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WO2013133375A1 - Procédé de fabrication de feuille à transfert thermique et de matériau imprimé - Google Patents

Procédé de fabrication de feuille à transfert thermique et de matériau imprimé Download PDF

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Publication number
WO2013133375A1
WO2013133375A1 PCT/JP2013/056282 JP2013056282W WO2013133375A1 WO 2013133375 A1 WO2013133375 A1 WO 2013133375A1 JP 2013056282 W JP2013056282 W JP 2013056282W WO 2013133375 A1 WO2013133375 A1 WO 2013133375A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
thermal transfer
transfer sheet
protective layer
release layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/056282
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English (en)
Japanese (ja)
Inventor
佳子 北村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kimoto Co Ltd
Original Assignee
Kimoto Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kimoto Co Ltd filed Critical Kimoto Co Ltd
Priority to CN201380011754.0A priority Critical patent/CN104136233A/zh
Priority to JP2014503541A priority patent/JP6110843B2/ja
Publication of WO2013133375A1 publication Critical patent/WO2013133375A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive

Definitions

  • the present invention relates to a thermal transfer sheet used when transferring a pattern such as a pattern or a character to a textile product such as cloth or paper or wood, and in particular, it has a good releasability during thermal transfer and is on the transferred pattern.
  • the present invention relates to a thermal transfer sheet capable of forming a protective layer.
  • a technique for forming a release layer containing a filler in a curable binder resin and roughening the surface is known as a technique for forming a printed matter having a matte (matte) surface by thermal transfer.
  • Patent Document 2 a technique for forming a printed matter having a matte (matte) surface by thermal transfer.
  • the rough surface shape of the release layer is transferred to the surface of the protective layer, and a matte feeling can be given to the print.
  • JP 2011-201177 A (paragraph number 0007) JP 2007-83472 A (Claim 1)
  • the thermal transfer sheet is cut into a desired shape, or only the colored layer and the protective layer are cut (half-cutting). After that, the colored layer and the protective layer are heated and transferred using a heating / pressurizing member having a pressurizing surface having a desired shape. A method of transferring to a shape is adopted. In this case, until the protective layer is transferred, it is required that the protective layer and the release layer are bonded with good adhesion so as not to be lifted or peeled off, and that both are neatly peeled off after the transfer.
  • the properties (adhesiveness and releasability) of the release layer appropriately selected in relation to the protective layer with respect to the protective layer It may change and may cause floating or peeling due to poor adhesion before transfer, or may cause poor peeling after thermal transfer.
  • the present invention provides a thermal transfer sheet that has excellent adhesion between the protective layer and the release layer until thermal transfer and has excellent releasability between the protective layer and the release layer after thermal transfer. It aims at providing the sheet
  • the present invention uses a material containing a cellulosic resin as the material of the protective layer provided with the colored layer, and does not contain particulate matter as the material of the release layer, and three-dimensionally crosslinks the amino resin and the hydroxyl group-containing resin.
  • a material containing the prepared resin is used.
  • using a base material with irregularities formed on the surface as a base material used for the thermal transfer sheet, and providing a release layer with a thickness that can reflect the concave and convex shape of the base material on the surface of the release layer Give the uneven shape. This uneven shape is transferred to the surface of the protective layer formed thereon, and gives a matte feeling to the printed material.
  • the sheet for thermal transfer of the present invention that solves the above-described problem is a base material having a concavo-convex shape on the surface, a release layer provided on the surface having the concavo-convex shape of the base material, and the release layer.
  • the release layer does not contain particulate matter, includes a resin obtained by three-dimensionally crosslinking an amino resin and a hydroxyl group-containing resin, It has an uneven shape reflecting the uneven shape, and the protective layer contains a cellulosic resin.
  • the surface of the release layer “has an uneven shape reflecting the uneven shape of the substrate” means that the protective layer can be given a matte feeling with the release layer covering the entire uneven shape of the substrate. It means that an uneven shape is formed.
  • the method for producing a printed material according to the present invention includes a substrate having a concavo-convex shape on the surface thereof, including a resin in which an amino resin and a hydroxyl group-containing resin are three-dimensionally cross-linked without including a particulate substance, and the thickness of the substrate is uneven.
  • a surface of the thermal transfer sheet having a release layer having a thickness capable of reflecting the shape and a protective layer containing a cellulose-based resin in this order after the colored layer is formed on the protective layer, the surface provided with the colored layer of the thermal transfer sheet The protective layer and the colored layer are transferred onto the adherend by heating and adhering to the adherend.
  • the protective layer and the release layer adhere well before transfer, and after the thermal transfer of the colored layer and the protective layer, the peelability between the protective layer and the release layer is good.
  • a protective layer can be well formed on the colored layer. Further, by transferring the uneven shape of the release layer to the protective layer, it is possible to obtain a printed material having a matte design transferred with the colored layer protected by the protective layer.
  • the figure which shows typically the relationship between a base-material shape and the thickness of a mold release layer The figure which shows an example of the manufacturing method of the printed matter by this invention.
  • the figure which shows another example of the manufacturing method of the printed matter by this invention The figure which shows another example of the manufacturing method of the printed matter by this invention.
  • the thermal transfer sheet of the present invention is a thermal transfer sheet having a release layer and a protective layer in this order on a substrate, the substrate has an uneven shape on the surface, and the release layer includes an amino resin and In addition, the protective layer contains a cellulosic resin.
  • the thickness of the release layer is a thickness at which an uneven shape reflecting the uneven shape of the substrate is formed on the surface.
  • the base material used for the thermal transfer sheet of the present invention has an uneven shape on the surface.
  • a substrate having a concavo-convex shape on the surface for example, polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and various plastic films such as polyimide films and polyaramid films can be used. it can.
  • a method for forming a concavo-convex shape on one surface of these plastic films in addition to a blast treatment, an embossing treatment, a shaping treatment, etc., it is possible to appropriately select formation of a coating film having concavo-convex. In particular, a blast treatment that can obtain an uneven shape at low cost and can maintain the uneven shape even at high temperatures is preferable.
  • the arithmetic average roughness (Ra) based on JIS B0601: 2001 is preferably 0.3 ⁇ m or more, and more preferably 0.7 ⁇ m or more. As an upper limit, it is preferable that it is 1.3 micrometers or less, More preferably, it is 1.0 micrometers or less.
  • the arithmetic average roughness (Ra) By setting the arithmetic average roughness (Ra) to 0.3 ⁇ m or more, an uneven shape can be reliably imparted to the surface of the protective layer via the release layer. By setting the thickness to 1.3 ⁇ m or less, the release layer can be formed without unevenness.
  • each plastic film is preferably 25 to 200 ⁇ m, more preferably 50 to 100 ⁇ m.
  • the thickness is preferably 25 to 200 ⁇ m, more preferably 50 to 100 ⁇ m.
  • the release layer plays a role of adjusting the adhesion between the base material and the protective layer, and also plays a role of transmitting the uneven shape of the base material surface to the protective layer. Therefore, the release layer is required to maintain an uneven shape after the release layer is formed. Therefore, the release layer has a thickness having a concavo-convex shape reflected in the concavo-convex shape on the surface of the substrate. In FIG. 1, the relationship between the uneven
  • the coating amount (basis weight) of the release layer 12 coating is large as shown in FIG.
  • corrugated shape of the base material 11 will be buried in the thickness of the release layer 12, and the uneven
  • FIG. 1C when the coating amount (basis weight) of the paint for the release layer 12 is too small, the unevenness of the thickness of the release layer 12 becomes large, and the release layer 12 As a result, a convex portion that is not covered with, that is, a portion where the release layer 12 is not formed is formed.
  • the release layer 12 has an uneven shape that covers the entire surface of the substrate 11 and follows the uneven shape of the surface of the substrate 11 as shown in FIG.
  • the thickness of the release layer is preferably 30% or more, more preferably 50% or more of the arithmetic average roughness (Ra) of the substrate surface.
  • a release layer can be formed uniformly, and to be 120% or less of the arithmetic average roughness (Ra) of the substrate surface.
  • the specific thickness is preferably 0.2 to 1.5 ⁇ m.
  • the material of the release layer is amino resin, for example, urea resin such as methylated urea resin, butylated urea resin, butylated urea / melamine resin, butylated melamine, ethylated melamine, methylated melamine, iminized melamine, iminoethyl A resin obtained by three-dimensionally cross-linking a hydroxyl group-containing resin with a melamine resin such as a melamine resin, an iminomethylated melamine, a butyrolol melamine, an ethylolated melamine, a methylolated melamine, or a benzoguanamine resin such as a methylated benzoguanamine resin or a butylated benzoguanamine resin. Is included.
  • urea resin such as methylated urea resin, butylated urea resin, butylated urea / melamine resin, butylated
  • hydroxyl group-containing resin an acrylic polyol resin, a polyester polyol resin, an alkyd resin, an epoxy polyol resin, or the like can be used.
  • the use of a hydroxyl group-containing resin copolymerized with a long-chain alkyl improves the releasability. Therefore, it is preferable.
  • the protective layer can be prevented from peeling off or floating from the release layer. Moreover, the peelability after thermal transfer can be made favorable.
  • the ratio of the hydroxyl group-containing resin to the amino resin is preferably 9: 1 to 1: 9, more preferably 7: 3 to 3: 7, and still more preferably 6: 4 to 4: 6, in terms of mol of amino group and hydroxyl group. And By setting it as such a range, it is easy to adjust the adhesiveness before thermal transfer with the protective layer and the peelability after thermal transfer.
  • amino resin and hydroxyl group-containing resin are three-dimensionally cross-linked within a range that does not impair the properties required for the release layer, such as adhesion to the base material and protective layer, and peelability from the protective layer.
  • Resins other than the resin made can be contained.
  • other resins that can be used include thermosetting resins such as epoxy resins, and thermoplastic resins such as polyester resins and acrylic resins.
  • thermosetting resins such as epoxy resins
  • thermoplastic resins such as polyester resins and acrylic resins.
  • a thermosetting resin is used as the other resin, it is preferably 80% or less, more preferably 50% or less of the total resin component.
  • a resin other than a thermosetting resin is used as the other resin, it is preferably 20% or less of the total resin component, and more preferably 10% or less.
  • the protective layer provided on the release layer is a layer for adhering the colored layer to the adherend and imparting durability such as washing resistance, abrasion resistance, and chemical resistance to the colored layer.
  • the protective layer contains a cellulose resin.
  • cellulose resin for example, cellulose esters such as cellulose acetate butyrate, cellulose acetate propionate, nitrocellulose, and cellulose acetate can be used.
  • a cellulose-based resin By using such a cellulose-based resin as a protective layer, even when transferred to a textile product such as a cloth, it is possible to follow the elongation of the fiber and prevent the protective layer from cracking. it can.
  • a curing agent to the protective layer.
  • an isocyanate resin or a metal chelate can be used, and the ratio of the curing agent is preferably 10% or less, more preferably 5% or less of the cellulose resin.
  • the protective layer has a thickness of preferably 0.2 ⁇ m or more, more preferably 0.5 ⁇ m or more, preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less.
  • the thickness By setting the thickness to 0.2 ⁇ m or more, the colored layer can be protected and durability can be obtained.
  • cutting property can be acquired.
  • the cutting property means that when only a part of the protective layer is thermally transferred to the adherend together with the colored layer, the part of the protective layer that has been thermally transferred can be cleanly cut with the other part (the part that is not thermally transferred). To tell.
  • additives such as a leveling agent, an antioxidant, and an ultraviolet absorber may be added to each layer.
  • a colored layer can be provided on the protective layer side of the thermal transfer sheet of the present invention.
  • the colored layer is a layer that forms a pattern such as a character, a figure, or a pattern.
  • the colored layer is formed by dispersing or dissolving a dye or pigment in a film-forming resin or resin solution.
  • resins include vinyl chloride resins, vinyl acetate resins, vinylidene chloride resins, cellulose resins, polyester resins, urethane resins, polyamide resins, polystyrene resins, acrylic resins, epoxy resins, olefin resins.
  • One or more resins such as nitrile rubber can be used.
  • the colored layer is thermally melted, it is preferable that the colored layer is not excessively melted by the heat at the time of pasting. In the case where the colored layer is not thermally melted, a separate hot melt layer can be provided.
  • a resin having flexibility to follow the elongation of the fabric and water resistance so as not to be peeled off by washing or the like is preferably used.
  • urethane resin is suitable.
  • the thickness of the colored layer is such that the strength of the coating film is not lost, is easy to cut when cut with a cutter or a punching die, and is preferably not too thick from the viewpoint of productivity. Specifically, 10 to 150 ⁇ m is preferable.
  • the colored layer is usually colored by mixing a dye or pigment, but if a metal thin film layer or the like is provided above or below the colored layer, the colored layer may be colorless without mixing the dye or pigment. In addition, the colored layer may be replaced with a metal thin film layer or the like.
  • the method for producing a printed product of the present invention uses the thermal transfer sheet of the present invention described above, and heat-sticks the surface provided with the colored layer of the thermal transfer sheet to the adherend, thereby providing a protective layer and The colored layer is transferred onto the adherend.
  • FIGS. 1 There are several methods for transferring a colored layer and a protective layer having a desired shape (characters, figures, etc.) as shown in FIGS.
  • the thermal transfer sheet 10 is cut into a desired shape, and the surface of the thermal transfer sheet 10 on which the colored layer is provided is heated and adhered to the adherend 20 (FIG. 2: Method 1)
  • the protective layer 13 and the colored layer 14 are cut (half cut) into a desired shape without separating the base material 11 and the release layer 12.
  • FIG. 3 Method 2
  • the surface of the thermal transfer sheet 10 on which the colored layer 14 is provided is brought into contact with the adherend 20 to form a pressure surface having a desired shape.
  • the heating / pressurizing means 30 is heated and pressed from the substrate side of the thermal transfer sheet.
  • a method of transferring a colored layer 14 of the same shape of the pressing surface and the portion of the protective layer 13 located thereon to the adherend 20 above Figure 4: Method 3
  • the temperature at the time of heating and sticking is preferably about 140 to 200 ° C., and it is preferable to apply pressure appropriately.
  • the adherend fiber products such as cloth, paper, wood and the like can be used.
  • the surface of the release layer is not made uneven by the particulate matter, so that it is possible to maintain appropriate adhesion between the protective layer and the release layer before the thermal transfer (at room temperature).
  • the workability is good because the protective layer is not peeled off or floated from the release layer.
  • the protective layer has good cutting properties (property that allows a portion to be thermally transferred to be separated cleanly from other portions), and when the thermal transfer method of Method 3 is adopted, a beautiful print can be obtained.
  • the thermal transfer sheet of the present invention can impart a concavo-convex shape to the surface of the heat-transferred protective layer by using a substrate having a concavo-convex shape on the surface and setting the release layer to an appropriate thickness.
  • the transferred protective layer has excellent matte properties, and the gloss of the protective layer does not impair the texture of the adherend.
  • the printed matter of the present invention has a concavo-convex shape on the surface of the protective layer that has been thermally transferred, the transferred protective layer has excellent matting properties, and the texture of the adherend is imparted by the gloss of the protective layer. It is not damaged.
  • thermal transfer sheet [Example 1] One surface of a 100 ⁇ m resin film (Lumirror S10: Toray Industries, Inc.) was subjected to sand blasting to produce a substrate having an uneven shape (Ra: 0.9 ⁇ m). A release layer coating solution having the following composition was applied to the surface of the base material having an uneven shape so that the thickness (hereinafter, the same) calculated from the coating amount in Formula (1) was 0.3 ⁇ m and dried. Then, a release layer was formed. Next, a protective layer coating solution having the following composition was applied on the release layer so as to have a thickness of 1.5 ⁇ m and dried to prepare a thermal transfer sheet of Example 1.
  • ⁇ Release layer coating solution > ⁇ 3 parts of long chain alkyl group-containing amino alkyd resin (Tesfine 303: Hitachi Chemical Co., Ltd., solid content 48%) -Alkyd resin 0.6 parts (Beccosol 1308: DIC, solid content 50%, OH value 4-13) ⁇ Paratoluenesulfonic acid (curing catalyst) 0.6 part ⁇ Diluting solvent 13.8 parts
  • ⁇ Protective layer coating solution > ⁇ 3 parts of cellulose resin (CAB-381-2: Eastman Chemical Co., 10% solid content) ⁇ Curing agent 1 part (Takenate D110N: Mitsui Chemicals, solid content 60%) ⁇ 32 parts of diluted solvent
  • Example 2 A thermal transfer sheet of Example 2 was produced in the same manner as in Example 1 except that the thickness of the release layer of Example 1 was changed to 0.5 ⁇ m.
  • Example 3 A thermal transfer sheet of Example 3 was produced in the same manner as in Example 1 except that the thickness of the release layer of Example 1 was 1.0 ⁇ m.
  • Example 4 A thermal transfer sheet of Example 4 was produced in the same manner as in Example 1 except that the release layer coating solution of Example 1 was changed to a release layer coating solution having the following composition.
  • ⁇ Release layer coating solution > ⁇ 3 parts of long chain alkyl group-containing amino alkyd resin (Tesfine 303: Hitachi Chemical Co., Ltd., solid content 48%) ⁇ 0.2 parts of epoxy resin (jER1010: Mitsubishi Chemical Corporation, solid content 100%) -0.6 parts of paratoluenesulfonic acid-13.2 parts of diluent solvent
  • Example 5 A thermal transfer sheet of Example 5 was produced in the same manner as in Example 1 except that the release layer coating solution of Example 1 was changed to a release layer coating solution having the following composition.
  • ⁇ Release layer coating solution > ⁇ 3 parts of long chain alkyl group-containing amino alkyd resin (Tesfine 303: Hitachi Chemical Co., Ltd., solid content 48%) ⁇ 0.2 parts of polyester resin (Byron 200: Toyobo Co., Ltd., 100% solid content) -0.6 parts of paratoluenesulfonic acid-13.2 parts of diluent solvent
  • Comparative Example 1 A thermal transfer sheet of Comparative Example 1 was produced in the same manner as in Example 1 except that the thickness of the release layer of Example 1 was changed to 0.2 ⁇ m.
  • Comparative Example 2 A thermal transfer sheet of Comparative Example 2 was produced in the same manner as in Example 1 except that the thickness of the release layer of Example 1 was changed to 1.2 ⁇ m.
  • Comparative Example 3 A thermal transfer sheet of Comparative Example 3 was produced in the same manner as in Example 1 except that the release layer coating solution of Example 1 was changed to a release layer coating solution having the following composition.
  • a urethane-based colored layer having a thickness of 30 ⁇ m is provided on the protective layer of the thermal transfer sheet of Examples 1 to 5 and Comparative Examples 1 to 3, and after half-cutting, the colored layer surface faces the nylon fabric.
  • the release layer and the base material of the thermal transfer sheet were peeled off, and a printed material in which the colored layer and the protective layer were transferred to the fabric was produced.
  • the peel strength between the release layer and the protective layer was measured. The peel strength was measured by measuring the force (average load per unit width) required for peeling when the thermal transfer sheet side was peeled off at a speed of 300 mm / min in the 180 ° direction.
  • the release layer includes a resin in which an amino resin and a hydroxyl group-containing resin are three-dimensionally cross-linked, and the thickness of the release layer is the arithmetic average roughness (Ra) of the substrate. Since it is within the range of 30 to 120% and the protective layer contains a cellulose-based resin, the adhesion between the protective layer before transfer and the release layer is good, and the protective layer and release layer after transfer The peelability of was good. Moreover, since the uneven
  • the thermal transfer sheet of Comparative Example 1 is formed so that the thickness of the release layer is less than 25% of the arithmetic average roughness (Ra) of the substrate, and the release layer covers the entire uneven shape of the substrate. As a result, the adhesion between the protective layer and the release layer before transfer was inferior.
  • the thickness of the release layer was 130% or more of the arithmetic average roughness (Ra) of the base material, and the uneven shape could not be maintained in the release layer. Later, the adhesive force between the protective layer and the release layer was slightly increased, and the peelability was poor. Further, since the uneven shape could not be maintained on the release layer, the uneven shape could not be transferred to the surface of the protective layer, and the matte property could not be imparted to the printed material.
  • Ra arithmetic average roughness
  • the release layer of the thermal transfer sheet of Comparative Example 3 is a silicone resin, the adhesiveness to the protective layer before thermal transfer was poor, and floating and peeling occurred during cutting. Moreover, the adhesiveness with the protective layer after thermal transfer was also poor.

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PCT/JP2013/056282 2012-03-08 2013-03-07 Procédé de fabrication de feuille à transfert thermique et de matériau imprimé Ceased WO2013133375A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201380011754.0A CN104136233A (zh) 2012-03-08 2013-03-07 热转印用片材及印相物的制造方法
JP2014503541A JP6110843B2 (ja) 2012-03-08 2013-03-07 熱転写用シートおよび印画物の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012051613 2012-03-08
JP2012-051613 2012-03-08

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WO2013133375A1 true WO2013133375A1 (fr) 2013-09-12

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JP (1) JP6110843B2 (fr)
CN (1) CN104136233A (fr)
WO (1) WO2013133375A1 (fr)

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WO2017018135A1 (fr) * 2015-07-24 2017-02-02 富士フイルム株式会社 Pellicule anti-adhésive et stratifié adhésif
JP2017052124A (ja) * 2015-09-07 2017-03-16 大日本印刷株式会社 転写箔及び印画物の製造方法
WO2017062191A1 (fr) * 2015-10-09 2017-04-13 3M Innovative Properties Company Procédé de fabrication d'un objet décoratif, procédé de réparation d'un objet décoratif, élément de transfert, et kit de décoration
JP2017101185A (ja) * 2015-12-03 2017-06-08 株式会社ミマキエンジニアリング コーティング剤、印刷物の製造方法、印刷物
WO2018181775A1 (fr) * 2017-03-31 2018-10-04 大日本印刷株式会社 Feuille décorative, article décoratif moulé en résine, et procédé de fabrication associé
WO2018225336A1 (fr) * 2017-06-09 2018-12-13 株式会社ダイセル Film de démoulage de moule de transfert et procédé de fabrication de corps moulé en forme de mat

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JP6098754B1 (ja) * 2015-09-30 2017-03-22 大日本印刷株式会社 印画物の形成方法、転写層のピールオフ方法
US10864702B2 (en) * 2015-12-25 2020-12-15 Dai Nippon Printing Co., Ltd. Thermal transfer sheet
JP6525074B2 (ja) * 2017-07-31 2019-06-05 大日本印刷株式会社 熱転写シート、印画シートと熱転写シートとの組合せ、及び熱転写印画装置
CN114523782B (zh) * 2018-01-31 2023-11-14 大日本印刷株式会社 热转印片、脱模层用涂布液以及热转印片的制造方法
WO2020203661A1 (fr) * 2019-03-29 2020-10-08 大日本印刷株式会社 Feuille de transfert et procédé de fabrication d'un moulage décoratif
JP6919843B1 (ja) * 2019-11-20 2021-08-18 大日本印刷株式会社 熱転写受像シート、印画物の製造方法及び印画物
EP4223480A4 (fr) * 2020-09-29 2024-10-23 Dai Nippon Printing Co., Ltd. Feuille de transfert et méthode de production d'un article moulé en résine l'utilisant

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