JPH07216034A - Fine particle of polymer and coating material using the same - Google Patents

Abstract

PURPOSE:To obtain a fine particle of a polymer useful for coating, etc., suitable for producing a polymer film having excellent slipperiness, serviceability and smoothness by polymerizing a given amount of a specific monomer component in the presence of an aqueous dispersion of a polyester resin. CONSTITUTION:This fine particle of a polymer is obtained by polymerizing (A) 1-1,900 pts. wt. of a monomer component such as styrene containing >=5wt.% of a cross-linkable monomer such as divinylbenzene containing two or more vinyl groups in one molecule in the presence of (A) 100 pts.wt. (calculated as solid content) of an aqueous dispersion of a polyester resin such as a polyester having 0.01-2mum average particle diameter and containing a sulfonic acid metal base.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polymer fine particles suitable for coating polymer films and the like, and more specifically, for magnetic tape, photography, vapor deposition, capacitors,
By forming irregularities on the surface of polymer films for metal plate lamination processing, packaging, etc., to improve its slipperiness and smoothness, and to prevent polymer fine particles from falling off from the film, excellent durability The present invention relates to polymer fine particles suitable for producing a resin film.

2. Description of the Related Art Conventionally, polyesters, especially polyethylene terephthalate, have been widely used as fibers, films and other molded articles because of their excellent physical and chemical properties. However, contrary to its excellent characteristics, undesired troubles such as deterioration of workability due to poor processability in the molding step for obtaining the above-mentioned molded product or slipperiness in handling of the product itself, reduction of product value occur. It is also known. As a method for solving such a problem, JP-A-3-36030 and JP-B-3-804
10, JP-A-1-156337, JP-A-2-73833
A method of applying fine particles is known, as disclosed in US Pat. However, most of them are inorganic particles such as silica particles, alumina, titanium oxide, aluminum carbonate, and carbon black, so that the adhesion between the particles and the binder and the film is poor, and the particles are easily peeled off.
Further, since the fine particles are too high in height, they also cause scratches on the tape. These are known to significantly reduce the performance of final products such as video tapes. Furthermore, most of the inorganic particles have a wide particle size distribution,
Further, since the particles are likely to aggregate, the film surface lacks uniformity, and thus the smoothing of the surface is limited. Recently, however, the demand for smoothing of the film surface has become stronger and stronger as the density and performance of magnetic recording have been further promoted, and these inorganic particles cannot meet the demand. .

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide fine particles suitable for producing a polymer film having excellent slipperiness and smoothness of the film surface, and a coating material using the same. To do.

[0002]

That is, the present invention contains 5% by weight or more of a crosslinkable monomer containing 2 or more vinyl groups per molecule in the presence of 100 parts by weight (in terms of solid content) of a polyester resin aqueous dispersion. 1 to 19 of the monomer component A
The present invention provides polymer fine particles obtained by polymerization of 100 parts by weight and a coating material using the same.

The present invention will be described in detail below.
As the polyester resin aqueous dispersion used in the present invention, a polymer compound having an ester bond (-CO-O-) in the main chain of the molecular structure is preferably used in an aqueous medium, preferably having an average particle size of 0.01 to 2 µm. Then, those dispersed in the form of fine particles can be used. As the polyester resin aqueous dispersion used in the present invention, 2 to 20 mol% of a sulfonic acid metal group-containing aromatic dicarboxylic acid as a dicarboxylic acid component, 98 to 50 mol% of a sulfonic acid metal group-free aromatic dicarboxylic acid, and Aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid having 4 to 36 carbon atoms 0 to 30
A polyester resin composed of 80 to 0 mol% of alicyclic glycol having 2 to 8 carbon atoms and / or alicyclic glycol and 80 to 0 mol% of ethylene oxide or propylene oxide adduct of bisphenol A. It is possible to use those obtained by dispersing in a mixed solvent with a compatible organic compound.
The amount of the sulfonic acid metal group-containing aromatic dicarboxylic acid in the polyester resin for polyester resin aqueous dispersion used in the present invention is preferably 2 to 20 mol%, more preferably 3 to 15 mol%. When it is 2 mol% or less, the particle diameter of the obtained polyester resin aqueous dispersion becomes coarse, which is not preferable. Further, if it is 20 mol% or more, the adhesion of the final product to the film is deteriorated, which is not preferable. Moreover, you may introduce an amino group, an epoxy group, an isocyanate group etc. into the polyester resin used for this invention as needed. The particle size (weight average) of the polyester resin aqueous dispersion is preferably 0.01 to 2 μm, more preferably 0.02 to 1 μm, and particularly preferably 0.03 to 0.5 μm. Although not particularly limited, specific examples include the following.・ Nichigo Polyester manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
WR-901, XWR-930, XWR-950-Vylonal MD-1200, M manufactured by Toyobo Co., Ltd.
D1400, MD1530, MD-1900 ・ Pesresin A 200, 1231, manufactured by Takamatsu Yushi Co., Ltd.
G, 1243, 1243G, 1230D, 2151, 3
60, 375, 375G, 510, 513G, 513D
-515G, 810, 813G, 813GL, 81
4G-2, 4000, etc. Examples of the crosslinkable monomer having two or more groups having a polymerizable double bond in the molecule used in the present invention (hereinafter, simply referred to as “crosslinkable monomer”) include, for example, divinylbenzene, ethylene glycol dimethacrylate, 1, Examples thereof include 3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, neopentyl glycol dimethacrylate, and methylenebisacrylamide, and divinylbenzene and ethylene glycol dimethacrylate are particularly preferable.
You may use these in combination of 2 or more types.

In the present invention, the proportion of the crosslinkable monomer used in the monomer component A is 5% by weight or more, preferably 10%.
The content is preferably at least 20% by weight, more preferably at least 20% by weight, particularly preferably at least 30% by weight. If the amount of the crosslinkable monomer is less than 5% by weight, the particles are deformed during use of the film, resulting in poor durability of the film, which is not suitable as the polymer fine particles of the invention.

In the present invention, a non-crosslinkable polymerizable monomer can be used together with the above-mentioned crosslinkable monomer, specifically, aromatic monovinyl compounds such as styrene, α-methylstyrene, fluorostyrene and vinylpyridine,
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, N,
Acrylic ester monomers such as N'-dimethylaminoethyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate,
Methacrylic acid ester monomers such as 2-hydroxyethyl methacrylate, glycidyl methacrylate, N, N'-dimethylaminoethyl methacrylate, etc., acid anhydrides of mono- or dicarboxylic acids and dicarboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, Amide-based monomers such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide, and ionic monomers such as sodium styrenesulfonate and sulfonated isoprene can be used. Further, within a range that is allowable in terms of polymerization rate and polymerization stability, conjugated double bond compounds such as butadiene and isoprene, vinyl ester compounds such as vinyl acetate, 4-methyl-1-pentene, and other α-olefins. Compounds can also be used.

The amount of the monomer component A used is 1 to 100 parts by weight (based on the solid content) of the polyester resin aqueous dispersion.
1900 parts by weight, preferably 2-1000 parts by weight, more preferably 5-500 parts by weight, particularly preferably 10-
If it is less than 1 part by weight, the unevenness of the film will be insufficient and the effect as a slipping agent will be lost.
If the amount is more than 00 parts by weight, the particles will slip when the film is used, and the effect as a slipping agent will be lost. The average particle size of the polymer fine particles of the present invention is preferably 0.01 to 2 μm, more preferably 0.02 to 1 μm, particularly preferably 0.03 to 0.5 μm, and especially 0.05 to 0.3 μm.
Is.

The polymer particles of the present invention are produced by the following production method, and the particle diameter can be controlled mainly by controlling the particle diameter of the polyester resin particles and the amount of the crosslinkable monomer component A. The polymer fine particles of the invention are obtained by polymerizing the monomer A in the presence of an aqueous polyester resin dispersion, optionally using an emulsifier and usually using a polymerization initiator. In the present invention, the monomer component A may be added to the reaction vessel at one time before starting the reaction, or may be sequentially added to the reaction vessel while performing the polymerization reaction. The polymerization reaction is 40 to 90 ° C, preferably 50 to 85 ° C.
For 1 to 30 hours, preferably 2 to 15 hours, more preferably 3 to 9 hours. The reaction is carried out in an appropriate atmosphere such as a nitrogen gas atmosphere, preferably with moderate stirring. Most of the polymer fine particles obtained by this method are polymer fine particles (particle a) in which the polymer of the monomer A is formed inside and / or on the surface of the polyester resin particles. However, there are some polymer fine particles of only the monomer A (particle B) and polyester resin fine particles (particle C) in which the polymer of the monomer A is not formed. The content of the particles a in the polymer particles of the present invention is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more.

The monomer A used in the present invention
It is not necessary to use an emulsifier when polymerizing, but when used, those used in ordinary emulsion polymerization can be used, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium dialkylsulfosuccinate, naphthalene. Anionic surfactants such as formalin condensate of sulfonic acid and polyoxyethylene alkylphenyl ether sulfate ammonium salt can be exemplified, and further polyoxyethylene nonylphenyl ether, polyethylene glycol monostearate,
Nonionic surfactants such as sorbitan monostearate can be exemplified. Furthermore, commercially available emulsifiers New Frontier A-229E, N177E, Aqualon RN-20, HS-10 [manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.], Eleminol JS-2, RS-30 [Sanyo Kasei ( Co., Ltd.], Latemur S-120A, the same S-
180 (manufactured by Kao Corporation) or the like can also be used.
One kind of these emulsifiers may be used, but if two or more kinds are used in combination, it is more effective in terms of stability. A more preferable combination is a combination of an anionic surfactant and a nonionic surfactant. Further, if necessary, a water-soluble polymer such as polyvinyl alcohol, polyvinylpyrrolidone or hydroxypropyl cellulose may be used as a stabilizer.

The polymerization initiator used in the present invention is not particularly limited as long as it is used in ordinary emulsion polymerization or dispersion polymerization, but persulfate salts such as potassium persulfate, sodium persulfate and ammonium persulfate are used. Initiator,
The azo initiator, hydrogen peroxide and organic peroxide may be used alone or in combination with various reducing agents such as ascorbic acid. By the above method, an aqueous dispersion of polymer fine particles having a highly cross-linked polymer inside the particles or on the surface of the particles can be efficiently produced with good polymerization stability. The polymer fine particles of the present invention are useful as a coating material for polymer films, glass, metals, natural materials, paper and the like. For other uses,
It can also be used as a painter for paints, a surface treatment agent for coating surfaces, a fiber treatment agent, an ink binder, an adhesive, and the like. Among these, it is particularly preferable for coating on a polymer film. In the present invention, as the polymer film to which the polymer fine particles can be coated or attached, for example, polyethylene terephthalate,
Polyester film such as polybutylene terephthalate, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . Examples include hydrogenated ring-opening polymer films of norbornene-based monomers such as 1 ^2,7 ] -3-dodecene, polyolefin films such as polyethylene and polypropylene, polyvinylidene chloride films, soft vinyl chloride films, polycarbonate films, and aramid films. The thickness of these polymer films is usually 1 to 500 μm, preferably 2 to 300 μm, more preferably 3 to 200 μm, and particularly preferably 5 to 100 μm.
m. In the present invention, as a method for adhering polymer particles to a polymer film, 5 to 60% by weight of polymer particles are dispersed in a liquid dispersion medium to prepare a coating solution, and the coating solution is applied to the polymer film and dried. The method is preferred. Here, as the liquid dispersion medium, water, a hydrophilic organic solvent, or a water / hydrophilic organic solvent mixture is preferable, and a water-soluble polymer having a molecular weight of 1 to 2,000,000, for example, polyvinyl alcohol, polyvinylpyrrolidone, gum arabic, Polymer solutions of casein, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like can also be used. The coating amount of the fine polymer particles of the present invention is, for example, usually 0.1 to 20 g / m ² , preferably 0.2 to 1 in the case of being attached to a polymer film.
5 g / m ² , more preferably 0.3 to 12 g / m ² ,
Particularly preferably, it is 0.5 to 10 g / m ² . The coating liquid for coating the polymer fine particles of the present invention on a polymer film or the like contains methylol as a cross-linking agent in order to improve the adhesion (blocking property), water resistance, solvent resistance and mechanical strength of the coating layer. Alternatively, alkylolated urea compounds, melamine compounds, guanamine compounds, acrylamide compounds, polyamide compounds, epoxy compounds, aziridine compounds,
Block polyisocyanate, silane coupling agent,
It may contain a titanium coupling agent, a zirco-aluminate coupling agent, heat, a peroxide, a photoreactive vinyl compound, a photosensitive resin and the like. Further, if necessary, a defoaming agent, a coating property improving agent, a thickener, an antistatic agent, an organic lubricant, an antioxidant, an ultraviolet absorber, a dye, a pigment and the like may be added. The step of applying the particles is preferably performed on the surface of the synthetic resin film immediately after the polymer is melt extruded and cast, or immediately after the polymer is stretched in one of the longitudinal direction and the lateral direction. As a method for applying the coating liquid containing the polymer particles of the present invention, a known method can be applied. For example, a spray coating method, an air knife method, a reverse coating method, a kiss coating method, a gravure coating method, a Meyer bar coating method, a roll brush method and the like can be applied.

[0010]

The present invention will be described below with reference to examples.
The present invention is not limited to the following examples unless it exceeds the gist. Parts and% are based on weight. Example 1 The following raw materials were placed in a 5 liter autoclave and polymerized under nitrogen atmosphere at 75 ° C. for 4 hours under stirring. Polyester resin fine particle emulsion pesresin 4000 [manufactured by Takamatsu Yushi Co., Ltd., solid concentration 14%] 2800 parts, ion-exchanged water 1500 parts, styrene 20 parts, divinylbenzene 55
[Sankyo Kasei Co., Ltd., purity 55%, balance is ethyl vinyl benzene, inert solvent] 80 parts, sodium persulfate 2
As a result, an emulsion composed of fine polymer particles having good dispersion stability was obtained. Test Example (1) The average particle size of the obtained polymer particles was measured by Coulter Submicron Particle Analyzer (Coulter Mode).
It was 0.067 μm when measured with an N4 type). After negative staining with phosphotungstic acid, observation with a transmission electron microscope reveals that highly crosslinked polymer fine particles having an average particle diameter of 0.039 μm are present inside the polyester fine particles having an average particle diameter of 0.069 μm. all right. 1.0% of this polymer fine particle
A coating liquid containing 0.30% of methylcellulose was prepared. (2) Polyethylene terephthalate was melt extruded at a temperature of 290 ° C. and cast on a drum controlled at 20 ° C. to obtain an amorphous film having a thickness of 960 μm. After stretching this film at 130 ° C. in the machine direction 2.9 times,
The coating solution obtained above was applied on both sides by 2.5 g / m ² using a metering bar coater. Drying was completed in 25 seconds, and then transverse stretching was performed at 21 ° C by 3.5 times to obtain a thickness of 12
A polyethylene terephthalate film having a thickness of μm was obtained. As a result of running test of this film and observing the running surface of the film with an electron microscope, scratches on the film and falling of polymer particles were hardly observed.

Comparative Example 1 The same as Example 1 except that the polyester resin fine particle emulsion of Example 1 was replaced with a copolymer fine particle emulsion of methyl methacrylate / butyl acrylate / methacrylic acid = 70/25/15 parts. To produce polymer fine particles having an average particle diameter of 0.065 μm. Test (1) A coating liquid was obtained in the same manner as in Test (1) of Example 1 except that the polymer particles obtained in Comparative Example 1 were used instead of the polymer particles obtained in Example 1. (2) The coating liquid obtained in (1) above was applied to a film in the same manner as in Test (2) of Example 1. As a result of running test of the obtained film, scratches on the film and dropping of polymer fine particles were considerably observed.

[0012]

INDUSTRIAL APPLICABILITY The polymer fine particles of the present invention, when used as a coating material for a polymer film, exhibit the effect of improving the slipperiness of the film and the adhesion of the particle surface,
It is possible to produce a polymer film having excellent durability. Therefore, the polymer film coated with the polymer fine particles of the present invention is particularly useful for applications such as magnetic tape, photography, vapor deposition, capacitors, laminating of metal plates, and packaging.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuyuki Ito 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. A monomer component A containing 5% by weight or more of a crosslinkable monomer containing 2 or more vinyl groups in one molecule in the presence of 100 parts by weight of a polyester resin aqueous dispersion (as solid content). Poimer fine particles characterized by being polymerized at 1900 parts by weight. 2. A coating material comprising the polymer fine particles according to claim 1.