylic esters. Using the above-mentioned monomers, polymerization is carried out by a polymerization method known per se, for example, solution polymerization, suspension polymerization, emulsion polymerization, etc., and by performing necessary post-treatment, the functional group of the present invention is prepared. It is possible to produce a vinyl polymer having the following. Among these polymerization methods, solution polymerization is preferably carried out in a suitable inert solvent in the presence of a polymerization initiator (polymerization catalyst), usually from 0 to about 200°C, preferably from 30°C to 150
℃ (0° to 90°C, preferably 30°C to 80°C when using an unsaturated monomer having an epoxy group) for about 0.5 to 20 hours, preferably about 2 to 10 hours. This can be done by letting The solvent to be used is preferably one that dissolves the polymer to be produced. If a monomer having an epoxy group or an acid halide functional group is used, a solvent that does not have active hydrogen should be selected to dissolve the functional group. It is desirable to prevent deterioration of the group. Further, as the polymerization catalyst, any known polymerization catalyst may be used, such as an azo compound, an organic peroxide,
Common radical initiators are used, such as sulfides, sulfines, nitroso compounds, etc. Further, as a chain transfer agent, generally known mercaptans, α-methylstyrene dimer, etc. are used. The molecular weight of the vinyl polymer having functional groups produced in this way is about 300 to about 200,000,
Preferably it is about 300 to 20,000. This is because the molecular weight is
This is because if it is larger than 200,000, the cellulose content will decrease when using this vinyl polymer-bonded cellulose ester. The number of functional groups in one molecule is preferably 1 for epoxy groups and acid halides, and 1 or more for acids and acid anhydrides. For epoxy groups and acid halides, 0.5
It can be adjusted to ~1.0. The cellulose ester of the present invention to be reacted with a functional group-containing vinyl polymer includes at least one of the functional group groups of the vinyl polymer described above.
Nitrocellulose, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, cellulose acetate, cellulose propionate are not particularly limited as long as they have a functional group such as a hydroxyl group, carboxyl group, or amino group that can react with , cellulose butyrate, cellulose phosphate, cellulose sulfate, and the like. Note that the molecular weight and degree of substitution of the cellulose ester are not particularly limited. Bonding (grafting) of vinyl polymer of the present invention
The cellulose ester can be synthesized by mixing the vinyl polymer having a functional group and the cellulose ester and reacting the mixture at 0°C to 200°C.
Generally, a solution polymer of a vinyl polymer having a functional group and a solution of cellulose ester are mixed, a temperature suitable for the reaction is set in the range of 0°C to 200°C, and the temperature is set for 1 minute to about 200°C. By reacting for 5 hours, a cellulose ester to which a vinyl polymer is bonded can be obtained, but the method is not limited to this method. For example, a solvent-free vinyl polymer having a functional group and a cellulose ester, And, if necessary, it can also be produced by melt-mixing a cellulose ester plasticizer using a conventional mixing device such as a hot roll, a Banbury mixer, or an extruder. Further, in the synthesis of cellulose ester bonded with a vinyl polymer, the mixing method and reaction time are not particularly limited. Furthermore, there is no particular problem in adding a reaction accelerator as necessary during this synthesis. In the present invention, at least one radically polymerizable unsaturated monomer used as a mixture with the vinyl polymer-bonded cellulose ester is
There are no particular restrictions on the monomer as long as it has a radically polymerizable ethylenically unsaturated bond, and all unsaturated monomers as described above for the production of vinyl polymers having functional groups are suitable. Next, the dispersion stabilizer used in the present invention is prepared by adding a mixture of at least one type of cellulose ester bonded to a vinyl polymer and at least one type of radically polymerizable unsaturated monomer in an aqueous medium. It is not particularly limited as long as it can be emulsified and dispersed and can stably maintain the emulsion obtained by emulsion polymerization, including anionic, nonionic, and cationic surfactants, amphoteric surfactants, etc. surfactants, organic protective colloids, hydrophilic or water-soluble resins, etc. Typical dispersion stabilizers are shown below. (i) Anionic surfactants Carboxylates (e.g. fatty acid soaps, etc.), sulfates (e.g. sodium lauryl sulfate, etc.), sulfated natural oils and esters (e.g. alkylaryl polyether sulfates, etc.), sulfonates (e.g. alkylaryl polyether sulfonates, isopropylnaphthalene sulfonates, etc.), sulfosuccinates and sulfosuccinamates, phosphate esters (such as partial esters of short chain aliphatic alcohols of complex phosphates, etc.), and orthophosphate esters of polyethoxylated aliphatic alcohols. etc. are included. These anionic surfactants are often used in the form of alkali metal, ammonium or amine salts. (ii) Nonionic surfactants Ethylene oxide derivatized monohydric and polyhydric alcohols, ethylene oxide/propylene oxide block copolymers, esters (e.g. glyceryl monostearate) dehydration products of sorbitol (sorbitan monostearate, etc.) ), amides (for example, lauric acid isopropanolamide), and the like. (iii) Cationic surfactants include, for example, lauryldimethylbenzylammonium chloride, N(laurylcolamine formylmethyl)pyridinium chloride, and other amine salts and quaternary ammonium salts. (iv) Organic protective colloids include, for example, polyvinyl alcohol, hydroxyethyl and hydroxypropyl cellulose, sodium salts of carboxymethyl cellulose, alginates, polysaccharides, and the like. (v) Hydrophilic or water-soluble resins For example, water-soluble acrylic resins, maleated polybutadiene, maleated oils, maleated alkyd resins, polymers of water-soluble acrylic resins and vinyl resins having functional groups (e.g. epoxy groups) This includes intermediate reaction products, etc. The above dispersion stabilizers can be used alone or in combination of two or more. The amount of dispersion stabilizer used is usually about
It is generally 0.1 to 20%, but is not particularly limited. A mixture consisting of at least one cellulose ester bonded (grafted) with a vinyl polymer and at least one radically polymerizable unsaturated monomer is emulsion polymerized in an aqueous medium in the presence of a dispersion stabilizer. Generally known polymerization catalysts (radical initiators) and chain transfer agents may be used, and their amounts are not particularly limited. The above-mentioned cellulose ester bound (grafted) with a vinyl polymer may contain terminally reacted cellulose ester due to its synthesis method.
The cellulose ester bonded (grafted) with the vinyl polymer is sufficient to mediate the miscibility of the unreacted cellulose derivative with the polymer from at least one radically polymerizable unsaturated monomer to be mixed. A good compatibility state is obtained. Therefore, if necessary, unreacted cellulose ester of the same type as the cellulose ester bonded (grafted) with vinyl polymer is added, and the unreacted cellulose ester,
The present invention also includes an emulsion composition obtained by emulsion polymerization of a mixture of a cellulose ester bonded (grafted) with a vinyl polymer and a radically polymerizable unsaturated monomer. Furthermore, when performing emulsion polymerization, in addition to the above-mentioned mixture, there is no problem in adding a solvent, a plasticizer, etc. as a film forming aid to the emulsion polymerization system. The coating film from the resin composition emulsion thus obtained is different from that of conventional cellulose because the compatibility between the cellulose ester and the polymer from the unsaturated monomer is increased and they are well dispersed in each other. It is tougher and has better gloss than coatings made from ester-containing emulsions, and can be widely applied to fields such as general-purpose paints, adhesives, resin processing additives, and molding plastics. Furthermore, if necessary, film-forming aids, plasticizers, dyes and pigments, antifoaming agents, rust preventive agents, antifungal agents, water-soluble resins, crosslinking agents such as melamine, etc. are usually used in this emulsion composition. It can be contained in the amount. Further, if necessary, other emulsions may be blended and used. Further, the present invention will be explained below with reference to examples. Example 1 (1) 43.5 parts of ethylene glycol monobutyl ether is charged into a reactor equipped with a stirrer, a reflux condenser, and a dropping device under a nitrogen atmosphere and heated to 120°C. In this one, methyl methacrylate 15.1
parts, ethyl acrylate 6.7 parts, acrylic acid 9.4 parts
parts, 17.2 parts of 2-ethylhexyl methacrylate,
A mixture of 2.8 parts of α,α′-azobis(isobutyronitrile) was added dropwise over 2 hours.
One hour after the completion of the dropwise addition, a mixture of 0.4 parts of α,α'-azobis(isobutyronitrile) and 4.9 parts of ethylene glycol monobutyl ether is added. Thereafter, a polymerization reaction was carried out at 120°C for 7 hours.
A water-soluble polymer solution with a solid content of 50.2% was thus obtained. (2) On the other hand, 43.1 parts of ethylene glycol methyl ether acetate was charged into a separate reactor equipped with a stirrer, a reflux condenser, and a dropping device under a nitrogen atmosphere.
Heat to ℃. This product contains methacrylic acid n-
Butyl 47.4 parts, glycidyl methacrylate 1.5 parts
parts, n-dodecyl mercaptan 0.7 parts and α,
A mixture of 2.2 parts of α'-azobis(isobutyronitrile) is added dropwise over 2 hours. One hour after the completion of the dropwise addition, a mixture of 0.4 parts of α,α'-azobis(isobutyronitrile) and 4.7 parts of acetic acid ethylene glycol methyl ether is added. Thereafter, a polymerization reaction is carried out at 70°C for 7 hours. A polymer solution containing epoxy groups with a solids content of 50.6% was thus obtained. (3) Next, add 83.4 parts of the water-soluble polymer solution from (1) above and
16.6 parts of the epoxy group-containing polymer solution of (2) was mixed, heated to 140°C under a nitrogen atmosphere, and reacted for 4 hours. A water-soluble polymer solution with branches bonded by reaction of epoxy and carboxyl groups was thus obtained with a solids content of 50.3%. (4) Meanwhile, 2.4 parts of the epoxy group-containing polymer solution of (2) above, 21.7 parts of xylene, and 3.6 parts of cellulose acetate butyrate (CAB-381 0.1 manufactured by Eastman Chemical Company) were mixed, and The reaction is carried out at ℃ for 4 hours. after that,
Cool to room temperature, add 39.5 parts of water, remove part of the water and xylene by distillation, and cool to room temperature. To this, add 13.8 parts of the water-soluble polymer solution having branches bonded by the reaction between epoxy groups and carboxyl groups, 1.0 part of 25% ammonia water, and n-butyl methacrylate, and add enough Disperse while stirring. An aqueous solution of 0.1 part of potassium persulfate dissolved in 3.5 parts of water is added to the obtained aqueous dispersion, and a polymerization reaction is carried out at 80° C. for 3 hours in a nitrogen atmosphere. Thus, the viscosity
A cellulose ester-containing emulsion composition with a solid content of 380 cps and 39.7% was obtained. The coating film of the emulsion composition was transparent and glossy (60° specular reflectance: 85). The emulsion composition was applied to a glass plate using a 4 mil ablator. The following Examples and Comparative Examples were carried out in the same manner. Example 2 (1) 45.4 parts of ethylene glycol methyl ether acetate is charged into a reactor equipped with a stirrer, a reflux condenser, and a dropping device under a nitrogen atmosphere and heated to 70°C. To this, 47.3 parts of methyl acrylate,
A mixture of 2.4 parts of glycidyl methacrylate, 3.6 parts of α,α'-azobis(isobutyronitrile) and 0.7 parts of n-dodecylmercaptan is added dropwise over 2 hours. 1 hour after the end of dripping, α,
Add 0.6 part of α'-azobis(isobutyronitrile) and carry out a polymerization reaction at 70°C for 7 hours. A polymer solution containing epoxy groups with a solids content of 54.1% was thus obtained. (2) Water-soluble polymer solution obtained in (1) of Example 1
84.3 parts and 15.7 parts of the epoxy group-containing polymer solution of (1) above are mixed, heated to 140° C. under a nitrogen atmosphere, and reacted for 4 hours. Thus the solid content
A water-soluble polymer solution with branches attached by reaction of 50.8% epoxy and carboxyl groups was obtained. (3) Add and dissolve 6.5 parts of the epoxy group-containing polymer solution of (1) above and 23.6 parts of acetic acid ethylene glycol monomethyl ether to 3.5 parts of acetylcellulose (acetylation degree 55%, manufactured by Daicel Chemical Industries, Ltd.). The reaction was then carried out at 140°C for 4 hours under a nitrogen atmosphere. Thereafter, 15.1 parts of the water-soluble polymer solution having branches bonded by the reaction of epoxy groups and carboxyl groups in (2) above was added, and then ethylene glycol monobutyl ether and ethylene glycol methyl ether acetate were separated by vacuum distillation. 28.3 parts of the mixture were removed. In this one, water 33.0
1 part, 0.8 parts of 25% aqueous ammonia, and 14.0 parts of methyl acrylate, and dispersed with thorough stirring. An aqueous solution of 0.1 part of potassium persulfate dissolved in 3.4 parts of water is added to the aqueous dispersion thus obtained, and a polymerization reaction is carried out at 80° C. for 3 hours under a nitrogen atmosphere. Thus, an emulsion composition containing cellulose ester with a viscosity of 580 cps and a solid content of 38.9% was obtained. The coating film of the emulsion composition was transparent and glossy (60° specular reflectance: 76). Example 3 (1) 42.3 parts of ethylene glycol methyl ether acetate is charged into a reactor equipped with a stirrer, a reflux condenser, and a dropping device under a nitrogen atmosphere and heated to 70°C. To this, 33.3 parts of methyl methacrylate,
A mixture of 14.3 parts of 2-ethylhexyl acrylate, 1.8 parts of glycidyl methacrylate, 0.5 parts of n-dodecylmercaptan and 2.7 parts of α,α'-azobis(isobutyronitrile) is added dropwise over 2 hours. 1 hour after the completion of dropping, α, α′-
Add 0.4 parts of azobis(isobutyronitrile) and 4.7 parts of ethylene glycol methyl ether acetate, and then conduct a polymerization reaction at 70°C for 7 hours.
A polymer solution containing epoxy groups with a solids content of 52.1% was thus obtained. (2) Water-soluble polymer solution obtained in (1) of Example 1
83.8 parts and 16.2 parts of the epoxy group-containing polymer solution of (1) above are mixed, heated to 140°C under a nitrogen atmosphere, and reacted for 4 hours. Thus the solid content
A water-soluble polymer solution with branches attached by reaction of 50.5% epoxy and carboxyl groups was obtained. (3) Add 2.6 parts of the epoxy group-containing polymer solution of (1) above and 24.6 parts of acetic acid ethylene glycol methyl ether to 5.9 parts of 30% water-wet nitrified cotton (SS1/4, manufactured by Daicel Chemical Industries, Ltd.). Dissolve and react for 30 minutes at 130°C under nitrogen atmosphere. After that, 15.6 parts of the water-soluble polymer solution having branches bonded by the reaction of the epoxy group and the carboxyl group of (2) above was added, and then by vacuum distillation,
31.4 parts of a mixture of water, ethylene glycol monobutyl ether and acetic acid ethylene glycol methyl ether were removed. In this one, water 33.1
parts, 1.2 parts of 25% aqueous ammonia, 10.5 parts of methyl methacrylate, and 2-ethylhexyl acrylate.
Add 4.5 parts and disperse while stirring well. To the aqueous dispersion thus obtained is added 1.9 parts of an aqueous solution of 0.1 part of potassium persulfate dissolved in 1.9 parts of water, and a polymerization reaction is carried out at 80° C. for 3 hours under a nitrogen atmosphere. Thus, a cellulose ester-containing emulsion composition with a viscosity of 470 cps and a solids content of 39.1% was obtained. The coating film of the emulsion composition was transparent, glossy (60° specular reflectance: 86) and strong. Example 4 30% wet nitrified cotton (SS1/4, Daicel Chemical Industries, Ltd.
7.3 parts of the epoxy group-containing polymer solution obtained in (1) of Example 3, 67.7 parts of ethylene glycol methyl ether acetate, and 8.7 parts of ethylene glycol butyl ether acetate were added to 16.3 parts of Co., Ltd. and dissolved therein. The reaction is carried out for 30 minutes at 130°C under nitrogen atmosphere. Thereafter, 76.9 parts of a mixture of water, ethylene glycol methyl ether acetate, and ethylene glycol butyl acetate were removed by vacuum distillation to obtain an acrylic polymer-modified nitrified cotton solution. Next, the above acrylic polymer modified nitrified cotton solution
15.2 parts, methyl methacrylate 19.0 parts, 2-ethylhexyl acrylate 8.1 parts, methacrylic acid 0.4 parts,
Mix 52.1 parts of water, 1.4 parts of sodium dodecylbenzenesulfonate, 1.4 parts of Gafac RE-610 (anionic complex phosphate ester emulsifier; manufactured by Toho Chemical Industry Co., Ltd.), and 0.5 parts of sodium hydrogen carbonate, and stir thoroughly. Perform dispersion while doing so. An aqueous solution of 0.1 part of potassium persulfate dissolved in 1.8 parts of water is added to the resulting dispersion, and a polymerization reaction is carried out at 80° C. for 3 hours in a nitrogen atmosphere. Thus, a cellulose ester-containing emulsion composition with a viscosity of 50 cps and a solid content of 40.1% was obtained. The coating film of the emulsion composition was transparent and glossy (60° specular reflectance: 85) and tough. Example 5 (1) 47.3 parts of xylene is charged into a reactor equipped with a stirrer, a reflux condenser, and a dropping device under a nitrogen atmosphere and heated to 100°C. A mixture of 48.0 parts of n-butyl methacrylate and 4.2 parts of 4,4'-azobis(cyanobentanoyl chloride) was added dropwise to this mixture over 2 hours. One hour after the completion of the dropwise addition, 0.5 part of 4,4'-azobis(cyanopentanoic acid chloride) was further added, and a polymerization reaction was carried out at 100°C for 5 hours. A polymer solution containing acid chloride groups with a solids content of 52.5% was thus obtained. (2) Polymer solution containing an acid chloride group as described in (1) above
2.3 parts of xylene, 21.7 parts of xylene, and 3.6 parts of cellulose acetate butyrate (CAB-381 0.1, manufactured by Eastman Chemical Company) were mixed, and the mixture was reacted at 80°C for 1 hour under a nitrogen atmosphere. Then, cool to room temperature, add 39.4 parts of water and 1.3 parts of 25% ammonia water.
13.8 parts of the water-soluble polymer solution obtained in Example 1 (3) and having branches bonded by reaction between epoxy groups and carboxyl groups are added. Then some of the water and xylene are removed by distillation and cooled again to room temperature. In this, methacrylic acid n
- Add 14.4 parts of butyl and disperse while stirring well. Add an aqueous solution of 0.1 part of potassium persulfate and 3.4 parts of water to the obtained aqueous dispersion,
The polymerization reaction is carried out at 80° C. for 3 hours under a nitrogen atmosphere.
A cellulose ester-containing emulsion composition with a viscosity of 210 cps and a solids content of 39.5% was thus obtained. The coating film of the emulsion composition was transparent and glossy. (60° specular reflectance; 83). Comparative example 1 Gafac in a KD mill container with jacket
RE-610 (anionic complex phosphate ester emulsifier; manufactured by Toho Chemical Industry Co., Ltd.) 2.0 parts, sodium n-dodecylbenzenesulfonate 1.3 parts, sodium hydrogen carbonate 0.5 parts, water 33.5 parts, methacrylic acid 0.6 parts,
20.6 parts of methyl methacrylate, ethyl acrylate
20.6 parts, hydroquinone monomethyl ether 0.01
and cellulose acetate butyrate (CAB381 0.1, manufactured by Eastman Chemical Company) 13.9
30 minutes were added and the mixture was milled for 30 minutes. This dispersion was charged into a reactor equipped with a stirrer, a reflux condenser, and a dropping device, and 0.03 part of n-dodecyl mercaptan and 0.15% ferric ammonium sulfate were added.
0.01 part of the polymerization initiator mixture was added, followed by 3/5 of the total polymerization initiator mixture of 0.08 part of potassium persulfate, 0.6 part of Triton amount at 71-76℃
dropwise for 118 minutes, then the remainder of the polymerization initiator,
The dispersion was polymerized in a nitrogen atmosphere by adding 0.02 parts of sodium sulfite and 0.02 parts of sodium sulfite at 75-76°C for 45 minutes. The polymerization solution produced many grits, which were unstable and agglomerated during the polymerization. Comparative Example 2 In a reactor equipped with a stirrer, a reflux condenser, and a dropping device, 3.5 parts of Gafac RE-610, 3.5 parts of sodium n-dodecylbenzenesulfonate, 0.8 parts of sodium bicarbonate, and acetyl cellulose (degree of acetylation 55
%, manufactured by Daicel Chemical Industries, Ltd.) 5.1 parts, water 55.5 parts,
1.5 parts of 25% aqueous ammonia and methyl acrylate
Add 25.2 parts and mix, stirring well to disperse. An aqueous solution of 0.1 part of potassium persulfate dissolved in 4.8 parts of water was added to the resulting dispersion, and a polymerization reaction was carried out at 80°C in a nitrogen atmosphere, but grit was formed and the polymer and water separated. , it was difficult to continue the polymerization any further. Comparative Example 3 In a reactor equipped with a stirrer, a reflux condenser, and a dropping device, 9.3 parts of 30% water-wet nitrified cotton (SS1/4, manufactured by Daicel Chemical Industries, Ltd.), 22.5 parts of methyl methacrylate,
2-ethylhexyl acrylate 12.2 parts, methacrylic acid 0.3 parts, water 50.8 parts, sodium hydrogen carbonate 0.6 parts
parts, sodium dodecylbenzenesulfonate 1.3
1 part and 1.3 parts of Gafac RE-610, and disperse with thorough stirring. An aqueous solution of 0.1 part of potassium persulfate dissolved in 1.6 parts of water is added to the obtained aqueous dispersion, and a polymerization reaction is carried out at 80° C. for 3 hours in a nitrogen atmosphere. Thus, a cellulose ester-containing emulsion composition with a viscosity of 20 cps and a solid content of 43.8% was obtained. The coating film of the emulsion composition was transparent and glossy (60° specular reflectance: 85). However, the coating film was quite brittle.

Claims (1)

[Claims] 1 Epoxy group, carboxyl group, acid halide,
Acid anhydride, isocyanate group, active halogen, N
- A cellulose ester bonded to a vinyl polymer, obtained by intermolecular reaction of a vinyl polymer having at least one functional group selected from methylol groups and N-methylol ether groups and a cellulose ester. and at least one radically polymerizable unsaturated monomer, is emulsion-polymerized in an aqueous medium in the presence of a dispersion stabilizer.