JP2899905B2 - Non-aqueous resin dispersion and method for producing the same - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a resin dispersion using a non-aqueous solvent as a polymerization solvent and a method for producing the same, and more particularly, to treatment of fibers, paper, plastic surfaces, metal surfaces, etc. The present invention relates to a resin useful for an agent, a printing ink, an electrophotographic toner, a paint, a rubber roller material, a rubber roller coating material, and the like, and a method for producing the same.

[Conventional technology]

Many are known regarding non-aqueous resins (non-aqueous resin dispersions) and methods for producing the same.
JP-B-40-19186, JP-B-45-14545, JP-B-56-91
Publications such as 89.

By the way, the polymerization solvents described in these documents include aromatic hydrocarbons such as toluene, xylene, and benzene, esters, alcohols, n-hexane isododecane, and Isopar H, G, L, V, etc. of Ecrin Chemical Company. Aliphatic hydrocarbons and the like are used. These polymerization solvents are advantageous in that they are inexpensive, have excellent resin solubility, and have good volatility. However, it has the disadvantages of being highly toxic, flammable, and having a low boiling point, which limits the temperature during polymerization. In addition, when heat polymerization is performed as in the case of an aliphatic hydrocarbon solvent, the solvent may be oxidized and the odor may be increased. Furthermore, the conventional polymerization solvent has a high solubility of the resin, so to separate the resin from the polymerization solvent, a heat drying method,
It depends on the vacuum drying method and the method of precipitating the resin in a poor solvent.

In addition, since the polymerization rate of the monomer is low, it is a fact that the polymerized resin cannot expect much improvement in characteristics such as water / oil repellency and high electric resistance.

[Problems to be solved by the invention]

An object of the present invention is to provide a resin composition which is odorless, has high safety, is excellent in water / oil repellency and electric insulation, and can be easily separated from a polymerization solvent. Another object of the present invention is to provide a method for producing a non-aqueous resin dispersion in which the production process is simple, the reaction time is short, the productivity is high, and the dispersion is high and the dispersion is small.

[Means for solving the problem]

A first aspect of the present invention is characterized by comprising a non-aqueous solvent containing at least silicone oil, at least one resin hardly soluble or insoluble in the solvent, and a polymer obtained from at least one monomer in which the resin is soluble. Is a non-aqueous resin dispersion.

A second aspect of the present invention is to prepare a mixture containing at least one resin hardly soluble or insoluble in a non-aqueous solvent containing at least silicone oil and at least one monomer in which the resin is soluble, and then preparing the mixture. The method for producing a non-aqueous resin dispersion according to claim 1, wherein the polymerization is carried out in the presence of a non-aqueous solvent containing at least silicone oil.

Other conditions can be variously changed in such a gist. For example, the monomer can be polymerized while dropping the monomer solution in which the resin is dissolved into the above-mentioned non-aqueous solvent (a non-aqueous solvent containing at least silicone oil). It is also possible to directly polymerize, with or without addition, and then disperse the polymerization mixture in a non-aqueous solvent containing at least silicone oil to obtain the desired product.

Further, the dispersion of the present invention may contain, if necessary, a waxy substance or a polyolefin having a softening point of about 60 ° C to 130 ° C. In this case, these substances are added to the monomer solution before polymerization. To the dispersion obtained during or after the polymerization to enhance dispersibility.

Although various methods can be selected as the polymerization method, to perform the heat polymerization, a normal polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile is added to a monomer solution containing at least silicone oil or a non-aqueous solvent. It is preferably present and is carried out at a temperature of about 70-110 ° C.

The resin and monomer as raw materials can be selected singly or plurally. However, since the resin does not dissolve in a non-aqueous solvent (a non-aqueous solvent containing at least silicone oil), the monomer is polymerized and then precipitated in a dispersion. ing.

Silicone oils are known to have good heat resistance and acid resistance, small viscosity and temperature change, low surface tension, excellent electrical insulation, water and oil repellency, defoaming properties, and mold release properties. Therefore, it has different characteristics from various solvents, natural mineral oils, and animal and vegetable oils. Due to these characteristics, silicone oil has many applications such as transformers, capacitors, electronic equipment parts, moisture-proof fillers for transistors, heat transfer media, water and oil repellents, mold release agents, and defoamers.

Nevertheless, there has been no report on the application of silicone oil to a polymerization solvent. This is because silicone oil itself is a resin, the price of silicone oil is more expensive than general organic solvents, and the properties of polymers using silicone oil have not been measured. It seems to be because.

The present inventors have conducted research on a silicone oil as a polymerization solvent, and have found the following features and effects. In particular, improvements in the polymerization rate, water repellency, oil repellency, and electrical insulation were observed. This is considered to be because the purity of the silicone oil is higher than that of a general organic solvent, so that radicals are hardly trapped in the polymerization solvent. In addition, the oil repellency, water repellency, and electrical insulation properties of the obtained resin are improved because the silicone oil as the polymerization solvent partially participates in the reaction of the monomer during polymerization (hydrogen abstraction from the methyl group of the silicone oil). It is also conceivable to carry out polymerization by reaction.

Furthermore, silicone oils as polymerization media generally have low solubility. Therefore, the solubility of the resin polymerized in the silicone solvent is poor, so that the resin is easily separated from the polymerization solvent. For example, polylauryl methacrylate polymerized in toluene is sticky even after removing toluene, whereas polylauryl methacrylate polymerized in silicone oil solvent is not sticky even after removing silicone oil and obtains a plastic resin. I can do it. Of course, a polymerization solvent other than silicone oil may be mixed and used.

Silicone oils include dimethyl silicone oil, higher fatty acid modified silicone oil, methyl chlorinated phenyl silicone oil, alkyl modified silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, cyclic polydimethyl siloxane, amino modified silicone oil, epoxy modified And silicone oil.

Some examples of the viscosity (cs: centistokes) of the dialkyl silicone oil are as follows.

In addition, as commercial products of such silicone oil,
Here are some examples:

Shin-Etsu Chemical KF-96L 0.65 (cs), 1.0 (cs), 1.5 (cs), 2.0 (cs) KF-96 10 (cs), 20 (cs), 30 (cs), 50 ( cs), 500 (cs), 1000
(Cs), 3000 (cs) KF-56 KF-58 KF-54, etc.

TSF 451 series TSF 456 series TSF 410,411,440,4420,484,483,431,433 THF 450 series, TSF404,405,406,451-5A, 451-10A, 43 manufactured by Toshiba Silicone Co., Ltd.
7 TSF 4440,400,401,4300,4445,4700,4450,4702,4730 TSF 434,4600 etc.

 HS-200 manufactured by Toray Silicone Co., Ltd.

A polymerization initiator is used to form a polymer by polymerization, which includes benzoyl peroxide, lauryl peroxide, ditertiary butyl peroxide, cumene hydroperoxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, Azobisisobutyronitrile can be exemplified. Further, if necessary, dimethylaniline, pyridine, Co as promoters ^- or Mn ^- naphthenates the like.

Furthermore, in addition to the silicone oil, as a mixed polymerization solvent added as needed, toluene, xylene, aromatic solvents such as benzene, ethers, esters, alcohol solvents, n-hexane, n-octane and iso-octane, Examples include iso-dodecane, aliphatic hydrocarbons such as Isopar H, G, L, and V manufactured by Exxon Chemical Company, water, and the like. Solvent / monomer / polymerization initiator is 10 ~ 90/10 ~ 9
It is used at a polymerization ratio of 0 / 0.001 to 5.

Thus, a dispersion containing a resin substantially insoluble in a non-aqueous solvent (a non-aqueous solvent containing at least silicone oil) and a polymer solvated with the non-aqueous solvent is obtained. The resin substantially insoluble in the non-aqueous solvent contained in the dispersion also acts as a dispersion stabilizer, and the resin that solvates with the non-aqueous solvent depends on the type, amount, and polymerization conditions of the materials used. (temperature,
In general, the particle size is small, the specific gravity is close to that of the dispersion medium, so that the dispersion stability is good and the aggregation is difficult. For example, it is stable in a dispersion having a solid content of 15% for 3 years or more. . In addition, since this solvating resin has a dispersion stabilizing action, a polarity controlling action and a fixing property, it is well adsorbed by various pigments such as TiO ₂ , CaCO ₃ , SiO ₂ , carbon, etc. It is suitable for electrophotographic toners or paints because it maintains the clearness, stably disperses the pigment, and firmly adheres to paper, plastic plates, metal plates and the like.

In addition, the properties of such a solvating resin can be changed by using a wax-like substance or a polyolefin as described above or in combination with another monomer as described later. When a wax-like substance or a polyolefin is used in combination, it is found that these substances precipitate in the polymerization system in the form of fine particles by rapid cooling, and are dispersed in the polymer (or copolymer) during the precipitation. In addition, the dispersibility of the dispersion can be more effectively improved.

Ester gum as a resin substantially insoluble in non-aqueous solvents,
Suitable are natural resins such as cured rosin, and natural resin-modified thermosetting resins such as natural resin-modified maleic acid resin, natural resin-modified phenolic resin, natural resin-modified polyester resin, and natural resin-modified pentaerythritol resin. One or more of these resins are used. The following are commercially available products.

Examples of natural resin modified maleic resin MRG, MRG-411, MRG-S, MRG-E, MRA-L, MRM-42, MRM-5
3 (manufactured by Tokushima Essential Oil Co., Ltd.), Beccasite 1110, 1111,
F231, J811, 1120, P-720, J-898 (all manufactured by Dainippon Ink and Chemicals, Inc.) Examples of natural resin-modified phenolic resins PRG, PRP, SPR-N, SPR-A, SPR-H ( Tokushima Essential Oil Co., Ltd.), Beccasite 1100, 1123, 1126, F-171
Examples of natural resin-modified pentaerythritol resins Pentasite P-406 and P-423 (both manufactured by Dainippon Ink and Chemicals) Examples of natural resin-modified polyester resins RM-1000, RM-1300 , RM-4090, RM-4100 (all manufactured by Tokushima Essential Oil Co., Ltd.) Examples of ester gum EG-8000, EG-9000, HG-H, PE, PE-H (all manufactured by Tokushima Essential Oil Co., Ltd.) Examples of hardened rosin TLR-21 , TLR-37 (manufactured by Tokushima Essential Oil Co., Ltd.) The monomer constituting the polymer (or copolymer) solvable in a non-aqueous solvent is represented by the general formula [R is -H or -CH ₃ radical, A is -COOC _n H _{2n + 1} or -OC _n H
_{2n + 1} group (n is an integer of 6-20) vinyl monomer represented by represents a] (e.g. stearyl acrylate or methacrylate, lauryl, 2-ethylhexyl, or hexyl ester; t-butyl methacrylate; cetyl methacrylate octyl methacrylate ; Vinyl stearate)
(Hereinafter referred to as “monomer A”). As the monomer A, one or more of glycidyl methacrylate, glycidyl acrylate, propylene glycol monoacrylate, propylene glycol methacrylate, hydroxyethyl methacrylate, acrylonitrile, and methacrylonitrile (hereinafter, referred to as “monomer B”) can be mixed and used. After the polymerization of the monomer A, the monomer B may be added and copolymerized.

These monomers B dissolve the resin substantially insoluble in the non-aqueous solvent, and copolymerize with the monomer A in the presence of the polymerization initiator, but when polymerized alone, solvate with the non-aqueous solvent. It is not possible. The ratio of the monomer A to the monomer B is suitably about 70 to 99:30 to 1 (weight ratio).

Further, in the present invention, acrylic acid, methacrylic acid or their lower alkyl esters (1 to 4 carbon atoms), styrene, methylstyrene, vinyltoluene and vinyl acetate (hereinafter referred to as “monomer C”) are added to the mixture of monomer A and monomer B. ) Can be used as a mixture.
After the polymerization of monomers A and B, monomer C may be added and copolymerized. Like the monomer B, the monomer C dissolves a resin substantially insoluble in a non-aqueous solvent and can be copolymerized with the monomers A and B in the presence of a polymerization initiator. The ratio of the monomers A, B and C is suitably about 60 to 90:20 to 1:20 to 1 (weight ratio).

The ratio of the resin substantially insoluble in the non-aqueous solvent and the monomer A (or a mixture of the monomer A and the monomer B and / or the monomer C) is suitably about 5 to 50:50 to 95 (weight ratio). It may vary depending on the intended use of the final product.

That is, since the monomer A is solvated in the non-aqueous solvent after the polymerization, the resin insoluble in the non-aqueous solvent can be stably dispersed.
Further, the monomer B is copolymerized with the monomer A. However, since the monomer B has a polar group (glycidyl group, hydroxyl group, etc.), the copolymer and the resin or the monomer C insoluble in a non-aqueous solvent are crosslinked and esterified. It is considered that since a reaction other than polymerization is performed, it also contributes to a chemical bond between the solvated component and the non-solvated component, thereby making it possible to prepare a more stable dispersion.

Further, the monomer C substantially copolymerizes with the monomers A and B. However, since the polymer of the monomer C is insoluble in the non-aqueous solvent, the monomer C is polymerized while being compatible with the resin insoluble in the non-aqueous solvent, and further solvated. It is believed that it plays the role of the core component of the solvable resin by copolymerizing with the possible resin.

As described above, the monomer A must be used, but the monomer B and the monomer C can be appropriately selected, and the monomer A, the monomer B, and the monomer C can be used at the same time.

Further, a wax-like substance or a polyolefin having a softening point of 60 to 130 ° C. is added and dissolved, and the mixture is rapidly cooled after the completion of the reaction, whereby (1) stability of the dispersion, (2) redispersibility of the dispersion, (3) The viscosity of the dispersion and (4) the particle size can be controlled, and the dispersibility of paints and pigments can be improved even when the paints and pigments are dispersed.

Commercial products of polyethylene among waxy substances or polyolefins are as follows.

Examples of polyethylene Examples of wax (paraffin wax) Manufacturer Product name Softening point (° C) genuine chemical Paraffin wax 60-98 Kobayashi Chemical Co., Ltd. Bleached beeswax 65 Cetanol 80 Nagai Kako Bleached beeswax 65 It is usually used in an amount of about 10 to 50 parts by weight based on 100 parts by weight of the monomer constituting the polymer or copolymer, but may vary depending on the use of the final product.

 The features of the present invention are listed below.

1) The manufacturing process of the dispersion resin or the resin dispersion is simple,
In addition, it is possible to stably produce a uniform dispersion resin or a resin dispersion.

2) The dispersed resin generally has a small particle size and is excellent in dispersion stability, polarity controllability, and adhesiveness (or fixability).

〔Example〕

 Next, examples and comparative examples will be described.

Example 1 A 1.6-liter three-necked container equipped with a stirrer, a thermometer, and a reflux condenser was charged with 100 g of dimethyl silicone oil (viscosity 1.5 cs) and heated to 350 ° C. In this, 150 g of 2-ethylhexyl methacrylate, 50 g of glycidyl methacrylate,
A mixture of 50 g of Beccasite F231 and 3 g of benzoyl peroxide was dissolved over 1 hour, and further reacted at 95 ° C. for 4 hours.
Subsequently, 0.1 g of pyridine was added and reacted at 80 ° C. for 20 hours.
Further, 50 g of methyl methacrylate and 4 g of azobisisobutyronitrile were added and polymerized at 80 ° C. for 5 hours.

For comparison, polymerization was similarly carried out using toluene as a polymerization solvent instead of dimethyl silicone oil.

These resins were purified by reprecipitation with methanol, dissolved in toluene, and purified three times.

Example 2 500 g of KF96L (1.0 cs) was placed in a 1.6-liter three-necked vessel equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 90 ° C. On the other hand, 80 g of Beccasite F-171 was dissolved in 200 g of 2-ethylhexyl methacrylate, and 2 g of azobisisobutyronitrile was further mixed. Put this mixture in the container
After drop polymerization over a period of time, the mixture was further stirred for 1 hour to prepare a resin dispersion.

Example 3 300 g of KF96 (1.5 cs) was placed in the container used in Example 2,
Heated to 0 ° C. On the other hand, stearyl methacrylate 200g
And Beccasite JB111 in 5g of glycidyl methacrylate
Was dissolved in 50 g, and 2 g of lauryl dimethylamine, 0.2 g of hydroquinone and 2 g of benzoyl peroxide were further mixed. Next, this mixture was dropped into the vessel over 25 hours to carry out polymerization, and then heated at 90 ° C. for about 11 hours to prepare a resin dispersion.

Example 4 Silicone oil TSF400 400 was added to the container used in Example 2.
g and heated to 90 ° C. On the other hand, 80 g of pentasite P-406 was dissolved in a mixed monomer containing 18 g of glycidyl methacrylate and 10 g of acrylic acid, and 2 g of benzoyl peroxide and 25 g of lauryl dimethylamine were mixed. Next, this solution was dropped into the container over 4 hours to polymerize, thereby preparing a resin dispersion.

Example 5 In Example 2, 25 g of ORLIZON 705 was added to 300 g of TSF400.
A polyethylene-containing resin dispersion was prepared in the same manner except that the resin was dissolved and the vessel (90 ° C.) was quenched with cooling water at the end of the polymerization.

Example 6 In Example 4, Nucleol N-59 was added at the end of the polymerization.
9 was added to the polymerization system, and the mixture was heated and dissolved at 90 ° C., and after sufficiently stirring, the container was quenched with tap water to prepare a resin dispersion.

Example 7 The container used in Example 1 was charged with dimethyl silicone (3.0 c
s) 300 g were taken and heated to 90 ° C. On the other hand, 100 g of Beccasite J896 was dissolved in a mixed monomer of 200 g of 2-ethylhexyl methacrylate and 10 g of glycidyl methacrylate, and 2 g of benzoyl peroxide was further mixed. This mixed solution was added dropwise to the vessel over 3 hours, and the mixture was maintained at the above temperature for 3 hours to complete the reaction. Then, lauryl dimethylamine (1 g), methacrylic acid (3 g) and hydroquinone (0.1 g) were added.
1 g was added and reacted at 90 ° C. for 18 hours. Next, 500 g of isooctane was added to the reaction system, and methyl methacrylate 50 was added.
g and a mixture of 5 g of benzoyl peroxide were added dropwise over 5 hours, followed by a reaction for 5 hours to prepare a resin dispersion.

Example 8 In Example 7, 30 g of Sunwax 131-P was further added to 500 g of KF96L (0.65 cs), and after the reaction, a vessel (90 ° C.)
Was quenched with tap water to prepare a polyethylene-containing resin dispersion in the same manner.

Example 9 300 g of KF96L (1.5cs) was placed in the container used in Example 1,
Heated to 90 ° C. On the other hand, stearyl methacrylate 200g
Then, 50 g of pentasite F231 was dissolved in a mixed monomer of 5 g of glycidyl methacrylate and polymerized at 90 ° C. for 4 hours, and then 0.1 g of hydroquinone and 1 g of pyridine were mixed. After the mixture was further reacted at 90 ° C. for 15 hours, 500 g of Isopar G was added, and a mixture of 50 g of methyl methacrylate and 6 g of azobisisobutyronitrile was added dropwise at 90 ° C. over 3 hours to complete the reaction. A resin dispersion was prepared.

Example 10 A polyethylene-containing resin dispersion was prepared in the same manner as in Example 9 except that 30 g of Sunwax 165-P was added to 300 g of KF96L (1.5 cs).

Example 11 A resin dispersion was prepared in the same manner as in Example 9 except that 50 g of methyl methacrylate was not reacted.

EXAMPLE 12 Lauryl methacrylate 70 was added to the container used in Example 2.
g, 10 g of glycidyl methacrylate, Beccasite P
20 g of -231 were dissolved. After heating to 90 ° C., 1.5 g of benzoyl peroxide was added, polymerization was carried out for 8 hours, and then 100 g of Isopar H was added to prepare a resin dispersion having a solid content of 50%.

Example 13 15 g of methacrylic acid and pyridine were added to 200 g of the resin of Example 10.
1.2 g was added and polymerized at 90 ° C. for 15 hours to prepare a resin dispersion.

〔The invention's effect〕

According to the fat dispersion liquid and the method for producing the same according to the present invention, 1) an odorless and highly stable resin can be obtained, 2) the polymerization rate of the resin is increased, and 3) the properties of the resin (water repellency, oil repellency, electricity) Resistance) is improved, and 4) effects such as easy separation of the polymerization solvent and the resin are recognized.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hidemi Uematsu 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Shin Ogawara 2-2-1, Ookayama, Meguro-ku, Tokyo ( 56) References JP-A-3-223302 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 2/00-2/60 C08L 1/00-101/14

Claims (2)

(57) [Claims] 1. A non-aqueous solvent containing at least silicone oil, at least one resin hardly soluble or insoluble in said solvent, and a polymer obtained from at least one monomer in which said resin is soluble. Non-aqueous resin dispersion. 2. A mixture comprising at least one resin hardly soluble or insoluble in a non-aqueous solvent containing at least silicone oil and at least one monomer in which the resin is soluble is prepared. The method for producing a non-aqueous resin dispersion according to claim 1, wherein the polymerization is carried out in the presence of a non-aqueous solvent containing at least.