JPH0361041A - Sheet having water/oil repellency and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain a water/oil-repellent sheet having a uniform water/oil- repellent film by curing a specific composition consisting of fluoroalkyl acrylate or methacrylate, a compound having an ethylenic unsaturated bond and a solvent by the irradiation with active energy rays to form a film whose contact angles to water and n-heptane are specific values. CONSTITUTION:The water/oil-repellent film having a thickness of 1-20g/m<2> and a contact angle to water of 90 deg. or more and a contact angle to n-heptane of 45 deg. or more provided on a base material is composed of a copolymer of a fluorine type monomer and a compound having an ethylenic unsaturated bond. As the representative fluorine type monomer, fluoroalkyl acrylate or methacrylate is used and, as the compound having the ethylenic unsaturated bond being a component to be copolymerized, phenoxyethyl acrylate is used. Further, a solvent is compounded and the compounding ratio of components is set so that the fluorine type monomer is 0.15.0 pts.wt., the ethylenic unsaturated compound is 95.0-99.9 pts.wt. and the solvent is 20-200 pts.wt. After the evaporation of the solvent, for example, the composition is cured by the irradiation with active energy rays such as electron beam or ultraviolet rays.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a water-repellent/oil-repellent sheet, and more particularly to a water-repellent/oil-repellent sheet 1- provided with a surface film containing a fluorine-based compound as a minor component.

BACKGROUND OF THE INVENTION There are three known methods for imparting water-repellent and oil-repelling properties to base materials with the main purpose of stain resistance. Firstly, a lamination method in which a water-repellent material such as a fluororesin is bonded to a base material in the form of a film, etc., and secondly, a fiber material is impregnated with a reactive chemical solution and then heated. The so-called fiber finishing method involves fixing a repellent/oil-based resin to fibers through treatment, etc., and the third method is a coating method in which a base material is coated with a membranous material and then subjected to heat treatment to form a repellent/oil-based film. There is.

Among these, the last known coating method is a method in which the coated monomer is polymerized using active energy rays to form a water-repellent and oil-resistant film.

However, there have been various problems with this method of irradiation with active energy rays. That is, the fluorine-based monomers mainly used are generally expensive.

Next, fluoromonomers have low surface tension and are difficult to apply to substrates, making it impossible to obtain a uniform film. It is also possible to copolymerize expensive fluoromonomers with other inexpensive monomers, but fluoromonomers are difficult to mix with other monomers, so it is difficult to mix them successfully. In this case, a dispersant is required, and in that case, the presence of a dispersant reduces the important water replenishment and
There is a possibility that the oil properties may be inhibited.

Problems to be Solved by the Invention For the reasons mentioned above, the processing method for forming a repellent and oil repellent film by irradiation with active energy rays using a fluoromonomer is
What is considered to be promising has no precedent and has not yet been established, and the inventors have tackled this theme,
I have continued to research diligently in order to somehow establish something.

Means for Solving the Problems The present invention was made as a result of such research, and it is possible to reduce the amount of the fluoromonomer considerably and reduce the amount of the fluoromonomer when combining it with a specific other reactive compound. By also using a solvent, mixing and application can surprisingly be carried out smoothly, and even though the fluorine-based compound is a small component in the copolymer film made by irradiation with active energy rays, it does not remove water. - This is based on the findings recently discovered by the present inventors that the oil repellent properties are sufficiently exhibited.

That is, the present invention provides a sheet consisting of a sheet-like base material and a film with a thickness of 1 to 20 g/m2 provided on the base material, the sheet having a contact angle with water of 90° or more and n - having surface characteristics such that the contact angle with hegetane is 45° or more, and the coating contains 0.1 to 5.0 parts by weight of fluoroalkyl acrylate or 95.0 to 99.9 parts by weight of fluoroalkyl acrylate; The present invention provides a water repellent/oil repellent sheet characterized by being obtained by curing a composition comprising a compound having an ethylenically unsaturated bond and 20 to 200 parts by weight of a solvent by irradiation with active energy rays.

The repellent/oil repellent sheet of the present invention basically consists of a base material and a repellent/oil repellent film formed on the base material.

First, the base material used in the water repellent/oil repellent sheet of the present invention is not particularly limited as long as it is in the form of a sheet or film, but generally plastics (film) and rubber are used. Use a sheet. Examples of plastics include vinyl chloride (soft and hard), PET
(polyethylene terephthalate), polyethylene, polypropylene, polycarbonate, polyamide, etc. Among these, vinyl chloride is preferred. Further, examples of the rubber include NBR, 5BR1-butyl rubber, polyurethane, and the like. Although it is generally difficult to simply call them sheets or films, for example, fiber sheet-like materials (woven fabrics, non-woven fabrics) can be coated with the monomer composition without any problems as long as they are finely woven. The formed film is also continuous, so it can be used.

The water repellent/oil repellent sheet of the present invention is coated on such a base material with a thickness of 1
A water-repellent/oil-based film of ~20 g/m2 is provided, and the film is made of a copolymer of a fluoromonomer and a compound having an ethylenically unsaturated bond. Such a copolymer is obtained by curing a monomer composition prepared as described below by irradiating active energy rays.

To explain the copolymerization components, first, fluoroacrylate or fluoromethacrylate is typically used as the fluoromonomer.

Examples of fluoroacrylates include β-(pafluorooctylethyl acrylate 1-), 22.2-trifluoroethyl acrylate, 22.33-tetrafluoropyracrylate, lH,IH,51-1- Octafluoropentyl acrylate, LH, IH, 2H
, 2H-heptadecafluorodecyl acrylate-1 and the like.

Further, as an example of fluoromethacrylate, 2.2.
2-trifluoroethyl methacrylate, 2.2,3.
3-tetrafluoropropyl methacrylate]・, ]2,
2,3,4,4.4-hexafluoroptyl methacrylate β-(perfluorooctyl)ethyl methacrylate, 3 [4[l-trifluoromethyl-2,2-bis[bis(trifluoromethyl)fluoromethyl] Examples include ethynyloxy 1 benzoxy 12-hydroxypropyl methacrylate], ]IH, IH, 5H-octafluoropentyl methacrylate 1, and IH, LH, 2H, 2H-butadecafluorodecyl methacrylate.

These fluoroacrylates and fluoromethacrylate-1 are readily available commercially.

Next, examples of compounds having an ethylenically unsaturated bond to be used as a component to be copolymerized with a fluoromonomer include the following.

First, examples of compounds having one ethylenic double bond functional group include phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxypolyethylene glycol acrylate, methoxyethylene glycol acrylate, butoxydiethylene glycol acrylate, nonylphenoxyethyl acrylate, and methquine diethylene glycol methacrylate. Examples include compounds having the structures shown below, such as ray-1, methoxypolyethylene glycol methacrylate, and nonylphenoxyethyl methacrylate.

CH□=CHC00(C5H,,C00)-HCH2=
CHCOOC2H100CC2H4COOHH As a compound having two ethylenic double bond functional groups,
For example, polyethylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate,
Examples include 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, or compounds having the following structures.

OOHOH0 1! H2=CHCC0CH2cHcH20cH2CH2CH
2CH2CH2CI 20CH2CCH20CCH=C
Examples of compounds having three H-functional groups include trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethanetetraacrylate, trimethylopropane triacrylate, tetramethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, etc. can be mentioned.

Examples of oligomers and prepolymers having two or more functional groups (ethylenic double bonds) include polyester acrylate, epoxy acrylate, urethane acrylate, polyether methacrylate, and polyol acrylate-1.
−, melamine acrylate, polyester methacrylate, Epoquin methacrylate, urethane methacrylate,
Polyether methacrylate-1 includes polyol methacrylate, melamine methacrylate, and the like. These compounds having ethylenically unsaturated bonds are easily available commercially.

The water repellent/oil repellent sheath i~ of the present invention having the above-described structure is manufactured as follows.

First, a composition containing a solvent in addition to the fluorine-based monomer and ethylenically unsaturated metal compound described above is mixed.
Prepare. The blending ratio of the ingredients is 0.1% of the fluoromonomer.
~5.0 parts by weight, preferably 1.0 to 3.0 parts by weight, 95.0 to 99.9 parts by weight of the ethylenically unsaturated compound, preferably 97.0 to 99.0 parts by weight, and 20 to 99.0 parts by weight of the solvent. 200
Part by weight.

In this way, by significantly reducing the proportion of the fluoromonomer, it can be mixed with other copolymer components, and as a result, uniform coating on the substrate can be realized. What's more, surprisingly, despite the small amount, it has sufficient water repellent and oil repellent properties. If the amount of the fluoromonomer exceeds 5.0 parts by weight, it will separate from other copolymer components and will not be miscible. On the other hand, if the amount is less than 0.1 part by weight, the water-repelling and oil-repelling properties will decrease even if they can be mixed. If it is 0.1 to 5.0 parts by weight,
There is no such separation, and as a result, there is no need to add a dispersant or a leveling agent, and there is no adverse effect on water repellency or oil repellency.

Further, in the present invention, the solvent also plays a major role.

That is, due to the presence of this solvent as well as the above-mentioned components, the above-mentioned sufficient miscibility and coating properties, particularly coating properties, are exhibited for the first time, and smooth coating is possible. Examples of such solvents vary depending on the type of monomer used, and are generally methanol, ethanol, isobutyl alcohol,
-Butyl alcohol, isobutyl alcohol, ace1~
methyl ethyl ketone, ethyl acetate, benzene, toluene, carbon tetrachloride, 9 chloroform, dichloroethane, trichloroethylene,
Perchlorethylene and the like may be used alone or as a mixture, and a material that does not undergo phase separation during the period from application to irradiation and during the curing process by irradiation with active energy rays described below is selected. When the amount of solvent is less than 20 parts by weight, miscibility and
On the other hand, if it exceeds 200 parts by weight, it becomes difficult to apply uniformly and the concentration becomes too low, making it difficult to ensure the required thickness of the film.

In addition, colorants, fillers, antioxidants, ultraviolet absorbers, and the like may be added as appropriate, as long as they do not impair miscibility and applicability.

The method of applying such a composition to the substrate is not particularly limited, and any of the suitable methods include doctor knife coating, roll coating, wire coating, grapier coating, and spray coating. It can be used for. The amount to be applied is appropriately selected so that a film of 1 to 20 g/m2 is formed on the active energy ray irradiation (on the substrate).
If the amount is less than 20g/m2, the proofing and lubricant properties will not be sufficient, while if it exceeds 20g/m2, the film may be easily cracked.
There are problems such as it becoming too thick, and it is uneconomical as it does not improve performance.

After application, some or all of the solvent is allowed to evaporate.

Approximately 20% of the amount to be evaporated is sufficient, and either heat drying or cold air drying may be used, but it is desirable to evaporate within a short time, preferably within 3 minutes. At present, the detailed mechanism of action is not clear, but such evaporation, including natural evaporation, has a positive effect on imparting water repellency and oil repellency, and on the adhesion of the film to the base.

After evaporation, the composition is cured by irradiation with active energy rays.

Examples of the types of active energy rays used include electron beams, ultraviolet rays, gamma rays, and beta rays, with electron beams and ultraviolet rays being common.

When performing electron beam irradiation, the irradiation conditions are an acceleration voltage of 100-
3,000 Kv, line ffi0.1-2 0 Mrad.

Preferably it is 0.5~]OMrad. The irradiation atmosphere may be air or an inert gas atmosphere such as nitrogen is suitable. This type of curing method using electron beam irradiation has certain application conditions, such as sufficient curing even when the composition contains a large amount of filler or colorant, or when a part of the composition has penetrated into the base material. It has a wide range and can be used suitably.

When performing ultraviolet irradiation, it is usually necessary to add a photoinitiator such as pentuphenone or anthraquinone to the composition. The wavelength range used is near ultraviolet light of 2,000 to 8,000.

After irradiation with active energy rays, the water repellent/oil repellent sheet of the present invention is obtained.

The thus obtained water repellent/oil repellent material of the present invention can be widely used in applications requiring stain resistance, water repellency or exfoliating properties.

For example, tents, simple houses, wall materials, floor materials, rain gear, coats, table cloths, and various notebooks used as industrial materials and construction materials can all be suitably used.

5 Big Yabo The present invention will be explained in more detail with reference to Examples below.

Example 1 A soft PVC tarpaulin with a thickness of 0.5 mm made by laminating soft polyvinyl chloride films on both sides of a polyester woven fabric was used as a profiteer, and a monomer composition of the following composition was reacted with the tarpaulin to reduce the solid content. It was applied with a wire bar in an amount of 5 g/m2.

Precept: Part by weight alkylfluoroacrylate-1.(-12,0 urethane acrylate)
'83.0 Polyethylene glycol
15.0 diacrylate (eゝisopropyl alcohol 90.0"'CH
2-CHC00(CH2)2(CF2)aF.

Osaka Organic Chemical Industry Co., Ltd. TBL Bifunctional Urethane Acrylate - Product No. B5672-40 (°) Molecular Weight 200 6 Next, it was dried with cold air at 25°C for 5 seconds to remove about 1/2 of the solvent.
Immediately after evaporating 2, using an area beam type electron beam irradiation device, in a nitrogen atmosphere, acceleration voltage 150 KV, dose 2 Mr.
The monomer composition was cured by irradiation with an electron beam under ad conditions to obtain a water repellent/oil repellent sheet of the present invention.

Example 2 Flame retardant paper laminated with soft vinyl sheet, thickness 0.4m
An anti-moisture and anti-moisture sheet of the present invention was obtained in accordance with the method of Example 1, except that the vinyl wallpaper of No. m and the monomer composition having the following composition were used.

Part by weight (alkyl fluoroacrylate) 1.0 Ninomiya functional acrylate
) ”' 79 Polyethylene diacrylate
1-” 20 methyl ethyl ketone
70'''CH2=CHC00CH2(CF2), H
Lb1 manufactured by Osaka Organic Chemical Industry Co., Ltd. Kayarad R6041'' manufactured by Nippon Kayaku Co., Ltd., molecular weight 400 Water repellent/oil repellent sheet of the present invention obtained in Example 1 and Example 2, and PVC as a phantom product Tarpaulin (Comparative Example 1) and vinylidene fluoride film laminate product (
Using Comparative Example 2), the contact angle with pure water (indicator of the degree of oleaginous property: the larger the value is, the better the oleophilicity is). Excellent) and antifouling properties were evaluated.

The contact angle is measured by the usual method by observing with a magnifying glass. Also, the antifouling test is performed by placing the sheet test piece in a mixed staining agent such as humus, cement, kaolin, carbon black, mineral powder, etc. After contamination with shaking for 30 minutes at 'c', a five-level evaluation was performed by visual observation (evaluation criteria: 1: maximum contamination, 5: no contamination at all).

The results are shown in Table 1.

Table 1 As is clear from Table 1, the sheet of the present invention has excellent water repellency, oil repellency, and stain resistance compared to the control product; the sheet of Example 1 is suitable for tents, and the sheet of Example 2 is It could be suitably used as antifouling wallpaper, etc. In addition, Comparative Examples 1 and 2
The contact angle for n-heptane was too low to be measured.

Effects of the Invention The present invention provides a water-repellent/oil-repellent sheet having a uniform water-repellent/oil-repellent film using a fluoromonomer. In particular, the water-repellent and oil-repellent film in such sheets can provide properties such as adhesion to the substrate, hardness, and flexibility that are derived from other copolymer components, which account for the majority in quantity9. It has a wide range of technical applications.

Furthermore, the present invention provides a method for producing such anti-inflammatory and anti-inflammatory sheets. In particular, the manufacturing method of the present invention is superior in terms of process, with no problems in the steps of blending the composition, coating, and film formation.

Claims (2)

[Claims] (1) Base material and thickness of 1 to 20 g provided on the base material
/m^2, the sheet has surface properties such that the contact angle with water is 90° or more and the contact angle with n-heptane is 45° or more, and the film has a surface property of 0. .1 to 5.0 parts by weight of fluoroalkyl acrylate or fluoroalkyl methacrylate, 95.
Water repellent and oil repellent, characterized in that it is a composition comprising 0 to 99.9 parts by weight of a compound having an ethylenically unsaturated bond and 20 to 200 parts by weight of a solvent, which is cured by irradiation with active energy rays. sheet. (2) 0.1 to 5.0 parts by weight of fluoroalkyl acrylate or fluoroalkyl methacrylate, 95.
A composition consisting of 0 to 99.9 parts by weight of a compound having an ethylenically unsaturated bond and 20 to 200 parts by weight of a solvent is applied onto a substrate, and part or all of the solvent is evaporated,
Next, the composition is cured by irradiation with active energy rays to form a film with a thickness of 1 to 20 g/m^2, and has a contact angle with water of 90° or more and with respect to n-heptane. A method for producing a water-repellent/oil-repellent sheet having surface properties with a contact angle of 45° or more.