JP2019038140A - Antifogging film, and antifogging mirror - Google Patents

Abstract

To provide an antifogging film having excellent antifogging properties and alkali resistance.SOLUTION: An antifogging film has an adhesive layer, a substrate layer, and a hydrophilic surface layer, in the stated order. The hydrophilic surface layer has a water contact angle of 40° or less, and has a water contact angle of 40° or less after contacting with 1 N sodium hydroxide for 24 hours.SELECTED DRAWING: None

Description

  The present invention relates to an antifogging film and an antifogging mirror.

Mirrors are used everywhere in daily life, such as bathrooms, washstands, cars, and roads. For example, a mirror installed in a place where hot water such as a bathroom or a wash basin is used tends to become cloudy due to steam generated from the hot water.
Since a mirror that is cloudy has poor visibility and cannot serve its intended purpose, the mirror is required to have a property that makes it difficult to fog (hereinafter also referred to as “anti-fogging”).

As a method for imparting antifogging properties to a mirror, a method is known in which a sheet-like heater made of a heating element is attached to the back surface of a mirror plate (see, for example, Patent Document 1).
Although this method has a high anti-fogging effect and is reliable, it generates heat using electricity, so there is a risk of electric shock in places where hot water is used, and there is a problem that it is difficult to use and is not simple.
In addition, as an article for easily imparting an antifogging effect to a mirror, an antifogging film that is attached to a mirror and used is commercially available. The antifogging film is said to be excellent in antifogging property because the film surface is subjected to a hydrophilic treatment, for example.

JP-A-9-191987

As a result of investigations by the inventors, commercially available antifogging films may not have sufficient antifogging properties. Further, most of the antifogging films are resinous films, and there has been a problem that the antifogging properties may be impaired when washed with an alkaline mold remover. Therefore, the antifogging film is required to have excellent properties (hereinafter also referred to as “alkali resistance”) excellent in antifogging properties even after alkali treatment.
Therefore, an object of the present invention is to provide an antifogging film having excellent antifogging properties and alkali resistance.

In order to achieve the above object, the present invention includes the following aspects.
<1> An antifogging film having an adhesive layer, a base material layer, and a hydrophilic surface layer in this order, wherein the hydrophilic surface layer has a water contact angle of 40 ° or less, and An antifogging film having a water contact angle of 40 ° or less after contact with 1N sodium hydroxide for 24 hours.
<2> The antifogging according to <1>, wherein the hydrophilic surface layer has at least one functional group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, a carboxyl group, a silanol group, a hydroxyl group, and a salt thereof. Sex film.
<3> The hydrophilic surface layer is a polymer hydrophilic film having a sulfonic acid group, and the ratio (Sa / Da) of the surface sulfonic acid group concentration (Sa) to the deep sulfonic acid group concentration (Da) is 1. The antifogging film according to any one of <1> or <2>, which is 1 or more.
<4> Compound (I) in which the hydrophilic surface layer has a sulfonic acid group and at least one functional group having a polymerizable carbon-carbon double bond (however, when the hydrophilic group is a group having a hydroxyl group, There is one functional group having a polymerizable carbon-carbon double bond.), Compound (II) having two or more functional groups having a polymerizable carbon-carbon double bond (however, even if it has a hydroxyl group) A monolayer film made of a crosslinked resin obtained by polymerizing a polymerizable composition containing an anionic hydrophilic group and a cationic hydrophilic group). Hydrophilic group concentration of the surface concentration (Sa) of at least one hydrophilic group selected from an anionic hydrophilic group, a cationic hydrophilic group, and a hydroxyl group, and the deep concentration (Da) of the hydrophilic group at a point of 1/2 thickness of the monolayer film Of the slope (Sa / Da) of 1. Antifogging film according to the is either <1> or <2> or more.
An antifogging mirror having a <5> mirror and the antifogging film according to any one of <1> to <4>.

  According to the antifogging film of the present invention, an antifogging film having excellent antifogging properties and alkali resistance can be provided.

<< Anti-fogging film >>
The antifogging film of the present invention is an antifogging film having an adhesive layer, a base material layer, and a hydrophilic surface layer in this order, and the hydrophilic surface layer has a water contact angle of 40 °. The water contact angle after contact with 1N sodium hydroxide for 24 hours is 40 ° or less.

<Hydrophilic surface layer>
The antifogging film of the present invention has a hydrophilic surface layer having a water contact angle of 40 ° or less. The water contact angle of the hydrophilic surface layer is 40 ° or less, preferably 30 ° or less, more preferably 20 ° or less, and still more preferably 10 ° or less.
Since the hydrophilic surface layer having a water contact angle of not more than the above value is highly hydrophilic, it adheres to the mirror surface (that is, the hydrophilic surface layer of the antifogging film) when the antifogging film is attached to the mirror. Moisture spreads easily and the mirror is difficult to cloud.

(Measurement of water contact angle)
The value of the water contact angle of the hydrophilic surface layer in the present invention is an average value of values measured at three locations for one sample using a water contact angle measuring device CA-V type manufactured by Kyowa Interface Science Co., Ltd.

The glass used for the mirror can realize a low water contact angle of about 5 ° when polished with an abrasive such as a cleanser. However, when the polished glass is left in the air, the water contact angle becomes about 50 ° to 90 ° in about one day. Mirrors installed in bathrooms and the like tend to be inferior in anti-fogging properties because the water contact angle is thus high.
On the other hand, the antifogging film of the present invention has a hydrophilic surface layer having a water contact angle of a predetermined value or less. It is thought that haze can be imparted.

  In order to reduce the water contact angle, the hydrophilic surface layer in the present invention has a chemical structure that exhibits hydrophilicity, and includes a sulfonic acid group, a phosphoric acid group, a carboxyl group, a silanol group, a hydroxyl group, and a salt thereof. It preferably has at least one functional group selected. Among these, it is more preferable to have a sulfonic acid group.

  As the hydrophilic surface layer having a phosphoric acid (ester) group, for example, NOF Corporation “LIPIDURE” (registered trademark) or a hydrophilic polymer having a phosphorylcholine group described in JP-A-07-010892 is used. be able to.

  Examples of the hydrophilic surface layer having a silanol group include “LAMBIC” (registered trademark) of Osaka Organic Chemical Industry Co., Ltd., which is a comb polymer having a silanol group, or JP 2011-219637 and 2012- A hydrophilic polymer composed of a (meth) acrylate monomer and an alkoxysilane monomer described in Japanese Patent No. 007053 can be suitably used.

  The hydrophilic surface layer having a sulfonic acid group is, for example, a polymer hydrophilic film having a sulfonic acid group, and the ratio of the surface sulfonic acid group concentration (Sa) to the deep sulfonic acid group concentration (Da) (Sa / A film having a Da) of 1.1 or more can be mentioned. As such a sulfonic acid group-containing hydrophilic membrane, a polymer membrane described in WO2007 / 064003 International Publication Pamphlet can be used.

As the hydrophilic surface layer having a sulfonic acid group, the following are more preferable.
Compound (I) having a sulfonic acid group and at least one functional group having a polymerizable carbon-carbon double bond (in the case where the hydrophilic group is a group having a hydroxyl group, it has a polymerizable carbon-carbon double bond) One functional group).
Compound (II) having two or more functional groups having a polymerizable carbon-carbon double bond (however, it may have a hydroxyl group but neither an anionic hydrophilic group nor a cationic hydrophilic group). ), A hydrophilic film made of a crosslinked resin obtained by polymerizing a polymerizable composition.

  The polymerizable composition further comprises a surfactant (III) having an anionic hydrophilic group, a cationic hydrophilic group, or a hydrophilic part having two or more hydroxyl groups, and a hydrophobic part comprising an organic residue, and a siloxane bond. At least one compound selected from compound (IV) having a molecular weight of 200 to 1,000,000 having the formula (provided that surfactant (III) and compound (IV) do not have a polymerizable carbon-carbon double bond). ) May be included.

  The surface concentration (Sa) of at least one hydrophilic group selected from an anionic hydrophilic group, a cationic hydrophilic group, and a hydroxyl group of the monolayer film, and a deep concentration (Da) of the hydrophilic group at a film thickness 1/2 point of the monolayer film ) Of the hydrophilic group concentration (Sa / Da) is preferably 1.1 or more.

  The gradient (Sa / Da) of the sulfonic acid group concentration of the surface concentration (Sa) of the sulfonic acid group of the single layer film and the deep concentration (Da) of the sulfonic acid group at the film thickness 1/2 point of the single layer film, It is more preferable that it is 1.1 or more.

  As such a sulfonic acid group-containing hydrophilic membrane, for example, a polymer membrane described in WO2015 / 087810 International Publication Pamphlet can be used.

<Base material layer>
Examples of the base material for forming the base material layer in the present invention include polyacrylamide, polyisopropylacrylamide, polyacrylonitrile, polymethyl methacrylate (PMMA), polycarbonate, polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyurethane resin, epoxy resin, Examples include base materials made of organic materials such as vinyl chloride resin and silicone resin.
The substrate is preferably highly transparent from the viewpoint of maintaining visibility.

  For the purpose of activating the surface of the base material as necessary, the surface of these base materials is corona treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, chemicals, etc. A physical or chemical treatment such as an oxidation treatment or a flame treatment can be performed. In addition to or in addition to these treatments, primer treatment, undercoat treatment, and anchor coat treatment may be performed.

  Examples of the coating agent used in the primer treatment, undercoat treatment, and anchor coat treatment include, for example, polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, and polyvinyl acetate resins. A coating agent containing a resin, a polyolefin resin such as polyethylene and polypropylene, or a copolymer or modified resin thereof, a resin such as a cellulose resin as a main component of the vehicle can be used. The coating agent may be either a solvent type coating agent or an aqueous type coating agent.

Among these coating agents, modified polyolefin coating agents, ethyl vinyl alcohol coating agents, polyethyleneimine coating agents, polybutadiene coating agents, polyurethane coating agents;
Polyurethane emulsion coating agent, polyvinyl chloride emulsion coating agent, urethane acrylic emulsion coating agent, silicone acrylic emulsion coating agent, vinyl acetate acrylic emulsion coating agent, acrylic emulsion coating agent;
Styrene-butadiene copolymer latex coating agent, acrylonitrile-butadiene copolymer latex coating agent, methyl methacrylate-butadiene copolymer latex coating agent, chloroprene latex coating agent, rubber-based latex coating agent of polybutadiene latex, polyacrylic acid ester A latex coating agent, a polyvinylidene chloride latex coating agent, a polybutadiene latex coating agent, or a coating agent comprising a carboxylic acid-modified latex or a dispersion of a resin contained in these latex coating agents is preferable.

These coating agents can be applied, for example, by a gravure coating method, a reverse roll coating method, a knife coating method, a kiss coating method, etc., and the amount applied to the substrate is in a state where the solvent contained in the composition is removed, Usually ^{0.05g / m 2 ~10g / m 2} , preferably from ^{0.05g / m 2 ~5g / m 2} .

  Among these coating agents, polyurethane-based coating agents are more preferable. The polyurethane-based coating agent has a urethane bond in the main chain or side chain of the resin contained in the coating agent. A polyurethane-type coating agent is a coating agent containing the polyurethane obtained by making polyol and isocyanate compounds, such as polyester polyol, polyether polyol, or acrylic polyol, react, for example.

Among these polyurethane coating agents, polyurethane coating agents obtained by mixing polyester polyols such as condensation polyester polyols and lactone polyester polyols with polyisocyanates are preferable because of excellent adhesion.
Examples of the polyisocyanate include aliphatic (including alicyclic) polyisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and bis (isocyanatomethyl) cyclohexane, and derivatives thereof such as tolylene diisocyanate and diphenylmethane. Aromatic polyisocyanates such as diisocyanates and derivatives thereof, for example, polyisocyanates such as araliphatic polyisocyanates such as xylylene diisocyanate and derivatives thereof.
Among these, preferably, non-yellowing type isocyanate compounds, specifically, aliphatic (including alicyclic) polyisocyanates and derivatives thereof are mentioned.

  The method for mixing the polyol compound and the isocyanate compound is not particularly limited. Further, the blending ratio is not particularly limited, but if the isocyanate compound is too small, curing failure may be caused. Therefore, the OH group of the polyol compound and the NCO group of the isocyanate compound are equivalently converted to OH group / NCO group = 2/1 to 1/1 /. A range of 40 is preferred.

<Adhesive layer>
There is no restriction | limiting in particular as long as the adhesive used for an adhesion layer does not impair the effect of this invention, A well-known adhesive can be used. Examples of the adhesive include acrylic adhesives, rubber adhesives, vinyl ether polymer adhesives, and silicone adhesives.
Among these, acrylic adhesives are preferable because of excellent transparency.

  The thickness of the pressure-sensitive adhesive layer in the present invention is preferably in the range of 2 to 100 μm, and more preferably in the range of 5 to 50 μm.

<Other layers>
The antifogging film of the present invention may have a layer (hereinafter, also referred to as “other layer”) other than the pressure-sensitive adhesive layer, the base material layer, and the hydrophilic surface layer.
Examples of other layers include a covering material layer.
A covering material layer is a layer which coat | covers the surface which touches the outside air of a hydrophilic surface layer and an adhesion layer, and protects a hydrophilic surface layer and an adhesion layer. The hydrophilic surface layer covered with the covering material layer can prevent the hydrophilic surface layer from being damaged or soiled during transportation, storage, display, or the like.
The covering material layer is peeled off and removed when protection of the hydrophilic film and the adhesive layer becomes unnecessary.
The covering material layer may be provided only on one of the surface of the hydrophilic surface layer and the surface of the adhesive layer, or may be provided on both the surface of the hydrophilic surface layer and the surface of the adhesive layer.

  Examples of the material of the film preferably used as the coating material include, for example, polyvinyl alcohol (PVA), polyacetyl cellulose (TAC), vinyl alcohol polymers such as ethylene / vinyl alcohol copolymer, polyacrylamide, polyisopropylacrylamide, poly Examples include acrylonitrile, polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyacrylonitrile-butadiene-styrene copolymer (ABS), polystyrene (PS), and biaxially oriented polypropylene (OPP).

  The antifogging film of the present invention is, for example, an adhesive layer / base material layer / hydrophilic surface layer, an adhesive layer / base material layer / hydrophilic surface layer / coating material layer, or a coating material layer / adhesive layer / base material. The layer structure may be layer / hydrophilic surface layer / coating material layer or coating material layer / adhesive layer / base material layer / hydrophilic surface layer.

  The planar shape of the antifogging film of the present invention is not particularly limited, and examples thereof include a circle, an ellipse, a polygon such as a triangle and a quadrangle, and a combination of these.

  The antifogging film of the present invention may be provided with a pattern, a color, and a combination thereof (hereinafter also referred to as “decoration”). Examples of the decoration include a border and a picture. The transparency of these decorations is not particularly limited as long as it can be used as a mirror when attached to a mirror, and may be transparent, translucent, or opaque.

<Manufacturing method>
The antifogging film of the present invention can be produced by a known method as long as the effects of the present invention are not impaired. As a known method, for example, the production method described in WO2013 / 14733 can be mentioned.

  Since the antifogging film of the present invention is not easily fogged even when exposed to a high humidity environment, it is preferably used for imparting antifogging properties to a mirror in a washstand or a mirror in a bathroom, and is excellent in alkali resistance. It is more preferably used as a bathroom mirror.

<< Anti-fog mirror >>
The antifogging mirror of this invention has a mirror and the above-mentioned antifogging film.
The antifogging mirror of the present invention can be produced by attaching the above-described antifogging film to a mirror described later.

<Mirror>
The mirror in the present invention is not particularly limited as long as it can reflect light. Examples of the mirror in the present invention include a mirror in which a metal layer having a high reflectance such as silver or aluminum is formed on the surface of a glass plate.

The shape of the mirror in the present invention is not particularly limited. Examples of the shape of the mirror include a square, a rectangle, a circle, and an ellipse.
The mirror surface may be formed with irregularities or a curved surface.

  In the antifogging mirror in the present invention, either the mirror or the antifogging film may be large or the same size. That is, the antifogging film may be adhered to the entire surface of the mirror or may be adhered to a part of the mirror.

  The antifogging mirror of the present invention is preferably used as a mirror for a washstand or a bathroom mirror because it is not easily fogged even when exposed to a high humidity environment, and is more preferably used as a bathroom mirror because of excellent alkali resistance. It is done.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited only to these Examples.

[Example 1]
A coating composition A was prepared according to Example 6A described in the WO2015 / 087810 international publication pamphlet (however, the solid content was changed from 60% by mass to 40% by mass).
The coating composition A (solid content 40 wt%) is applied to an easy-adhesion PET Lumirror U40 (film thickness 100 μm, Toray Industries, Inc.) with a bar coater # 06, placed in a hot air dryer for 2 minutes at 50-60 ° C. The solvent contained in the composition was removed.

The sample from which the solvent has been sufficiently removed is passed through the UV conveyor once and UV irradiation (electrodeless H bulb 240 W / cm ² , output 100%, lamp height 40 mm, conveyor speed 8 m / min. Illuminance 743 mW / cm ² , (Measured with UV Power PuckII of Electronic Instrumentation & Technology, Inc., integrated light intensity of 434 mJ / cm ² ), and a single layer film (hydrophilic surface layer) made of a crosslinked resin having a hydrophilic surface of 3 μm thickness on PET Formed. Finally, the membrane surface was washed with running water, dried with an air gun, and then a part of the test piece obtained by cutting was used as an antifogging evaluation sample. In addition, the remaining part is used as a chemical resistance evaluation sample, as follows, antifogging after alkali treatment (alkali resistance), antifogging after mildew treatment, antifogging after neutral detergent treatment, and The antifogging property (acid resistance) after acid treatment was evaluated.

The following drugs were used in each test.
Alkaline solution: 1N sodium hydroxide (NaOH)
Mold remover: Brand name mold killer (manufactured by Johnson)
Neutral detergent: Product name Bath Magiclin (Kao Corporation)
Acid solution: 1N hydrochloric acid (HCl)

  Each of the above drugs was soaked in gauze, placed on the hydrophilic surface layer of the sample for chemical resistance evaluation, covered with a petri dish with grease applied to the edge, and allowed to stand for 24 hours. Thereafter, the gauze was removed, and the hydrophilic surface layer was washed with water and allowed to stand at 50 ° C. for 10 minutes and dried to obtain samples after treatment with each drug.

1. Measurement of water contact angle The water contact angle was measured by the above-described method for each of the antifogging evaluation sample and the sample after each chemical treatment. The results are shown in Table 1.

2. Antifogging evaluation (exhalation antifogging)
About each of the sample for anti-fogging evaluation and the sample after each chemical | medical agent process, the breath was sprayed on the hydrophilic surface layer from the distance of 5 cm, the degree of cloudiness was observed with the naked eye, and it evaluated according to the following evaluation criteria. The results are shown in Table 1.
-Evaluation criteria-
○: No fogging and excellent antifogging property.
X: Partially or entirely cloudy and inferior in antifogging properties.

3. Evaluation of appearance change About each sample after each chemical treatment, the appearance was observed with the naked eye, compared with the sample for evaluation of anti-fogging property, and evaluated according to the following evaluation criteria. The results are shown in Table 1.
-Evaluation criteria-
○: It was equivalent to the sample for antifogging evaluation.
(Triangle | delta): Peeling was recognized in part compared with the sample for anti-fogging evaluation.
X: Compared with the sample for anti-fogging evaluation, coloring or peeling was recognized by the whole.

4). Transparency Evaluation Transparency was confirmed with the naked eye for each of the antifogging evaluation sample and the sample after each chemical treatment, and evaluated according to the following evaluation criteria. The results are shown in Table 1.
-Evaluation criteria-
○: Transparent and excellent in visibility.
X: Opaque and inferior in visibility.

[Comparative Example 1]
A biaxially stretched polypropylene film (trade name: A-OP, manufactured by Mitsui Chemicals, Inc.) that was subjected to a surface hydrophilization treatment with polyvinyl alcohol was prepared. The hydrophilized surface was washed with running water, dried with an air gun, and then a part of the test piece obtained by cutting was used as an antifogging evaluation sample. Moreover, the sample after each chemical | medical agent process was obtained like Example 1 using the remaining one part. The gauze impregnated with the drug was placed on the hydrophilic treatment surface.

About each of the sample for anti-fogging evaluation and the sample after each chemical | medical agent process, it carried out similarly to Example 1, and implemented the measurement of the water contact angle, the breath anti-fogging evaluation, and the external appearance evaluation.
The results are shown in Table 1.

[Comparative Example 2]
An anti-fogging agent (trade name Riquemar A, sucrose laurate, HLB15, manufactured by Riken Vitamin Co., Ltd.) is applied to a polypropylene film (trade name HC-CP, film thickness 30 μm, manufactured by Mitsui Chemicals, Inc.) with a bar coater # 06. Then, it was placed in a hot air dryer for 2 minutes to remove the solvent contained in the composition at 50 to 60 ° C. to form an antifogging film (antifogging film). The film thickness of the antifogging agent film was 0.2 μm. Next, the anti-fogging agent film was washed with running water, dried with an air gun, and then cut to obtain a sample after washing with water. Moreover, the sample after each chemical | medical agent process was obtained like Example 1 using the remaining one part. The gauze impregnated with the drug was placed on the antifogging agent film.

About each of the sample for anti-fogging evaluation and the sample after each chemical | medical agent process, it carried out similarly to Example 1, and implemented the measurement of the water contact angle, the exhalation anti-fogging evaluation, and the external appearance evaluation.
The results are shown in Table 1.

[Comparative Example 3]
The water contact angle measurement, breath antifogging evaluation and appearance evaluation were carried out in the same manner as in Comparative Example 2 except that the film thickness of the antifogging film was changed from 0.2 μm to 1.5 μm in Comparative Example 2.
The results are shown in Table 1.

  In Table 1, “-” indicates that the corresponding evaluation is not performed.

Example 1 having a hydrophilic surface layer having a water contact angle of 40 ° or less and a water contact angle of 40 ° or less after contact with 1N sodium hydroxide for 24 hours is effective in antifogging and alkali resistance. It turns out that it is excellent.
On the other hand, it can be seen that Comparative Example 1 having a surface with a water contact angle exceeding 40 ° after contact with 1N sodium hydroxide for 24 hours is inferior in antifogging after alkali treatment. Comparative Examples 2 and 3 having a surface with a water contact angle exceeding 40 ° and a water contact angle exceeding 40 ° after contact with 1N sodium hydroxide for 24 hours are anti-fogging and alkali resistance. It turns out that it is inferior to.

Claims (5)

An antifogging film having an adhesive layer, a base material layer, and a hydrophilic surface layer in this order,
The hydrophilic surface layer is an antifogging film having a water contact angle of 40 ° or less and a water contact angle of 40 ° or less after contact with 1N sodium hydroxide for 24 hours.   The antifogging film according to claim 1, wherein the hydrophilic surface layer has at least one functional group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, a carboxyl group, a silanol group, a hydroxyl group, and a salt thereof.   The hydrophilic surface layer is a polymer hydrophilic film having a sulfonic acid group, and the ratio (Sa / Da) of the surface sulfonic acid group concentration (Sa) to the deep sulfonic acid group concentration (Da) is 1.1 or more. The antifogging film according to any one of claims 1 and 2. The hydrophilic surface layer is
Compound (I) having a sulfonic acid group and at least one functional group having a polymerizable carbon-carbon double bond (in the case where the hydrophilic group is a group having a hydroxyl group, it has a polymerizable carbon-carbon double bond) One functional group).
Compound (II) having two or more functional groups having a polymerizable carbon-carbon double bond (however, it may have a hydroxyl group but neither an anionic hydrophilic group nor a cationic hydrophilic group). ),
A monolayer film made of a crosslinked resin obtained by polymerizing a polymerizable composition containing
The surface concentration (Sa) of at least one hydrophilic group selected from an anionic hydrophilic group, a cationic hydrophilic group, and a hydroxyl group of the monolayer film, and the deep concentration of the hydrophilic group (Da) at the film thickness 1/2 point of the monolayer film The gradient of the hydrophilic group concentration (Sa / Da) is 1.1 or more, and the antifogging film according to claim 1.   The anti-fogging mirror which has a mirror and the anti-fogging film as described in any one of Claims 1-4.