JP2000230060A - Planing polymer composition coated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide water slipping polymer composition coated films which are further improved in planing properties, environmentally friendly and, simultaneously, safe in handling. SOLUTION: A water slipping polymer composition coated film is a film to be prepared from a composition containing a polymer having, as the part of its bound chain, a silicone obtained by copolymerizing a polymerizable silicone-containing monomer with a radically polymerizable monomer, and the cohesive force component γsd and the polarity force component γsp of the surface free energy of the coated film are γsd=25-40 erg/cm2 and γsp=0-5 erg/cm2, respectively, and a water droplet having a mass of 12 mg present on the coated film inclined at not greater than 30 degrees to the horizontal can slip off by its own weight. Further, the γsd and γsp are obtained from the contact angle θ of advance and the surface tension γL of water and methylene iodide by using the following formula: (1+cosθ).γL/2=(γsd.γLd)1/2+(γsp.γLp)1/2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-slidable polymer composition film, and more particularly to a technical field for reducing friction between water droplets, water, snow, and ice and a material which comes into contact therewith.

[0002]

2. Description of the Related Art A conventional solution to the above problem is to impart water repellency to a material surface. In other words, methods such as applying a water-repellent substance such as paraffin, silicone, or fluororesin to the surface of the workpiece, or chemically bonding the material, or forming fine irregularities on the applied surface on the applied material, have been reported as a general review. Yes (Akio Tokuumi and others 3
Name, paint and coating, No. 571, p. 37,199
8). Polytetrafluoroethylene, which is considered to have the largest contact angle with water, has a contact angle with water of about 120 degrees.
In search of a material having a contact angle with paraffin of 40 ° or more and a polytetrafluoroethylene or more, a copolymer of an alkoxysiloxane-containing monomer, a silicone-containing monomer, and a copolymerizable monomer with them is prepared. One example is a report in which silica fine particles are added and a film produced therefrom exhibits excellent water-dropping property (Japanese Patent Laid-Open No.
-8263). Further, from the viewpoint of maintaining water repellency, a proposal is made to form a surface layer from a water-repellent fluororesin, silicone, and photocatalytic oxide particles as an architectural window glass having a surface that is not easily stained and to which water droplets are not easily attached (for example,
No. 0-131134), but it is also said that it is preferable that the contact angle between water and the surface layer is 90 degrees or more.

On the other hand, a molecule containing a linear siloxane bond and / or a molecule containing a fluorocarbon group are bonded to the substrate surface by a covalent bond, and the contact angle with water is 97%.
There is also a proposal (JP-A-6-248095) of obtaining a high water separation film by controlling the temperature to ± 10 degrees.

[0004]

When displaying the water sliding characteristics, it is better to display the water sliding property itself rather than the water contact angle. This is because the contact angle does not always have a positive correlation with the minimum inclination angle at which a water droplet slides (hereinafter referred to as a sliding angle) (for example, H. MURASE, K. NANISH).
I, H .; KOGURE, T .; FUJIBAYASHHI,
K. TAMURA, and N.M. HARUTA, J. et al. A
Applied Polymer Sci. vol. 5
4, p. According to Nos. 2051 to 2062, when comparing polytetrafluoroethylene and polypropylene, the latter has a large water slip, but the contact angle to water is 104.3 degrees, whereas the latter has 96.4 degrees. (Small and small), it is easily understood, and in that sense, the ease of rolling of the water droplet is suitably represented by the slip angle.

[0005] Looking at the prior arts that have been publicly disclosed in that respect, a patent 280469 issued at the most recent time is disclosed.
In No. 3, the water droplet weight was 80 mg, and the water slip angle was 13 degrees to 6 degrees.
Degree. The slip angle increases dramatically when the weight of a water droplet becomes lighter than a certain value (for example, H. MURA described above).
According to the report of SE et al., In the case of polypropylene, when the water droplet weight is 80 mg, the slip angle rapidly increases to about 53 degrees when the water droplet weight is reduced to about 15 degrees and 10 mg), and the average weight of the water drops during rainfall is 0.004 to 100 mg. Considering this fact, it can be understood that further improvement in the slipperiness is required.

[0006] Apart from this, so-called conventional water-repellent substances are highly hydrophobic, such as silicone and fluororesin, and therefore are often applied as a solution using an organic solvent, which is a problem in terms of environmental conservation. . In addition, when a water-repellent substance is chemically bonded, the end of the substance containing a silicone or fluorohydrocarbon group is a chlorsilyl group, and hydrochloric acid is generated as a result of chemical bonding with the base substance, and improvement in handling safety is required. . That is, an object of the present invention is to provide a water-slidable polymer composition film having further improved water-slidability, being environmentally friendly and safe to handle.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a polymer having a silicone as a part of a bonding chain obtained by copolymerizing a polymerizable silicone-containing monomer and a radical polymerizable monomer, or a composition containing the polymer. A cohesive force component γ of the surface free energy of the film.
_s ^d and the same-polarity force component γ _sp are ^expressed by the following equations (1) and (2).
In the range of the inclination angle of ^{_{γ s d = 25~40erg / cm 2}} (1) γ s p = 0~ 5erg / cm 2 (2) and said coating be within 30 degrees to the horizontal direction, It is an object of the present invention to provide a water-slidable polymer composition film characterized in that a water droplet having a mass of 12 mg on the film can slide down by its own weight. However, gamma _s ^d and gamma _s ^p is the advancing contact angle of water and methylene iodide θ and surface tension gamma
_{L was determined} from the following equation (3) that combines the Owens equation and the Young equation, which is an extension of the Fowkes equation. _{(1 + cosθ) · γ L} / 2 = (γ s d · γ L d) 1/2 + (γ s p · γ L p) 1/2 (3) The present invention includes a part of the linking chain silicone The present invention provides the above water-slidable polymer composition film, wherein the polymer to be obtained is obtained in an aqueous dispersion system. Further, the present invention provides the above water-slidable polymer composition film in which a polymer having silicone as a part of a bonding chain is obtained as an organic solvent solution or a non-aqueous dispersion system using an organic solvent as a medium. Furthermore, the present invention relates to a polymer having silicone as a part of the bonding chain,
-Methacryloxypropyl polymethyl silicone, styrene, acrylate, methacrylate,
And a radically polymerizable monomer selected from the group consisting of acrylonitrile and methacrylonitrile, which is an essential component, and provides the above water-slidable polymer composition film obtained by copolymerizing them.

As will be described later, according to the present invention, 12 mg
Excellent results were obtained, in which fine water droplets slide down an extremely small inclined surface with a slip angle of 0.5 degrees only by the effect of gravity. And the surface free energy of the film obtained therefrom is γ _s ^d = 25 to 40 erg / cm ² and γ _s
^{Both p} = 0 to 5 erg / cm ² are essential. If one of these two conditions has a length, the above excellent water-sliding property cannot be obtained.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, γ _s ^d giving a small slip angle
And gamma _s ^p keep described regarding where the meaning of the above range. Silaplane FM represented by the following formula 1, which is a typical example of the polymerizable silicone-containing monomer used in the present invention.
-0721 (manufactured by Chisso Corporation)

[0010]

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Γ of_s ^dAnd γ_s ^pThe initial value of each is 43er
g / cm^TwoAnd 11.4 erg / cm^TwoAnd extended wet
After 7 minutes,_s ^d= 72.5erg / cm^Two
And γ_s ^p= 37.8 erg / cm^TwoAnd remarkably large value
Changed to On the other hand, polydimethylsiloxane chains
The surface free energy of the crosslinked silicone release paper is γ
_s ^d= 16.5 erg / cm^Two, Γ_s ^p= 0.9erg / c
m^TwoAnd small values for them, and the change over time
No (see Reference Example-2 below).

[0012] In the former, the polydimethylsiloxane chains are quite free to move and can change to the most favorable form for the water placed thereon, whereas in the latter the polydimethylsiloxane chains have a considerable mobility. It is considered to be restricted and more hydrophobic. Range of selected gamma _s ^d and gamma _s ^p in order to obtain a small water slip angle in the present invention is located between the two the former and the latter. In other words, the ease with which water droplets slide down is governed by the mobility and coordination of the silicone in contact with water,
Gamma _s ^d and gamma _s ^p referred to in the present invention be construed as either does not reflect the value makes it optimize its coordination. Therefore,
The present invention is different from many prior arts in which the contact angle with water is increased to facilitate the sliding of water droplets, in other words, γ _s ^d is reduced, and the contact angle with water is also reduced. The above-mentioned known example that there is an optimum range (Japanese Patent Laid-Open No. 6-24)
8095). It is the beginning of the present invention that the surface free energy is divided into a polar force component and a dispersive force component, and an excellent water-slidable polymer composition film is obtained using both of them.

As will be described later, the polymer used to obtain the water-slidable polymer composition film of the present invention includes an aqueous hydrocarbon or an aliphatic hydrocarbon solvent and an alicyclic solvent having a small effect on the human body including odors. It is obtained as a non-aqueous dispersion system using an organic solvent containing a hydrocarbon solvent as a main component, and meets the issues of improvement in both environmental conservation and handling safety.

Raw materials for obtaining a polymer having silicone as a part of the bonding chain in the present invention will be described below. Examples of the polymerizable silicone-containing monomer are the compounds represented by the above formula (where n is an integer of 1 or more). Further, the following chemical formula 2 similar to chemical formula 1 is also used.

[0015]

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A reaction product of a polydimethylsiloxane compound having a hydroxyl group at one end represented by the following formula 3 with 2-isocyanatoethyl methacrylate, glycidyl methacrylate, maleic anhydride, or the like;

[0017]

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Further, a polydimethylsiloxane compound having an epoxy group at one end represented by the following chemical formula 4

[0019]

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Alternatively, a compound having a carboxy group at one terminal represented by the following formula

[0021]

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A reaction product of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allylamine and the like can also be used. Thus, in the above examples, the repeating number n of the dimethylsiloxy group is an integer of 1 or more, and the size of the polydimethylsiloxane portion containing the same is preferably 500 or more in terms of number average molecular weight, more preferably 1,0 or more.
00 or more. The polymerizable silicone-containing monomer may be used in combination of two or more as necessary.
Further, a compound represented by the following formula 6 can also be used.

[0023]

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Radical polymerizable monomers copolymerized with the polymerizable silicone-containing monomer include, for example, acrylates such as butyl acrylate and 2-ethylhexyl acrylate; methacrylates such as methyl methacrylate and cyclohexyl methacrylate; Acrylic acid and methacrylic acid esters of fluoroalcohols;
For example, aromatic unsaturated compounds such as styrene; nitrile compounds such as acrylonitrile and methacrylonitrile; vinyl compounds such as vinyl acetate and vinyl laurate; and room-temperature gaseous monomers such as ethylene, tetrafluoroethylene, vinyl chloride, and vinylidene chloride And copolymerizable with them, for example, acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate, acrylamide, dimethylaminoethyl methacrylate, vinylpyridine; and acidic or basic groups such as a sulfo group, a phospho group, and an amino group. A radical polymerizable monomer; or a crosslinkable monomer such as N-methylolacrylamide, glycidyl methacrylate, and ethylene glycol dimethacrylate. Among them, it is preferable to select γ-methacryloxypropyl polymethyl silicone and a radical polymerizable monomer selected from the group consisting of styrene, acrylate, methacrylate, acrylonitrile and methacrylonitrile.

The weight ratio between the polymerizable silicone-containing monomer and the radical copolymerizable monomer copolymerized with the polymerizable monomer in the present invention may be a polymer containing the obtained silicone as a part of a bonding chain or containing the polymer. surface free energy gamma _s ^d of the film made from the composition, gamma _s ^p is, but must be adjusted to enter the supra predetermined range, the former /
The latter is often 1/99 or more, preferably 5/95 or more.

When the polymer having silicone as a part of the bonding chain in the present invention is prepared by emulsion polymerization in order to obtain an aqueous dispersion, a surfactant or a water-soluble surfactant known to those skilled in the art for stabilizing emulsion. A water-soluble polymer called a radical protective colloid and a radical polymerization initiator are used. As the surfactant, anionic surfactants, nonionic surfactants, cationic surfactants known as physical adsorption type, and those having a combination of anionic and nonionic, or allyl Reactive emulsifiers having radical polymerizability, such as a group, an acryloxy group, a methacryloxy group, and a vinyl group, which can be incorporated into a formed polymer by a chemical bond can be used. Examples of the radical polymerization initiator include water-soluble persulfates, perborates, hydrogen peroxide, azo-type compounds such as azobisisobutylamidine, and 2,2′-azobisisobutyronitrile (AIBN). An oil-soluble polymerization initiator such as an azo compound such as an organic peroxide and an organic peroxide can be used.

In the case of preparing a polymer having a silicone as a part of the bonding chain in the present invention by a polymerization reaction using an organic solvent as a medium, an organic solvent and a radical polymerization initiator known to those skilled in the art can be used. Is done. Examples of the organic solvent include general-purpose solvents such as aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chloroform, ketones such as methyl ethyl ketone, and esters such as ethyl acetate. Cyclic ethers such as dioxane and tetrahydrofuran, amides such as dimethylformamide, and sulfur-containing solvents such as dimethylsulfoxide can also be used.

The above is a good solvent for a polymer having a silicone as a part of the bonding chain according to the present invention, and the polymerization product is obtained as a solution, whereas, for example, alcohols such as isopropyl alcohol, hexane, heptane, Octane,
Decane, dodecane, cyclohexane, methylcyclohexane, "Loose", "Mineral Spirit EC", "Shellsol 72" (manufactured by "Inner Shell"), "Pegasol 3040", "Pegawhite 1520" (Mobil Oil Co., Ltd.) )) And aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents. However, when these are used, the product becomes a non-aqueous dispersion system. As the polymerization initiator, for example, the oil-soluble compounds described in the description of the emulsion polymerization are used.

The water-slidable polymer composition film of the present invention can contain a crosslinking agent, a filler, and other polymer compounds. Examples of the crosslinking agent include compounds containing a plurality of isocyanate groups, epoxy groups, alkoxysilyl groups, N-methylol groups, methylol groups, acetoacetoxy groups, carboxyl groups, hydroxyl groups, amino groups, and the like in the same or different combinations. Is used.

Aromatic, aliphatic, alicyclic and other diisocyanate compounds such as tolylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, or diisocyanates obtained by blocking these with phenol, methanol, caprolactam, etc. are useful as crosslinking agents having isocyanate groups. This is an example.

Diggrindyl ether of bisphenol A, its linear addition polymer and the like are examples of a crosslinking agent having an epoxy group.

Γ- (glycidpropyl) trimethoxysilane, γ- (glycidpropyl) methyldiethoxysilane, γ- (glycidpropyl) triethoxysilane, etc. have an epoxy group and an alkoxysilyl group in one molecule. Γ- (aminopropyl) trimethoxysilane is an example of a crosslinking agent having an amino group and an alkoxysilyl group in one molecule.

A urea formalin resin precondensate, a melamine formalin resin precondensate, for example, dimethylol melamine, trimethylol melamine, and those obtained by alcohol modification of, for example, hexamethoxyhexamethylol melamine, etc. are used as crosslinking agents having an N-methylol group. This is an example.

In the case where the polymer having silicone as a part of the bonding chain according to the present invention is prepared by emulsion polymerization, or water is added to a product obtained by a polymerization reaction using an organic solvent as a medium, and then the organic solvent is added. In the case of an aqueous dispersion obtained by distilling off, for example, a modified polysaccharide, which is commonly referred to as a self-emulsifying type, which has a hydrophilic portion such as polyethylene glycol or polyglycerin in a molecule and emulsifies itself when mixed with water. Isocyanate or polyepoxy compounds are preferably used. Furthermore, when the polymer in a form emulsified or dispersed in water is made by copolymerizing a monomer having a carbonyl group in a side chain such as methyl vinyl ketone, acrolein, and diacetone acrylamide, Diamines, dihydrazides and the like are used as crosslinking agents. The above-mentioned cross-linking agent is selected in consideration of reactivity depending on the type of the functional group of the polymer having a silicone as a part of the bonding chain according to the present invention.

The water-slidable polymer composition film of the present invention may be made of inorganic fillers such as silica, clay, talc, calcium carbonate, etc., white pigments such as titanium white, zinc leather, lead white, carbon black, iron black, black iron, insoluble It may contain azo pigments, other color pigments such as yellow, blue and purple, and rust preventive pigments such as zinc powder and zinc chromate. In addition, silicone oils, plasticizers, film-forming auxiliaries, and other auxiliaries can be contained according to the purpose of use.

The water-slidable polymer composition film of the present invention can be prepared by further adding another kind of polymer to the polymer having silicone as a part of the bonding chain according to the present invention. However, it specified in the present invention gamma _s ^d and gamma _s ^p, furthermore is within a range that does not impair the water slip performance. Generally, different polymers have poor compatibility. Therefore, the addition of the different polymer is advantageously performed when the polymer is emulsified in water or dispersed in water, and further dispersed in a non-aqueous solvent. For example, wax emulsion, polyethylene emulsion, polyester emulsion, polyurethane emulsion, polyacrylate emulsion, styrene / acrylate copolymer emulsion, polyvinyl acetate emulsion, ethylene / vinyl acetate copolymer emulsion, polyvinyl chloride emulsion, fluorine Acrylic ester copolymer, acrylate ester commonly called resin emulsion or non-aqueous dispersion (NAD)
A polymer in which a styrene copolymer or the like is dispersed as fine particles in an aliphatic or alicyclic hydrocarbon-based solvent is an example of the above-mentioned another kind of polymer.

When the polymer to be added is a solution, in order to avoid inconvenience due to demixing, compatibility is improved by grafting. For example, a radical polymerizable monomer having an epoxy group and an isocyanate group is added to a hydroxyl group-containing polymer, and in the coexistence thereof, a polymer having a silicone as a part of the bonding chain according to the present invention is formed. It is chemically bonded and becomes a compatibilizer to obtain a stable product. As the hydroxyl group-containing polymer, for example, monochlorotrifluoroethylene alkyl vinyl ether
Examples include a hydroxyalkyl vinyl ether copolymer, styrene / butyl acrylate, and 2-hydroxyethyl methacrylate copolymer. Examples of the radical polymerizable monomer added thereto include glycidyl methacrylate and 2-isocyanatoethyl methacrylate.

Next, a method for preparing a polymer having a silicone as a part of the bonding chain of the present invention will be described in the order of emulsion polymerization, solution polymerization, and the formation of an aqueous dispersion or non-aqueous dispersion of the resulting product. In emulsion polymerization, an aqueous phase containing an emulsion stabilizer such as a surfactant and a water-soluble polymer compound is mixed with an oil phase composed of a radically polymerizable unsaturated compound, a polymerization initiator is added thereto, and the mixture is stirred at a predetermined temperature. It is done by maintaining. As the emulsion stabilizer and the polymerization initiator, those obvious to those skilled in the art are used, but one or two special points are mentioned. The solubility of the polymerizable silicone-containing monomer of the present invention in water is extremely low, and it is practically impossible to diffuse through the aqueous phase into polymer fine particles, which are the main reaction sites. In order to solve this problem, it is desirable to disperse an oil phase composed of an unsaturated compound capable of radical polymerization in an aqueous phase as submicron fine particles by a high-performance mixer prior to the polymerization reaction. At this time, a so-called seed emulsion polymerization can be carried out by adding a polymer emulsion to the aqueous phase. Such dispersion is performed by, for example, an ultrasonic emulsifier, a Gaulin mixer, a membrane emulsifier, or the like.

The solution polymerization is carried out by a known method in which an organic solvent dissolving the polymer product, a radical polymerizable monomer containing a polymerizable silicone-containing monomer, and a radical polymerization initiator are stirred at a predetermined temperature. If a non-solvent of a polymer such as an aliphatic or alicyclic hydrocarbon or an aliphatic alcohol is used as the organic solvent, the product can be obtained as a non-aqueous dispersion system (NAD).

In order to disperse the obtained product in water, an acidic group or a basic group is always used as a radical polymerizable monomer, and a base or acid for neutralizing the acid is added, and then water is added. A well-known method of gradually adding and finally distilling and distilling off the organic solvent present in the system under reduced pressure is also applied.

In order to form a non-aqueous liquid dispersion, a solvent mainly composed of an aliphatic or alicyclic hydrocarbon having a boiling point higher than that of the organic solvent used for the solution polymerization is added to the solution polymerization product. A method of distilling off the organic solvent used for the solution polymerization is also applied.

The water-slidable polymer composition film of the present invention is usually made of a polymer having silicone as a part of the bonding chain or a composition containing the polymer, and spray-coating, brush-coating, roll-coating, It is prepared by applying the composition on a target object by a known coating means such as dip coating or curtain flow coater coating, and drying at normal temperature to 200 ° C, preferably 80 ° C to 150 ° C. However, when the above-mentioned polymer or a composition containing the same is obtained as a solid, the target film can be obtained by hot press molding, extrusion molding, blow molding, or the like. The thickness of the film may be appropriately selected according to the application, and is not particularly limited.
It is about 5 μm to 50 μm.

The water-sliding polymer composition film of the present invention thus obtained has a film inclination angle of 3 with respect to the horizontal direction.
Even if it is within 0 degrees, a water droplet having a mass of 12 mg on the film can slide down by its own weight. The water-slidable polymer composition film of the present invention can be used for wood-based boards such as metal plates, glass plates, inorganic boards, hardboards and chipboards, wood boards, and even such hard materials as well as high-quality paper, paperboard, and art. It is used by being formed on soft materials such as paper such as paper, woven fabric, and leather, but the water-sliding polymer or its composition is used in aqueous dispersion, or low odor aliphatic or alicyclic carbonized. Since it includes a non-aqueous dispersion system containing a solvent containing hydrogen as a main component, it has the advantages that it is safe not only for workers but also for the environment when coating and drying, and that it is easy to handle. According to the results of the present invention, an excellent water-sliding surface having a water-sliding angle of 0.5 degree with respect to 12 mg of water droplets is obtained. Prevention of snow accumulation, securing visibility during rainfall such as front, measurement, rear glass windows and side mirrors of cars,
Prevents dew condensation on the fin surface of the air conditioner, prevents icing in winter by preventing the adhesion of water droplets under the Shinkansen, and keeps water droplets from falling down in raincoats and umbrellas. It is expected to be used in applications where reduction of friction with water is desired, such as wet suits.

[0044]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not restricted to the scope of these examples. Before entering into specific examples, terms such as slip angle are explained. (Coating film formation) Substrate: Glass plate Coating: Coating bar # 10 Drying: Leave overnight in an atmosphere above the minimum temperature for film formation, or 100 ° C x 10 minutes Heat treatment: 135 ° C x 30 minutes Film thickness: 4 ~ 6 μm (Sliding angle measurement) Coating: Coating on glass plate of 2.6 cm × 3.5 cm Water droplet: 12 mg of water droplet is placed on the coating from a micro syringe. Device: Contact angle measuring device (goniometer type, ERMA)
INC. Measurement): Keep at a predetermined inclination for 1 minute and let the minimum inclination angle at which the water drops slide down be the slip angle. (Measurement of contact angle) For measuring the slippery angle except that the droplet was made smaller, the inclination angle was set to 0 °, and the contact angle was read every 5 minutes after placing the water droplet up to 5 minutes and the average of the four was used as the contact angle. I went according to. However, deionized water and methylene iodide (CH
The ₂ I ₂₎ special grade reagent was used for measurement. The droplet weight was 2.3 mg for water and 7.6 mg for methylene iodide.
Also, the dispersion force component γ _s ^d of the surface free energy of the polymer film
And polar force component gamma _s ^p is the advancing contact angle θ and surface tension gamma _L of water and methylene iodide, using the following equation combining of formula and Young of Owens that extends formula Fowkes a (3) I asked. _{(1 + cosθ) · γ L} / 2 = (γ s d · γ L d) 1/2 + (γ s p · γ L p) 1/2 (3)

Example 1 A five-neck separable flask equipped with a stirrer, a thermometer, a dropping funnel for catalyst, and a condenser for cooling (volume of 1
L) was prepared. 117 g of styrene, 38 g of methyl methacrylate, 61 g of 2-ethylhexyl acrylate, 2 g of 2-hydroxyethyl methacrylate, 2 g of methacrylic acid
g, Silaprene FM-0721 (Chemical Formula 1), which is a polymerizable silicone-containing monomer, (152 g) and 2,2′-azobisisobutyronitrile (AIBN) (0.8 g) were mixed to form a uniform solution. 88 g of a 10% aqueous solution of a reactive anionic nonionic surfactant (SE-10N, manufactured by Asahi Denka Kogyo KK), 518.8 g of deionized water, and the above-mentioned monomer mixture were mixed with a Menton-Gaulin Laboratory Homogenizer 15M. -8TA (APV-GAULIN) 40
The mixture was emulsified at 0 kg / cm ² to obtain a monomer dispersion having a particle diameter of 0.5 μm or less, and the whole amount was charged into the flask. After maintaining the monomer dispersion in the flask at 80 ° C. for 20 minutes by heating in a water bath, a mixed solution of 4 g of 2-hydroxyethyl methacrylate and 4 g of methacrylic acid was added from a small dropping funnel. However, the addition of the dropped components was performed over 3 hours. During this time, the reaction temperature was 78 ° C to 82 ° C. The temperature in the flask was lowered to 65 ° C., and perbutyl H (organic peroxide, manufactured by NOF CORPORATION) 0.7 was used to reduce unreacted monomers.
0 g and 10% of the above-mentioned anionic surfactant SE-10N
An aqueous solution obtained by dissolving 3.7 g of the aqueous solution and 0.4 g of Rongalite in 5.1 g of deionized water was added in three portions, each of which was reacted for 15 minutes, and kept at the same temperature for 1 hour. Thereafter, the solution in the flask was cooled to 35 ° C. and ammonia water was added.
5 g was added to terminate the reaction. Thus, the solid concentration 37.
3%, viscosity 140 mPa · s, average particle size 0.23μ,
An aqueous dispersion product with a pH of 7.9 was obtained. Product 1 obtained
100 g of self-emulsifying epoxy resin crosslinking agent Denacol E
2 g of X-512 (manufactured by Nagase Kasei Kogyo Co., Ltd.) was added to prepare a coating solution. Waterdrop slidable angle 1 degree obtained film thus surface free energy _{^{γ s d = 31.6erg / cm 2}} , γ s p
= 2.5 erg / cm ² . The water contact angle θ _W and the methylene iodide contact angle θ _I are θ _W = 90 ° and θ _I = 5.
It was 5 ゜.

Examples 2 to 8 Polymer emulsions were prepared in the same manner as in Example 1 except that the raw material compositions shown in Table 1 below were used, and post-additives were added, or films were prepared as they were. The surface free energy of the film γ _s ^d ,
gamma _s ^p were as shown in Table 1 lower. Example-6 is an example in which a polymer emulsion containing no silicone was added to Example-1. Examples -7 and 8 are examples in which a pigment paste was added to example 1 to form a paint.

[0047]

[Table 1]

(Description of abbreviations) SM: styrene, BA: butyl acrylate, AN: acrylonitrile, MMA: methyl methacrylate, 2EH
A: 2-ethylhexyl acrylate, MAA: methacrylic acid, HEMA: 2-hydroxyethyl methacrylate,
AIBN: 2,2′-azobisisobutyronitrile 1) Polymerizable silicone-containing monomer represented by Formula 1 (manufactured by Chisso Corporation) FM-0725 (average molecular weight = 10,000) FM-0721 (average molecular weight = 5,000) 2) SE-10N (10%): 10% aqueous solution of reactive anionic nonionic surfactant SE-10N (manufactured by Asahi Denka Kogyo KK) 3) Denacol EX-512: polyglycerol Polyglycidyl ether-based self-emulsifying epoxy resin-based crosslinking agent (manufactured by Nagase Kasei Kogyo Co., Ltd.) 4) Polysol AP-4775: acrylate copolymer emulsion (non-volatile content 50%, pH 9.0, average particle diameter) 0.146μ, glass transition point -8 ° C, manufactured by Showa Polymer Co., Ltd.) 5) Pigment paste: Titanium white paste with 70% non-volatile content (as specified in formulation) Water: 8.26 Natrosol 250HR (manufactured by Hercules Incorporated): 0.
08 g ammonia water (25%): 0.02 g Nopco SN Deformer 371 (San Nopco Co., Ltd.)
: 0.11 g Poise 5218 (manufactured by Kao Corporation): 0.42 g Amorden FS-140 (manufactured by Daiwa Chemical Co., Ltd.): 0.1
1g Titanium white (Taipec R-630) (Ishihara Sangyo Co., Ltd.)
21.0 g) Total 30.0 g 6) Addition amount (g) per 100 g of polymer emulsion 7) θ _W ; water contact angle, θ _I ; methylene iodide contact angle

Examples 9 to 11 Polymer emulsions were prepared in the same manner as in Example 1 except that the raw material compositions shown in Table 2 below were used, and post-additives were added, or films were prepared as they were. However, Example -9 is a self-crosslinking emulsion in which the film has a crosslinked structure without adding any post-additive.
Surface free energy gamma _s ^d of the film, the gamma _s ^p were as shown in the lower second table.

[0050]

[Table 2]

(Description of abbreviations) Same as Table 1. 1) N-MMAA: 60% aqueous solution of N-methylol methacrylamide 2) Same as 6) in Table 1 3) Same as 7) in Table 1

Example-12 A 1-L five-neck separable flask equipped with a stirrer, a dropping funnel, a cooling condenser, and a thermometer was prepared. 48 g of methyl methacrylate, 16 g of butyl acrylate, 48 g of Silaprene FM-725 (average molecular weight 1
000, manufactured by Chisso Corporation), acrylic acid 9
g, KBM-503 (γ- [methacryloxypropyl]
Trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.4
g, a total of 123.5 g, were weighed and mixed, and 45 g of the mixture, 45 g of isopropanol, and 0.3 g of AIBN were charged into the flask. To the remaining amount of the monomer mixture, 18 g of isopropanol and 0.3 g of AIBN were added to dissolve uniformly, and this was put into a dropping funnel. The flask was set in a 90 ° C. water bath, and stirring was started when the internal temperature reached 82 ° C. Thirty minutes later, the addition to the flask was started from the dropping funnel, and was completed in two hours. 80 ° C-82 for another 3 hours
After maintaining the temperature at 300 ° C., 303 g of isopropanol was added, and the mixture was uniformly cooled. The product has a nonvolatile content of 25.0%,
It showed a bluish translucent milky white color. 80 g of the product was transferred to a 300 ml separable flask, and 3.0 g of a 25% aqueous ammonia solution was added with stirring to make the mixture uniform, and 76 g of deionized water was added dropwise. 63 g of the product thus obtained and 40 g of deionized water were put into a vacuum evaporator, and isopropanol was distilled off under reduced pressure and heating. Decompression is 155 mmHg at the beginning, 95 mmHg at the end,
Heating was in a hot water bath at 60 ° C to 62 ° C. Distillate 27.5
g. The product has a nonvolatile content of 20.2% and a pH of 8.
0, indicating a bluish milky white. The water slip angle of the film obtained from this was 4 degrees, and the surface free energy was γ _s ^d = 31.
9erg / cm ^2, was ^{_{γ s p = 0.06erg / cm 2}} .

Example 13 A 300 ml five-neck separable flask equipped with a stirrer, a dropping funnel, a cooling condenser and a thermometer was prepared.
34 g of styrene, 0.9 g of acrylic acid, methacrylic acid 2
-Hydroxyethyl 0.9 g, Silaplane 721
(Chemical Formula 1) A monomer mixture consisting of 24 g was prepared, and 22.5 g of the monomer mixture, 22.5 g of toluene, and AIBN
0.15 g was charged to the flask. To the remaining 37.3 g of the monomer mixture, 0.15 g of AIBN was added and dissolved, and the mixture was placed in a dropping funnel. The flask was set in a 90 ° C. water bath, and stirring was started when the contents reached 80 ° C. Thirty minutes later, the addition to the flask was started from the dropping funnel, and was completed in two hours. After the end of the dropping, perhexyl O twice every hour
0.04 g of (organic peroxide, manufactured by NOF Corporation)
Was added. From the start of the reaction to the end of the dropwise addition, the temperature inside the flask was kept at 80 ° C to 86 ° C. Six hours after the completion of the dropwise addition, 69 g of toluene was added, and the mixture was cooled to uniformity. The obtained product was a slightly turbid solution with a nonvolatile content of 34.3%. Future waterdrop slidable angle of the produced coating 6 degrees, the surface free energy _{^{γ s d = 31.3erg / cm 2}} , γ s p = 0.
05 erg / cm ² .

Examples 14 and 17 to 19 A polymer solution was prepared in the same manner as in Example 13 except that the raw material compositions shown in Table 3 below were used, and a post-additive was added thereto to form a film. However, in Example-18, the post-addition hexamethylene diisocyanate was used in a large amount of 16.9 equivalents to the hydroxyl group formulated in the polymer (in other examples, 0.1%).
89 equivalents). The sliding angle and surface free energy of the obtained film were as shown in the lower part of Table 3. Example -19 is an example of a polymer film formed from a non-aqueous dispersion system.

[0055]

[Table 3]

(Description of abbreviations) AA: acrylic acid, KBM-
503: γ- (methacryloxypropyl) trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), IPA: isopropanol, perhexyl O: organic peroxide (manufactured by NOF Corporation), turpentine: Pegawhite 1520 (mobile oil) Co., Ltd., aliphatic hydrocarbon-based solvent), pegazole: pegazole 3040 (manufactured by Mobil Sekiyu KK, aliphatic hydrocarbon-based solvent), HDI: hexamethylene diisocyanate 1) Addition amount (g) per 100 g of product 2) Same as 7) in Table 1 3) Addition amount (g) per 100 g of the product of Example-13

Examples 15 and 16 Pegawhite 1520 containing 0.1% or less of aromatic hydrocarbon (0.1% or less aromatic, manufactured by Mobil Oil Co., Ltd.) was added to 100 g of the polymer solution obtained in Example 13 59 g was added to make the mixture uniform, and 111 g of this was applied to a vacuum evaporator to distill off toluene under heating under reduced pressure. Decompression is initial 9
The temperature of the oil bath at 3 mmHg, the final temperature of 125 mmHg, and the temperature was 175 ° C to 210 ° C, and the weight loss by distillation was 42 g. The product is translucent milky white and has a non-volatile content of 34.6.
%Met. To the 10 g, 0.035 g of hexamethylene diisocyanate was added (Example-16), or without (Example-15) to form a coating. Waterdrop slidable angle are both 15 degrees of the ^{_{film, γ s d = 30.8erg / cm}} 2, γ s p =
0.04 erg / cm ² (Example-15), γ _s ^d = 3
_{^{1.5erg / cm 2, γ s p}} = 0.01erg / cm
² (Example-16).

Example -20 The polymer emulsion composition of Example 1 was applied to a western umbrella (64.7 g / m ² ). It was applied with an 8-bar coater and heat-treated at 100 ° C. for 30 minutes. JIS P8 for measuring frictional resistance of paper
According to 147, the angle at which a 200 mg water drop started to slide was measured to obtain 10.7 degrees. The surface free energy _{^{γ s d = 31.9erg / cm 2}} , γ s p = 0.03er
g / cm ² . For reference, water repellent spray for umbrella, Scotch guard (component: fluororesin, isopropyl alcohol, carbon dioxide, manufactured by Sumitomo 3M Co., Ltd.) was evenly sprayed on the same western umbrella, and measured after 24 hours. The slip angle was 30.5 degrees. The surface free energy _{^{γ s d = 51.3erg / cm 2}} , γ s p =
0.4 erg / cm ² .

Example 21 The film of Example 1 was formed inside an ice making case of a household electric refrigerator. The thickness was about 10 μm. Tap water was poured into this, and it was frozen in an ice making room. Take out one night later,
When the ice making case was reversed and the tap was performed, the ice was detached from the case. When the above film formation was not performed, the ice adhered strongly to the case.

Comparative Examples 1 to 5 Polymer emulsions were prepared in the same manner as in Example 1 except that the raw material compositions shown in Table 4 below were used, and post-additives were added or films were prepared as they were. Waterdrop slidable angle of the film, gamma _s ^d and gamma _s ^p were as shown in Table 4 the lower.

[0061]

[Table 4]

(Description of abbreviations) Same as Table 1. Where VAc:
Vinyl acetate, CHMA: cyclohexyl methacrylate. 1) Polysol AP-3748; styrene-acrylate copolymer emulsion (nonvolatile content 50%, pH 9.
0, average particle diameter 0.14 μm, glass transition point 12 ° C., manufactured by Showa Polymer Co., Ltd.)

Comparative Examples -6 and 7 A polymer solution was prepared in the same manner as in Example 13 except that the raw material composition shown in Table 5 below was used, and a post-additive was added or a film was prepared as it was. Waterdrop slidable angle of the film, gamma _s ^d and gamma _s ^p were as shown in Table 5 lower. Note comparative Example -7 is an example other than gamma _s ^d and gamma _s ^p of addition coatings contain no silicone is specified in the present invention.

[0064]

[Table 5]

(Description of abbreviations) Same as in Table 3. 1) Vinylol S: polyvinyl acetate methanol solution (47% non-volatile content, manufactured by Showa Polymer Co., Ltd.) 2) Same as 7) in Table 1

Reference Example-1 Linda glass coat UV [manufactured by Yokohama Yushi Kogyo Co., Ltd.
Silicone, isopropyl alcohol (90%), acid]
The glass repellent for automobiles was applied evenly to the glass plate with a special felt, dried, and wiped with a wet towel until the glass plate became transparent. The sliding angle of this glass plate is 40
４５45 degrees, surface free energy is γ _s ^d = 24.6 erg
/ Cm ^2, and ^{_{γ s p = 3.28erg / cm 2}} .

Reference Example 2 Silicone-type release paper KP-8 (D) for adhesives (manufactured by Hayashi Paper Co., Ltd.) has a water sliding angle of 45 degrees and a surface free energy of γ _s ^d = 16.49 erg / cm ^2. , γ _s ^p = 0.88er
g / cm ² .

Reference Example-3 The scotch guard used in Example-20 was sprayed on a glass plate and dried at room temperature for 24 hours. The film obtained had a sliding angle of 90 degrees and a surface free energy of γ _s ^d = 11. .55erg
/ Cm ^2, and ^{_{γ s p = 1.39erg / cm 2}} .

Reference Example 4 A vinyl tape for electrical insulation was attached to a prepared glass for an optical microscope, and a polymerizable silicone-containing macromonomer syruprene FM-0721 was dropped thereon to form a thin film. A water drop or a methylene iodide drop was placed thereon, and the contact angle was measured. For the first 4 minutes, θ _W = 67.5 °, θ _I =
42.0 ° (calculated on ^{_{γ s d = 43erg / cm 2}} , γ s p =
11.4 erg / cm ² ). After that, the extension wetting rapidly progressed, and after 7 minutes, θ _W = 16.0 ° and θ _I = 11.1.
0 ° (calculated on ^{_{γ s d = 72.5erg / cm 2}} , γ s p = 3
7.8 erg / cm ² ).

[0070]

As described above, according to the present invention, planing polymer composition film of the present invention has an excellent water slip performance than conventional products, the said coating thereof that gamma _s ^d and gamma _s ^p Was deeply involved in the discovery that it originated in a specific area between the polymerizable silicone-containing monomer used as the raw material and the highly water-repellent coating such as a silicone crosslinked product or a fluorocarbon polymer. I have. The coating of the present invention is obtained from a dispersion system using water or a low-odor aliphatic or alicyclic hydrocarbon solvent, and is preferable in terms of environmental protection and the effect on the human body. It can be formed not only on a soft surface such as an umbrella but also on a wide range of fields where reduction of friction or adhesion with water or snow or ice is desired.

Continued on the front page F term (reference) 4D075 CA09 EA07 EB42 4F071 AA67 AF09 AH19 BC01

Claims (4)

[Claims] 1. A film produced from a polymer having silicone as a part of a bonding chain obtained by copolymerizing a polymerizable silicone-containing monomer and a radical polymerizable monomer, or a film formed from a composition containing the polymer. The cohesive force component γ _s ^d and the homopolar force component γ _s ^p of the surface free energy of the film
But the range of the following formula (1) and ^{_{(2), γ s d =}} 25~40erg / cm 2 (1) γ s p = 0~ 5erg / cm 2 (2) and the inclination angle of said coating horizontal A water-slidable polymer composition film, wherein a water droplet having a mass of 12 mg on the film can slide down by its own weight even within 30 degrees with respect to the direction. However, gamma _s ^d and gamma _s ^p is the advancing contact angle θ and surface tension gamma _L of water and methylene iodide, Fowke
The value was obtained using the following expression (3) that combines the Owens expression and the Young expression, which are obtained by expanding the expression of s. _{(1 + cosθ) · γ L} / 2 = (γ s d · γ L d) 1/2 + (γ s p · γ L p) 1/2 (3) 2. The water-slidable polymer composition film according to claim 1, wherein the polymer having silicone as a part of the bonding chain is obtained in an aqueous dispersion. 3. The water-slidable polymer composition film according to claim 1, wherein the polymer having silicone as a part of a bonding chain is obtained as an organic solvent solution or a non-aqueous dispersion system using an organic solvent as a medium. 4. A radical in which the polymer having silicone as a part of the bonding chain is selected from the group consisting of γ-methacryloxypropyl polymethyl silicone and styrene, acrylate, methacrylate, acrylonitrile and methacrylonitrile. The water-slidable polymer composition film according to claim 1, which is obtained by copolymerizing the polymerizable monomer with an essential component.