JP2002052847A - Heat sensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat sensitive recording material, in which the poor hardening in the heat hardening with a hardener, the transition of a siloxane compound or the like to an ink layer and the self-adhesion to a thermal head or the pollution of the thermal head at the high temperature usage thereof are prevented from developing, and which has an excellent lubricity and a rear surface layer, which can be formed easily. SOLUTION: This heat sensitive recording material consists of a base material and a heat sensitive recording layer provided onto one side of the base material sheet, on the other side of which a rear surface layer is provided. The rear surface layer is made of one including an acrylic resin having a siloxane segment in a main chain and/or in a side chain.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive recording material having a back layer (heat-resistant lubricating layer) using a siloxane-modified acrylate resin. Forming a crosslinked film by irradiation of ionizing radiation, based on an acrylic resin, a main chain and / or
Also, the present invention relates to a heat-sensitive recording material comprising a siloxane-modified acrylic resin obtained by copolymerizing a siloxane compound in a side chain and having a back layer excellent in lubricity, heat resistance, blocking resistance, low migration, and high hardness.

[0002]

2. Description of the Related Art A heat-sensitive recording material used in a recording apparatus of a thermal transfer recording system basically comprises a substrate made of various plastic films, sheets or resin moldings, and a sublimation type dye and wax or various resins. A heat transferable ink layer (a heat-meltable ink layer: referred to as a thermosensitive recording layer in the present invention) is generally provided.

In a thermal recording material having a thermal transfer ink layer provided on such a substrate, the thermal head in the recording apparatus comes into contact with the substrate during printing, so that the substrate is fused by a high-temperature thermal head. As a result, problems such as loss of lubrication and breakage of the base material occur in some cases. As means for solving such a problem, a resin film having excellent adhesion, heat resistance and lubricity is provided as a back layer (heat-resistant lubricating layer) on the back side of the thermal transfer ink layer of the substrate. ing.

Conventionally, as such a heat-resistant lubricating layer, an acrylic resin, a polysiloxane resin, a polyester resin, or a polyamide having an active hydrogen-containing functional group on one surface of the substrate (the back surface of the thermal transfer ink layer) has been used. A crosslinked film formed by crosslinking a thermoplastic resin such as a resin or a polyurethane resin with a polyisocyanate crosslinking agent or the like has been used. When performing two-component crosslinking using the thermoplastic resin and a polyisocyanate-based crosslinking agent or the like, problems such as poor working (cross-linking (curing)) may occur due to pot life or moisture or impurities in the air. As a result, various physical properties such as heat resistance, adhesion to a substrate, and film strength become insufficient, which causes printing defects.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a conventional heat-sensitive recording material by using a curing agent (crosslinking agent) to form a back layer. There is no problem of poor printing during printing due to insufficient curing due to insufficient aging when forming, no problem of transfer of ink or transfer of unreacted siloxane component, and it has excellent heat resistance and adhesiveness, furthermore, improvement of productivity and energy saving. Another object of the present invention is to provide a heat-sensitive recording material which does not require an aging step (heating and curing step) that also achieves space saving and the like.

[0006]

The above object is achieved by the present invention described below. That is, the present invention comprises a base sheet, a heat-sensitive recording layer provided on one side of the base sheet, and a back layer provided on the other side of the base sheet, wherein the back layer has a main chain and / or
Or, it is a thermosensitive recording material comprising a layer containing an acrylic resin having a siloxane segment in a side chain.

According to the present invention, a back surface containing a siloxane-modified acrylic resin which is crosslinked by heat and / or ionizing radiation such as ultraviolet rays or electron beams, and has excellent lubricity, heat resistance, blocking resistance, low migration, and high hardness. A thermal recording material having a layer is provided. Further, if necessary, by using a siloxane-modified acrylic resin and an unsaturated group-containing crosslinking agent or a reactive diluent in combination,
Non-adhesiveness, lubricity, heat resistance, high hardness, stain resistance, chemical resistance, solvent resistance, low coefficient of friction, anti-blocking due to crosslinking of reactive unsaturated groups by heat and / or ionizing radiation The present invention provides a heat-sensitive recording material having, as a back layer, a novel heat-resistant lubricating layer having excellent low migration property and excellent bleeding resistance in addition to the properties.

[0008] Compared with the conventional two-pack type crosslinking of a thermoplastic resin and a polyisocyanate-based crosslinking agent, the siloxane-modified acrylate-based resin has a higher ionizing radiation such as heat, ultraviolet rays, and electron beams. Is not cross-linked unless irradiated, so that it can be stored and used in one liquid using an unsaturated group-containing cross-linking agent, a reactive diluent, a photopolymerization initiator, and other paint additives. In addition, since crosslinking is instantaneous upon irradiation with ionizing radiation, a ripening step (for example, 60 ° C. /
5 days) becomes unnecessary, and the process can be simplified.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments of the invention. The siloxane-modified acrylic resin used in the present invention is a resin that can be cured by irradiation with heat and / or ionizing radiation such as ultraviolet rays or electron beams. When forming the back layer of the thermal recording material,
If necessary, a siloxane-modified acrylic resin further added with a photopolymerization initiator, an unsaturated group-containing crosslinking agent and / or a reactive diluent, or another binder resin, etc. The composition is applied to a base sheet to form a coating, and the coating is irradiated with heat and / or ionizing radiation such as ultraviolet rays or electron beams to form a cured coating. The resulting cured film has excellent physical properties such as adhesion to the substrate, non-adhesion, lubricity, heat resistance, high hardness, mechanical strength, low friction coefficient, anti-blocking, and low migration, and has a high crosslinking density. By adjusting, it is possible to give desired physical property values.

The siloxane-modified acrylic resin is not particularly limited as long as it is an acrylate resin having a siloxane segment in a main chain and / or a side chain which can be crosslinked by heat and / or ionizing radiation. A preferred siloxane-modified acrylic resin is a copolymer of a radically polymerizable unsaturated group-containing siloxane compound and acrylate and / or methacrylate. Examples of the radically polymerizable unsaturated group-containing siloxane compound include siloxane compounds having an unsaturated group such as an acryloyl group, a methacryloyl group, a vinyl group or an allyl group at both terminals, one terminal or a side chain. A siloxane compound having a radical polymerizable unsaturated group having a roisopropyl group is easily available and is preferable.

An example of the radical polymerizable unsaturated group-containing siloxane compound is shown below. (1) Radical polymerizable unsaturated group-containing siloxane compound (one terminal type) (X represents H or CH ₃ , and m represents an integer of 1 or more.)

(2) Radical polymerizable unsaturated group-containing siloxane compound (both terminal type) (X represents H or CH ₃ , and m represents an integer of 1 or more.)

(3) Radical polymerizable unsaturated group-containing siloxane compound (side chain type) (X represents H or CH ₃ , and m and n represent an integer of 1 or more.)

A radically polymerizable acrylic monomer copolymerized with a radically polymerizable unsaturated group-containing siloxane compound (in the present invention, acrylate and methacrylate are collectively referred to as an acrylic monomer, and may be described as (meth) acrylate. Examples of ()) include a monofunctional acrylic monomer and a polyfunctional acrylic monomer, and a monofunctional acrylic monomer is preferable. Examples of the monofunctional acrylic monomer include, for example, ethyl acrylate, butyl acrylate, propyl acrylate, n-butyl acrylate, and 2-acrylate.
Ethyl hexyl, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, lauryl methacrylate, and other acrylic acids and esters of methacrylic acid with aliphatic or alicyclic monoalcohols; acrylic acid-2-hydroxyethyl, acrylic acid- 2-hydroxypropyl,
4-hydroxybutyl acrylate, methacrylic acid-2
-Hydroxyethyl, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, etc., obtained by ring-opening polymerization of a monoester of methacrylic acid with an aliphatic diol or a lactone such as ε-caprolactone. And a monoester of hydroxyl group polylactone (aliphatic polyester) with acrylic acid and methacrylic acid. These can be used alone or in combination of two or more. If necessary, other monomers copolymerizable with these monomers can also be used.

The siloxane compound containing a radical polymerizable unsaturated group and the acrylic monomer as described above are examples of preferred compounds constituting the siloxane-modified acrylate resin used in the present invention, and the present invention is not limited to these examples. It is not something to be done. Therefore, not only the exemplified compounds described above but also other compounds that are currently commercially available and easily available from the market can be used in the present invention.

The siloxane-modified acrylic resin can be obtained by copolymerizing the above-described radical-polymerizable unsaturated group-containing siloxane compound and an acrylic monomer by a known radical polymerization method. The content of the siloxane segment in the siloxane-modified acrylic resin is preferably from 1 to 75% by weight. Further, a preferable weight average molecular weight (measured by GPC and in terms of standard polystyrene) is
5,000 to 500,000.

The heat-sensitive recording material of the present invention has a structure in which a heat-sensitive recording layer is formed on one surface of a base sheet and a back layer is formed on the other surface, and the back layer is formed of the siloxane-modified acrylic resin. It is characterized in that it is formed of a layer (composition) containing a base sheet and a heat-sensitive recording layer, both of which have been used in conventionally known heat-sensitive recording materials. These are particularly used in the present invention. Not limited.

The back layer can be composed of only a siloxane-modified acrylic resin, but is preferably composed of a composition obtained by adding a photopolymerization initiator to a siloxane-modified acrylic resin. If necessary, an unsaturated group-containing crosslinking agent, a reactive diluent, another binder resin, or a solvent can be used as a crosslinking agent.

The photopolymerization initiator used in the present invention generates radicals by light, initiates radical polymerization of the siloxane-modified acrylic resin, monofunctional and polyfunctional monomers, and forms the above-mentioned siloxane-modified acrylic resin. It is preferable that the resin is grafted to a resin or that the resin is crosslinked, and any of those conventionally used in the field of photosensitive resins can be used, and is not particularly limited. For example, benzophenone, acetophenone, benzoin, benzoin isobutyl ether, benzoin isopropyl ether, benzoin ethyl ether, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, ethylanthraquinone, 4,4'-bisdimethylaminobenzophenone, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, benzyldimethyl ketal and the like. When a cationic polymerization diluent is used, a cationic photopolymerization initiator is used. As the cationic photopolymerization initiator, for example, aryldiazonium salt type compound,
Triarylsulfonium salt type compounds, diaryliodonium salt type compounds and the like can be mentioned. These photopolymerization initiators can be used alone or in combination of two or more in accordance with the type of the crosslinking agent or the reactive diluent to be used. The amount of the photopolymerization initiator used is not particularly limited, and is usually 0.01 to 100 parts by weight per 100 parts by weight of the siloxane-modified acrylic resin to be crosslinked by ionizing radiation such as ultraviolet rays or electron beams.
It is used in a proportion of 10 parts by weight, preferably about 1 to 10 parts by weight.

As the crosslinking agent used in the present invention, those conventionally used in the field of photosensitive resins can be used and are not particularly limited. Particularly preferred crosslinking agents are unsaturated group-containing crosslinking agents, for example, polyfunctional acrylic monomers having an unsaturated group (eg, trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, trimethylol propane EO). (Ethylene oxide) added triacrylate, glycerin PO (propylene oxide) added triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, and the like. Further, when the siloxane-modified acrylic polymer has a reactive functional group other than the unsaturated group, a polyisocyanate-based, melamine resin-based, epoxy resin-based compound and the like reactive with the reactive functional group as a crosslinking agent, Alternatively, their derivatives can also be used. The amount of the curing agent is not particularly limited, but is usually about 5 to 100 parts by weight per 100 parts by weight of the siloxane-modified acrylic resin.

As the reactive diluent used in the present invention, any organic compound having an unsaturated group conventionally used in the field of photosensitive resins can be used. An acrylic monomer, a vinyl monomer, a polyfunctional acrylic monomer, a cationic polymerizable monomer, and the like can be used. Examples of the monofunctional acrylic monomer include tetrahydrofurfuryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, phenyl (meth) acrylate, and 2-hydroxyethyl (meth).
Acrylate, diethylene glycol (meth) acrylate, phenoxydiethylene glycol acrylate,
Ethyl carbitol acrylate, isobornyl acrylate, acryloyl morpholine and the like can be mentioned. or,
Examples of the vinyl monomer include a norbornene monomer and N-vinylpyrrolidone.

Examples of the polyfunctional acrylic monomer include 1,6-hexanediol diacrylate, EO
Modified bisphenol A diacrylate, neopentyl glycol diacrylate, hydroxypivalate neopentyl glycol ester diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, PO-modified neopentyl glycol diacrylate, trimellilol propane tri (meth) acrylate, pentaerythritol Hexa (meth) acrylate, diethylene glycol di (meth) acrylate,
Examples include trimethylolpropane di (meth) acrylate and derivatives thereof. Examples of the cationic polymerizable diluent include an epoxy compound, an okitacene compound, a vinyl ether compound and the like. These reactive diluents can be used alone or in combination of two or more. The amount of the reaction diluent used is not particularly limited, but is usually about 10 to 600 parts by weight per 100 parts by weight of the siloxane-modified acrylic resin.

Other binder resins used in the present invention are not particularly limited. For example, conventionally known silicone resins, polyester resins, polyamide resins, polyimide resins, polystyrene resins, polyurethane resins, polycarbonate resins Resin, norbornene resin,
Cellulose resins, polyvinyl alcohol resins, polyvinyl formal resins, polyvinyl butyral resins, polyvinyl pyrrolidone resins, polyvinyl acetate resins, polyvinyl acetal resins, and the like.

If necessary, other additives such as a lubricant and an antistatic agent can be used. As the lubricant, for example, organic resin fine particles or inorganic fine particles are used. As the organic resin particles and the inorganic particles, for example, silicone resin fine particles, fluororesin fine particles, acrylic resin fine particles,
Fine particles such as urethane resin fine particles and polyethylene fine particles can be mentioned. In addition, reactive siloxane (silanol compound), various waxes and the like can also be used.
The antistatic agent is used to prevent the surface of the back layer from being charged by irradiation with ultraviolet rays or electron beams. As an antistatic agent,
For example, inorganic fillers such as siloxane-based fillers such as silica, and surfactants such as modified ethylene oxide may be used.

In the present invention, in order to form the back layer of the heat-sensitive recording material, a composition containing a siloxane-modified acrylic resin or the above-mentioned photopolymerization initiator, crosslinking agent, reactive diluent, etc. ) Is prepared. In addition, in the back layer forming paint, ortho-nitrotoluene, hydroquinone, hydroquinone monomethyl ether, copper chloride, etc. should be blended as a polymerization inhibitor in order to suppress thermal polymerization of a cross-linking agent or a reactive diluent during storage. Is preferred. Further, in the back layer forming paint, as an additive other than the above, an antioxidant,
A light stabilizer, a paint additive, a function imparting agent, and the like can be appropriately compounded.

The back layer forming paint used in the present invention is:
It may be prepared without solvent or may be prepared using an organic solvent. Preferred examples of the organic solvent include methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate and the like. Also, acetone, cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchlorethylene, trichloroethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, and the like can be used.

The back layer of the heat-sensitive recording material is formed by applying the above-mentioned back layer forming paint to a substrate sheet by a conventionally known coating means so as to have a dry thickness of about 0.01 to 1 μm and drying to form a film. After that, it is formed by irradiating ultraviolet rays or electron beams or the like to crosslink. The siloxane-modified acrylic resin of the present invention can form a tough crosslinked film having improved adhesion to a substrate and improved performance such as high hardness, stain resistance, and light resistance. In addition, a crosslinked film using a crosslinking agent or a reactive diluent is more excellent in non-adhesiveness, lubricity, heat resistance and blocking resistance than a crosslinked film of a siloxane-modified acrylic resin alone, high hardness, low friction coefficient, Excellent low migration and low bleeding.

Therefore, the siloxane-modified acrylic resin of the present invention is formed on a binder for forming a magnetic layer of a magnetic recording medium in a magnetic tape or the like and on the back surface of those magnetic layers, in addition to the formation of the back layer of the thermosensitive recording material. Back coat layer forming material, binder for thermal transfer film etc. and back layer (heat-resistant lubricating layer) forming material to prevent adhesion of thermal head, synthetic artificial leather material, fiber coating agent, various surface treatment agents, release paper, etc. It is very effective as a material for forming a release layer, a material for forming a coating film of paint, a vehicle resin for printing ink, a resin modifier, and the like.

[0029]

Next, the present invention will be described more specifically with reference to examples and comparative examples. The parts or percentages in the text are based on weight.

Examples 1 to 4 and Comparative Examples 1 to 4 A back layer forming paint containing a siloxane-modified acrylate resin was prepared according to the formulation shown in Table 1 below. Further, a back layer forming paint containing no siloxane-modified acrylate resin was prepared according to the formulation shown in Table 2 below.

[0031]

(Note) (1) Nippon Shokubai Co., Ltd .: toluene / isopropyl alcohol solution of polysiloxane-grafted acrylic polymer (nonvolatile content: 25%) (2) Shin-Etsu Chemical Co., Ltd .: polysiloxane-grafted acrylic polymer (Tg = 80 ° C) toluene solution (nonvolatile content 40%) (3) Shin-Etsu Chemical Co., Ltd .: toluene solution of polysiloxane graft acrylic polymer (Tg = 60 ° C) (nonvolatile content 40%) (4) Shin-Etsu Chemical Co., Ltd. : Polysiloxane grafted acrylic polymer (Tg = 40 ° C.) in isopropyl alcohol (nonvolatile content: 50%) (5) Daicel UCB: Trimethylolpropane triacrylate (6) Daiichi Kogyo Seiyaku: Higher alcohol・ Sodium phosphate (7) manufactured by Daicel UCB

[0033]

(Note) (8) Nippon Shokubai Co., Ltd .: Special acrylic resin (hydroxyl value 25)
Xylene / butyl acetate solution (non-volatile content 50%) (9) Nippon Shokubai Co., Ltd .: Special acrylic resin (hydroxyl value 40)
(10) Daicel UCB: aromatic urethane acrylate (11) Daicel UCB: Bisphenol A type epoxy acrylate (12) Shin-Etsu Chemical Co., Ltd. : Dimethyl silicone oil (13) Polyisocyanate having hexamethylene diisocyanate (HMDI) based isocyanurate ring (NCO
100 parts, 50 ppm of hydroquinone and 397 parts of ethyl acetate were charged into a vessel, and heated to 60 ° C. while stirring, and 70 parts of 2-hydroxyethyl acrylate was gradually added, followed by heating to 70 ° C. 4. A curing agent that was allowed to react for 4 hours and no residual NCO was confirmed by IR. (14) HMDI trimer (buret bond), NCO content 24%.

Next, the heat-sensitive recording material of the present invention will be specifically described. A polyethylene terephthalate film having a thickness of 6 μm was used as a substrate, and a coating for a back surface forming layer was applied to one surface of the substrate by gravure printing so as to have a dry thickness of 0.3 μm, and dried. Thereafter, those using the paints of Examples 1 to 4 and Comparative Examples 2 to 4 were irradiated with ultraviolet rays to form a crosslinked back layer (heat-resistant lubricating film) on the surface of the substrate. The ultraviolet irradiation conditions are as follows: a metal halide lamp, an integrated light amount of 202 mJ / cm ² , and a peak illuminance of 1
97 mw / cm ² . In the case of using the coating material of Comparative Example 1, the coating material was applied and dried, and then aged at 50 ° C. for 2 days for thermal crosslinking.

Next, the ink composition shown in Table 3 below was heated to 100 ° C. on the surface of the substrate film opposite to the back layer formed as described above, and the coating thickness was applied by a roll coating method using hot melt. Was applied to form a heat-sensitive recording layer (ink layer) to obtain a heat-sensitive recording material.

[0037]

Using each of the heat-sensitive recording materials of the examples and comparative examples obtained above, a thin-film thermal head was used.
Printing was performed under a printing energy condition of 1 mj / dot (4 × 10 ⁻⁴ cm ² ), and sticking properties, head contamination properties, and transfer properties were observed. Further, the adhesion between the back layer and the substrate was measured. Table 4 shows the results. The measurement method and the display of the result are as follows.

[Sticking property] A mounting test was carried out using the heat-sensitive recording material, and the detachability of the heat-sensitive recording material from the thermal head during the pressing operation between the thermal head and the heat-sensitive recording material was visually observed. A five-point evaluation was performed in which the case where the releasability was good was 5 and the case where the releasability was the worst was 1. [Dirt of Thermal Head] A mounting test was performed using a thermosensitive recording material, and the state of dirt on the thermal head was observed. A five-point evaluation was performed, with 5 being the least stained and 1 being the most stained. [Adhesion] The adhesion of the back layer to the substrate sheet was evaluated by a fifth cellophane tape peel test. [Transferability] The degree of transfer of the unreacted siloxane compound in the back layer to the ink layer after leaving the heat-sensitive recording material wound in a roll in an oven at 40 ° C. for 3 days was evaluated by finger touch and visual observation. A five-point evaluation was performed, with 5 indicating no migration and 1 indicating that migration was clearly recognized.

[0040]

[0041]

According to the present invention, there is provided a heat-sensitive recording material having a back layer which is free from sticking and blocking phenomena and has excellent heat resistance and lubricity. In particular, the back layer can be formed by crosslinking by irradiating heat and / or ionizing radiation such as ultraviolet rays or electron beams,
In addition, the transfer of the unreacted siloxane component to the heat-sensitive recording layer and less bleeding provide a heat-sensitive recording material having excellent performance such as no contamination of the thermal head and no loss of printing characteristics.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuyuki Hanada 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Dai-Niseika Chemical Industry Co., Ltd. (72) Inventor Atsuhiro Awaji 1-7- Nihonbashi Bakurocho, Chuo-ku, Tokyo 6 Dai-ichi Seika Industry Co., Ltd. F-term (reference) 2H111 AA16 AA26 AA27 AA33 BA08 BA53 BA55 BA64 BA73 BA76 BA78

Claims (9)

[Claims] 1. A base sheet, comprising a heat-sensitive recording layer provided on one side of the base sheet and a back layer provided on the other side of the base sheet, wherein the back layer has a siloxane segment in a main chain and / or a side chain. A heat-sensitive recording material comprising a layer containing an acrylic resin having the formula: 2. The acrylic resin comprises a siloxane compound having a radical polymerizable unsaturated group and an acrylate and / or
2. The heat-sensitive recording material according to claim 1, which is a copolymer with methacrylate. 3. The heat-sensitive recording material according to claim 1, wherein the back layer further contains a photopolymerization initiator. 4. The heat-sensitive recording material according to claim 1, wherein the back layer further contains an unsaturated group-containing crosslinking agent and / or a reactive diluent. 5. The heat-sensitive recording material according to claim 1, wherein the back layer further contains another binder resin. 6. A photopolymerization initiator content of 0.01 to 10
4. The heat-sensitive recording material according to claim 3, wherein the content is by weight. 7. The heat-sensitive recording material according to claim 4, wherein the content of the crosslinking agent is 1 to 100% by weight, and the content of the reactive diluent is 1 to 600% by weight. 8. The content of the other binder resin is from 1 to 40.
The heat-sensitive recording material according to claim 5, which is 0% by weight. 9. The method according to claim 1, wherein the back layer is a coating cross-linked by irradiation with heat and / or ionizing radiation.
The heat-sensitive recording material according to any one of the above items.