JP2895850B2 - Method for producing fluorine-containing resin dispersion - Google Patents

Description

The present invention relates to a fluorine-containing resin useful for water- and oil-repellent treatment of fibers, paper, plastic surfaces, metal surfaces, or dry or wet toners for electrophotography, paints, etc. The present invention relates to a method for producing a dispersion.

(Prior art)

Conventionally, fluorine-containing acrylate-based copolymers, fluorine-containing polyether-based copolymers, fluorine-containing urethane-based oligomers, etc. as water / oil repellents for binders for fibers, paper, plastic surfaces, metal surfaces, paints, printing inks, etc. Is used. However, although they are satisfactory in terms of water and oil repellency, they have other properties such as durability, flexibility (especially when used for fibers and paper), adhesion (also related to durability), dispersion stability (especially (When used for paints and printing inks). For the purpose of improving durability and flexibility, a method has been proposed in which an organopolysiloxane is used in combination with the above-mentioned fluorinated treating agent as a softening component or is separately used in a two-stage process (JP-A-59-157380). ing. However, this method has not yet been sufficiently effective in terms of flexibility even if the durability is at a satisfactory level. As an attempt to introduce a softening component into the water / oil repellent treating agent, a method of copolymerizing a fluorine-containing (meth) acrylate and a siloxane-containing (meth) acrylate (JP-A-60-130408), A method using a reaction product with a reactive organopolysiloxane (JP-A-60-81278), a method using an organopolysiloxane having a perfluoroalkyl group in a side chain (JP-B-61-6187), and the like. As is known, a treatment agent having high flexibility tends to have low initial performance or durability, and a treatment agent having high durability tends to have poor texture.

As described above, it is difficult for the conventional water- and oil-repellent treatment agent to simultaneously satisfy durability, flexibility, adhesiveness, dispersion stability, and the like even though water- and oil-repellency can be imparted.

[Problems to be solved by the invention]

An object of the present invention is to remove the above-mentioned drawbacks of the conventional oil-repellent and water-repellent treating agents, and to simultaneously provide oil-repellent water repellency and performance such as flexibility, durability, adhesion, and dispersion stability. It is to provide a method for producing a liquid.

[Configuration and operation of the invention]

The process for producing a fluorine-containing resin dispersion containing a fluorine-containing resin which is hardly soluble or insoluble in a non-aqueous solvent according to the present invention comprises the steps of: separating a fluorine-containing monomer from a monomer capable of forming a resin solvable in a non-aqueous solvent; It is characterized by dissolving in a water solvent and polymerizing these monomers in the presence of a resin that is hardly soluble or insoluble in a non-aqueous solvent.

According to the method of the present invention, a mixed monomer solution containing a fluorine-containing monomer capable of forming a resin which is hardly soluble or insoluble in a non-aqueous solvent is dropped into the non-aqueous solvent in order to reduce variation in production and obtain high reliability. While it is preferable to polymerize the above monomer, polymerization may be carried out in water or an aqueous solvent, or bulk polymerization may be carried out without a solvent, and an appropriate solvent may be added after polymerization.

The fluororesin dispersion thus obtained may contain a waxy substance or a polyolefin having a softening point of about 60 to 130 ° C. In this case, these substances can be added to the monomer solution before the polymerization, or to the dispersion obtained during or after the polymerization to further enhance the dispersibility.

Although various polymerization conditions can be selected, in the case of heating polymerization, for example, a general polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile is present in a monomer solution or a non-aqueous solvent, and about 70 to 70% is used. 110 ° C, preferably 80-1
Heat to 00 ° C.

The monomers capable of producing a resin that is hardly soluble or insoluble in the non-aqueous solvent as the raw material and the respective monomers are used alone or in combination of two or more.

Thus, a dispersion containing a resin that is hardly soluble or insoluble in the nonaqueous solvent and a fluorine-containing polymer that is solvated with the nonaqueous solvent is obtained. The insoluble resin contained in the dispersion acts as a dispersion stabilizer. On the other hand, the fluorine-containing polymer is water- and water-repellent, depending on the type and amount of the material used and the polymerization conditions (temperature, stirring, cooling, etc.). In addition to acting as an oil agent, it is thought to act as a dispersion stabilizer, a polarity controlling agent and a fixing agent. The effect of the insoluble resin and the fluorine-containing polymer in the solvent can be changed by using the above-mentioned wax-like substance or polyolefin, or another monomer described later in combination. When a wax or polyolefin is used in combination, these substances precipitate in the polymerization system by quenching into fine particles, and during the precipitation, are dispersed in the fluorine-containing polymer. As a result, the dispersion stability and the redispersibility of the dispersion liquid are improved. Not only can it be further improved, but also the water and oil repellency can be improved.

Examples of resins that are hardly soluble or insoluble in non-aqueous solvents include ester gums, natural resins such as cured rosin, natural resin-modified maleic acid resins, natural resin-modified phenol resins, natural resin-modified polyester resins, and natural resin-modified pentaerythritol resins. A natural resin-modified thermosetting resin may be used. Commercial products include the following.

Examples of natural resin modified maleic resin: MRG, MRG-411, MRG-S, MRG-H, MRP, MRA-L, MRM-42, MR
M-53 (manufactured by Tokushima Essential Oil), Beccasite 1110, 1111, F231, J811, 112
0, P-720, J-896 (all manufactured by Dainippon Ink and Chemicals) Examples of natural resin-modified phenolic resins: PRG, PRP, SPR-N, SPR-A, SPR-H (all manufactured by Tokushima Essential Oil), Bekka Sites 1110, 1123, 1126, and F-171 (all manufactured by Dainippon Ink and Chemicals) Examples of natural resin-modified pentaerythritol resins: Pentasite P-406 and P-423 (all manufactured by Dainippon Ink and Chemicals) Examples of resin-modified polyester resins: RM-1000, RM-1300, RM-4090, RM-4100 (all manufactured by Tokushima Essential Oil) Examples of ester gums: EG-8000, EG-9000, HG-H, PE, PE-H Examples of hardened rosin: TLR-21, TLR-57 (from Tokushima essential oil) Monomers that form a polymer that can be solvated in a non-aqueous solvent and that can dissolve the resin are represented by the general formula [Where R is -H or CH ₃ group, A is -COOCnH _{2n + 1} or -O
Represents a CnH _{2n + 1} group (n is an integer of 6 to 20). (Hereinafter referred to as monomer A), for example, stearyl, lauryl, acrylic acid or methacrylic acid,
-Ethylhexyl or hexyl ester; t-butyl methacrylate; cetyl methacrylate; octyl methacrylate; vinyl stearate.

Fluoroalkyl acrylate (fluoroalkyl moiety as fluorine-containing monomer (hereinafter referred to monomer B) is _{-CH 2 CF 3, -CH 2 C} 2 F 5, -CH 3 C 3 F 7, -CH 2 C 4 H 9, - CH ₂ C _{5
F 11, -CH 2 C 7 F} 15, -CH 2 C 8 F 17, -CH 2 C 9 F 19, -CH 2 C 10 F
_21, etc.), fluoroalkyl methacrylate (fluoroalkyl moiety _{-CH 2 CF 3, -CH 2 (} CF 2 CF 2) 2 H, -CH 2 CH 2 C
₃ F ₇ ,-(CH ₂ ) ₅ C ₈ F ₁₇ , CH ₂ (CF ₂ CF ₂ ) ₃ H, -CH ₂ (CF ₂ C
_{F 2) 4 H, - (} CH 2) 2 (CF 2) 7 CF 3, -CH 2 C 20 F 41 , etc.) and the like.

The monomer B is usually added to the monomer A and polymerized before the polymerization of the monomer A, but may be added to the polymerization system and polymerized after the polymerization of the monomer A.

The ratio of monomer A to monomer B is 50 to 99:50 to
About 1 (weight ratio) is appropriate.

Further, in the present invention, acrylic acid, methacrylic acid or their lower alkyl esters (1 to 4 carbon atoms), styrene, methylstyrene,
One or more of vinyl toluene and vinyl acetate (hereinafter, referred to as monomer C) may be used in combination. These monomers C are added to the mixture of the monomers A and B before the polymerization of the monomers A and B, or added to the polymerization system after the polymerization of the monomers A and B, to be polymerized. Like the monomer B, the monomer C dissolves a resin that is hardly soluble or insoluble in a non-aqueous solvent. When the monomer C is used in combination, the ratio of the monomer A, the monomer B and the monomer C is suitably about 40 to 80: 1 to 50: 1 to 50 (weight ratio).

The ratio of the resin which is hardly soluble or insoluble in the non-aqueous solvent and the monomer A (or the 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).

The wax or the like is used in an amount of about 10 to 50 parts by weight based on 100 parts by weight of the monomer, and may vary depending on the use of the final product.

The following are commercially available products such as wax.

Non-aqueous solvents include petroleum aliphatic hydrocarbons such as kerosene, ligroin, n-hexane, n-heptane, n-
Pentane, n-octane, i-octane, i-dodecane (the above-mentioned commercially available Exoper Isopar EH, G, L,
K; naphtha No. 6; Solvesso 100, etc.); halogenated aliphatic hydrocarbons, for example, carbon tetrachloride, perfluoroethylene; and mixtures thereof, preferably a fat having a Kauributanol value of 30 or less Group hydrocarbons (eg, isododecane, isooctane) and the like.

 Hereinafter, the present invention will be described with reference to examples.

Example 1 In a 1.6-liter three-necked container equipped with a stirrer, a thermometer, and a reflux condenser, 300 g of Isopar H was taken and heated to 90 ° C. On the other hand, 200 g of 2-ethylhexyl methacrylate and 50 g of fluoromethacrylate of the following formula 80 g of Beccasite F-171 was dissolved in the mixture, and 2 g of azobisisobutyronitrile was further mixed. After the mixture was polymerized dropwise in the vessel for 4 hours, the mixture was further stirred for 1 hour,
A fluorinated resin dispersion was prepared. The contact angle of this resin was 26 ° to water and 19 ° to kerosene, indicating that the resin was made of water and oil repellent.

Example 2 300 g of isooctane was placed in the container used in Example 1,
° C. On the other hand, stearyl methacrylate 200 g and glycidyl methacrylate 5 g and fluoroacrylate 20 g of the following formula 50 g of Beccasite J8111 was dissolved in the mixture, and 2 g of lauryl dimethylamine, 0.2 g of hydroquinone and benzoyl peroxide were further dissolved.
2 g were mixed. Next, this mixture was dropped and polymerized in the vessel over 2.5 hours, and then heated at 90 ° C. for about 11 hours to prepare a fluorine-containing resin dispersion.

The contact angle of this resin was 32 ° with respect to water and 29 ° with respect to n-hexane, indicating water and oil repellency, and also having good durability and adhesion.

Example 3 400 g of Isopar L was put into the container used in Example 1, and 90
Heated to ° C. Meanwhile, glycidyl methacrylate 18 g,
Lauryl methacrylate 100 g and fluoromethacrylate 60 g of the following formula 80 g of pentasite P-406 was dissolved in the mixed monomer of above, and 2 g of benzoyl peroxide and 2.5 g of lauryl dimethylamine were further dissolved.
Was mixed. Next, this mixed solution was dropped into the vessel over 4 hours and polymerized to prepare a fluorine-containing resin dispersion.

The contact angle of this resin was 62 ° for water and 53 ° for kerosene. The adhesiveness, durability and flexibility were all good.

Example 4 In Example 1, ORLIZON 705 was added to 300 g of Isopar H.
A resin dispersion was prepared in the same manner except that 5 g was dissolved and the container (90 ° C.) was rapidly cooled with cooling water at the end of the polymerization.

Example 5 A resin dispersion was prepared in the same manner as in Example 3 except that paraffin wax having a softening point of 80 ° C was added to the polymerization system at the end of the polymerization, heated and dissolved at 90 ° C, sufficiently stirred, and then rapidly cooled in a container with tap water. Prepared.

Example 6 300 g of isooctane was placed in the container used in Example 1,
Heated to ° C. On the other hand, 200 g of 2-ethylhexyl methacrylate, 10 g of glycidyl methacrylate and 60 g of fluoromethacrylate of the following formula Was mixed with 100 g of Beccasite J896, 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, 1 g of lauryl dimethylamine, 3 g of methacrylic acid and 0.1 g of hydroquinone were added, and the mixture was added at 90 ° C. The reaction was performed for 18 hours. Next, after adding 500 g of isooctane to the reaction system, a mixture of 50 g of methyl methacrylate and 3 g of benzoyl peroxide was added dropwise over 3 hours.
Subsequently, the reaction was carried out for 5 hours to prepare a resin dispersion.

Its contact angle was 43 ° with water and 39 ° with kerosene. The adhesiveness and dispersion stability were both good.

Example 7 A resin dispersion was prepared in the same manner as in Example 6 except that 500 g of isooctane was further added with 30 g of sunwax 131-P, and after the reaction, the container (90 ° C.) was rapidly cooled with tap water.

Example 8 300 g of Isopar G was placed in the container used in Example 1, and
Heated to ° C. On the other hand, stearyl methacrylate 200 g,
Glycidyl methacrylate 5 g and fluoromethacrylate 50 g of the following formula 50 g of pentaside P-423 was dissolved in the above mixed monomer, and 0.1 g of hydroquinone and 1 g of lauryl dimethylamine were further mixed. This mixture was added dropwise to the vessel over 4 hours, and further allowed to stand at 90 ° C. for 15 hours. Then, 500 g of Isopar G was added, and a mixture of 50 g of methyl methacrylate and 4 g of azobisisobutyronitrile was added at 90 ° C. Dripping over time,
The reaction was completed, and a resin dispersion was prepared.

Its contact angle was 69 ° with water and 56 ° with kerosene.

Example 9 In Example 8, sun wax 1 was added to 800 g of Isopar G.
A resin dispersion was prepared in the same manner except that 30 g of 65-P was added.

Example 10 A resin dispersion was prepared in the same manner as in Example 8, except that 50 g of methyl methacrylate was not reacted.

Example 11 Lauryl methacrylate 70 was added to the container used in Example 1.
g and 10 g of glycidyl methacrylate were dissolved in 20 g of Beccasite (F-231). After heating to 90 ° C., 1.5 g of benzoyl peroxide was added, polymerization was carried out for 8 hours, and 100 g of Isobar H was added to prepare a resin dispersion.

[Function and effect of the invention]

Since the fluorine-containing resin dispersion of the present invention has sufficient water and oil repellency, and also satisfies other properties such as durability, flexibility, adhesion, and dispersion stability, it can be used for paint printing inks and electrophotographic toners. It is suitable as a water / oil repellent treating agent for fibers, paper, plastic surfaces, metal surfaces and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kazuhiko Umemura 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Toshihiko Takahashi 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Hidemi Uematsu 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.

Claims (1)

(57) [Claims] (1) dissolving a fluorine-containing monomer and a monomer capable of forming a resin solvable in a non-aqueous solvent in a non-aqueous solvent,
A method for producing a fluorine-containing resin dispersion containing a resin which is hardly soluble or insoluble in a non-aqueous solvent, wherein the polymerization reaction is carried out in the presence of a resin which is hardly soluble or insoluble in a non-aqueous solvent.