JP3149213B2 - Method for forming transfer layer on molded article and transfer sheet used in the method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a transfer layer on a transfer surface of various molded articles and a transfer sheet used in the method for forming the transfer layer.

[0002]

2. Description of the Related Art When a transfer layer is transferred to a transfer surface of a molded article, a coating layer of an uncured thermosetting resin is used as an adhesive layer between the transfer surface and the transfer layer. There is a method of forming the transfer surface in advance (JP-A-61-89899, JP-B-63-58103, etc.).

[0003]

The conventional method of using the coating layer of the thermosetting resin in the uncured state as an adhesive layer involves only the adhesive property of the thermosetting resin in the uncured state. When the adhesive layer is a coating layer formed by coating a thermosetting resin with a solvent diluted with a solvent, the transfer layer is transferred to the adhesive layer after drying. is there.

For this reason, the adhesive force required for transferring the transfer layer to the transfer object is determined by the type and molecular weight of the resin itself in the thermosetting resin coating layer formed as the adhesive layer. Therefore, when a thermosetting resin having a kind and a molecular weight that satisfies various physical properties required for the adhesive layer is selected, for example, the adhesive strength between the transfer layer and the adhesive layer after the thermosetting and the heat can be reduced. When the type and molecular weight of the thermosetting resin that satisfies the physical properties such as the light resistance of the cured adhesive layer are selected, the transfer layer of the transfer sheet is transferred to the surface of the adhesive layer formed on the surface of the transfer object. In this case, it becomes extremely difficult to make the adhesive strength required for the adhesive layer a desired value.

In the case where a coating layer of a coating agent obtained by diluting a thermosetting resin with a solvent is used as an adhesive layer, the transfer layer is applied to the adhesive layer surface of the coating layer after the solvent is dried in advance. Because of the transfer, the curing reaction in the adhesive layer proceeds by heating during the drying step of the solvent, and the adhesive strength of the adhesive layer often decreases. It becomes extremely difficult to obtain the required adhesive strength to a desired value.

Further, when a coating layer composed of a non-solvent type thermosetting resin layer is used as an adhesive layer, the transfer layer caused by the flow and deformation of the resin caused by the application of pressure and heat in the transfer step. For reasons such as the prevention of pattern distortion, cracks in the transfer layer, and the occurrence of irregularities on the transfer surface, etc., `` a thermosetting resin that becomes a non-adhesive solid even in an uncured state when no solvent is used. Is preferred, but the adhesive layer made of a resin having such properties does not have an adhesive force enough to transfer and fix the transfer layer.

On the other hand, the first aspect of the present invention provides a method for forming a transfer layer on a molded article, the method comprising:
In advance, to form an adhesive layer consisting of a coating layer of a solvent solution of an uncured thermosetting resin presenting a non-adhesive solid in an uncured solvent-free state, and in the adhesive layer by this coating layer A part of the transfer layer is dissolved and swelled by the solvent to exhibit tackiness, and thermosetting is completed in a state where the transfer layer and the coating layer forming the adhesive layer are partially compatible. This provides a method for forming a transfer layer on a molded product from which a transfer layer having good adhesion between the adhesive layer and the transfer layer can be obtained.

Further, the second invention provides a transfer sheet used in the method of forming a transfer layer according to the first invention.

[0009]

The above object can be attained by a method for forming a transfer layer on a molded article of the present invention having the following constitution and a transfer sheet used in the method. That is, the method for forming a transfer layer on a molded article according to the first invention uses a solvent solution of an uncured thermosetting resin that exhibits a non-adhesive solid in an uncured nonsolvent state on the transfer surface of the molded article. After forming the coating layer, imparting tackiness to the coating layer by drying the coating layer so that at least a part of the solvent in the coating layer remains,
Subsequently, the transfer layer surface of the transfer sheet comprising the transfer sheet base material and the transfer layer is pressed against the surface of the adhesive coating layer, and then the transfer sheet base material is peeled off. After transferring the transfer layer to the transfer surface, the coating layer of the thermosetting resin formed on the transfer surface is heat-cured, or a pressing body of a transfer sheet and a formed body that is the transfer object is pressed. Forming a transfer layer on the transfer surface of a molded product by peeling off the transfer sheet substrate after heat-setting the coating layer of the thermosetting resin formed on the transfer surface by heating It is.

A second aspect of the present invention is a transfer sheet used in the method of forming a transfer layer on the molded article according to the first aspect of the present invention, wherein the transfer sheet base material has a releasable surface. And a transfer sheet comprising a decorative layer and a primer layer having solvent resistance which are sequentially formed on the release surface of the transfer sheet base material.

In the method of the present invention for forming a transfer layer on a molded article of the present invention, examples of the molded article used as an object to be transferred include single wood, wood composite, particle board, medium density fiberboard, and the like. Wood-based molded products, gypsum-based molded products such as gypsum and gypsum slag, calcium silicate-based molded products such as calcium silicate and asbestos slate, lightweight foam concrete, hollow extruded cement, pulp cement, asbestos cement, wood chip cement, glass fiber reinforced concrete Moldings such as cement moldings, fiber cement moldings, ceramic moldings such as pottery, porcelain, earthenware, glass, enamel, iron, galvanized steel, polyvinyl chloride sol coated steel, metal moldings such as aluminum and copper, polyethylene, Polypropylene, polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate Thermoplastic resin molding such as polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, thermosetting resin molding such as phenolic resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin, melamine resin Body, glass fiber non-woven fabric, fabric, paper and other various fibrous base materials are impregnated with a resin such as phenol resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin, melamine resin or diallyl phthalate resin, A so-called cured FRP molded product, a composite molded product obtained by laminating two or more types of molded products such as plates using an adhesive or a heat fusion method, or the like is used. These are used as a three-dimensional molded article such as a foil-thick sheet-like article, a rod-like article, an injection molded article, and the like. Particularly, an aluminum molded body is preferable.

The coating layer of the uncured thermosetting resin formed on the transfer surface of the molded article with the solvent solution is formed of a solvent of the uncured thermosetting resin presenting a non-adhesive solid in an uncured nonsolvent state. A coating layer of a coating agent composed of a solution, for example, melamine resin, diallyl phthalate resin, phenol resin, urea resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd resin, melamine / urea copolymer resin , A silicone resin, a thermosetting resin such as a polysiloxane resin, a solvent, and additives that are optionally added, for example, a curing agent such as a crosslinking agent or a polymerization initiator, a polymerization accelerator, a viscosity modifier, and the like. And a coating layer of a coating agent comprising a mixture of

The solvent used for the coating agent is appropriately selected according to the type of the thermosetting resin to be used. For example, esters such as ethyl acetate and butyl acetate, acetone and methyl ethyl ketone , Methyl isobutyl ketone, cyclohexanone, isophorone, and other ketones, pentane, hexane, heptane, and mixtures thereof, such as gasoline, mineral spirits, aliphatic hydrocarbons such as petroleum benzine, benzene, toluene,
Aromatic hydrocarbons such as xylene and cyclohexane, halogenated hydrocarbons such as trichloroethylene, perchlorethylene, and carbon tetrachloride; monohydric alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol; ethylene glycol and glycerin And ethers such as ethyl ether and methyl ether, and mixtures of two or more of these.

Particularly, in order to stably maintain a certain amount of the residual solvent in the coating layer of the thermosetting resin, a slow drying solvent such as xylene, cyclohexane and mineral spirit, methyl ethyl ketone and ethyl acetate are used. It is preferred to use a mixed solvent with a quick-drying solvent such as

As the coating layer of the solvent-based thermosetting resin formed on the transfer surface, an adhesive for dry lamination used in a usual dry lamination process is preferable.

A transfer sheet applicable to the method for forming a transfer layer on a molded article of the present invention comprises a transfer sheet base material and a transfer layer, and the transfer sheet having a releasable surface. The transfer sheet includes a sheet substrate and a transfer layer formed on a release surface of the transfer sheet substrate.

The release surface of the transfer sheet substrate, for example, in the case of a plastic sheet having a releasable surface, the sheet can be used as it is as the transfer sheet substrate. Is treated with a fluorine resin, silicone, or the like, so that the treated surface has a release surface.

After the coating layer of the solvent-based thermosetting resin formed on the transfer surface of the molded article is completely cured, the mold release between the transfer sheet substrate and the transfer layer is performed. In order to ensure that the transfer can be performed, and to form a surface protective layer on the transfer layer transferred to the transfer surface of the molded body, the surface of the transfer sheet base material has scratch resistance and chemical resistance. sex,
It is preferable to form a release layer having excellent properties such as stain resistance.

In particular, the molded article having the transfer layer obtained by the method of the present invention is made to have heat resistance and water resistance, such as materials for windows around exteriors, interiors such as bathrooms, and blinds. In the case where it is used for an application that needs to have both functions, it is preferable to form the release layer with a resin having a glass transition point of 60 ° C. or higher, and the action of the surface protective layer by the release layer causes warm water or sunlight. It is preferable to prevent peeling of the transfer layer and occurrence of blisters due to the above.

The release layer formed on the surface of the transfer sheet substrate is usually formed to a thickness of about 0.1 to 10 μm using a thermosetting resin or an ionizing radiation-curable resin as described below. It is preferably formed.

Thermosetting resin Melamine resin, diallyl phthalate resin, phenol resin, urea resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd resin, melamine / urea copolymer resin, silicon resin, polysiloxane Resins and other thermosetting resins include, as necessary, a crosslinking agent, a polymerization initiator, a curing agent, a polymerization accelerator, a solvent,
A viscosity modifier, an extender and the like are added.

A mixed resin composition of a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule is used for the ionizing radiation-curable resin. Specific examples of the prepolymer or oligomer include unsaturated polyesters such as a condensate of an unsaturated dicarboxylic acid and a polyhydric alcohol, and methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate; Acrylates such as polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate are used.

Further, specific examples of the monomer include styrene monomers such as styrene, α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, and the like.
Acrylates such as butyl acrylate, methoxybutyl acrylate, and phenyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, and phenyl methacrylate 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dibenzylamino) ethyl acrylate, methacrylic acid-2 Substitution of unsaturated acids with-(N, N-dimethylamino) methyl, 2- (N, N-diethylamino) propyl acrylate, etc., amino alcohol esters, unsaturated carboxylic acid amides with acrylamide, methacrylamide, etc., ethylene glycol Diacrylate, B propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6
Diacrylate compounds such as hexanediol diacrylate, diethylene glycol diacrylate, and triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol acrylate,
Polythiols having two or more thiol groups in the molecule, such as polyfunctional compounds such as propylene glycol dimethacrylate and diethylene glycol dimethacrylate, and trimethylolpropanetrithioglycolate, trimethylolpropanetrithiopropylate, and pentaerythritol tetrathioglycol. And the like.

Incidentally, ionizing radiation-curable resins usually include:
5 to 95% by weight of the aforementioned prepolymer or oligomer
And a mixed composition of 95-5% by weight of the monomer and / or polythiol compound.

Further, when the release layer is formed of an ionizing radiation-curable resin and the release layer is cured by irradiation with ultraviolet rays, for example, acetophenones, benzophenones, Michler benzoyl benzoate, α ·
A photopolymerization initiator such as an amiloxime ester, tetramethylmeuram monosulfide, or thioxanthone;
It goes without saying that a coating agent containing a photosensitizer added as needed, for example, a photosensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine, or the like is used.

The transfer layer formed on the release surface of the transfer sheet substrate has at least a decorative layer, and if necessary, has a solvent resistance with respect to the decorative layer. A transfer layer having a laminated structure in which a primer layer, an adhesive layer, and the like are laminated is used. The transfer sheet according to the second aspect of the present invention includes a primer layer having solvent resistance as an essential component.

The decorative layer includes a printing layer made of printing ink, a metal film layer made of aluminum, chromium, or the like, and may be a solid decorative layer on the entire surface, or may be wood grain, stone grain, polka dot, lattice pattern, character , A partial pattern layer expressing a figure, etc., or a combination of a solid decorative layer and a partial pattern layer on the entire surface. The printing layer made of the printing ink is preferably formed of a printing ink using a resin having a glass transition temperature of 60 ° C. or higher as a vehicle in order to provide the decorative layer with hot water resistance and heat resistance.

"Solvent-resistant primer layer" which is an essential component of the transfer sheet of the second invention.
During the transfer step, due to the solvent present in the coating layer with the solvent solution of the uncured thermosetting resin presenting a non-adhesive solid in the uncured non-solvent state formed on the transfer surface of the molded article A resin having a property of preventing the decoration layer from dissolving, flowing, or deteriorating, and hardly dissolved by a solvent remaining in a coating layer formed by a solvent solution of the thermosetting resin. That is, the difference between the SP value of the solvent remaining in the coating layer and a resin having a large SP value or a crosslinked / cured resin, and formed of a resin having good adhesion to another transfer layer. It is generally preferable to use an isocyanate-curable polyurethane, a melamine / acrylic mixed resin, an unsaturated polyester resin, an epoxy resin, or the like.

The adhesive layer, which is the uppermost layer of the transfer layer formed on the transfer sheet base material, is formed as needed similarly to the release agent layer, and the transfer layer is covered with the adhesive layer. Transfers to a transfer body and acts to adhere. As the adhesive layer, a heat-sensitive adhesive, a solvent-activated adhesive, an ionizing radiation-curable adhesive, or the like is used, and the adhesive described below is used.

Cellulose derivatives such as ethyl cellulose, cellulose nitrate, ethyl hydroxyethyl cellulose, cellulose acetate propionate and cellulose acetate; styrene resins and styrene copolymer resins such as polystyrene and poly-α-methylstyrene; polymethyl methacrylate and polymethyl methacrylate Acrylic resins such as acrylics such as ethyl methacrylate, polyethyl acrylate and polyacrylbutyl, vinyl polymers such as polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral resin, rosin and rosin Rosin ester resin such as modified maleic acid resin, rosin modified phenol resin, polymerized rosin, polyisoprene rubber, polyisobutyl rubber, rubber resin with styrene / butadiene rubber, butadiene / acrylonitrile rubber, Malonic resin, vinyl toluene resin, polyurethane, polyamide resins, polychlorinated olefins, other resins such as various ionomers, furthermore,
Mixtures thereof and the like.

The adhesive layer is coated with an extender such as calcium carbonate, silica, magnesium carbonate or the like in order to make the adhesive layer in a sufficiently dry state.
About 1 to 15% by weight may be added.

Further, the adhesive layer is preferably formed of a resin having a glass transition temperature of 90 ° C. or higher, for the purpose of imparting hot water resistance and heat resistance to the transfer layer formed on the transfer object.

After the transfer sheet is transferred to the transfer object by peeling off the transfer sheet base material, the thermosetting resin coating layer formed on the transfer object is thermally cured, or The transfer sheet base material is peeled off after the coating layer of the thermosetting resin formed on the transfer receiving body is thermally cured by heating the pressurized body with the transfer receiving body. In the step prior to the step of forming the transfer layer on the transfer surface, that is, in the step of pressing the transfer layer in the transfer sheet including the transfer sheet base material and the transfer layer in contact with the transfer surface of the molded body, Needless to say, heating may be performed simultaneously with pressurization.

[0034]

The method for forming the transfer layer on the molded article of the present invention is as follows.
After forming a coating layer with a solvent solution of an uncured thermosetting resin presenting a non-adhesive solid in an uncured non-solvent state on the transfer surface of the molded body, at least one of the solvents in the coating layer is formed. The coating layer is dried so that the part remains, and the coating layer is provided with tackiness by drying. Subsequently, the transfer layer surface of the transfer sheet including the transfer sheet base material and the transfer layer is coated with the adhesive layer. The thermosetting resin formed on the transfer surface after the transfer is transferred to the transfer surface by peeling off the transfer sheet substrate and then transferring the transfer sheet substrate to the transfer surface, Either heat-curing the coating layer or heat-curing the thermosetting resin coating layer formed on the transfer-receiving surface by heating the pressurizing body of the transfer sheet and the molded body that is the transfer-receiving body. After the transfer, the transfer sheet substrate is peeled off, and the transfer layer It consists of formation.

Therefore, in the method for forming a transfer layer on a molded article of the present invention, the uncured thermosetting type, which exhibits a non-adhesive solid in an uncured solventless state, as the adhesive layer on the transfer surface of the molded article. A coating layer made of a solvent solution of a resin is used.

In the method for forming a transfer layer on a molded article according to the present invention, the transfer layer is formed by a solvent contained in the adhesive layer comprising the coating layer formed on the transfer surface of the molded article. Part of the transfer layer transferred to the surface is dissolved,
It swells to exhibit tackiness, and completes thermosetting of the adhesive layer in a state where the transfer layer and the adhesive layer are partially compatible with each other. Good adhesive strength.

The transfer sheet of the present invention is a transfer sheet for use in the method for forming a transfer layer on the molded article of the present invention, and a primer layer having solvent resistance formed on the transfer sheet. Due to the presence of the adhesive layer formed on the transfer surface of the molded body, that is, an adhesive layer composed of a coating layer of a solvent solution of an uncured thermosetting resin exhibiting a non-adhesive solid in an uncured solventless state Since the decoration layer in the transfer sheet is prevented from dissolving, flowing, and deteriorating due to the solvent present in the agent layer, an extremely good quality transfer layer can be obtained.

[0038]

EXAMPLES Hereinafter, specific examples of a method of forming a transfer layer on a molded article of the present invention and a transfer sheet used in the method of forming the transfer layer will be described with reference to examples.

Example 1 Transfer sheet 25 μm thick polyethylene terephthalate film [X
-45, Toray Co., Ltd.] is coated with an acrylic resin gravure ink medium [Showa Ink Co., Ltd.] on one side of the transfer sheet substrate, and dried to obtain a thickness of 1%.
A release layer of μ was formed.

Next, on the surface of the release layer, a pattern was printed with a gravure ink using a mixed resin of 80% by weight of polymethyl methacrylate resin and 20% by weight of vinyl chloride / vinyl acetate resin as a vehicle. A urethane-based resin solution containing a curing agent by weight was applied and dried to form a 2 μm-thick solvent-resistant primer layer.

Thereafter, a polybutyl methacrylate resin (glass transition temperature: 50 ° C.) is applied to the surface of the primer layer.
Is applied and dried to form a 2μ thick adhesive layer.
Further, this was left in an atmosphere of 40 ° C. for 3 days to obtain a transfer sheet.

Transfer object A solution of a urethane resin (Showa Ink Co., Ltd.) is applied to one surface of an aluminum sheet having a length of 200 cm, a width of 30 mm and a thickness of 0.15 mm by a gravure coating method, and dried. By doing so, an adhesive layer having a thickness of 30 μm was formed in which the adhesiveness appeared in the coating layer due to a part of the solvent remaining in the coating layer.

The formation of this adhesive layer was carried out by using ethyl acetate / toluene / xylene / cyclohexanone = 80/1.
Using a urethane-based resin solution with a mixed solvent of 0/7/3 (weight ratio), after coating, the coating is left in an atmosphere of 25 ° C. for 5 minutes, so that the adhesive having the tackiness caused by the solvent is applied. An agent layer was formed.

Transfer Step After the adhesive layer surface of the transfer sheet made of polybutyl methacrylate resin is brought into contact with the adhesive layer surface of the above-mentioned transfer member made of an aluminum sheet, the superposed body of both of them is put on the transfer sheet. ℃ between the rubber roll,
After heating and pressing under the transfer conditions of 10 kg / 10 mm and 10 m / min., The transfer sheet substrate made of a polyethylene terephthalate film was peeled off.

Subsequently, the aluminum sheet having the transfer layer transferred to the surface of the transfer sheet was left in an atmosphere at 40 ° C. for one week to obtain an aluminum sheet having the intended transfer layer.

On the transfer layer surface of the obtained aluminum sheet, a pattern printing layer exhibiting a sharp high-grade feeling by gravure ink appeared. Further, when the transfer layer surface was subjected to a peeling test using an adhesive tape, there was no peeling of the transfer layer transferred to the adhesive tape surface.

Comparative Example 1 Transfer Sheet A transfer sheet having the same structure as that used in Example 1 was used.

Transferred Object A solution of a urethane resin (Showa Ink Co., Ltd.) was applied to one surface of an aluminum sheet having a length of 200 cm, a width of 30 mm, and a thickness of 0.15 mm by a gravure coating method, and the coating was completed. By drying until the solvent disappeared, an adhesive layer having a thickness of 30 μm without a residual solvent was formed in the coating layer.

For the formation of this adhesive layer, a urethane resin solution with a mixed solvent of ethyl acetate / acetone = 20/80 (weight ratio) is used.
The solvent in the coating layer was completely evaporated by leaving it in hot air of 0 ° C. for 15 minutes.

Transfer Step The adhesive layer surface of the transfer sheet made of polybutyl methacrylate resin is brought into contact with the adhesive layer surface of the above-described transfer member made of an aluminum sheet, and corresponds to the transfer step in Example 1. Transfer was performed under transfer conditions to obtain an aluminum sheet having a transfer layer for comparison.

On the transfer layer surface of the obtained aluminum sheet, a part of the transfer layer remains adhered to the transfer sheet base when the transfer sheet base and the transfer layer are peeled off. Transfer of a fine pattern printing layer could not be performed.

When the transfer layer surface was subjected to a peeling test using an adhesive tape, about one-fifth of the area of the picture print layer was transferred to the adhesive tape surface, and the transfer layer and the surface of the object were transferred. The bonding strength was not sufficient.

The cause of these defects is that the adhesive layer formed on the surface of the transfer-receiving member is completely dried in the transfer step, and thus the adhesive layer has no adhesive force. It is because of that.

[0054]

According to the method for forming a transfer layer on a molded article of the first invention, a molded article provided with a transfer layer having high quality characteristics can be obtained by:
It is easy and reliable.

Further, if the method of forming a transfer layer on the molded article of the first invention is carried out using the transfer sheet of the second invention, a molding having a transfer layer of high quality characteristics can be performed. The body is more easily and accurately obtained.

Claims (2)

(57) [Claims] An uncured solvent-free solvent is applied to the transfer surface of a molded article.
Soluble in the uncured state of the thermoset resins exhibiting non-adhesive solid
Agent after forming the coating layer by the solution, so as to at least a portion of the solvent of the coating Engineering layer remains tack imparted to coating coating layer I by the drying of the coating layer Followed by
Pressurized by Setto the transfer layer surface coating layer surface which bears the adhesive in the transfer sheet comprising a transcription sheet substrate and the transfer layer pressure, thereafter, the transfer is peeled off the transfer sheet substrate After transferring the layer to the surface to be transferred, the coating layer of the thermosetting resin formed on the surface to be transferred is thermally cured, or the pressing body between the transfer sheet and the molded body as the member to be transferred is heated. By heat-curing the thermosetting resin coating layer formed on the transfer-receiving surface by removing the transfer sheet base material, or forming a transfer layer on the transfer-receiving surface of the molded body. A method for forming a transfer layer on a molded article characterized by the following. 2. A transfer sheet base material having a release surface, a decorative layer sequentially formed on the release surface of the transfer sheet base material, and a primer having solvent resistance. A transfer sheet for use in the method for forming a transfer layer on a molded product according to claim 1, comprising a layer.