JP2016016605A - Primer-less laminate member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate member with an adhesive layer directly placed on a foamed resin layer without using a primer.SOLUTION: A laminate member has a substrate layer, a foamed resin layer, and an adhesive layer that are laminated in this order, with the adhesive layer directly placed on the foamed resin layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a primer-less laminated member, and more particularly, to a laminated member having a foamed resin layer and an adhesive layer directly laminated on the foamed resin layer without a primer.

  Sheet or film-like laminates having a foamed resin layer are widely used in automobile interior materials, wire harnesses, building materials, and the like. These laminated materials are applied to a wire or the like through an adhesive layer applied on the foamed resin layer. As shown in FIG. 3, the laminated material usually has a foamed resin layer 32 laminated on a base material 31 via an adhesive layer 34, and an adhesive layer 33 via a primer layer 35 on the foamed resin layer 32. Are stacked. The laminated material is made by a process as shown in FIG. That is, after the first layer base material and the second foamed resin layer are formed in separate steps, for example, by extrusion molding, an adhesive layer is formed on the first layer by coating, etc., and then the second layer And dry laminate, and dry as needed. Next, a primer for the adhesive layer, that is, an undercoat is applied on the second layer, and after drying as necessary, a third adhesive layer is applied, and the solvent is dried and wound up. . In this way, many processes are required, which is cumbersome and costly.

  Therefore, it has been proposed to laminate a foamed resin layer without using an adhesive layer. For example, a vibration-damping and sound-proofing sheet for vehicles (Patent Document 1) in which a vibration-damping layer forming agent made of a rubber-based adhesive compound and a sound-proofing layer-forming material made of a foamed rubber compound are bonded and laminated. There is a foam composite (Patent Document 2) including a foam layer that adheres to an adherend.

JP 61-104836 A JP 2002-30262 A

However, in fact, no consideration has been given to the gap between the foamed resin layer and the adhesive layer laminated thereon. If the pressure-sensitive adhesive can be directly applied onto the foamed resin layer, steps such as primer selection, application, and drying are unnecessary, which is very advantageous in terms of process and economy.

Accordingly, an object of the present invention is to provide a laminated member in which an adhesive layer is directly laminated on a foamed resin layer without using a primer.

A first embodiment of the present invention is a laminated member in which a base material layer, a foamed resin layer, and an adhesive layer are laminated in this order, and the adhesive layer is directly laminated on the foamed resin layer. It is a laminated member.
In a second embodiment of the present invention, the absolute value of the difference in Hansen solubility parameter between the foamed resin contained in the foamed resin layer and the adhesive resin contained in the adhesive layer is 0.5 or less. It is a laminated member.
A third embodiment of the present invention is a laminated member in which the foamed resin is a polyvinyl chloride resin and the adhesive resin is a nitrile rubber or an acrylic resin.
A fourth embodiment of the present invention is a laminated member in which the foamed resin is a polypropylene resin and the adhesive resin is natural rubber.
A fifth embodiment of the present invention is a laminated member in which the foamed resin layer is laminated directly on the base material layer.
A sixth embodiment of the present invention is a laminated member in which the base material layer is made of a polyvinyl chloride resin, and the polyvinyl chloride resin of the foamed resin layer has a K value of 55 to 90.
In a seventh embodiment of the present invention, the base material layer is made of a polypropylene resin, and the foamed resin layer comprises 35 to 50% by mass of polypropylene resin and 10 to 40% by mass of plant based on the mass of the foamed resin layer. It is a laminated member which consists of a fiber and 25-40 mass% starch.
The eighth embodiment of the present invention is an automotive wire harness using the above laminated members.

In the laminated member of the present invention, it is not necessary to form a primer layer, preferably an adhesive layer, and it can be produced by a simple process and at a low cost.

FIG. 1 is a cross-sectional view showing an embodiment of the laminated member of the present invention. FIG. 2 is a process diagram showing an example of a manufacturing process of the laminated member shown in FIG. FIG. 3 is a cross-sectional view showing an example of a conventional laminated member. FIG. 4 is a process diagram showing an example of a manufacturing process of the conventional laminated member shown in FIG.

  FIG. 1 is a cross-sectional view showing an example of the most preferred embodiment of the laminated member of the present invention. In the figure, a base material layer (11), a foamed resin layer (12) and an adhesive layer (13) are laminated in this order, and the adhesive layer (13) is laminated directly on the foamed resin layer (12). The foamed resin layer (12) is directly laminated on the base material layer (11). Here, “direct lamination” means that the two layers are laminated and integrated without using an adhesive or sticky material, for example, an adhesive or a primer, between the two layers. Although not shown in FIG. 1, a peelable sheet made of paper or the like that is peeled off during use may be provided on the adhesive layer (13).

  In order to laminate directly, preferably, as an adhesive resin constituting the adhesive layer (13), a solubility parameter (hereinafter sometimes referred to as "SP value") with the foamed resin contained in the foamed resin layer (12) The absolute value of the difference in is less than 0.5, preferably less than 0.3. Examples of the solubility parameter include those estimated by a predetermined method and those measured by a cloud point titration method. In the present invention, the Hansen solubility parameter is used.

  The foamed resin layer (12) may contain components other than the foamed resin, and the adhesive layer (13) may contain components other than the adhesive resin. Preferably, the amount of the foamed resin contained in the foamed resin layer (12) is 35% by mass or more, more preferably 50% by mass or more of the foamed resin layer (12), and the adhesiveness contained in the adhesive layer (13). The amount of the resin is preferably 80% by mass or more, more preferably 90% by mass or more of the adhesive layer (13). And when foaming resin and adhesive resin are a mixture, the sum total of the value which multiplied the composition (mass%) to SP value is used.

  As a first combination satisfying the above SP difference, there is a combination in which the foamed resin is a polyvinyl chloride resin and the adhesive resin is a nitrile rubber or an acrylic resin. The respective SP values are 9.5 for polyvinyl chloride resin, 9.0 for nitrile rubber, and 9.3 for acrylic resin.

  Examples of the polyvinyl chloride resin include copolymers mainly composed of polyvinyl chloride, such as vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-ethylene copolymer resin, vinyl chloride-propylene copolymer, vinyl chloride- Styrene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride -A methacrylic acid ester copolymer or a vinyl chloride-acrylonitrile copolymer is mentioned, Preferably vinyl chloride is used.

  More preferably, polyvinyl chloride having a K value of 55 to 90, more preferably 60 to 80 is used. The K value can be determined according to Japanese Industrial Standard (JIS) K 7367 and is a measure of the average degree of polymerization. Polyvinyl chloride having a K value in the above range can be laminated on the base material layer without using an adhesive layer when a polyvinyl chloride resin is used as the base material.

  The polyvinyl chloride may be polyvinyl chloride obtained by any of bulk polymerization, suspension polymerization, and emulsion polymerization. Polyvinyl chloride obtained by suspension polymerization or emulsion polymerization is preferably used in that it can be paste-formed and heat-foamed.

  The expansion ratio of polyvinyl chloride is preferably 1.2 or more, and more preferably 2 or more. It is preferable that it is 5-15 especially for the protective material use of the assembled wire for motor vehicles.

  Next, as the nitrile rubber as the pressure-sensitive adhesive, not only a copolymer of butadiene and acrylonitrile (NBR) but also a copolymer containing other components, for example, methacrylic acid, as long as the SP value does not change greatly. (XNBR), copolymerized isoprene (NBIR), or a blend of vinyl chloride may be used. Preferably, NBR having an acrylonitrile content of 25 mass% to 36 mass% of the nitrile rubber is used.

  As the acrylic adhesive resin, a polymer containing an alkyl acrylate ester as a main component is preferably used. The alkyl acrylate ester preferably has 2 to 15 carbon atoms in the alkyl group, for example, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl. Examples thereof include acrylate and lauryl acrylate, and two or more of these may be used in combination.

  A second combination that satisfies the above SP difference is a combination in which the foamed resin is polypropylene and the adhesive resin is natural rubber. The SP values are 8.0 for polypropylene and 8.3 for natural rubber.

  As the foam of polypropylene, any one of a low foam having a foaming ratio of 5 times or less, a high foam having a foam ratio of 5 times or more, and a bead foam having 15 to 45 times may be used. Preferably, a high foam having an expansion ratio of 5 times or more is used.

  As described above, the foamed resin layer may contain components other than polypropylene. As the other component, preferably, a fiber component such as vegetable fiber and an auxiliary agent for linking polypropylene and the fiber component such as starch are used. By extruding what knead | mixed these components with water, the water vapor | steam becomes a foaming agent and the molded object which polypropylene expanded can be obtained. JP-A-2001-354895 discloses a foam containing such vegetable fibers that uses government-made postcard paper. The amount of each component in the foamed resin layer is preferably 10 to 40% by mass of vegetable fiber, 25 to 40% by mass of auxiliary agent, and 35 to 50% by mass of polypropylene.

  The natural rubber as the pressure-sensitive adhesive may be any rubber used for normal pressure-sensitive adhesive applications, and may be any of raw rubber, vulcanized rubber, and recycled rubber treated with vulcanized rubber.

  In the laminate of the present invention, various materials can be used as the base material layer (11). For example, various polymer substrates such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyester, polyamide, polycarbonate, polyacrylic resin, and polyurethane; various paper substrates such as fine paper and kraft paper; various metal foils such as aluminum; And fabric substrates can be used. Of these, polymer base materials are preferably used, and among them, polyvinyl chloride and polypropylene are preferable.

  As the polyvinyl chloride used as the substrate, a copolymer mainly composed of the above-mentioned polyvinyl chloride can be used. Preferably, a polyvinyl chloride base material, a polyvinyl chloride resin as the foamed resin, and a nitrile rubber or an acrylic resin as the adhesive resin are used in combination. In this case, the foamed resin layer can be directly laminated on the base material without using an adhesive layer for laminating, and the adhesive layer can be directly laminated on the foamed resin layer without using a primer. it can.

  As the polypropylene used as the substrate, either a stretched polypropylene sheet or an unstretched polypropylene sheet may be used. Preferably, a polypropylene base material, polypropylene as the foamed resin, and natural rubber as the adhesive resin are used in combination. Also in this case, the foamed resin layer can be directly laminated on the base material without using an adhesive layer for laminating, and the adhesive layer can be directly laminated on the foamed resin layer without using a primer. Can do.

  Next, the manufacturing method of the laminated member of this invention is demonstrated, referring FIG. FIG. 2 is a process diagram illustrating an example of a method for manufacturing the laminated member illustrated in FIG. 1. In the first step, the base material layer as the first layer and the foamed resin layer as the second layer are extruded and formed in separate steps. Alternatively, the base material layer and the foamed resin layer may be coextruded.

  In the second step, the foamed resin layer is directly laminated on the base material layer by thermocompression bonding or hot lamination. In the third step, a composition for forming an adhesive layer as the third layer is applied on the foamed resin layer by, for example, a roll coater method, a die coating method, a wire bar coating method, a knife coating method, etc. At this time, the primer treatment on the surface of the foamed resin layer may not be performed. As the composition for forming the adhesive layer, a composition obtained by dispersing or dissolving an adhesive resin in an appropriate solvent can be used.

  In the fourth step, the solvent is removed from the pressure-sensitive adhesive composition, and a curing treatment or the like is further performed as necessary. A protective peelable sheet may be stuck on the obtained adhesive layer. Alternatively, after separately applying an adhesive on the peelable sheet, the adhesive layer may be transferred by sticking on the foamed resin layer. As the peelable sheet, for example, paper such as glassine paper, coated paper, laminated paper, or a plastic film coated with a release agent such as a silicone resin can be used.

  In the case of the above-mentioned constitution of the polyvinyl chloride base material, the polyvinyl chloride resin foam layer, and the nitrile rubber or acrylic resin adhesive layer, the following method is used instead of the first step and the second step described above. Can do. First, in a 1st process, only shaping | molding of a polyvinyl chloride resin base material is performed.

  In the second step, the foamable polyvinyl chloride composition for forming the foamed polyvinyl chloride layer is directly applied on at least one surface of the polyvinyl chloride resin substrate. As a method of applying, the above-mentioned roll coater method or the like can be used. Next, the polyvinyl chloride resin substrate and the foamable polyvinyl chloride composition on the substrate are heated to foam the foamable polyvinyl chloride composition to form a foamed polyvinyl chloride layer. The heating condition varies depending on the foaming agent contained in the foamable polyvinyl chloride composition, but is typically about 1 to 3 minutes at a temperature of 150 to 230 ° C. The third and subsequent steps are as described above.

  The foamable polyvinyl chloride composition (hereinafter sometimes referred to as “vinyl chloride composition”) is based on 100 parts by mass of the polyvinyl chloride in addition to the above-mentioned polyvinyl chloride having a K value of 55 to 90. 50 to 150 parts by weight of plasticizer, 10 to 30 parts by weight of filler, 1 to 10 parts by weight of stabilizer, and 10 to 20 parts by weight of foaming agent. The vinyl chloride composition may be in the form of a liquid or a paste having a viscosity suitable for application on the base material layer, and is preferably a paste.

  Examples of the plasticizer include di-n-butyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, diisononyl phthalate, octyldecyl phthalate, diisodecyl phthalate, and phthalic acid. Phthalic acid plasticizers such as butylbenzyl and di-2-ethylhexyl isophthalate; di-2-ethylhexyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, etc. Fatty acid ester plasticizers; phosphate ester plasticizers such as tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, trixyl phosphate; chlorinated plasticizers such as chlorinated paraffin and chlorinated fatty acid ester; From epoxy plasticizer and polyester plasticizer It can be used at least one barrel. Preferably diisononyl phthalate is used. The compounding amount of the plasticizer is 50 to 150 parts by mass, preferably 60 to 120 parts by mass with respect to 100 parts by mass of polyvinyl chloride.

  As the filler, inorganic fillers such as calcium carbonate, talc, kaolin clay, synthetic silicic acid, quartz powder, calcium sulfate, calcium sulfite, calcium hydroxide, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium oxide, asbestos , Silica, glass fiber, mineral fiber; organic fillers such as wood powder, coconut shell powder, pulp powder, crosslinked polyester particles, polystyrene particles, carbon fibers, and natural fibers can be used. Preferably, calcium carbonate is used. The blending amount of the filler is 10 to 30 parts by mass, preferably 15 to 25 parts by mass with respect to 100 parts by mass of polyvinyl chloride.

  Examples of the stabilizer include carboxylic acid metal salts such as calcium stearate and barium stearate; organotin stabilizers such as dibutyltin laurate and dioctyltin maleate; lead stabilizers such as lead sulfate and lead phosphite; alkyl At least one selected from non-metallic stabilizers such as aryl phosphite, dibenzoylmethane, pentaerythritol and the like can be used. Preferably, calcium / zinc based carboxylates are used. The blending amount of the stabilizer is 1 to 10 parts by mass, preferably 2 to 5 parts by mass with respect to 100 parts by mass of polyvinyl chloride.

  As the foaming agent, a pyrolytic foaming agent is preferably used. Examples of the pyrolytic organic foaming agent include inorganic foaming agents such as sodium bicarbonate, ammonium bicarbonate, ammonium carbonate, sodium borohydride, calcium azide; organic foaming agents such as azodicarbonamide, azobisisobutyronitrile. , Barium azodicarboxylate, N, N′-dinitropentamethylenetetramine, p, p′-oxybis (benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide can be used. Preferably, azodicarbonamide is used, and the blending amount of the foaming agent is 10 to 20 parts by mass, preferably 14 to 18 parts by mass with respect to 100 parts by mass of polyvinyl chloride.

  The vinyl chloride composition may further contain a foaming aid. Examples of the foaming aid include metal oxides such as zinc oxide, lead oxide, cadmium oxide, magnesium oxide, calcium stearate, barium stearate, and zinc acetate; urea foaming aid, salicylic acid foaming aid, benzoic acid At least one selected from a foaming aid, glycerin, and diethylene glycol can be used. Preferably, zinc oxide is used.

  The blending amount of the foaming aid is 2 to 20 parts by mass, preferably 3 to 18 parts by mass with respect to 100 parts by mass of polyvinyl chloride.

  In addition to the above components, the vinyl chloride composition may contain a solvent, a flame retardant, an antioxidant, a weathering agent, a lubricant, a crosslinking agent, a dispersion accelerator, and the like in amounts that do not impair the object of the present invention. .

  The vinyl chloride composition can be produced by mixing the above-mentioned components and, if desired, various additives according to a conventional method. As a mixing means, a Henschel mixer, a kneader, a Banbury mixer, a roll mill, or the like can be used.

  The foamed resin layer containing 10 to 40% by mass of the vegetable fiber, 25 to 40% by mass of the auxiliary agent, and 35 to 50% by mass of the polypropylene is described in JP-A No. 2001-35495. It can be made by pulverizing waste paper made from government postcards, mixing with starch, kneading the resulting mixture with polypropylene resin granules and an appropriate amount of water, and extruding the kneaded product with a heated extruder. The obtained foam can be directly laminated on the polypropylene base layer by hot lamination or the like.

  As described above, the laminated member of the present invention can be produced with fewer steps than before, and is suitably used for building materials, automotive interior materials, automotive wire harnesses, and sound insulation materials.

各成分の詳細は以下のとおりである。
ポリ塩化ビニル：ＰＳＬ−６７５(商品名)、（株）カネカ製、Ｋ値６０
ポリ塩化ビニル：ＰＣＨ−１７５(商品名)、（株）カネカ製、Ｋ値７６
ポリ塩化ビニル：ＰＣＨ−８４３(商品名)、（株）カネカ製、Ｋ値８０
ポリ塩化ビニル（比較用）：ＴＨ−５００(商品名)、大洋塩ビ（株）製、Ｋ値５２
ポリビニル樹脂（比較用）：ＴＨ−３８００(商品名)、大洋塩ビ（株）製、Ｋ値９３
可塑剤：フタル酸ジイソノニル
充填剤：炭酸カルシウム
安定剤：アデカスタブ(商品名)
発泡剤：アゾジカルボンアミド Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
[Examples 1-3, Comparative Examples 1-3]
A laminate having the structure of polyvinyl chloride sheet base layer / polyvinyl chloride foamed resin layer / nitrile rubber adhesive layer was prepared by the following procedure.
(1) Each composition was obtained by mixing vinyl chloride having various K values shown in Table 2 with other components in a blending amount (parts by mass) shown in Table 1 below with a dissolver mixer.

Details of each component are as follows.
Polyvinyl chloride: PSL-675 (trade name), manufactured by Kaneka Corporation, K value 60
Polyvinyl chloride: PCH-175 (trade name), manufactured by Kaneka Corporation, K value 76
Polyvinyl chloride: PCH-843 (trade name), manufactured by Kaneka Corporation, K value 80
Polyvinyl chloride (for comparison): TH-500 (trade name), manufactured by Taiyo PVC Co., Ltd., K value 52
Polyvinyl resin (for comparison): TH-3800 (trade name), manufactured by Taiyo PVC Co., Ltd., K value 93
Plasticizer: Diisononyl phthalate
Filler: Calcium carbonate Stabilizer: Adeka Stub (trade name)
Foaming agent: Azodicarbonamide

  (2) Next, each vinyl chloride composition was applied to a thickness of about 0.3 mm on one surface of a polyvinyl chloride sheet having a thickness of 0.2 mm (manufactured by Yazaki Parts Co., Ltd.) using an applicator. A laminate was obtained. Each laminate was placed in an oven at 230 ° C. for 1.5 minutes to foam each vinyl chloride composition.

(3) For Examples 1 to 3, an aqueous solution of nitrile rubber (manufactured by Nippon Zeon Co., Ltd.) was applied on the vinyl chloride foamed resin layer so that the thickness after drying was 0.03 mm. The laminate was obtained by drying in an oven at ° C.
For Comparative Example 3, an aqueous solution of natural rubber (Unimac) was applied onto the vinyl chloride foamed resin layer so that the thickness after drying was 0.03 mm, and then dried in an oven at 120 ° C. Obtained.
In Comparative Examples 1 and 2, since the foamed resin layer did not adhere to the base material layer, no adhesive layer was formed.

From the ratio of thickness before and after foaming, the foaming ratio shown in Table 2 was obtained. Further, whether the foamed resin layer and the base material layer, and the foamed resin layer and the adhesive layer can be peeled by hand was examined.

  As shown in Table 2, each of the examples using polyvinyl chloride having a predetermined K value was able to obtain a foamed resin layer showing good adhesion to the base material layer and good foaming ratio. . On the other hand, in Comparative Examples 1 and 2 using polyvinyl chloride lacking this requirement, the foam was not foamed as a whole, the expansion ratio could not be measured, and the adhesion to the polyvinyl chloride sheet was poor. Moreover, when nitrile rubber was used as an adhesive (Examples 1 to 3), good adhesion to the foamed resin layer was exhibited without using a primer. On the other hand, when natural rubber was used (Comparative Example 3), the adhesion to the foamed resin layer was poor.

[Examples 4 to 6]
A laminate having the structure of polypropylene film base layer / polypropylene-containing foamed resin layer / natural rubber adhesive layer was prepared by the following procedure. As the foamed resin, those shown in Table 3 below are used, and details thereof are as follows.
PP1: Expanded polypropylene resin, manufactured by JSP Co., Ltd. PP2: Expanded polypropylene resin, Kaneka Plastic Foam Co., Ltd.
PP / cellulose: Expanded polypropylene resin / cellulose (100 parts / 40 parts), manufactured by Gifu Parts Co., Ltd.

  (1) Each of the foamed resin layers was directly laminated by hot lamination on a 0.2 mm thick polypropylene film (manufactured by Yazaki Parts Co., Ltd.).

  (2) Next, an aqueous solution of natural rubber (manufactured by Unimac Co., Ltd.) was applied on each of the foamed resin layers so that the thickness after drying was 0.03 mm, and then dried in an oven at 120 ° C. to obtain a laminate. Obtained.

Whether or not the foamed resin layer and the base material layer and the foamed resin layer and the adhesive layer could be peeled by hand was examined.

  As shown in the above table, in any of the examples, a laminated member could be formed without using an adhesive and a primer.

  The laminated member of the present invention can be made by a simple process. The foamed member is useful as a protective material for automobile assembled wires.

11, 31 Base material layer 12, 32 Foamed resin layer 13, 33 Adhesive layer 34 Adhesive layer 35 Primer layer

Claims (8)

  A laminated member in which a base material layer, a foamed resin layer, and an adhesive layer are laminated in this order, wherein the adhesive layer is directly laminated on the foamed resin layer.   The laminated member according to claim 1, wherein an absolute value of a difference in Hansen solubility parameter between the foamed resin contained in the foamed resin layer and the adhesive resin contained in the adhesive layer is 0.5 or less.   The laminated member according to claim 2, wherein the foamed resin is a polyvinyl chloride resin, and the adhesive resin is a nitrile rubber or an acrylic resin.   The laminated member according to claim 2, wherein the foamed resin is a polypropylene resin, and the adhesive resin is natural rubber.   The laminated member according to any one of claims 1 to 4, wherein the foamed resin layer is directly laminated on the base material layer.   The laminated member according to claim 3 or 5, wherein the base material layer is made of a polyvinyl chloride resin, and the polyvinyl chloride resin of the foamed resin layer has a K value of 55 to 90.   The base material layer is made of polypropylene resin, and the foamed resin layer comprises 35 to 50% by mass of polypropylene resin, 10 to 40% by mass of vegetable fiber, and 25 to 40% by mass of starch of the mass of the foamed resin layer. The laminated member according to claim 4 or 5, comprising: The wire harness for motor vehicles which uses the laminated member of any one of Claims 1-7.

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