WO2024105886A1 - Composition de résine composite, article moulé et procédé de production d'une composition de résine composite - Google Patents

Composition de résine composite, article moulé et procédé de production d'une composition de résine composite Download PDF

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Publication number
WO2024105886A1
WO2024105886A1 PCT/JP2022/042894 JP2022042894W WO2024105886A1 WO 2024105886 A1 WO2024105886 A1 WO 2024105886A1 JP 2022042894 W JP2022042894 W JP 2022042894W WO 2024105886 A1 WO2024105886 A1 WO 2024105886A1
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WIPO (PCT)
Prior art keywords
resin composition
composite resin
glass fibers
composition according
glass
Prior art date
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PCT/JP2022/042894
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English (en)
Japanese (ja)
Inventor
善弘 高井
千草 井手
一正 藤村
文明 馬場
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三菱電機株式会社
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Priority to PCT/JP2022/042894 priority Critical patent/WO2024105886A1/fr
Publication of WO2024105886A1 publication Critical patent/WO2024105886A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

Definitions

  • This disclosure relates to a composite resin composition, a molded article, and a method for producing the composite resin composition.
  • vacuum insulation panels have been used in the fields of home appliances and housing equipment to keep equipment warm while saving energy.
  • Glass fiber is generally used as the core material of vacuum insulation panels.
  • the core material, glass fiber is processed to form it into a shape that matches the equipment, but the glass fiber scraps cut during processing are disposed of as waste. From the perspective of reducing the burden on the environment, composites with resin materials are being considered as an effective way to utilize such glass fiber scraps.
  • Patent Document 1 JP Patent Publication No. 2016-222808 discloses a resin composition made of polyolefin resin, thermoplastic elastomer, and glass fiber, which has excellent rigidity, impact resistance, and appearance.
  • Patent Document 2 JP Patent Publication No. 11-226977 discloses a building board manufactured by crushing recovered glass fiber and mixing it with a binder resin.
  • Patent Document 3 JP Patent Publication No. 2019-14804 discloses a resin material molded from crushed glass fiber with a small average fiber length and aspect ratio.
  • Patent Document 4 JP Patent No. 5220394 discloses a composite forming material containing glass fiber with a fiber diameter of 1 to 7 ⁇ m, an average fiber length of 30 to 300 ⁇ m, and an aspect ratio of 10 or more.
  • JP 2016-222808 A Japanese Patent Application Laid-Open No. 11-226977 JP 2019-14804 A Patent No. 5220394
  • the present disclosure has been made to solve the problems described above, and aims to provide a composite resin composition and molded article that have improved strength and elastic modulus and little warpage.
  • a composite resin composition comprising a resin and a glass fiber,
  • the average fiber length of the glass fibers is 10 ⁇ m or more and 50 ⁇ m or less,
  • the average aspect ratio of the glass fibers is 1 or more and 30 or less,
  • the composite resin composition, wherein the geometric standard deviation of the average fiber length of the glass fibers is 0.4 or more.
  • the geometric standard deviation of the average fiber length of the glass fibers is large and has a wide distribution of 0.4 or more, so that components shorter than the average fiber length of the glass fibers suppress fiber orientation during molding, reducing the anisotropy of the shrinkage rate and elastic modulus associated with fiber orientation and making it possible to suppress warpage.
  • components longer than the average fiber length of the glass fibers improve strength, making it possible to maintain the strength of the molded product.
  • the present disclosure makes it possible to provide a composite resin composition and molded article that have improved strength and elastic modulus and reduced warpage.
  • FIG. 1 is an example of a schematic flow chart of a method for producing a composite resin composition according to the first embodiment.
  • FIG. 2 is a schematic diagram showing an example of a compression granulator used in producing the composite resin composition in the first embodiment.
  • FIG. 3 is a graph showing the distribution of the average fiber length of the glass fibers used in Example 2.
  • Embodiment 1 ⁇ Composite resin composition>
  • the composite resin composition according to the present embodiment includes a resin and glass fibers.
  • the average fiber length of the glass fibers is 10 ⁇ m or more and 50 ⁇ m or less.
  • the average aspect ratio of the glass fibers is 1 or more and 30 or less.
  • the geometric standard deviation of the average fiber length of the glass fibers is 0.4 or more.
  • the "average fiber length of the glass fibers” is simply referred to as the "average fiber length”
  • the "average aspect ratio of the glass fibers” is simply referred to as the “average aspect ratio”
  • the "average fiber diameter of the glass fibers” is simply referred to as the “average fiber diameter”
  • the "geometric standard deviation of the average fiber length of the glass fibers” is simply referred to as the “geometric standard deviation”.
  • the resin contained in the composite resin composition of the present embodiment is not particularly limited, and examples thereof include thermoplastic resins, thermosetting resins, and biodegradable resins, with thermoplastic resins being preferred.
  • thermoplastic resin a commercially available thermoplastic resin can be used.
  • commercially available thermoplastic resin for example, an olefin-based resin, a styrene-based resin, a polyester-based resin, a polyamide-based resin, a biodegradable resin, and a super engineering plastic (super engineering plastic) can be used.
  • olefin resins examples include polyethylene, polypropylene, propylene-ethylene block copolymers, propylene-butene block copolymers, propylene- ⁇ -olefin block copolymers, propylene-ethylene random copolymers, propylene-butene random copolymers, propylene- ⁇ -olefin random copolymers, and propylene- ⁇ -olefin graft copolymers.
  • styrene resins include polymers obtained by polymerizing monomers made of monovinyl aromatic monomers such as styrene, ⁇ -methylstyrene, p-methylstyrene, and p-t-butylstyrene, and polymers obtained by polymerizing monomers made of vinyl cyanide monomers such as acrylonitrile and methacrylonitrile having a cyano group, which is a polar group.
  • Polymers obtained by polymerizing monomers made of monovinyl aromatic monomers include general-purpose polystyrene (GPPS), and high-impact polystyrene (HIPS) and medium-impact polystyrene (MIPS), which are rubber-modified styrene polymers produced by dissolving rubber-like substances such as polybutadiene (PBD) and styrene-butadiene copolymer (SBR) in styrene monomers and using bulk or bulk suspension polymerization methods.
  • GPPS general-purpose polystyrene
  • HIPS high-impact polystyrene
  • MIPS medium-impact polystyrene
  • PBD polybutadiene
  • SBR styrene-butadiene copolymer
  • Examples of polymers obtained by polymerizing monomers consisting of vinyl cyanide monomers include acrylonitrile-styrene copolymer (AS resin), acrylonitrile-ethylene-styrene copolymer (AES resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin) which is obtained by polymerizing acrylonitrile and styrene with polybutadiene.
  • AS resin acrylonitrile-styrene copolymer
  • AES resin acrylonitrile-ethylene-styrene copolymer
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • polyester resins include polyethylene terephthalate, polybutylene terephthalate, polycarbonate, etc.
  • polyamide-based resins examples include polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 12, and polyamide 46.
  • the polyamide-based resin may be an aromatic polyamide or a plant-derived polyamide.
  • biodegradable resins examples include polylactic acid, polyglycolic acid, polyhydroxybutyrate, polyhydroxyalkanoate, polyvinyl alcohol, etc.
  • super engineering plastics examples include polyphenylene ether and polyphenylene sulfide.
  • Thermoplastic resins are further classified into crystalline resins and amorphous resins.
  • a crystalline resin is preferable. From this viewpoint, among the above-mentioned thermoplastic resins, it is preferable to use a crystalline resin such as polypropylene, polybutylene terephthalate, polyamide, or polyphenylene sulfide.
  • the glass fiber contained in the composite resin composition of the present embodiment is not particularly limited, and existing glass fibers can be used.
  • existing glass fibers include E glass used for adding to resins, ECR glass with excellent electrical insulation and acid resistance, AR glass with excellent alkali resistance, A glass which is an alkali-containing glass, S glass with excellent strength, C glass with excellent acid resistance, and D glass with low dielectric constant. These glass fibers may be used alone or in combination of two or more.
  • the glass fibers may also be recycled glass fibers that have been crushed into layers.
  • Examples of such glass fibers include the core material of vacuum insulation panels.
  • the average fiber length is 10 ⁇ m or more and 50 ⁇ m or less. If the average fiber length is less than 10 ⁇ m, the shape of the glass fiber approaches a sphere, reducing the load sharing ratio in the composite resin composition and reducing the reinforcing effect. If the average fiber length exceeds 50 ⁇ m, the reinforcing effect is high, but the orientation of the glass fibers is promoted, causing warpage deformation when the composite resin composition is molded.
  • the average fiber length is preferably 10 ⁇ m or more and 30 ⁇ m or less.
  • the average aspect ratio is 1 or more and 30 or less.
  • the average aspect ratio means the value obtained by dividing the average fiber length by the average fiber diameter. If the average aspect ratio is less than 1, the reinforcing effect is small. If the average aspect ratio is more than 30, warpage deformation occurs when the composite resin composition is molded. It is preferable that the average aspect ratio is 1 or more and 10 or less.
  • the average fiber length and average fiber diameter are obtained by particle size distribution measurement using a laser diffraction/scattering method.
  • they may be average values obtained by measuring 500 or more glass fibers.
  • the geometric standard deviation is 0.4 or more. If the geometric standard deviation is less than 0.4, the distribution width of the fiber length of the glass fibers will be narrow and the fiber lengths of the glass fibers will be uniform, so the degree of orientation of each fiber during molding will also be uniform. As a result, the anisotropy of the molding shrinkage rate, elastic modulus, etc. will be strong, making warpage more likely to occur.
  • the geometric standard deviation refers to the standard deviation calculated by dividing the data on the fiber length of the glass fiber into multiple intervals so that they are evenly distributed on a logarithmic scale, organizing the data as a frequency distribution using the frequency (%) and cumulative (%) in each interval, and calculating the standard deviation from the average fiber length and frequency in the interval using the following formula (1).
  • the glass fiber content in the composite resin composition of the present disclosure is preferably 60% by mass or less. If the glass fiber content in the composite resin composition exceeds 60% by mass, the fluidity of the resin decreases, making molding difficult. It is more preferable that the glass fiber content in the composite resin composition is 40% by mass or less. From the viewpoint of the expression of the effect of containing glass fiber, the glass fiber content in the composite resin composition may be, for example, 5% by mass or more.
  • the composite resin composition of the present disclosure may also be used in the form of pellets (master batch) containing a high concentration of glass fibers.
  • master batch containing a high concentration of glass fibers.
  • the glass fiber content may exceed 60 mass%.
  • the glass fiber may be surface-treated with a surface treatment agent to improve adhesion to the resin.
  • surface treatment agents include silane coupling agents.
  • silane coupling agent There are no particular limitations on the silane coupling agent, and examples include aminosilane-based, epoxysilane-based, allylsilane-based, and vinylsilane-based silane coupling agents.
  • the surface treatment may involve directly treating the surface of the glass fiber with a silane coupling agent, or the surface of the resin may be treated with a silane coupling agent.
  • the content of the silane coupling agent in the composite resin composition of the present disclosure may be 0.1% by mass or more and 2.0% by mass or less, or 0.15% by mass or more and 1.0% by mass or less.
  • the composite resin composition of the present embodiment may contain a filler as long as it does not impede the object of the present disclosure.
  • the filler include carbon fiber, metal fiber, metal powder, various ceramics, minerals, etc. These fillers may be used alone or in combination of two or more.
  • the filler content in the composite resin composition of the present disclosure is not particularly limited, and the composition ratio when two or more types are mixed is also not particularly limited, but it is desirable to adjust each time depending on the required physical properties.
  • the filler content in the composite resin composition of the present disclosure may be, for example, 0.1 mass% or more and 30 mass% or less.
  • the composite resin composition of this embodiment may contain additives such as stabilizers, lubricants, processing aids, plasticizers, colorants, and flame retardants, as long as they do not impede the objectives of this disclosure. These additives may be used alone or in combination of two or more.
  • the amount of additives contained in this disclosure is not particularly limited, and the composition ratio when two or more types are mixed is also not particularly limited, but it is desirable to adjust each time depending on the required physical properties.
  • the method for producing the composite resin composition of the present embodiment is not particularly limited, and the composite resin composition can be produced, for example, by mixing the above-mentioned glass fibers and resin.
  • the method for mixing the glass fiber and resin is not particularly limited.
  • the glass fiber and resin may be mixed and molded simultaneously using a pellet molding device, or the glass fiber and resin may be mixed and then molded into a desired shape.
  • devices used for mixing the glass fiber and resin include a tumbler, hammer mill, ball mill, roller mill, etc.
  • the mixing conditions may be changed appropriately depending on the resin and glass fiber used.
  • the composite resin composition of this embodiment may be manufactured by preparing a master batch containing the glass fiber and resin as an intermediate product, and then further mixing the resin into the master batch.
  • the composite resin composition of this embodiment may be manufactured as follows (see FIG. 1). That is, the composite resin composition of this embodiment includes a crushing step (S1) in which laminated glass fibers are crushed by a compression granulator, and a mixing step (S2) in which the crushed glass fibers are mixed with a resin.
  • the compression granulator has a flat die with multiple opening holes and a rotating roller, and the diameter of the opening holes of the flat die is 7 mm or more and 15 mm or less. Each step will be described below.
  • the compression granulator 10 includes a pulverization chamber 2.
  • the pulverization chamber 2 has a rotating roller 3 and a flat die 4.
  • laminated glass fibers 1 hereinafter also referred to as "laminate" are fed into the pulverization chamber 2.
  • the fed laminate 1 is sent to the flat die 4 by the rotating roller 3, and is compressed and pulverized by the flat die 4.
  • the pulverized laminate 1 (hereinafter also referred to as "pulverized material”) is conveyed out of the pulverization chamber 2 through an opening hole (not shown) of the flat die 4.
  • the laminate 1 compressed and pulverized by the rotating rollers 3 and flat die 4 clogs the opening holes of the flat die, and when the holes are clogged to a certain extent, the laminate 1 is pushed in further to clear the clog.
  • the compression action changes depending on the state of clogging of the flat die 4, so the compression force applied to the laminate 1 also changes, causing the length of the pulverized material 5 to change, and it is possible to obtain pulverized products 5 with a wide length distribution.
  • This cycle occurs constantly while the compression granulator 10 is in operation. Therefore, there is no need to stop the device or perform other operations to clear the clogged holes.
  • the diameter of the opening hole of the flat die 4 is 7 mm or more and 15 mm or less. If the diameter of the opening hole of the flat die 4 is less than 7 mm, the pressure applied by the rotating roller 3 becomes stronger, the residence time of the crushed material 5 stuck in the opening hole becomes shorter, and the fiber length of the crushed material 5 becomes longer due to the loss of compression opportunities, resulting in greater warpage deformation of the molded product. If the diameter of the opening hole of the flat die 4 exceeds 15 mm, the pressure applied is weak, the residence time of the crushed material 5 stuck in the opening hole becomes longer, and the fiber length of the crushed material 5 becomes shorter due to the increase in compression opportunities, resulting in a loss of the reinforcing effect of the molded product.
  • the arrangement of the opening holes of the flat die 4 is not particularly limited, and for example, multiple opening holes of the same diameter may be arranged, or multiple opening holes of different diameters may be arranged.
  • the compression granulator 10 may be equipped with a sieve 6.
  • the pulverized material 5 that passes through the sieve 6 is transported to the mixing process.
  • the pulverized material 5 that does not pass through the sieve 6 may be returned to this process again.
  • crushing can be performed by existing methods that do not use flat dies, crushing using flat dies is preferable for the following reasons.
  • Existing methods include, for example, a crushing method using rotary blades and a roller compaction method in which the target material is passed between rotating rollers.
  • crushing is difficult because the thin and flexible laminate 1 gets tangled in the rotary blades.
  • the roller compaction method the compression force can be adjusted by adjusting the gap between the rollers to control the size of the crushed material, but the frequency at which the laminate 1 is roller compacted is uniform for all materials, making it difficult to obtain crushed material with a wide size distribution.
  • the method for producing a composite resin composition according to the present embodiment may include a cutting step of cutting the laminate 1 into a size that can pass through the compression granulator 10, prior to the pulverization step.
  • the laminate 1 is cut by, for example, a rotary blade.
  • the size of the glass fibers in a laminated state after cutting may be, for example, about 30 cm x 30 cm.
  • the method for producing a composite resin composition according to the present embodiment may include a surface treatment step of surface-treating the glass fibers with a surface treatment agent such as a silane coupling agent.
  • the surface treatment step may be performed simultaneously with the pulverization step, or may be performed between the pulverization step and the mixing step.
  • the surface of the resin may be previously surface-treated, and the surface-treated resin may be mixed with the pulverized product.
  • the pulverization process and the surface treatment process are preferably carried out simultaneously.
  • the surface treatment agent may be added from a surface treatment agent sprayer 7 installed in the pulverization chamber 2 (see FIG. 2).
  • Embodiment 2 The molded article according to the present embodiment is made of the composite resin composition described above. Since the molded article according to the present embodiment is made of the composite resin composition described above, it has the effects of improving the elastic modulus and reducing warpage while maintaining strength.
  • the molded product of this embodiment can be produced by molding a composite resin composition containing the above-mentioned resin and glass fiber, for example, by injection molding, extrusion molding, compression molding, vacuum molding, pressure molding, inflation molding, or a composite molding method thereof. Among these, injection molding is preferred.
  • the shape of the molded product is not particularly limited, but can be appropriately selected depending on the application and purpose of the molded product. Examples of shapes include box-like, plate-like, cylindrical, ring-like, circular, and lattice-like shapes.
  • Applicable molded products include, for example, various fans and housing parts for home appliances, air conditioners, automobiles, factory automation equipment, etc.
  • housing parts and rotating fans for air conditioners are preferably used because they require appropriate rigidity and dimensional accuracy.
  • An example of a housing part is the cover for the outdoor unit of an air conditioner.
  • An example of a rotating fan is a propeller fan, a centrifugal fan, a line flow fan (registered trademark), a turbo fan, etc.
  • Example 1 As the laminated glass fiber, the core material of the vacuum insulation panel was used as the scrap, and as the compression granulator, the compression granulator having the configuration shown in Fig. 2 was used as the compression granulator.
  • the diameters of the opening holes of the flat die provided in the compression granulator were 7 mm and 8 mm.
  • the scrap was crushed by the compression granulator to obtain glass fiber (crushed material).
  • polypropylene resin (Sumitomo Chemical Co., Ltd., Noblen AZ564) was prepared, and as the mixing device, a pellet molding device was prepared. The crushed material and polypropylene resin were placed in the pellet molding device so that the content of the crushed material was 20 mass %, and pellets of the composite resin composition were produced.
  • the obtained pellets were molded into flat test pieces and dumbbell-shaped tensile test pieces (JIS K7139:2009 Type 1A) for evaluation using an injection molding machine (NEX110IV-9EG, manufactured by Nissei Plastics Co., Ltd.).
  • the basic conditions for injection molding were a cylinder temperature of 220°C, a mold temperature of 40°C, and an injection speed of 100 mm/sec.
  • Each test piece was 100 mm long, 100 mm wide, and 2 mm thick.
  • Example 2 Flat test pieces and dumbbell-shaped tensile test pieces for evaluation were molded under the same conditions as in Example 1, except that the diameter of the opening hole of the flat die provided in the compression granulator was changed to 14 mm and 15 mm.
  • Example 2 A roller compression crusher with a roller gap of 1 mm was prepared. The end material of the core material of the above-mentioned vacuum insulation panel was crushed by the roller compression crusher to obtain a crushed product. After that, a flat test piece and a dumbbell-shaped tensile test piece for evaluation were molded under the same conditions as in Example 1.
  • test piece of Comparative Example 1 had a large warpage deformation. Also, the test piece of Comparative Example 2 had a decrease in strength.

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Abstract

Composition de résine composite contenant une résine et des fibres de verre, la longueur moyenne des fibres de verre étant de 10 à 50 µm, le rapport d'aspect moyen des fibres de verre étant de 1 à 30, et l'écart type géométrique de la longueur moyenne des fibres de verre étant de 0,4 ou plus.
PCT/JP2022/042894 2022-11-18 2022-11-18 Composition de résine composite, article moulé et procédé de production d'une composition de résine composite WO2024105886A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63156856A (ja) * 1986-12-22 1988-06-29 Japan Synthetic Rubber Co Ltd ポリアミド樹脂成形物
JPH01185364A (ja) * 1988-01-18 1989-07-24 Japan Synthetic Rubber Co Ltd 補強剤含有ポリアミド組成物
JPH10120900A (ja) * 1996-10-14 1998-05-12 Asahi Chem Ind Co Ltd ポリアミド樹脂組成物およびその成型品
CN1112407C (zh) * 1998-12-18 2003-06-25 旭化成株式会社 聚酰胺树脂组合物及其模制制品
JP2015054916A (ja) * 2013-09-11 2015-03-23 旭化成ケミカルズ株式会社 ポリアミド樹脂組成物及びその製造方法
WO2017043089A1 (fr) * 2015-09-10 2017-03-16 株式会社イハラ合成 Matériau de fil constitué de plastique renforcé de fibres de verre pour le traitement de surface

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63156856A (ja) * 1986-12-22 1988-06-29 Japan Synthetic Rubber Co Ltd ポリアミド樹脂成形物
JPH01185364A (ja) * 1988-01-18 1989-07-24 Japan Synthetic Rubber Co Ltd 補強剤含有ポリアミド組成物
JPH10120900A (ja) * 1996-10-14 1998-05-12 Asahi Chem Ind Co Ltd ポリアミド樹脂組成物およびその成型品
CN1112407C (zh) * 1998-12-18 2003-06-25 旭化成株式会社 聚酰胺树脂组合物及其模制制品
JP2015054916A (ja) * 2013-09-11 2015-03-23 旭化成ケミカルズ株式会社 ポリアミド樹脂組成物及びその製造方法
WO2017043089A1 (fr) * 2015-09-10 2017-03-16 株式会社イハラ合成 Matériau de fil constitué de plastique renforcé de fibres de verre pour le traitement de surface

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