WO2018096834A1 - Procédé de production d'objet en résine moulé - Google Patents

Procédé de production d'objet en résine moulé Download PDF

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Publication number
WO2018096834A1
WO2018096834A1 PCT/JP2017/037343 JP2017037343W WO2018096834A1 WO 2018096834 A1 WO2018096834 A1 WO 2018096834A1 JP 2017037343 W JP2017037343 W JP 2017037343W WO 2018096834 A1 WO2018096834 A1 WO 2018096834A1
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WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
resin
melting point
resin composition
fine powder
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/JP2017/037343
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English (en)
Japanese (ja)
Inventor
祐一郎 角
重樹 黒木
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.)
TBM Co Ltd
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TBM 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 TBM Co Ltd filed Critical TBM Co Ltd
Publication of WO2018096834A1 publication Critical patent/WO2018096834A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • 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
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethylene
    • 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

  • the present invention relates to a method for producing a resin molded body.
  • Patent Document 1 a resin composition containing 60% to 82% by weight of an inorganic substance powder and 18% to 40% by weight of a thermoplastic resin is kneaded and then formed into a sheet shape through a die, and then longitudinally and / or A manufacturing method of a thin film sheet with high blending of inorganic substance powder, which is stretched in the transverse direction to improve whiteness and opacity, is disclosed.
  • a plastic sheet mainly composed of a thermoplastic resin is generally transparent or nearly transparent.
  • this sheet is filled with inorganic fine powder, the opacity of the sheet is improved, but the whiteness remains at a low level.
  • a heat treatment is usually performed after the stretching at a glass transition point, a softening point, or a softening point of the raw thermoplastic resin.
  • annealing treatment a heat treatment
  • the purpose is to prevent dimensional changes and strength reductions that occur after a product is produced due to the residual stress in the sheet generated up to the previous process.
  • the heat treatment referred to as the annealing treatment there are usually many methods for maintaining the temperature at a high temperature for a long time.
  • the present invention has been made in view of the above circumstances, and provides a method for producing a resin molded article excellent in elastic modulus and bending strength while keeping optical properties such as whiteness and opacity as high as possible. For the purpose.
  • the present inventors first conducted an experiment on how the balance between the optical properties of the whiteness and opacity of the sheet and the bending strength changed by stretching, and obtained the results shown in Table 1 below. That is, when the inorganic fine powder is filled and the stretching is strengthened, the whiteness is remarkably improved, the opacity is slightly increased, and some of the measured values reach 100%. However, the bending strength was remarkably reduced, and a tendency to decrease the tensile strength was recognized.
  • the present inventors performed a heat treatment temperature after stretching at a temperature higher than one melting point and lower than the other melting point for two types of thermoplastic resins having different melting points.
  • the inventors have found that it is possible to obtain a resin molded article excellent in elastic modulus and bending strength while maintaining opacity as high as possible, and have completed the present invention. More specifically, the present invention aims to provide the following.
  • thermoplastic resin a thermoplastic resin having a higher melting point than the first thermoplastic resin, and an inorganic fine powder to obtain a resin composition; Stretching the resin composition below the melting point of the first thermoplastic resin; Heat-treating the stretched resin composition at a temperature not lower than the melting point of the first thermoplastic resin and lower than the melting point of the second thermoplastic resin.
  • thermoplastic resin is polyethylene and the second thermoplastic resin is polypropylene.
  • a first thermoplastic resin, a second thermoplastic resin having a melting point higher than that of the first thermoplastic resin, and an inorganic fine powder are mixed to obtain a resin composition.
  • a step of heat-treating at a temperature is also included in the temperature.
  • the present invention includes a step of stretching the resin composition containing the first thermoplastic resin, the second thermoplastic resin, and the inorganic fine powder at a temperature lower than the melting point of the first thermoplastic resin.
  • a large number of pores are formed in the resin composition.
  • the elastic modulus and the bending strength are improved by heat-treating the resin composition at a temperature not lower than the melting point of the first thermoplastic resin and lower than the melting point of the second resin, While the internal strain is removed, many of the pores derived from the first thermoplastic resin are blocked, and many of the pores derived from the second thermoplastic resin remain, so the whiteness and opacity are relatively high. Maintained. As a result, it is possible to obtain a resin molded article having an excellent balance between optical properties such as whiteness and opacity, and mechanical properties such as elastic modulus and bending strength.
  • the first thermoplastic resin, the second thermoplastic resin, and the inorganic fine powder are mixed to obtain a resin composition.
  • the first thermoplastic resin, the second thermoplastic resin, and the inorganic fine powder are melted and kneaded at a temperature equal to or higher than the melting point of the second thermoplastic resin to obtain a resin composition.
  • the resin composition can be obtained by kneading in advance with a kneading machine, once producing mixed pellets, then forming into a sheet with an extrusion molding machine, or directly kneading by biaxial extrusion molding or the like.
  • the molding may be performed with a single machine to form a sheet.
  • the inorganic fine powder in the thermoplastic resin it is preferable to knead by applying a high shear stress, for example, kneading with a biaxial kneader.
  • a high shear stress for example, kneading with a biaxial kneader.
  • the resin composition containing an inorganic fine powder has a high viscosity at the time of melting, the design is such that the kneading part of the extruder is lengthened.
  • Step of stretching resin composition In the step of stretching the resin composition in the present invention, the resin composition is stretched at a temperature lower than the melting point of the first thermoplastic resin. By stretching the resin composition below the melting point of the first thermoplastic resin, pores are likely to be generated in the resin composition, and a resin molded product having high opacity and whiteness can be easily obtained.
  • the stretching conditions need to be set as appropriate according to the desired specific gravity (density) according to the resin molded body, and are uniaxial in the longitudinal or lateral direction, or sequentially or simultaneously biaxially stretched in the longitudinal and lateral directions.
  • Adopt one of the following.
  • the necessary draw ratio can also be calculated by calculation.
  • the weight per square meter (also referred to as basis weight) W (g / m 2 ) of the resin composition before being stretched is measured, and the apparent specific gravity D and aspect ratio (longitudinal direction and vertical direction) of the product determined in the production plan are measured.
  • the ratio R of the draw ratio in the transverse direction (R) and the target value T (cm) of the thickness of the product after transverse stretching In addition, it can be easily estimated by operating experience for each device.
  • the stretched resin composition is heat-treated at a temperature not lower than the melting point of the first thermoplastic resin and lower than the melting point of the second thermoplastic resin.
  • the heat-treated resin molded body is freed from internal strain, and at least a part of the pores derived from the first thermoplastic resin is blocked, leaving the pores derived from the second thermoplastic resin. .
  • the whiteness and opacity values vary greatly.
  • the stretched resin composition is heat-treated at a temperature lower than the melting point of the first thermoplastic resin, even if opacity and whiteness are ensured, bending strength and elastic modulus are lowered.
  • the stretched resin composition is heat-treated at a temperature above the melting point of the second thermosetting resin, the opacity and whiteness are lowered even if the bending strength and the elastic modulus are ensured.
  • the temperature for the heat treatment is not particularly limited as long as the temperature is equal to or higher than the melting point of the first thermoplastic resin and lower than the melting point of the second thermoplastic resin, and may be appropriately set according to the melting points of both.
  • the melting point of the second thermoplastic resin is preferably closer to the melting point of the second thermoplastic resin than the melting point of the first thermoplastic resin.
  • the melting point of the second thermoplastic resin is ⁇ 40 ° C.
  • the melting point of the second thermoplastic resin is preferable, the melting point of the second thermoplastic resin is ⁇ 30 ° C., more preferably the melting point of the second thermoplastic resin, and the melting point of the second thermoplastic resin.
  • the melting point is ⁇ 20 ° C. to the melting point of the second thermoplastic resin, and it is even more preferable that the melting point of the second thermoplastic resin is ⁇ 10 ° C. to the melting point of the second thermoplastic resin.
  • the heat treatment temperature is preferably closer to the melting point of the first thermoplastic resin than the melting point of the second thermoplastic resin, for example, the first thermoplastic resin.
  • the melting point of the first thermoplastic resin is more preferably + 40 ° C., more preferably the melting point of the first thermoplastic resin to the melting point of the first thermoplastic resin + 30 ° C., and the first heat
  • the melting point of the plastic resin to the melting point of the first thermoplastic resin + 20 ° C. is even more preferable, and the melting point of the first thermoplastic resin to the melting point of the first thermoplastic resin + 10 ° C. is even more preferable.
  • the selection of the first thermoplastic resin and the second thermoplastic resin is not particularly limited as long as the second thermoplastic resin has a higher melting point than the first thermoplastic resin.
  • polyethylene high density polyethylene / low density
  • Polyethylene ultra high molecular weight polyethylene
  • ultra high molecular weight polyethylene polypropylene
  • polystyrene polyethylene terephthalate
  • the first thermoplastic resin and the second thermoplastic resin can be selected in consideration of the melting point. it can.
  • polyethylene resin especially high-density polyethylene or ultra-high molecular weight polyethylene
  • polypropylene resin especially isotactic
  • tic homopolypropylene it is preferable to use
  • the blending ratio of the first thermoplastic resin and the second thermoplastic resin may be appropriately set according to a desired resin molded body, and is not particularly limited.
  • the stretching temperature, whiteness, opacity, and bending are not particularly limited. From the viewpoint of easily balancing strength and elastic modulus, the ratio is preferably 1: 0.2 to 5, more preferably 1: 0.3 to 3.3, and 1: 0.5 to 2. It is particularly preferred that
  • the molecular weight distribution Mw / Mn which is the ratio of the weight average molecular weight Mw and the number average molecular weight Mn of the second thermoplastic resin, is preferably 1 or more and 20 or less, and more preferably 5 or more and 15 or less.
  • the molecular weight distribution Mz / Mn which is the ratio of the average molecular weight Mz and the number average molecular weight Mn of the second thermoplastic resin, is preferably 10 or more and 100 or less, and more preferably 20 or more and 50 or less.
  • the molecular weight distributions Mw / Mn and Mz / Mn of the second thermoplastic resin are in the above ranges, it is easy to obtain a resin molded body having an excellent balance between whiteness and opacity, bending strength, and elastic modulus. If the molecular weight distribution is too narrow, the kneadability of the two thermoplastic resins deteriorates, the whiteness and the opacity tend to be nonuniform, and the physical properties of the sheet also become nonuniform. When the molecular weight distribution is too wide, the spot of the melting point becomes wide, so that it becomes difficult to control the stretching temperature and the heat treatment temperature, and it becomes difficult to obtain desired whiteness, opacity, bending stiffness and elastic modulus.
  • the molecular weight distribution Mw / Mn which is the ratio of the weight average molecular weight Mw and the number average molecular weight Mn of the first thermoplastic resin, is preferably 1 or more and 100 or less, and more preferably 10 or more and 40 or less.
  • the molecular weight distribution Mz / Mn which is the ratio of the average molecular weight Mz and the number average molecular weight Mn of the first thermoplastic resin, is preferably 50 or more and 200 or less, and more preferably 80 or more and 150 or less.
  • the molecular weight distribution Mw / Mn ⁇ Mz / Mn of the first thermoplastic resin is in the above range, it is easy to obtain a resin molded body having an excellent balance of whiteness, opacity, bending strength, and elastic modulus. If the molecular weight distribution is too narrow, the kneadability of the two thermoplastic resins deteriorates, the whiteness and the opacity tend to be nonuniform, and the physical properties of the sheet also become nonuniform. When the molecular weight distribution is too wide, the spot of the melting point becomes wide, so that it becomes difficult to control the stretching temperature and the heat treatment temperature, and it becomes difficult to obtain desired whiteness, opacity, bending stiffness and elastic modulus.
  • the weight average molecular weight Mw, the number average molecular weight Mn, and the average molecular weight Mz are measured by a gel permeation (GPC) method.
  • the melt mass flow rate (MFR) of the first thermoplastic resin is preferably 0.02 g / 10 or more and 2.0 g / 10 minutes or less, and 0.1 g / 10 or more and 1.0 g / 10 minutes or less. More preferably, when the melt mass flow rate of the first thermoplastic resin is in the above range, it is easy to obtain a resin molded article excellent in balance between whiteness and opacity, bending strength and elastic modulus.
  • the melt mass flow rate (MFR) of the second thermoplastic resin is preferably 0.02 g / 10 or more and 2.0 g / 10 minutes or less, and 0.1 g / 10 or more and 1.0 g / 10 minutes or less. Preferably there is.
  • MFR melt mass flow rate
  • Melt mass flow rate is an index indicating the fluidity at the time of melting, and means a value measured according to JIS K 7210.
  • a melt indexer is used with a load of 21.18 N, a temperature of 230 ° C. for polypropylene resin and a temperature of 190 ° C. for polyethylene resin. There is a way to measure.
  • the blending ratio of the inorganic fine powder is not particularly limited. However, the larger the amount, the more easily the voids are formed during stretching, and the opacity is improved. Preferably, 60 mass% or more is even more preferable.
  • the upper limit of the amount of the inorganic fine powder contained in the entire composition is not particularly limited, but is preferably 80% by mass or less from the viewpoint of kneadability and bending strength.
  • the average particle size of the inorganic fine powder is preferably from 0.1 ⁇ m to 50 ⁇ m, more preferably from 1.0 ⁇ m to 15 ⁇ m.
  • the average particle size of the inorganic fine powder is in the above range, it is easy to obtain a resin molded body having an excellent balance between whiteness and opacity, bending strength, and elastic modulus.
  • the average particle diameter of the inorganic fine powder is too large, the inorganic fine powder is easily detached from the surface of the resin molded body. If the average particle size of the inorganic fine powder is too small, the viscosity increases when kneaded with the thermoplastic resin, and the kneadability tends to deteriorate.
  • the average particle size of the inorganic fine powder in the present invention is a 50% particle size (d50) obtained from a cumulative distribution curve measured with a laser diffraction particle size distribution analyzer.
  • the inorganic fine powder examples include calcium carbonate, titanium oxide, silica, clay, talc, kaolin and aluminum hydroxide, and calcium carbonate is particularly preferable. These may be used alone or in combination of two or more. In order to improve the dispersibility or reactivity of the inorganic fine powder, the surface of the inorganic fine powder may be modified in advance according to a conventional method.
  • the resin composition of the present invention is selected from lubricants, antioxidants, UV absorbers, pigments for coloring, dispersants, antistatic agents, flame retardants, etc. in addition to the above-described thermoplastic resin and inorganic fine powder 1 More than one kind of auxiliary agent can be added within a range not contrary to the purpose.
  • the use of the produced resin molded body is not particularly limited, but is particularly suitable for the balance of whiteness and opacity, bending strength and elastic modulus.
  • printing paper, information paper, packaging, card use For example, it is suitable for business cards, processed cardboard, and the like.
  • Sample A was kneaded directly with a fine powder of calcium carbonate and polyethylene resin at a mass ratio of 60:40 using a twin-screw coaxial extruder, and extruded into a sheet form from a ⁇ die. It produced by extending
  • Sample B was prepared by changing the mass ratio of the fine powder of calcium carbonate and the polyethylene resin to 70:30, extruding into a sheet shape in the same manner as Sample A, and then stretching under the conditions shown in Table 1 below.
  • PE melting point 133 ° C.
  • CC Calcium carbonate
  • the sheet resin molded bodies of Example 1, Example 2, and Example 3 have moderate strengths such as breaking strength, breaking elongation, and tear strength, as in Comparative Example 1. It can be seen that the bending stiffness is improved as compared with Comparative Example 1 while ensuring opacity and whiteness. In particular, it can be seen that the sheet resin molded body of Example 1 is greatly improved in bending strength and elastic modulus as compared with Comparative Example 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé de production d'un objet en résine moulé qui présente d'excellents modules d'élasticité et de résistance à la flexion tout en conservant des propriétés optiques comprenant une blancheur et une opacité ayant un degré le plus élevé possible. Le procédé de production d'un objet en résine moulé selon la présente invention comprend une étape dans laquelle une première résine thermoplastique, une deuxième résine thermoplastique, qui a un point de fusion supérieur à celui de la première résine thermoplastique, et une poudre inorganique fine sont mélangées pour obtenir une composition de résine, une étape dans laquelle la composition de résine est étirée à une température inférieure au point de fusion de la première résine thermoplastique, et une étape dans laquelle la composition de résine étirée est soumise à un traitement thermique à une température non inférieure au point de fusion de la première résine thermoplastique mais inférieure au point de fusion de la deuxième résine thermoplastique.
PCT/JP2017/037343 2016-11-25 2017-10-16 Procédé de production d'objet en résine moulé Ceased WO2018096834A1 (fr)

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JP2016-229412 2016-11-25
JP2016229412A JP6749640B2 (ja) 2016-11-25 2016-11-25 樹脂成形体の製造方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021005880A1 (fr) * 2019-07-08 2021-01-14 株式会社Ｔｂｍ Feuille d'impression et méthode de fabrication de feuille d'impression
WO2021010002A1 (fr) * 2019-07-17 2021-01-21 株式会社Ｔｂｍ Structure stratifiée, récipient d'emballage alimentaire et procédés de production associés
JP2021033171A (ja) * 2019-08-28 2021-03-01 株式会社Ｔｂｍ 光拡散シート

Citations (8)

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Publication number Priority date Publication date Assignee Title
JPS5621830A (en) * 1979-07-31 1981-02-28 Oji Yuka Gouseishi Kk Film being excellent in printing property
JPS6481828A (en) * 1987-09-24 1989-03-28 Oji Yuka Goseishi Kk Synthetic resin film with outstanding printability
JPS6481829A (en) * 1987-09-24 1989-03-28 Oji Yuka Goseishi Kk Synthetic resin film with outstanding printability
JPH04107127A (ja) * 1990-08-29 1992-04-08 Teijin Ltd 磁気カード用ポリエステルフイルム
JPH0966564A (ja) * 1995-08-31 1997-03-11 Nan Ya Plast Corp 合成紙の製造方法とその製品
JP2001214013A (ja) * 1999-11-24 2001-08-07 Yupo Corp 樹脂延伸フィルムおよびその製造方法
JP2013010931A (ja) * 2011-05-31 2013-01-17 Tbm Co Ltd 無機物質粉末高配合薄膜シートの製造方法
WO2015186808A1 (fr) * 2014-06-04 2015-12-10 三菱樹脂株式会社 Film perméable à l'humidité

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5621830A (en) * 1979-07-31 1981-02-28 Oji Yuka Gouseishi Kk Film being excellent in printing property
JPS6481828A (en) * 1987-09-24 1989-03-28 Oji Yuka Goseishi Kk Synthetic resin film with outstanding printability
JPS6481829A (en) * 1987-09-24 1989-03-28 Oji Yuka Goseishi Kk Synthetic resin film with outstanding printability
JPH04107127A (ja) * 1990-08-29 1992-04-08 Teijin Ltd 磁気カード用ポリエステルフイルム
JPH0966564A (ja) * 1995-08-31 1997-03-11 Nan Ya Plast Corp 合成紙の製造方法とその製品
JP2001214013A (ja) * 1999-11-24 2001-08-07 Yupo Corp 樹脂延伸フィルムおよびその製造方法
JP2013010931A (ja) * 2011-05-31 2013-01-17 Tbm Co Ltd 無機物質粉末高配合薄膜シートの製造方法
WO2015186808A1 (fr) * 2014-06-04 2015-12-10 三菱樹脂株式会社 Film perméable à l'humidité

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021005880A1 (fr) * 2019-07-08 2021-01-14 株式会社Ｔｂｍ Feuille d'impression et méthode de fabrication de feuille d'impression
JP2021011080A (ja) * 2019-07-08 2021-02-04 株式会社Ｔｂｍ 印刷用シート及び印刷用シートの製造方法
WO2021010002A1 (fr) * 2019-07-17 2021-01-21 株式会社Ｔｂｍ Structure stratifiée, récipient d'emballage alimentaire et procédés de production associés
JP2021016953A (ja) * 2019-07-17 2021-02-15 株式会社Ｔｂｍ 積層構造体、食品包装容器及びその製造方法
US11958671B2 (en) 2019-07-17 2024-04-16 Tbm Co., Ltd. Laminated structure, food packaging container, and method for producing the same
JP2021033171A (ja) * 2019-08-28 2021-03-01 株式会社Ｔｂｍ 光拡散シート

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JP2018083926A (ja) 2018-05-31

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