WO2020054774A1 - Heat-resisting paper material and heat-resisting paper container - Google Patents

Heat-resisting paper material and heat-resisting paper container Download PDF

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Publication number
WO2020054774A1
WO2020054774A1 PCT/JP2019/035735 JP2019035735W WO2020054774A1 WO 2020054774 A1 WO2020054774 A1 WO 2020054774A1 JP 2019035735 W JP2019035735 W JP 2019035735W WO 2020054774 A1 WO2020054774 A1 WO 2020054774A1
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WO
WIPO (PCT)
Prior art keywords
heat
resistant paper
container
polybutylene terephthalate
terephthalate resin
Prior art date
Application number
PCT/JP2019/035735
Other languages
French (fr)
Japanese (ja)
Inventor
敏雄 中根
Original Assignee
ポリプラスチックス株式会社
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 ポリプラスチックス株式会社 filed Critical ポリプラスチックス株式会社
Priority to JP2020544542A priority Critical patent/JP6895023B2/en
Publication of WO2020054774A1 publication Critical patent/WO2020054774A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/34—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within the package

Definitions

  • the present invention relates to a heat-resistant paper material and a heat-resistant paper container.
  • containers made of paper are widely used because of their advantages such as low cost and easy disposal.
  • a container using paper a composite material obtained by laminating a heat-resistant synthetic resin film on one or both surfaces of paper is used.
  • the heat-resistant synthetic resin polyethylene terephthalate resin, polymethylpentene resin, polypropylene resin and the like are used. Containers using such paper are also widely used in applications other than holding food.
  • paper containers laminated with polymethylpentene resin are required to have improved heat sealing properties and gas barrier properties.
  • paper odor is hardly transferred to food, and the content of food is reduced. It has been demanded that the odor hardly leaks out.
  • it is also required to increase the impact strength at low temperature, and it has been required that the container is hardly damaged even when dropped at the time of transfer (for example, at the time of removal from a freezer or the like).
  • paper containers laminated with a polypropylene resin are required to have high heat resistance and to cope with high-temperature heat treatment. Particularly in applications for holding food, containers suitable for high-temperature cooking of oily foods. Was required. In addition, it is required to enhance gas barrier properties, and particularly in applications for holding foods, it is also required to make it difficult for paper odor to be transferred to foods and for food odors in contents to be hardly leaked out.
  • Patent Document 1 discloses a paper container in which a polybutylene terephthalate resin is laminated. This paper container has a great advantage of not impairing the flavor of the food after cooking, especially when used for holding food, and is suitable as a paper container for cooking food.
  • the paper container for heating cooking proposed in Patent Document 1 is suitable for cooking in a microwave oven, it also sufficiently withstands high-temperature heat treatment and has high moldability into a container. Was required.
  • Patent Document 2 discloses that a base film or sheet of paper or the like contains polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, polyethylene terephthalate-isophthalate copolymer or 1,4-dicyclohexane dimethylene terephthalate-isophthalate copolymer.
  • a polyester coat laminated film provided with a low crystallinity polyester layer formed by extrusion lamination while maintaining the ratio of the intrinsic viscosity of the resin after extrusion to the intrinsic viscosity of the resin before extrusion at 85% or more. Proposed. It is described that this laminate is excellent in the chemical resistance, oil resistance, gas barrier properties, and immersion resistance of polyester, and exhibits an appropriate heat seal property.
  • polyester-coated laminated film of Patent Document 2 is not suitable for use in heat treatment at a high temperature as assumed for the paper container of the present invention in terms of deformation and discoloration.
  • Patent Document 3 proposes a molded article comprising a resin composition composed of a polybutylene terephthalate resin having a terminal carboxyl group content of 35 meq / kg or less and an antioxidant. Although this molded article has resistance to solvent extraction, the container made of this molded article is not intended for heat treatment at high temperature, etc. None is suggested about the usefulness of the paper container.
  • Patent Document 4 proposes a heat-resistant paper container for heating and cooking formed by laminating a polybutylene terephthalate resin having a terminal carboxyl group content of less than 60 meq / kg on heat-resistant paper. ing.
  • the adhesiveness between the polyester and the base paper is further improved, and the shape is maintained when the heat-resistant paper material is formed into a heat-resistant paper container even when a particularly thick paper is used.
  • the present invention has been made in order to solve the above-described problems, and has excellent adhesiveness between polyester and paper as a base material, and a heat-resistant paper material having excellent shape retention when molded. It is an object of the present invention to provide a heat-resistant paper container using the same.
  • the present inventors have intensively studied to solve the above problems. As a result, they have found that the above-mentioned problems can be solved by laminating a polybutylene terephthalate resin on the surface of the heat-resistant paper having a small smoothness, and have completed the present invention. More specifically, the present invention provides the following.
  • the heat-resistant paper container of the present invention is formed by laminating a polybutylene terephthalate resin on heat-resistant paper, and forming a laminate in which the crystallization ratio of the polybutylene terephthalate resin after lamination is 10 to 30%.
  • the polybutylene terephthalate resin has a terminal carboxyl group content of less than 60 meq / kg, and the heat-resistant paper container is used for cooking. ).
  • the heat-resistant paper container of the present invention is used for applications in which [content weight (g) ⁇ volume (cm 3 )] ⁇ [weight (g / m 2 )] is 0.001 or more.
  • the heat-resistant paper material of the present invention comprises a laminate in which polybutylene terephthalate resin is laminated on heat-resistant paper, and the crystallization ratio of the polybutylene terephthalate resin after lamination is 10 to 30%.
  • the polybutylene terephthalate resin has a terminal carboxyl group content of less than 60 meq / kg, and the heat-resistant paper material is used for cooking. ).
  • the heat-resistant paper material of the present invention is used for a container having a content of [weight (g) / volume (cm 3 )] / [weight (g / m 2 )] of 0.001 or more.
  • the heat-resistant paper material according to any one of (5) to (7).
  • the method for producing a heat-resistant paper material according to the present invention is a microwave oven in which a polybutylene terephthalate resin is laminated on heat-resistant paper, and the crystallization ratio of the laminated polybutylene terephthalate resin is 10 to 30%.
  • a method for producing a heat-resistant paper material for heat treatment which can be used in a heat treatment reaching 160 to 220 ° C., wherein the heat-resistant paper has a smoothness specified in JIS P8119 on a laminate surface of less than 50 seconds, and is weighed. Is 100 g / m 2 or more.
  • the polybutylene terephthalate resin has a terminal carboxyl group content of less than 60 meq / kg, and the heat-resistant paper material is heated and cooked.
  • the heat-resistant paper having a smoothness specified by JIS P8119 of less than 30 seconds is used as the heat-resistant paper. (9) or (10) 3.
  • a method for manufacturing a heat-resistant paper container according to the present invention wherein the heat-resistant paper material is formed using a heat-resistant paper material obtained by the manufacturing method according to any one of (9) to (11).
  • a method for producing a heat-resistant paper container comprising:
  • a polybutylene terephthalate resin is laminated on a heat-resistant paper laminated surface having a smoothness of less than 50 seconds according to JIS P8119 and a weighing of 100 g / m 2 or more.
  • the laminated body has a polybutylene terephthalate resin having a crystallization ratio of 10 to 30% after lamination.
  • a heat-resistant paper having a lamination surface with a smoothness specified in JIS P8119 of less than 50 seconds and a weighing of 100 g / m 2 or more is used. And laminating a polybutylene terephthalate resin on the heat-resistant paper so that the crystallization ratio of the polybutylene terephthalate resin after lamination becomes 10 to 30%. This is to obtain a heat-resistant paper material that can be used in heat treatment.
  • the polybutylene terephthalate resin used for the heat-resistant paper material is composed of a diol component mainly composed of 1,4-butanediol which is a polyhydric alcohol component and a dicarboxylic acid mainly composed of terephthalic acid which is a polyvalent carboxylic acid component. It is a polyester having a butylene terephthalate unit as a main repeating unit obtained by condensing a component or an alcohol ester component thereof, and may be a copolymer mainly composed of polybutylene terephthalate as long as the effects of the present invention are not impaired. .
  • the polybutylene terephthalate resin may contain a butylene terephthalate unit in an amount of 60 mol% or more of the ester unit of the polycarboxylic acid-polyhydric alcohol.
  • This polybutylene terephthalate resin has a carboxyl group content at the polymer chain terminal (a value obtained by dissolving in benzyl alcohol at 215 ° C. and titrating with sodium hydroxide) of 60 meq / kg (hereinafter referred to as “m equivalent”). / Kg "), and more preferably less than 50 meq / kg.
  • the carboxyl group content By setting the carboxyl group content to 60 meq / kg or less, hydrolysis of the resin can be suppressed even when heat treatment is performed at a high temperature, and the gloss of the polybutylene terephthalate resin on the surface of the heat-resistant paper material is lost. Problems such as poor tactile sensation can be reduced. Further, since the polymer odor from the heat-resistant paper material is reduced, the transfer of the polymer odor to the contents can be reduced. On the other hand, when the heat-resistant paper is used for holding other than food, or when the heat-resistant paper does not require an excellent appearance, the carboxyl group content may be more than 60 meq / kg.
  • a method for obtaining such a polybutylene terephthalate resin for example, a method for reducing the amount of an oligomer of an eluting component by a solid-phase polymerization, a method for reducing an oligomer amount of a polybutylene terephthalate resin obtained by a known synthesis method, or a method using a carboxyl group (—OH For example, by reacting with a reactive monomer containing a group).
  • Polybutylene terephthalate resin used for heat-resistant paper materials within the range not hindering the effects of the present invention, coloring agents such as dyes and pigments, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, surfactants, Additives such as lubricants, crystallization promoters and retarders can be included. These may be contained plurally depending on the purpose. In addition, other thermoplastic resins and inorganic fillers can be contained according to required performance as long as the effects of the present invention are not impaired. In particular, when using a heat-resistant paper material for holding food, use a substance that is not extracted by the food when heat-treated and does not contaminate the food, as these additives, thermoplastic resin, and inorganic filler. Is preferred.
  • the heat-resistant paper used for the heat-resistant paper material has a weighing of 100 g / m 2 or more, and has a smoothness according to JIS P8119 of the surface on which the polybutylene terephthalate resin is laminated (hereinafter referred to as “laminated surface”). Use less than a second.
  • the smoothness of the laminated surface of the heat-resistant paper according to JIS P8119 is preferably less than 30 seconds, and more preferably 28 seconds or less.
  • the present inventors have found that even when the smoothness of the laminated surface is set to less than 50 seconds, necking does not occur in the film when laminating a film of polybutylene terephthalate resin on heat-resistant paper.
  • the smoothness (Beck's method smoothness) in JIS P8119 is defined as a value obtained when a certain amount of atmospheric pressure air flows between a test piece brought into contact with a specific condition and a ring-shaped plane under a specific initial differential pressure. Required time (seconds).
  • the smoothness test piece was placed on the test stand on a glass plane (diameter 37.4 mm ⁇ 0.05 mm, circular effective plane area 10cm 2 ⁇ 0.05cm 2), a rubber pressing plate (or diameter 45 mm) And pressurized with a pressure of 1000 kPa.
  • the heat-resistant paper a paper having a basis weight of 100 g / m 2 or more is used.
  • the basis weight of the heat-resistant paper can be preferably 120 g / m 2 or more, and more preferably 150 g / m 2 or more.
  • the upper limit of the basis weight of the heat-resistant paper is preferably 500 g / m 2 , more preferably 400 g / m 2 , and still more preferably 300 g / m 2 .
  • a heat-resistant paper having a basis weight of 500 g / m 2 or less when obtaining a heat-resistant paper container by heat molding, it is possible to reduce cracks and tears at corners and edges of the obtained paper container. Can be.
  • heat-resistant paper used in the present invention either synthetic paper without pulp fibers or pulp paper made from pulp fibers such as wood pulp can be used. Among them, it is more preferable to use pulp paper from the viewpoint of heat resistance. Further, when heat-resistant paper is used for holding food, it is preferable to use one that can be used as a cooking paper container or wrapping paper for wrapping food or the like.
  • the heat-resistant paper used in the present invention is within an allowable range of heat resistance, such as stretched polyethylene terephthalate film or polyvinylidene chloride-coated stretched polyethylene terephthalate film, cellophane, low-density, medium-density or high-density polyethylene, ionomer, ponopropylene, etc.
  • a laminate of a plastic film or a sheet or an aluminum foil and heat-resistant paper may be used. However, such a laminate may not be used from the viewpoint of cost, problems of polymer odor, disposal problems, and the like.
  • the heat-resistant paper material of the present invention comprises a laminate in which a polybutylene terephthalate resin is laminated on a heat-resistant paper laminated surface.
  • a method of heating and melting the polybutylene terephthalate resin and supplying the resin to the laminated surface of the heat resistant paper to form a laminate layer is used.
  • the crystallization ratio of the laminated polybutylene terephthalate resin (the value measured by the X-ray diffraction method) is 10 It is preferable to be within the range of 30%.
  • the crystallization ratio of the polybutylene terephthalate resin By setting the crystallization ratio of the polybutylene terephthalate resin to 10% or more, the crystallization of the polybutylene terephthalate resin during the heat treatment can be reduced, and the deformation of the container caused by the shrinkage accompanying the crystallization during the heat treatment can be suppressed. it can. Further, by setting the crystallization ratio of the polybutylene terephthalate resin to 30% or less, the flexibility, stretchability, and toughness when the laminated laminate is formed into a container or the like by hot pressing or the like is improved, and the laminate layer is broken. Can be reduced. Therefore, by controlling the crystallization ratio in the range of 10 to 30%, it is possible to suppress the container formability, shape collapse, deformation, and change in appearance during heat treatment.
  • the temperature of the resin when laminating the polybutylene terephthalate resin can be, for example, 260 ° C. or higher, and preferably 280 ° C. or higher.
  • the upper limit of the resin temperature can be, for example, 300 ° C. or less.
  • the temperature of the chill roll is preferably adjusted to 40 to 70 ° C, more preferably to 50 to 70 ° C.
  • a conventional method such as extrusion molding, injection molding, vacuum molding, compression molding, press molding, or the like can be used. Further, the laminated product may be subjected to secondary processing such as cutting.
  • the thickness of the polybutylene terephthalate resin layer in the laminate obtained by lamination can be appropriately set in accordance with the characteristics of the polybutylene terephthalate resin and the like, and can be set, for example, in the range of 5 ⁇ m to 60 ⁇ m. By setting the thickness to 5 ⁇ m or more, the occurrence of pinholes and thickness unevenness due to surging can be reduced, so that a laminate layer can be stably obtained.
  • the upper limit of the thickness of the polybutylene terephthalate resin layer is preferably 60 ⁇ m or less from the viewpoint of ease of forming a laminate layer, ease of forming a container, and economic reasons.
  • the laminate obtained by laminating the polybutylene terephthalate resin may be composed of two layers of the polybutylene terephthalate resin and heat-resistant paper, or may be composed of three or more layers including other layers. At this time, it is preferable that a polybutylene terephthalate resin layer is provided on at least one surface of the laminate.
  • a molten polybutyl terephthalate resin at 290 to 300 ° C. is melted with a T-die having a slit width of 1.0 mm using an extruder having a diameter of 115 mm.
  • lamination is performed on a paperboard weighing 150 to 350 g / m 2 at a lamination speed of 35 m / min so as to have a thickness of 10 to 50 ⁇ m.
  • the laminate obtained by performing lamination using this method and winding while cooling and pressing with a chill roll whose temperature is adjusted to 40 to 60 ° C. is controlled to the crystallization ratio in the above range. .
  • the heat-resistant paper material of the present invention has excellent heat resistance and moldability, has no collapse or deformation of the container shape when the contents are filled, and has no change in appearance after heat treatment, and has appropriate adhesion and peeling with the contents. It has nature. At the same time, it is excellent in maintaining the shape and surface properties of the container after heat treatment at a high temperature, and there is no transfer of polymer odor to the contents. Therefore, the heat-resistant paper material of the present invention may be used for heat treatment in a microwave oven, or for heat treatment at a high temperature where the temperature of the heat-resistant paper material reaches about 160 to 190 ° C. or more severe 190 to 220 ° C. For example, it can be preferably used for heating and cooking using a microwave oven or an oven.
  • heat treatment of the heat-resistant paper at a temperature higher than the melting point of the polybutylene terephthalate resin is not preferable because the polybutylene terephthalate resin melts.
  • heat treatment in the case where food is used as a content is the baking of tarts, sponge cakes, fruit cakes, pound cakes, shoes, madeleine, etc., which are generally referred to as low to medium temperature ranges. It is most suitable for cooking of gratin and doria. Of course, as long as it does not exceed the melting point of the polybutylene terephthalate resin, it is suitable for heat treatment of other foods and contents other than foods.
  • such a heat-resistant paper material can be suitably used for manufacturing a heat-resistant paper container such as a food container. Further, it can be used as a thick wrapping paper or the like for wrapping foods or the like as it is, and can be formed into a bag or the like.
  • the polybutylene terephthalate resin is laminated on a laminated surface of a heat-resistant paper having a smoothness of less than 50 seconds according to JIS P8119 and a weighing of 100 g / m 2 or more.
  • the laminate is made of a polybutylene terephthalate resin having a crystallization ratio of 10 to 30% after lamination.
  • the method of manufacturing a heat-resistant paper container according to the present invention is obtained by molding the heat-resistant paper material using the above-described heat-resistant paper material.
  • the means for forming the heat-resistant paper material is not particularly limited as long as the laminated structure of the heat-resistant paper material is maintained, and various known methods can be employed.
  • a heat-resistant paper container can be obtained by cutting a heat-resistant paper material into an appropriate size using a hot press molding machine and heat-molding with a hot press or the like.
  • the heat-resistant paper container according to the present invention is manufactured using heat-resistant paper having a specific weighing amount, and has excellent shape retention when the contents are filled in the container.
  • the weight of the contents relative to the volume can be increased.
  • it can withstand contents having a large specific gravity.
  • it is preferably used for applications in which the value of [content weight (g) ⁇ volume (cm 3 )] ⁇ [weight (g / m 2 )] is 0.001 or more. It is more preferably used for applications where the content is 0.003 or more, and even more preferably used for applications where the content is 0.005 or more.
  • the upper limit of this value is not particularly limited, but in applications where this value is extremely large, there is a concern that the container may not bear the weight of the contents and may be deformed. , 0.01 or less.
  • This heat-resistant paper container may be configured so that one or both of the innermost layer (the surface layer on the side in contact with the contents) and the outermost layer (the surface layer on the side not in contact with the contents) include a polybutylene terephthalate resin layer.
  • a polybutylene terephthalate resin layer preferable.
  • a heat-resistant paper may be formed as the innermost layer.
  • the polybutylene terephthalate resin layer for one or both of the innermost layer and the outermost layer, it is possible to obtain containers according to the respective requirements. .
  • the outermost layer of the laminate may be configured to be heat-resistant paper.However, by configuring the polybutylene terephthalate resin to be the outermost layer, paper swelling or oil stain due to moisture attached to the outside of the container is performed. Can be prevented, and a glossy and glossy appearance can be obtained, so that the commercial value can be further improved.
  • the heat sealing property, gas barrier property, low-temperature impact resistance, and easy peeling property of the polybutylene terephthalate resin can be obtained.
  • a container utilizing characteristics such as heat resistance can be obtained.
  • the container after filling the container with gratin, doria and the like, the container can be completely sealed by heat sealing and stored frozen.
  • the lid when this is cooked, after taking out from the freezer, the lid can be easily peeled off by the easy peeling property, so that it can be cooked immediately using an oven or the like.
  • the obtained heat-resistant paper material was cut into a predetermined size by punching using a hot press molding machine, and was heat-molded at 140 ° C. so that the polybutylene terephthalate resin layer was on the inside, and heat was applied. By setting, a heat-resistant paper container having a volume of 400 cm 3 was obtained.
  • the obtained heat-resistant paper material was subjected to a test piece width of 25 mm and a crosshead speed of 100 mm / min in accordance with a 180 ° peel test specified in JIS K 684-2.
  • the butylene terephthalate resin was peeled off from the heat-resistant paper, and the state of the peeled surface was visually observed.
  • the adhesion of the laminate layer to the heat-resistant paper was "x", and the result was inferior in the adhesiveness to the heat-resistant paper.
  • the heat-resistant paper material and the heat-resistant paper container obtained in Comparative Examples 1 to 3 one or both of the adhesiveness and the shape retention of the container became “ ⁇ ” or “X”, and one or both of these were obtained. Inferior results.
  • the heat-resistant paper materials obtained in Reference Example 1 and Comparative Examples 1 to 3 had a handleability of “ ⁇ ” and were excellent in handleability, but compared with Examples 1 and 2. Was inferior.
  • a heat-resistant paper having excellent adhesion between the polyester and the paper as the base material, and also excellent in handleability and moldability, and in maintaining the shape of the container and the surface properties. It is presumed that a heat-resistant paper container which is excellent in the retention of polymer, does not transfer polymer odor to the contents, and is suitable as a heat-resistant container for heat treatment at a high temperature can be obtained.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Package Specialized In Special Use (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

Provided are: a heat-resisting paper material having excellent adhesion between polyester and a paper serving as a base material and having excellent shape retention when molded; and a heat-resisting paper container using the same. The heat-resisting paper material comprises a polybutylene terephthalate resin laminated on a heat-resisting paper. The heat-resisting paper container, which is usable in a microwave and heat processing reaching 160 to 220°C, is formed by molding a laminate so that the polybutylene terephthalate resin after lamination has a crystallization ratio of 10 to 30%. The heat-resisting paper has a smoothness degree stipulated in JIS P8119 of less than 50 seconds in a laminate surface and has a basis weight of 100 g/m2 or more.

Description

耐熱性紙材及び耐熱性紙容器Heat resistant paper materials and heat resistant paper containers
　本発明は、耐熱性紙材及び耐熱性紙容器に関する。 The present invention relates to a heat-resistant paper material and a heat-resistant paper container.
　近年、電子レンジやオーブン等の加熱調理機を用いてそのまま調理できる食品が一般化している。その容器としては、紙、陶器、プラスチック、耐熱ガラス、アルミニウム等が用いられ、其々用途に応じて使い分けされている。 In recent years, foods that can be cooked as they are using a cooking device such as a microwave oven or an oven have become common. As the container, paper, pottery, plastic, heat-resistant glass, aluminum and the like are used, and each is properly used according to the use.
　その中でも、紙を用いた容器は、安価であり、また廃棄処理が容易である等の利点があるため、広く使用されている。ここで、紙を使用した容器としては、紙の片面又は両面に耐熱性のある合成樹脂フイルムを積層して複合材料化したものが用いられている。耐熱性のある合成樹脂としては、ポリエチレンテレフタレート樹脂、ポリメチルペンテン樹脂、ポリプロピレン樹脂等が用いられている。また、食品を保持する以外の用途においても、このような紙を用いた容器は広く用いられている。 中 で も Among them, containers made of paper are widely used because of their advantages such as low cost and easy disposal. Here, as a container using paper, a composite material obtained by laminating a heat-resistant synthetic resin film on one or both surfaces of paper is used. As the heat-resistant synthetic resin, polyethylene terephthalate resin, polymethylpentene resin, polypropylene resin and the like are used. Containers using such paper are also widely used in applications other than holding food.
　しかし、ポリエチレンテレフタレート樹脂をラミネートした紙容器では、加熱調理等の熱処理を行った際、食品等の内容物との剥離性を高めることが求められており、パンやケーキ等の付着を低減することが求められていた。また、特に食品を保持する用途では、その紙容器が原因となる食品の味や臭いへの変化を少なくすることが求められていた。 However, in a paper container laminated with a polyethylene terephthalate resin, when heat treatment such as heat cooking is performed, it is required to enhance the releasability from contents such as foods, and it is necessary to reduce adhesion of bread and cake. Was required. In addition, particularly for use in holding food, it has been required to reduce the change in taste and odor of the food caused by the paper container.
　また、ポリメチルペンテン樹脂を積層した紙容器では、ヒートシール性、ガスバリア性を高めることが求められており、特に食品を保持する用途では、紙臭を食品に移行し難くし、内容物の食品臭を外に洩れ難くすることが求められていた。また、低温時の衝撃強度を高めることも求められており、移送時（例えば、冷凍庫等からの取り出し時）に落下しても容器が破損し難いことが求められていた。 In addition, paper containers laminated with polymethylpentene resin are required to have improved heat sealing properties and gas barrier properties.Especially in applications for holding food, paper odor is hardly transferred to food, and the content of food is reduced. It has been demanded that the odor hardly leaks out. Further, it is also required to increase the impact strength at low temperature, and it has been required that the container is hardly damaged even when dropped at the time of transfer (for example, at the time of removal from a freezer or the like).
　また、ポリプロピレン樹脂を積層した紙容器では、耐熱性を高めて高温の熱処理にも対応することが求められており、特に食品を保持する用途では、油分を多く含む食品の高温調理に適した容器が求められていた。また、ガスバリア性を高めることが求められるとともに、特に食品を保持する用途では、紙臭を食品に移行し難くし、内容物の食品臭を外に洩れ難くすることも求められていた。 In addition, paper containers laminated with a polypropylene resin are required to have high heat resistance and to cope with high-temperature heat treatment. Particularly in applications for holding food, containers suitable for high-temperature cooking of oily foods. Was required. In addition, it is required to enhance gas barrier properties, and particularly in applications for holding foods, it is also required to make it difficult for paper odor to be transferred to foods and for food odors in contents to be hardly leaked out.
　こうした課題を解決すべく、特許文献１には、ポリブチレンテレフタレート樹脂を積層した紙容器が開示されている。この紙容器は、特に食品を保持する用途に用いた場合に、加熱調理後の食品の風味を損なわないという大きな利点を持っており、食品の加熱調理用の紙容器として好適である。しかしながら、特許文献１にて提案されている加熱調理用の紙容器は、電子レンジの調理には適しているものの、さらに高温の熱処理にも十分に耐えるとともに、容器への成形性の高い紙容器が求められていた。 べ く In order to solve such problems, Patent Document 1 discloses a paper container in which a polybutylene terephthalate resin is laminated. This paper container has a great advantage of not impairing the flavor of the food after cooking, especially when used for holding food, and is suitable as a paper container for cooking food. However, although the paper container for heating cooking proposed in Patent Document 1 is suitable for cooking in a microwave oven, it also sufficiently withstands high-temperature heat treatment and has high moldability into a container. Was required.
　また、特許文献２には、紙等の基材フイルムもしくはシートに、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリブチレンテレフタレート、ポリエチレンテレフタレート－イソフタレートコポリマーあるいは１，４－ジシクロヘキサンジメチレンテレフタレート－イソフタレートコポリマーを、押出加工前の樹脂の極限粘度に対する押出加工後の樹脂の極限粘度の比率を、８５％以上に保持して押出ラミネートしてなる低結晶化度ポリエステル層が設けられているポリエステルコート積層フイルムが提案されている。この積層体は、ポリエステルの持つ耐薬品性、耐油性、ガス遮断性、防浸性に優れ、且つ適度のヒートシール性を呈することが記載されている。しかしながら、実施例に具体的に記載されているものはポリエチレンテレフタレートやその共重合体であり、ポリブチレンテレフタレート樹脂は記載されていない。また、特許文献２のポリエステルコート積層フイルムは、本発明の紙容器が想定しているような高温での熱処理の用途には、変形や変色等の面で不向きである。 Patent Document 2 discloses that a base film or sheet of paper or the like contains polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, polyethylene terephthalate-isophthalate copolymer or 1,4-dicyclohexane dimethylene terephthalate-isophthalate copolymer. A polyester coat laminated film provided with a low crystallinity polyester layer formed by extrusion lamination while maintaining the ratio of the intrinsic viscosity of the resin after extrusion to the intrinsic viscosity of the resin before extrusion at 85% or more. Proposed. It is described that this laminate is excellent in the chemical resistance, oil resistance, gas barrier properties, and immersion resistance of polyester, and exhibits an appropriate heat seal property. However, what is specifically described in the examples is polyethylene terephthalate or a copolymer thereof, and no polybutylene terephthalate resin is described. Further, the polyester-coated laminated film of Patent Document 2 is not suitable for use in heat treatment at a high temperature as assumed for the paper container of the present invention in terms of deformation and discoloration.
　また、特許文献３には、末端カルボキシル基含量が、３５ミリ当量／ｋｇ以下のポリブチレンテレフタレート系樹脂と酸化防止剤とで構成される樹脂組成物からなる成形品が提案されている。この成形品は、耐溶剤抽出性を有しているが、この成形品からなる容器も高温での熱処理等を意図したものではなく、耐熱紙にラミネートした積層体やそれを成形してなる耐熱性紙容器の有用性については、何も示唆していない。 Patent Document 3 proposes a molded article comprising a resin composition composed of a polybutylene terephthalate resin having a terminal carboxyl group content of 35 meq / kg or less and an antioxidant. Although this molded article has resistance to solvent extraction, the container made of this molded article is not intended for heat treatment at high temperature, etc. Nothing is suggested about the usefulness of the paper container.
　さらに、特許文献４には、末端カルボキシル基含有量が６０ミリ当量／ｋｇ未満であるポリブチレンテレフタレート樹脂を耐熱紙にラミネートした積層体を成形してなる加熱調理用の耐熱性紙容器が提案されている。これに対し、ポリエステルと、基材である紙との密着性をより高めるとともに、特に厚い紙を用いた場合であっても、耐熱性紙材を耐熱性紙容器に成形した際の形状の保持を高める手法が求められていた。 Further, Patent Document 4 proposes a heat-resistant paper container for heating and cooking formed by laminating a polybutylene terephthalate resin having a terminal carboxyl group content of less than 60 meq / kg on heat-resistant paper. ing. On the other hand, the adhesiveness between the polyester and the base paper is further improved, and the shape is maintained when the heat-resistant paper material is formed into a heat-resistant paper container even when a particularly thick paper is used. There was a need for a technique to increase
特開平０１－０７０６２０号公報JP-A-01-070620 特開昭５５－１６６２４７号公報JP-A-55-166247 特開平１０－０２５４０４号公報Japanese Patent Application Laid-Open No. 10-025404 特開２０００－０９３２９６号公報JP 2000-093296 A
　本発明は、以上のような課題を解決するためになされたものであり、ポリエステルと、基材である紙との密着性が優れ、成形した際の形状の保持に優れた耐熱性紙材と、これを用いた耐熱性紙容器を提供することを目的とする。 The present invention has been made in order to solve the above-described problems, and has excellent adhesiveness between polyester and paper as a base material, and a heat-resistant paper material having excellent shape retention when molded. It is an object of the present invention to provide a heat-resistant paper container using the same.
　本発明者らは、上記課題を解決するために鋭意研究を重ねた。その結果、耐熱紙の平滑度の小さい面に、ポリブチレンテレフタレート樹脂をラミネートすることにより、上記の課題を解決できることを見出し、本発明を完成するに至った。
　より具体的に、本発明は、以下のものを提供する。 The present inventors have intensively studied to solve the above problems. As a result, they have found that the above-mentioned problems can be solved by laminating a polybutylene terephthalate resin on the surface of the heat-resistant paper having a small smoothness, and have completed the present invention.
More specifically, the present invention provides the following.
　（１）本発明の耐熱性紙容器は、ポリブチレンテレフタレート樹脂が耐熱紙にラミネートされており、ラミネート後のポリブチレンテレフタレート樹脂の結晶化割合を１０～３０％となるようにした積層体が成形されてなる、電子レンジ及び１６０～２２０℃に達する熱処理で使用可能な耐熱性紙容器であって、前記耐熱紙は、ラミネート面のＪＩＳ　Ｐ８１１９に規定される平滑度が５０秒未満であり、秤量が１００ｇ／ｍ２以上である、耐熱性紙容器である。 (1) The heat-resistant paper container of the present invention is formed by laminating a polybutylene terephthalate resin on heat-resistant paper, and forming a laminate in which the crystallization ratio of the polybutylene terephthalate resin after lamination is 10 to 30%. A heat-resistant paper container usable in a microwave oven and a heat treatment reaching 160 to 220 ° C., wherein the heat-resistant paper has a smoothness specified by JIS P8119 of a laminate surface of less than 50 seconds, and is weighed. Is 100 g / m 2 or more.
　（２）また、本発明の耐熱性紙容器は、前記ポリブチレンテレフタレート樹脂は、末端カルボキシル基含有量が６０ミリ当量／ｋｇ未満であり、前記耐熱性紙容器が加熱調理に用いられる、（１）に記載の耐熱性紙容器である。 (2) In the heat-resistant paper container of the present invention, the polybutylene terephthalate resin has a terminal carboxyl group content of less than 60 meq / kg, and the heat-resistant paper container is used for cooking. ).
　（３）また、本発明の耐熱性紙容器は、前記耐熱紙は、ラミネート面のＪＩＳ　Ｐ８１１９に規定される平滑度が３０秒未満である、（１）又は（２）に記載の耐熱性紙容器である。 (3) The heat-resistant paper container according to (1) or (2), wherein the heat-resistant paper has a lamination surface having a smoothness specified in JIS P8119 of less than 30 seconds. Container.
　（４）また、本発明の耐熱性紙容器は、［内容物重量（ｇ）÷容積（ｃｍ３）］÷［秤量（ｇ／ｍ２）］が０．００１以上となる用途に用いられる、（１）から（３）のいずれかに記載の耐熱性紙容器である。 (4) The heat-resistant paper container of the present invention is used for applications in which [content weight (g) ÷ volume (cm 3 )] ÷ [weight (g / m 2 )] is 0.001 or more. A heat-resistant paper container according to any one of (1) to (3).
　（５）本発明の耐熱性紙材は、ポリブチレンテレフタレート樹脂が耐熱紙にラミネートされており、ラミネート後のポリブチレンテレフタレート樹脂の結晶化割合が１０～３０％となるようにした積層体からなる、電子レンジ及び１６０～２２０℃に達する熱処理で使用可能な耐熱性紙材であって、前記耐熱紙は、ラミネート面のＪＩＳ　Ｐ８１１９に規定される平滑度が５０秒未満であり、秤量が１００ｇ／ｍ２以上である、耐熱性紙材である。 (5) The heat-resistant paper material of the present invention comprises a laminate in which polybutylene terephthalate resin is laminated on heat-resistant paper, and the crystallization ratio of the polybutylene terephthalate resin after lamination is 10 to 30%. A heat-resistant paper material usable in a microwave oven and a heat treatment reaching 160 to 220 ° C., wherein the heat-resistant paper has a smoothness of less than 50 seconds specified in JIS P8119 on a laminate surface and a weighing of 100 g / g. it is m 2 or more, a heat-resistant sheet member.
　（６）また、本発明の耐熱性紙材は、前記ポリブチレンテレフタレート樹脂は、末端カルボキシル基含有量が６０ミリ当量／ｋｇ未満であり、前記耐熱性紙材が加熱調理に用いられる、（５）に記載の耐熱性紙材である。 (6) In the heat-resistant paper material of the present invention, the polybutylene terephthalate resin has a terminal carboxyl group content of less than 60 meq / kg, and the heat-resistant paper material is used for cooking. ).
　（７）また、本発明の耐熱性紙材は、前記耐熱紙は、ラミネート面のＪＩＳ　Ｐ８１１９に規定される平滑度が３０秒未満である、（５）又は（６）に記載の耐熱性紙材である。 (7) The heat-resistant paper according to (5) or (6), wherein the heat-resistant paper has a lamination surface having a smoothness specified in JIS P8119 of less than 30 seconds. Material.
　（８）また、本発明の耐熱性紙材は、［内容物重量（ｇ）÷容積（ｃｍ３）］÷［秤量（ｇ／ｍ２）］が０．００１以上となる容器の用途に用いられる、（５）から（７）のいずれかに記載の耐熱性紙材である。 (8) The heat-resistant paper material of the present invention is used for a container having a content of [weight (g) / volume (cm 3 )] / [weight (g / m 2 )] of 0.001 or more. The heat-resistant paper material according to any one of (5) to (7).
　（９）本発明の耐熱性紙材の製造方法は、ポリブチレンテレフタレート樹脂を耐熱紙にラミネートし、ラミネート後のポリブチレンテレフタレート樹脂の結晶化割合を１０～３０％となるようにする、電子レンジ及び１６０～２２０℃に達する熱処理で使用可能な加熱処理用耐熱性紙材の製造方法であって、前記耐熱紙として、ラミネート面におけるＪＩＳ　Ｐ８１１９に規定される平滑度が５０秒未満であり、秤量が１００ｇ／ｍ２以上であるものを用いる、耐熱性紙材の製造方法である。 (9) The method for producing a heat-resistant paper material according to the present invention is a microwave oven in which a polybutylene terephthalate resin is laminated on heat-resistant paper, and the crystallization ratio of the laminated polybutylene terephthalate resin is 10 to 30%. And a method for producing a heat-resistant paper material for heat treatment which can be used in a heat treatment reaching 160 to 220 ° C., wherein the heat-resistant paper has a smoothness specified in JIS P8119 on a laminate surface of less than 50 seconds, and is weighed. Is 100 g / m 2 or more.
　（１０）また、本発明の耐熱性紙容器の製造方法は、前記ポリブチレンテレフタレート樹脂として、末端カルボキシル基含有量が６０ミリ当量／ｋｇ未満であるものを用い、前記耐熱性紙材が加熱調理に用いられる、（９）に記載の耐熱性紙材の製造方法である。 (10) In the method for producing a heat-resistant paper container of the present invention, the polybutylene terephthalate resin has a terminal carboxyl group content of less than 60 meq / kg, and the heat-resistant paper material is heated and cooked. The method for producing a heat-resistant paper material according to (9), which is used for (1).
　（１１）また、本発明の耐熱性紙容器の製造方法は、前記耐熱紙として、ラミネート面のＪＩＳ　Ｐ８１１９に規定される平滑度が３０秒未満であるものを用いる、（９）又は（１０）に記載の耐熱性紙材の製造方法。 (11) Further, in the method for producing a heat-resistant paper container of the present invention, the heat-resistant paper having a smoothness specified by JIS P8119 of less than 30 seconds is used as the heat-resistant paper. (9) or (10) 3. The method for producing a heat-resistant paper material according to item 1.
　（１２）本発明の耐熱性紙容器の製造方法は、（９）から（１１）のいずれかに記載の製造方法によって得られる耐熱性紙材を用いて、前記耐熱性紙材を成形する工程を有する、耐熱性紙容器の製造方法である。 (12) A method for manufacturing a heat-resistant paper container according to the present invention, wherein the heat-resistant paper material is formed using a heat-resistant paper material obtained by the manufacturing method according to any one of (9) to (11). A method for producing a heat-resistant paper container, comprising:
　（１３）また、本発明の耐熱性紙容器の製造方法は、前記成形によって、［内容物重量（ｇ）÷容積（ｃｍ３）］÷［秤量（ｇ／ｍ２）］が０．００１以上となる容器を成形する、（１２）に記載の耐熱性紙容器の製造方法である。 (13) Further, in the method for producing a heat-resistant paper container of the present invention, [content weight (g) ÷ volume (cm 3 )] ÷ [weight (g / m 2 )] is 0.001 or more by the molding. The method for producing a heat-resistant paper container according to (12), wherein the container is formed as follows.
　本発明によることで、ポリエステルと、基材である紙との密着性が優れ、成形した際の形状の保持に優れた耐熱性紙材と、これを用いた耐熱性紙容器を提供することができる。 According to the present invention, it is possible to provide a heat-resistant paper material excellent in adhesion between polyester and paper as a base material and excellent in holding a shape when molded, and a heat-resistant paper container using the same. it can.
　また、本発明によることで、取扱性及び成形性に優れた耐熱性紙材を提供することもでき、また、高温での熱処理を行った後の容器の表面性状の保持に優れ、内容物へのポリマー臭の移行がなく、高温での熱処理用の耐熱性容器として好適な耐熱性紙容器を提供することもできる。したがって、特に食品を保持する場合であっても、食品の保存性に優れ、そのまま電子レンジやオーブンレンジ等の加熱調理機で調理することができ、無味無臭であり、容器による食品の味や臭いへの変化がない耐熱性紙材と、これを用いた耐熱性紙容器を提供することもできる。 Further, according to the present invention, it is possible to provide a heat-resistant paper material excellent in handleability and moldability, and also excellent in maintaining the surface properties of the container after heat treatment at a high temperature, and is suitable for contents. It is also possible to provide a heat-resistant paper container which does not transfer polymer odor and is suitable as a heat-resistant container for heat treatment at a high temperature. Therefore, especially when holding food, the food is excellent in preservability, can be cooked as it is in a cooking device such as a microwave oven or a microwave oven, is tasteless and odorless, and tastes and smells the food in a container. And a heat-resistant paper container using the same.
　以下、本発明の具体的な実施形態について、詳細に説明する。本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。 Hereinafter, specific embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments at all, and can be implemented with appropriate modifications within the scope of the present invention.
＜耐熱性紙材及びその製造方法について＞
　本発明に係る耐熱性紙材は、ポリブチレンテレフタレート樹脂が、ラミネート面のＪＩＳ　Ｐ８１１９における平滑度が５０秒未満であり、且つ秤量１００ｇ／ｍ２以上である耐熱紙のラミネート面にラミネートされており、成形時に破れが発生せず且つ熱処理時の変形を防ぐため、ラミネート後のポリブチレンテレフタレート樹脂の結晶化割合が１０～３０％となるようにした積層体からなるものである。 <About heat-resistant paper and its manufacturing method>
In the heat-resistant paper material according to the present invention, a polybutylene terephthalate resin is laminated on a heat-resistant paper laminated surface having a smoothness of less than 50 seconds according to JIS P8119 and a weighing of 100 g / m 2 or more. In order to prevent breakage during molding and to prevent deformation during heat treatment, the laminated body has a polybutylene terephthalate resin having a crystallization ratio of 10 to 30% after lamination.
　また、本発明に係る耐熱性紙材の製造方法は、耐熱紙として、ラミネート面におけるＪＩＳ　Ｐ８１１９に規定される平滑度が５０秒未満であり、且つ秤量が１００ｇ／ｍ２以上であるものを用い、この耐熱紙にポリブチレンテレフタレート樹脂を耐熱紙にラミネートし、ラミネート後のポリブチレンテレフタレート樹脂の結晶化割合を１０～３０％となるようにするものであり、電子レンジ及び１６０～２２０℃に達する熱処理で使用可能な耐熱性紙材を得るものである。 In the method for producing a heat-resistant paper material according to the present invention, a heat-resistant paper having a lamination surface with a smoothness specified in JIS P8119 of less than 50 seconds and a weighing of 100 g / m 2 or more is used. And laminating a polybutylene terephthalate resin on the heat-resistant paper so that the crystallization ratio of the polybutylene terephthalate resin after lamination becomes 10 to 30%. This is to obtain a heat-resistant paper material that can be used in heat treatment.
［ポリブチレンテレフタレート樹脂］
　耐熱性紙材に用いられるポリブチレンテレフタレート樹脂は、多価アルコール成分である１，４－ブタンジオールを主成分とするジオール成分を、多価カルボン酸成分であるテレフタル酸を主成分とするジカルボン酸成分又はそのアルコールエステル成分とを縮合して得られるブチレンテレフタレート単位を主たる繰り返し単位とするポリエステルであり、本発明の効果を阻害しない範囲でポリブチレンテレフタレートを主体とする共重合体であってもよい。ここで、ポリブチレンテレフタレート樹脂は、多価カルボン酸－多価アルコールのエステル単位のうち、ブチレンテレフタレート単位を６０モル％以上含むものとしてもよい。 [Polybutylene terephthalate resin]
The polybutylene terephthalate resin used for the heat-resistant paper material is composed of a diol component mainly composed of 1,4-butanediol which is a polyhydric alcohol component and a dicarboxylic acid mainly composed of terephthalic acid which is a polyvalent carboxylic acid component. It is a polyester having a butylene terephthalate unit as a main repeating unit obtained by condensing a component or an alcohol ester component thereof, and may be a copolymer mainly composed of polybutylene terephthalate as long as the effects of the present invention are not impaired. . Here, the polybutylene terephthalate resin may contain a butylene terephthalate unit in an amount of 60 mol% or more of the ester unit of the polycarboxylic acid-polyhydric alcohol.
　このポリブチレンテレフタレート樹脂は、高分子鎖末端のカルボキシル基含有量（２１５℃のベンジルアルコールに溶解し、水酸化ナトリウムで滴定して求めた値）が、６０ミリ当量／ｋｇ（以下、「ｍ当量／ｋｇ」と略称する。）未満のものが好ましく、５０ｍ当量／ｋｇ未満のものがより好ましい。 This polybutylene terephthalate resin has a carboxyl group content at the polymer chain terminal (a value obtained by dissolving in benzyl alcohol at 215 ° C. and titrating with sodium hydroxide) of 60 meq / kg (hereinafter referred to as “m equivalent”). / Kg "), and more preferably less than 50 meq / kg.
　カルボキシル基含有量を６０ｍ当量／ｋｇ以下にすることで、高温で熱処理を行った際にも樹脂の加水分解が抑えられるため、耐熱性紙材の表面にあるポリブチレンテレフタレート樹脂の艶がなくなって触感が悪くなる等の不具合を低減することができる。また、耐熱性紙材からのポリマー臭が低減されるため、内容物へのポリマー臭の移行を低減することができる。他方で、耐熱性紙材を食品以外の保持に用いる場合や、耐熱性紙材に優れた外観を要しない場合には、カルボキシル基含有量を６０ｍ当量／ｋｇ超としてもよい。 By setting the carboxyl group content to 60 meq / kg or less, hydrolysis of the resin can be suppressed even when heat treatment is performed at a high temperature, and the gloss of the polybutylene terephthalate resin on the surface of the heat-resistant paper material is lost. Problems such as poor tactile sensation can be reduced. Further, since the polymer odor from the heat-resistant paper material is reduced, the transfer of the polymer odor to the contents can be reduced. On the other hand, when the heat-resistant paper is used for holding other than food, or when the heat-resistant paper does not require an excellent appearance, the carboxyl group content may be more than 60 meq / kg.
　このようなポリブチレンテレフタレート樹脂を得る方法としては、公知の合成方法により得られたポリブチレンテレフタレート樹脂を、例えば、固相重合により、溶出成分のオリゴマー量を低減させる方法や、カルボキシル基（－ＯＨ基）を含む反応性モノマーと反応させることにより減少させる等の方法がある。 As a method for obtaining such a polybutylene terephthalate resin, for example, a method for reducing the amount of an oligomer of an eluting component by a solid-phase polymerization, a method for reducing an oligomer amount of a polybutylene terephthalate resin obtained by a known synthesis method, or a method using a carboxyl group (—OH For example, by reacting with a reactive monomer containing a group).
　耐熱性紙材に用いるポリブチレンテレフタレート樹脂には、本発明の効果を妨げない範囲で、染料や顔料等の着色剤、可塑剤、酸化防止剤、紫外線吸収剤、帯電防止剤、界面活性剤、潤滑剤、結晶化促進剤並びに遅延剤等の添加剤を含有させることができる。これらは目的に応じて複数含有してもよい。また、本発明の効果を妨げない範囲であれば、他の熱可塑性樹脂や無機充填剤を要求性能に応じて含有させることもできる。特に、耐熱性紙材を食品の保持に用いる場合には、これらの添加剤や熱可塑性樹脂、無機充填剤として、熱処理したときに食品により抽出されず、且つ、食品を汚染しない物質を用いることが好ましい。 Polybutylene terephthalate resin used for heat-resistant paper materials, within the range not hindering the effects of the present invention, coloring agents such as dyes and pigments, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, surfactants, Additives such as lubricants, crystallization promoters and retarders can be included. These may be contained plurally depending on the purpose. In addition, other thermoplastic resins and inorganic fillers can be contained according to required performance as long as the effects of the present invention are not impaired. In particular, when using a heat-resistant paper material for holding food, use a substance that is not extracted by the food when heat-treated and does not contaminate the food, as these additives, thermoplastic resin, and inorganic filler. Is preferred.
［耐熱紙］
　耐熱性紙材に用いられる耐熱紙としては、秤量が１００ｇ／ｍ２以上であり、且つ、ポリブチレンテレフタレート樹脂をラミネートする面（以下、「ラミネート面」という。）のＪＩＳ　Ｐ８１１９における平滑度が５０秒未満のものを用いる。その中でも、耐熱紙のラミネート面のＪＩＳ　Ｐ８１１９における平滑度は、３０秒未満であることが好ましく、２８秒以下であることがより好ましい。本発明者らは、ラミネート面の平滑度を５０秒未満にした場合であっても、耐熱紙にポリブチレンテレフタレート樹脂のフイルムをラミネートする際のフイルムにはネッキングが発生しないことを見出した。そして、耐熱紙としてラミネート面の平滑度が低い（平滑度の秒数が小さい）ものを用いることで、ラミネート面が粗面となってポリブチレンテレフタレート樹脂が保持され易くなるため、ポリブチレンテレフタレート樹脂と耐熱紙との密着性を高めることができる。このことで、耐熱紙の秤量を大きくして厚みを大きくした場合であっても、耐熱性紙材を成形した際の接合部の強度が高められて耐熱紙の形状が保持されるため、得られる耐熱性紙容器の形状保持性を高めることができる。 [Heat-resistant paper]
The heat-resistant paper used for the heat-resistant paper material has a weighing of 100 g / m 2 or more, and has a smoothness according to JIS P8119 of the surface on which the polybutylene terephthalate resin is laminated (hereinafter referred to as “laminated surface”). Use less than a second. Among them, the smoothness of the laminated surface of the heat-resistant paper according to JIS P8119 is preferably less than 30 seconds, and more preferably 28 seconds or less. The present inventors have found that even when the smoothness of the laminated surface is set to less than 50 seconds, necking does not occur in the film when laminating a film of polybutylene terephthalate resin on heat-resistant paper. By using a heat-resistant paper having low lamination smoothness (small seconds of smoothness), the lamination surface becomes rough and the polybutylene terephthalate resin is easily held. And heat-resistant paper. With this, even when the thickness of the heat-resistant paper is increased by increasing the weighing of the heat-resistant paper, the strength of the joint when the heat-resistant paper material is formed is increased and the shape of the heat-resistant paper is maintained, so Shape retention of the heat-resistant paper container to be obtained can be enhanced.
　ここで、ＪＩＳ　Ｐ８１１９における平滑度（ベック法平滑度）は、特定の条件で接触させた試験片とリング状の平面との間を特定の初期差圧下で一定量の大気圧空気が流れるのに必要な時間（秒）である。この平滑度は、試験台のガラス平面上に置いた試験片（直径３７．４ｍｍ±０．０５ｍｍ、有効平面積１０ｃｍ２±０．０５ｃｍ２の円形）を、ゴム製押え板（直径４５ｍｍ以上）を用いて１０００ｋＰａの圧力で押さえつけ、４８．０～５０．７ｋＰａまで真空引きされたガラス平面と試験片の接触面から大気圧の空気を吸い込ませて、１０ｃｃの空気の侵入に時間な時間（秒）を計測することで求められる。特に平滑度が高い（平滑度が３００秒以上）試料については、１０ｃｃの空気の侵入に時間な時間（秒）を計測し、その値を１０倍して平滑度の数値（秒）としてもよい。 Here, the smoothness (Beck's method smoothness) in JIS P8119 is defined as a value obtained when a certain amount of atmospheric pressure air flows between a test piece brought into contact with a specific condition and a ring-shaped plane under a specific initial differential pressure. Required time (seconds). The smoothness test piece was placed on the test stand on a glass plane (diameter 37.4 mm ± 0.05 mm, circular effective plane area 10cm 2 ± 0.05cm 2), a rubber pressing plate (or diameter 45 mm) And pressurized with a pressure of 1000 kPa. Then, air at atmospheric pressure was sucked from the contact surface between the glass surface and the test piece evacuated to 48.0 to 50.7 kPa, and time required for intrusion of 10 cc of air (seconds) ) Is measured. In particular, for a sample having a high degree of smoothness (smoothness of 300 seconds or more), the time (seconds) required for the intrusion of 10 cc of air is measured, and the value is multiplied by 10 to obtain a numerical value of the degree of smoothness (seconds). .
　また、耐熱紙としては、坪量が１００ｇ／ｍ２以上のものを用いる。ここで、耐熱紙の坪量は、好ましくは１２０ｇ／ｍ２以上、より好ましくは１５０ｇ／ｍ２以上とすることができる。耐熱紙として、坪量が１００ｇ／ｍ２以上のものを用いることで、容器形状への加工性を損なわずに、内容物の重量が大きい場合であっても変形が起こり難い耐熱性紙容器と、その材料としての耐熱性紙材を得ることができる。他方で、耐熱紙の坪量の上限は、好ましくは５００ｇ／ｍ２、より好ましくは４００ｇ／ｍ２、さらに好ましくは３００ｇ／ｍ２とする。耐熱紙として、坪量が５００ｇ／ｍ２以下のものを用いることで、加熱成形によって耐熱性紙容器を得る際に、得られる紙容器のコーナー部分やエッジ部分への割れや破れを低減することができる。 As the heat-resistant paper, a paper having a basis weight of 100 g / m 2 or more is used. Here, the basis weight of the heat-resistant paper can be preferably 120 g / m 2 or more, and more preferably 150 g / m 2 or more. By using a heat-resistant paper having a basis weight of 100 g / m 2 or more, a heat-resistant paper container that is unlikely to be deformed even when the weight of the content is large without impairing the processability into a container shape. As a result, a heat-resistant paper material can be obtained. On the other hand, the upper limit of the basis weight of the heat-resistant paper is preferably 500 g / m 2 , more preferably 400 g / m 2 , and still more preferably 300 g / m 2 . By using a heat-resistant paper having a basis weight of 500 g / m 2 or less, when obtaining a heat-resistant paper container by heat molding, it is possible to reduce cracks and tears at corners and edges of the obtained paper container. Can be.
　本発明で用いられる耐熱紙としては、パルプ繊維を用いない合成紙と、木材パルプ等のパルプ繊維を原料とするパルプ紙のいずれを用いることができる。その中でも、耐熱性の観点からパルプ紙を用いることがより好ましい。また、耐熱紙を食品の保持に用いる場合には、食品等を包む調理用紙容器や包装紙等として使用可能なものを用いることが好ましい。 As the heat-resistant paper used in the present invention, either synthetic paper without pulp fibers or pulp paper made from pulp fibers such as wood pulp can be used. Among them, it is more preferable to use pulp paper from the viewpoint of heat resistance. Further, when heat-resistant paper is used for holding food, it is preferable to use one that can be used as a cooking paper container or wrapping paper for wrapping food or the like.
　本発明で用いられる耐熱紙は、耐熱性の許容できる範囲内で、延伸ポリエチレンテレフタレートフイルムやポリ塩化ビニリデンコート延伸ポリエチレンテレフタレートフイルム、セロハン、低密度、中密度又は高密度のポリエチレン、アイオノマー、ポノプロピレン等のプラスチックフイルムもしくはシートあるいはアルミニウム箔等と、耐熱紙との積層体であってもよいが、コスト面やポリマー臭の問題、廃棄の問題等の観点から、このような積層体にしなくてもよい。 The heat-resistant paper used in the present invention is within an allowable range of heat resistance, such as stretched polyethylene terephthalate film or polyvinylidene chloride-coated stretched polyethylene terephthalate film, cellophane, low-density, medium-density or high-density polyethylene, ionomer, ponopropylene, etc. A laminate of a plastic film or a sheet or an aluminum foil and heat-resistant paper may be used. However, such a laminate may not be used from the viewpoint of cost, problems of polymer odor, disposal problems, and the like.
［ポリブチレンテレフタレート樹脂の耐熱紙へのラミネート］
　本発明の耐熱性紙材は、ポリブチレンテレフタレート樹脂が、耐熱紙のラミネート面にラミネートされた積層体からなるものである。耐熱紙へのポリブチレンテレフタレート樹脂のラミネートには、例えば、ポリブチレンテレフタレート樹脂を加熱溶融して、この樹脂を耐熱紙のラミネート面に供給してラミネート層を形成する方法が用いられる。このとき、ポリブチレンテレフタレート樹脂を加熱溶融して耐熱紙にラミネートする際の条件を制御することで、ラミネートされたポリブチレンテレフタレート樹脂の結晶化割合（Ｘ線回折法により測定した値）を、１０～３０％の範囲内とすることが好ましい。 [Lamination of polybutylene terephthalate resin on heat-resistant paper]
The heat-resistant paper material of the present invention comprises a laminate in which a polybutylene terephthalate resin is laminated on a heat-resistant paper laminated surface. For laminating the polybutylene terephthalate resin on the heat resistant paper, for example, a method of heating and melting the polybutylene terephthalate resin and supplying the resin to the laminated surface of the heat resistant paper to form a laminate layer is used. At this time, by controlling the conditions when the polybutylene terephthalate resin is heated and melted and laminated on heat-resistant paper, the crystallization ratio of the laminated polybutylene terephthalate resin (the value measured by the X-ray diffraction method) is 10 It is preferable to be within the range of 30%.
　ポリブチレンテレフタレート樹脂の結晶化割合を１０％以上にすることで、熱処理の際におけるポリブチレンテレフタレート樹脂の結晶化を低減し、熱処理時に結晶化に伴う収縮によって引き起こされる、容器の変形を抑えることができる。また、ポリブチレンテレフタレート樹脂の結晶化割合を３０％以下にすることで、ラミネートした積層体を熱プレス等によって容器等に成形する際の柔軟性や延伸性、靭性を高め、且つラミネート層の破れを低減することができる。したがって、結晶化割合を１０～３０％の範囲にコントロールすることにより、容器成形性や熱処理時の形状崩れや変形、外観の変化を抑えることができる。 By setting the crystallization ratio of the polybutylene terephthalate resin to 10% or more, the crystallization of the polybutylene terephthalate resin during the heat treatment can be reduced, and the deformation of the container caused by the shrinkage accompanying the crystallization during the heat treatment can be suppressed. it can. Further, by setting the crystallization ratio of the polybutylene terephthalate resin to 30% or less, the flexibility, stretchability, and toughness when the laminated laminate is formed into a container or the like by hot pressing or the like is improved, and the laminate layer is broken. Can be reduced. Therefore, by controlling the crystallization ratio in the range of 10 to 30%, it is possible to suppress the container formability, shape collapse, deformation, and change in appearance during heat treatment.
　耐熱紙にラミネートする際、このような結晶化割合のポリブチレンテレフタレート樹脂積層体を得る手段としては、ポリブチレンテレフタレート樹脂を耐熱紙にラミネートする際の樹脂の温度を管理することや、ラミネートした後の積層体を冷却及び加圧するチルロールの温度を管理することが挙げられ、これらにより所望の結晶化割合にコントロールすることができる。 When laminating on heat-resistant paper, as a means of obtaining a polybutylene terephthalate resin laminate of such a crystallization ratio, to control the temperature of the resin when laminating the polybutylene terephthalate resin on the heat-resistant paper, or after laminating The temperature of a chill roll for cooling and pressurizing the laminate is controlled, whereby the desired crystallization ratio can be controlled.
　ここで、ポリブチレンテレフタレート樹脂をラミネートする際の樹脂の温度は、例えば２６０℃以上にすることができ、２８０℃以上にすることが好ましい。他方で、樹脂温度の上限は、例えば３００℃以下にすることができる。 Here, the temperature of the resin when laminating the polybutylene terephthalate resin can be, for example, 260 ° C. or higher, and preferably 280 ° C. or higher. On the other hand, the upper limit of the resin temperature can be, for example, 300 ° C. or less.
　また、ポリブチレンテレフタレート樹脂をラミネートした後の積層体を冷却及び加圧する際、チルロールの温度を４０～７０℃に調節することが好ましく、５０～７０℃に調節することがより好ましい。 (4) When cooling and pressurizing the laminate after laminating the polybutylene terephthalate resin, the temperature of the chill roll is preferably adjusted to 40 to 70 ° C, more preferably to 50 to 70 ° C.
　ポリブチレンテレフタレート樹脂の耐熱紙へのラミネートの方法としては、慣用の方法、例えば、押出成形、射出成形、真空成形、圧縮成形、プレス成形等の方法等を用いることができる。また、ラミネート品は切削加工等の二次加工を施してもよい。 As a method for laminating the polybutylene terephthalate resin on the heat-resistant paper, a conventional method such as extrusion molding, injection molding, vacuum molding, compression molding, press molding, or the like can be used. Further, the laminated product may be subjected to secondary processing such as cutting.
　ラミネートにより得られる積層体における、ポリブチレンテレフタレート樹脂層の厚さは、ポリブチレンテレフタレート樹脂の特性等に応じて適宜設定することができ、例えば５μｍ以上６０μｍ以下の範囲に設定することができる。この厚さを５μｍ以上にすることで、ピンホールの発生や、サージングによる厚みムラを低減することができるため、ラミネート層を安定して得ることができる。また、ポリブチレンテレフタレート樹脂層の厚さの上限は、ラミネート層の形成し易さや容器成形のし易さ、経済的理由により、６０μｍ以下が好ましい。 厚 The thickness of the polybutylene terephthalate resin layer in the laminate obtained by lamination can be appropriately set in accordance with the characteristics of the polybutylene terephthalate resin and the like, and can be set, for example, in the range of 5 μm to 60 μm. By setting the thickness to 5 μm or more, the occurrence of pinholes and thickness unevenness due to surging can be reduced, so that a laminate layer can be stably obtained. The upper limit of the thickness of the polybutylene terephthalate resin layer is preferably 60 μm or less from the viewpoint of ease of forming a laminate layer, ease of forming a container, and economic reasons.
　ここで、ポリブチレンテレフタレート樹脂をラミネートした積層体は、ポリブチレンテレフタレート樹脂と耐熱紙との２層で構成してもよく、他の層を加えた３層以上で構成してもよい。このとき、積層体の少なくとも一方の表面に、ポリブチレンテレフタレート樹脂層が設けられていることが好ましい。 Here, the laminate obtained by laminating the polybutylene terephthalate resin may be composed of two layers of the polybutylene terephthalate resin and heat-resistant paper, or may be composed of three or more layers including other layers. At this time, it is preferable that a polybutylene terephthalate resin layer is provided on at least one surface of the laminate.
　ラミネートの方法の一例としては、実施例に記載される例のほか、１１５ｍｍφの押出機を使用して、スリット幅１．０ｍｍのＴ－ダイにより、２９０～３００℃の溶融ポリブチルテレフタレート樹脂を、秤量１５０～３５０ｇ／ｍ２の板紙に、１０～５０μｍの厚さとなるように、ラミネート速度３５ｍ／分でラミネートを行う例が挙げられる。そして、この方法を用いてラミネートを行い、且つ、温度を４０～６０℃に調節したチルロールで冷却及び加圧しながら巻き取ることで得られる積層体は、上記範囲の結晶化割合にコントロールされている。 As an example of a laminating method, in addition to the example described in the examples, a molten polybutyl terephthalate resin at 290 to 300 ° C. is melted with a T-die having a slit width of 1.0 mm using an extruder having a diameter of 115 mm. There is an example in which lamination is performed on a paperboard weighing 150 to 350 g / m 2 at a lamination speed of 35 m / min so as to have a thickness of 10 to 50 μm. The laminate obtained by performing lamination using this method and winding while cooling and pressing with a chill roll whose temperature is adjusted to 40 to 60 ° C. is controlled to the crystallization ratio in the above range. .
［耐熱性紙材の特性及び用途］
　本発明の耐熱性紙材は、耐熱性や成形性に優れ、内容物を充填した際の容器形状の崩れや変形や熱処理後の外観の変化がなく、内容物との適度な密着性並びに剥離性を有している。それとともに、高温での熱処理を行った後における容器の形状や表面性状の保持に優れており、内容物へのポリマー臭の移行がない。そのため、本発明の耐熱性紙材は、電子レンジによる加熱処理の用途や、耐熱性紙材の温度が１６０～１９０℃程度、又は、より厳しい１９０～２２０℃に達する高温での熱処理の用途、例えば電子レンジやオーブンによる加熱調理の用途に、好ましく用いることができる。 [Characteristics and uses of heat-resistant paper materials]
The heat-resistant paper material of the present invention has excellent heat resistance and moldability, has no collapse or deformation of the container shape when the contents are filled, and has no change in appearance after heat treatment, and has appropriate adhesion and peeling with the contents. It has nature. At the same time, it is excellent in maintaining the shape and surface properties of the container after heat treatment at a high temperature, and there is no transfer of polymer odor to the contents. Therefore, the heat-resistant paper material of the present invention may be used for heat treatment in a microwave oven, or for heat treatment at a high temperature where the temperature of the heat-resistant paper material reaches about 160 to 190 ° C. or more severe 190 to 220 ° C. For example, it can be preferably used for heating and cooking using a microwave oven or an oven.
　但し、耐熱性紙材に対する、ポリブチレンテレフタレート樹脂の融点以上の温度での熱処理は、ポリブチレンテレフタレート樹脂が溶融するため好ましくない。この意味から、食品を内容物とした場合の熱処理を例に挙げれば、一般的に低温域～中温域と言われている、タルト、スポンジケーキ、フルーツケーキ、パウンドケーキ、シュー、マドレーヌ等の焼成や、グラタン、ドリア等の加熱調理には最適である。勿論、ポリブチレンテレフタレート樹脂の融点を超えない範囲であれば、他の食品や、食品以外の内容物の熱処理にも好適である。 However, heat treatment of the heat-resistant paper at a temperature higher than the melting point of the polybutylene terephthalate resin is not preferable because the polybutylene terephthalate resin melts. In this sense, for example, heat treatment in the case where food is used as a content is the baking of tarts, sponge cakes, fruit cakes, pound cakes, shoes, madeleine, etc., which are generally referred to as low to medium temperature ranges. It is most suitable for cooking of gratin and doria. Of course, as long as it does not exceed the melting point of the polybutylene terephthalate resin, it is suitable for heat treatment of other foods and contents other than foods.
　このような耐熱性紙材は、後述するように、食品容器等の耐熱性紙容器の作製に好適に用いることができる。また、そのまま食品等を包む厚手の包装紙等として用いることができ、袋等の形状にすることもできる。 As described later, such a heat-resistant paper material can be suitably used for manufacturing a heat-resistant paper container such as a food container. Further, it can be used as a thick wrapping paper or the like for wrapping foods or the like as it is, and can be formed into a bag or the like.
＜耐熱性紙容器及びその製造方法について＞
　本発明に係る耐熱性紙容器は、ポリブチレンテレフタレート樹脂が、ラミネート面のＪＩＳ　Ｐ８１１９における平滑度が５０秒未満であり、且つ秤量が１００ｇ／ｍ２以上である耐熱紙のラミネート面にラミネートされており、成形時に破れが発生せず且つ熱処理時の変形を防ぐため、ラミネート後のポリブチレンテレフタレート樹脂の結晶化割合が１０～３０％となるようにした積層体からなるものである。 <About heat-resistant paper container and its manufacturing method>
In the heat-resistant paper container according to the present invention, the polybutylene terephthalate resin is laminated on a laminated surface of a heat-resistant paper having a smoothness of less than 50 seconds according to JIS P8119 and a weighing of 100 g / m 2 or more. In order to prevent breakage during molding and to prevent deformation during heat treatment, the laminate is made of a polybutylene terephthalate resin having a crystallization ratio of 10 to 30% after lamination.
　また、本発明に係る耐熱性紙容器の製造方法は、上述の耐熱性紙材を用いて、この耐熱性紙材を成形することで得られるものである。 The method of manufacturing a heat-resistant paper container according to the present invention is obtained by molding the heat-resistant paper material using the above-described heat-resistant paper material.
　耐熱性紙材を成形する手段については、耐熱性紙材の積層構造が保持される限り、特に限定されるものではなく、公知の種々の方法を採用することができる。一例として、熱プレス成形機を用いて、耐熱性紙材を適当な大きさにカッティングし、熱プレス等により加熱成形することで、耐熱性紙容器を得ることができる。 (4) The means for forming the heat-resistant paper material is not particularly limited as long as the laminated structure of the heat-resistant paper material is maintained, and various known methods can be employed. As an example, a heat-resistant paper container can be obtained by cutting a heat-resistant paper material into an appropriate size using a hot press molding machine and heat-molding with a hot press or the like.
　本発明に係る耐熱性紙容器は、特定の秤量を有する耐熱紙を用いて製造されるものであり、容器内に内容物を充填した際の形状の保持に優れたものとなっているため、容積に対する内容物の重量を多くすることができる。また、比重の大きい内容物にも耐えることができる。具体的には、［内容物重量（ｇ）÷容積（ｃｍ３）］÷［秤量（ｇ／ｍ２）］の値が０．００１以上となる用途に用いることが好ましく、前記式の値が０．００３以上となる用途に用いることがより好ましく、０．００５以上となる用途に用いることがさらに好ましい。なお、この値の上限については特に限定されないが、この値が極端に大きい用途では、容器が内容物の重量に耐えられずに変形する懸念があるため、例えば０．０５以下としてもよく、また、０．０１以下としてもよい。 The heat-resistant paper container according to the present invention is manufactured using heat-resistant paper having a specific weighing amount, and has excellent shape retention when the contents are filled in the container. The weight of the contents relative to the volume can be increased. In addition, it can withstand contents having a large specific gravity. Specifically, it is preferably used for applications in which the value of [content weight (g) ÷ volume (cm 3 )] ÷ [weight (g / m 2 )] is 0.001 or more. It is more preferably used for applications where the content is 0.003 or more, and even more preferably used for applications where the content is 0.005 or more. The upper limit of this value is not particularly limited, but in applications where this value is extremely large, there is a concern that the container may not bear the weight of the contents and may be deformed. , 0.01 or less.
　この耐熱性紙容器は、最内層（内容物と接する側の表層）及び最外層（内容物と接しない側の表層）の一方又は両方に、ポリブチレンテレフタレート樹脂層があるように構成することが好ましい。その中でも、内容物と容器が適度に密着していることが好ましい場合は、ポリブチレンテレフタレート樹脂を最内層として構成することが好ましいが、内容物と容器が強固に密着していることが好ましい場合には、耐熱紙を最内層として構成してもよい。内容物の種類や、内容物を充填した後の工程に応じて、最内層及び最外層の一方又は両方にポリブチレンテレフタレート樹脂層を用いることで、其々要求に応じた容器を得ることができる。 This heat-resistant paper container may be configured so that one or both of the innermost layer (the surface layer on the side in contact with the contents) and the outermost layer (the surface layer on the side not in contact with the contents) include a polybutylene terephthalate resin layer. preferable. Among them, when it is preferable that the contents and the container are in close contact with each other, it is preferable to configure the polybutylene terephthalate resin as the innermost layer, but it is preferable that the contents and the container are in close contact with each other. , A heat-resistant paper may be formed as the innermost layer. Depending on the type of the contents and the process after filling the contents, by using the polybutylene terephthalate resin layer for one or both of the innermost layer and the outermost layer, it is possible to obtain containers according to the respective requirements. .
　また、積層体の最外層が耐熱紙となるように構成してもよいが、ポリブチレンテレフタレート樹脂を最外層となるように構成することで、容器の外側に付着した水分による紙のふやけや油染みを防ぐことができるとともに、艶、光沢のある外観となるため、商品価値をさらに向上することができる。 In addition, the outermost layer of the laminate may be configured to be heat-resistant paper.However, by configuring the polybutylene terephthalate resin to be the outermost layer, paper swelling or oil stain due to moisture attached to the outside of the container is performed. Can be prevented, and a glossy and glossy appearance can be obtained, so that the commercial value can be further improved.
　特に、ポリブチレンテレフタレート樹脂層を耐熱性紙容器の最内層とし、且つ、公知の適切な蓋材を組み合わせることで、ポリブチレンテレフタレート樹脂のヒートシール性、ガスバリア性、耐低温衝撃性、イージーピーリング性、耐熱性等の特長を生かした容器を得ることができる。その一例として、グラタン、ドリア等を容器に充填した後、ヒートシールにより完全密閉して冷凍保存することができる。また、これを調理する際には、冷凍庫から取り出した後、イージーピーリング性によって簡単に蓋を剥がすことができるため、すぐにオーブン等を用いて調理することができる。 In particular, by using the polybutylene terephthalate resin layer as the innermost layer of a heat-resistant paper container and combining a known suitable lid material, the heat sealing property, gas barrier property, low-temperature impact resistance, and easy peeling property of the polybutylene terephthalate resin can be obtained. In addition, a container utilizing characteristics such as heat resistance can be obtained. As an example, after filling the container with gratin, doria and the like, the container can be completely sealed by heat sealing and stored frozen. In addition, when this is cooked, after taking out from the freezer, the lid can be easily peeled off by the easy peeling property, so that it can be cooked immediately using an oven or the like.
　以下、実施例、比較例及び参考例を示し、本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples, Comparative Examples, and Reference Examples, but the present invention is not limited to these Examples.
　ＪＩＳ　Ｐ８１１９における平滑度と、秤量が、表１の各実施例、比較例及び参考例に記載の値を有する、パルプ紙からなる各種板紙を耐熱紙として用い、固有粘度０．８８ｄＬ／ｇ、末端カルボキシル基含有量が１５ｍ当量／ｋｇのポリブチレンテレフタレート樹脂を、それぞれの耐熱紙にラミネートした。ここで、ポリブチレンテレフタレート樹脂のラミネートは、９０ｍｍφの押出機を使用して、スリット幅０．８ｍｍのＴ－ダイにより、２９０～３００℃の溶融ポリブチルテレフタレート樹脂を、２５μｍの厚さとなるように、ラミネート速度３５ｍ／分でラミネートを行った。次いで、温度を６０℃に調節したチルロールで冷却及び加圧しながら、得られる積層体を巻き取ることで、耐熱性紙材を得た。 Various paperboards made of pulp paper having a smoothness and a weighing value according to JIS P8119 having values described in Examples, Comparative Examples, and Reference Examples in Table 1 are used as heat-resistant paper, and have an intrinsic viscosity of 0.88 dL / g and a terminal. A polybutylene terephthalate resin having a carboxyl group content of 15 meq / kg was laminated on each heat-resistant paper. Here, the lamination of the polybutylene terephthalate resin is performed by using a 90 mmφ extruder, and using a T-die having a slit width of 0.8 mm to apply a molten polybutyl terephthalate resin having a thickness of 290 to 300 ° C. to a thickness of 25 μm. Lamination was performed at a lamination speed of 35 m / min. Next, the resulting laminate was wound up while cooling and pressing with a chill roll whose temperature was adjusted to 60 ° C., to obtain a heat-resistant paper material.
　得られた耐熱性紙材に積層されたポリブチレンテレフタレート樹脂を耐熱紙から引き剥がし、Ｘ線回折法により結晶化割合を測定したところ、２０％となった。 (4) The polybutylene terephthalate resin laminated on the obtained heat-resistant paper material was peeled off from the heat-resistant paper, and the crystallization ratio was measured by an X-ray diffraction method. The result was 20%.
　また、得られた耐熱性紙材について、熱プレス成形機を用いて、打抜き加工によって所定の大きさにカッティングするとともに、ポリブチレンテレフタレート樹脂層が内側になるように１４０℃で加熱成形し、ヒートセットすることで、容積４００ｃｍ３の耐熱性紙容器を得た。 Further, the obtained heat-resistant paper material was cut into a predetermined size by punching using a hot press molding machine, and was heat-molded at 140 ° C. so that the polybutylene terephthalate resin layer was on the inside, and heat was applied. By setting, a heat-resistant paper container having a volume of 400 cm 3 was obtained.
［評価］
　得られた耐熱性紙材と、内部で重量１５０ｇのケーキ生地を焼成した耐熱性紙容器について、以下の項目についての性能評価を各々行った。評価結果を表１に示す。 [Evaluation]
With respect to the obtained heat-resistant paper material and a heat-resistant paper container in which a 150 g weight of cake dough was baked, performance evaluation of the following items was performed. Table 1 shows the evaluation results.
　ラミネート層の密着性については、得られた耐熱性紙材を、ＪＩＳ　Ｋ６８５４－２に規定の１８０°剥離試験に準じて、試験片幅２５ｍｍ、クロスヘッド速度１００ｍｍ／ｍｉｎにて、積層されたポリブチレンテレフタレート樹脂を耐熱紙から引き剥がし、剥離面の状態を目視観察した。このとき、耐熱紙とポリブチレンフタレート樹脂が強固に接合していて、ポリブチレンテレフタレート樹脂側に耐熱紙のラミネート面が全体的に付着してくる場合を「◎」及び「○」とし、このうち、基材である耐熱紙層に破れが生じる場合を「◎」、耐熱紙層に破れは生じないものの耐熱紙層内が剥離する場合を「○」とした。また、ポリブチレンテレフタレート樹脂側に耐熱紙が一部付着した状態で界面剥離する場合を「△」、ほぼ全体がポリブチレンテレフタレート樹脂のラミネート層と耐熱紙の界面で剥離する（ポリブチレンテレフタレート樹脂側に耐熱紙が付着してこない）場合を「×」とした。結果を表１に示す。 Regarding the adhesiveness of the laminate layer, the obtained heat-resistant paper material was subjected to a test piece width of 25 mm and a crosshead speed of 100 mm / min in accordance with a 180 ° peel test specified in JIS K 684-2. The butylene terephthalate resin was peeled off from the heat-resistant paper, and the state of the peeled surface was visually observed. At this time, the case where the heat-resistant paper and the polybutylene phthalate resin are firmly bonded and the laminated surface of the heat-resistant paper is entirely adhered to the polybutylene terephthalate resin side is referred to as “」 ”or“ ○ ”. The case where the heat-resistant paper layer as the base material was torn was evaluated as “◎”, and the case where the heat-resistant paper layer did not tear but the inside of the heat-resistant paper layer was peeled was evaluated as “○”. In addition, when the heat-resistant paper partially adheres to the polybutylene terephthalate resin side and peels off at the interface, "△" indicates that almost the entire surface peels off at the interface between the polybutylene terephthalate resin laminate layer and the heat-resistant paper (the polybutylene terephthalate resin side). (Heat-resistant paper does not adhere to the paper). Table 1 shows the results.
　また、耐熱性紙材の取扱性については、得られた耐熱性紙材に対して熱プレス成形機を用いて打抜き加工を行う際に、耐熱性紙材のロールを熱プレス成形機にセットする際のハンドリング性と、生産性（打抜き加工における、捨てショット数や、縁桟や送り桟の必要量を指し、これらによるロスがいずれも少ない方が生産性は良好となる）をもとに判定した。ハンドリング性及び生産性において、いずれも優れるものを「○」、これらのいずれかが劣るものを「△」、これらがいずれも劣るものを「×」とした。また、特にハンドリング性に優れ、連続成形を開始するまでの捨てショットが僅かで済むものを「◎」とした。結果を表１に示す。 Regarding the handling properties of the heat-resistant paper material, when performing punching on the obtained heat-resistant paper material using a hot press molding machine, the roll of the heat-resistant paper material is set in the hot press molding machine. Judgment based on handling characteristics and productivity (indicating the number of discarded shots and the required amount of edge bars and feed bars in punching, the smaller the loss due to these, the better the productivity) did. In both of the handling properties and the productivity, “○” indicates that both were excellent, “△” indicates that any of these were inferior, and “×” indicates that all of them were inferior. Further, those which were particularly excellent in handling properties and required only a few shots to be discarded before the start of continuous molding were designated as “◎”. Table 1 shows the results.
　また、成形性については、耐熱性紙材を成形してヒートセットした際に、コーナー部分やエッジ部分に、割れや破れが発生したものを「×」、白化が発生したものを「△」、問題なく成形できたものを「○」とした。結果を表１に示す。 Regarding the moldability, when a heat-resistant paper material was molded and heat-set, cracks and tears occurred at the corners and edges, `` x '', whitening occurred `` △ '', The sample that could be molded without any problem was marked with “○”. Table 1 shows the results.
　また、容器の形状保持性については、市販の家庭用ケーキ生地（日本製粉社製ケーキミックスＭ５２０）を該ケーキ生地の調理指示に従って調理したものを、得られた耐熱性紙容器に充填し、容器の変形状態を目視にて確認した。ケーキ生地を充填しても、容器の変形が見られなかったものを「○」、充填されたケーキ生地の重みにより、容器の変形が見られたものを「×」として、形状安定性を評価した。結果を表１に示す。
Regarding the shape retention of the container, a commercially available home-made cake dough (Cake Mix M520 manufactured by Nippon Flour Milling Co., Ltd.) was cooked according to the cooking instructions for the cake dough, and the resulting heat-resistant paper container was filled into the container. Was visually checked. Evaluate the shape stability of containers that did not deform even when filled with cake dough as “O” and those with deformed containers as “X” due to the weight of the filled cake dough. did. Table 1 shows the results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示されるとおり、実施例１～２で得られた耐熱性紙材及び耐熱性紙容器では、ラミネート層の耐熱紙への密着性や、成形性、容器の形状保持性のいずれについても「○」となり、いずれも優れた結果となった。また、実施例１～２で得られた耐熱性紙材及び耐熱性紙容器では、耐熱性紙材の取扱性が「◎」であり、取扱性の面で特に優れた結果となった。他方で、参考例１で得られた耐熱性紙材及び耐熱性紙容器については、密着性及び容器の形状保持性について「○」となり優れた結果となったが、成形性については「△」となり、成形性の面ではやや劣る結果となった。また、比較例１で得られた耐熱性紙材では、ラミネート層の耐熱紙への密着性が「×」であり、耐熱紙への密着性の面で劣る結果となった。また、比較例１～３で得られた耐熱性紙材及び耐熱性紙容器については、密着性及び容器の形状保持性の一方又は両方が「△」又は「×」となり、これらの一方又は両方の面で劣る結果となった。また、参考例１及び比較例１～３で得られた耐熱性紙材については、取扱性が「○」であり、取扱性の面で優れてはいるものの、実施例１～２に比べては劣る結果となった。 As shown in Table 1, in the heat-resistant paper material and the heat-resistant paper container obtained in Examples 1 and 2, the adhesiveness of the laminate layer to the heat-resistant paper, the moldability, and the shape retention of the container were all different. "O" was obtained, and all were excellent results. Further, in the heat-resistant paper material and the heat-resistant paper container obtained in Examples 1 and 2, the handling property of the heat-resistant paper material was “◎”, and the handling property was particularly excellent. On the other hand, for the heat-resistant paper material and the heat-resistant paper container obtained in Reference Example 1, the adhesiveness and the shape retention of the container were evaluated as “た”, and excellent results were obtained. , Resulting in slightly poor moldability. Moreover, in the heat-resistant paper material obtained in Comparative Example 1, the adhesion of the laminate layer to the heat-resistant paper was "x", and the result was inferior in the adhesiveness to the heat-resistant paper. Further, with respect to the heat-resistant paper material and the heat-resistant paper container obtained in Comparative Examples 1 to 3, one or both of the adhesiveness and the shape retention of the container became “Δ” or “X”, and one or both of these were obtained. Inferior results. Further, the heat-resistant paper materials obtained in Reference Example 1 and Comparative Examples 1 to 3 had a handleability of “○” and were excellent in handleability, but compared with Examples 1 and 2. Was inferior.
　また、各実施例、比較例及び参考例の耐熱性紙容器について、形状保持性の評価に用いたケーキ生地を充填したものを、該ケーキ生地の調理指示に従って２００℃で１８分間焼成した後、容器表面の艶（焼成前に比べてのポリブチレンテレフタレート樹脂層表面の光沢の減損）、容器表面の平滑性（ポリブチレンテレフタレート樹脂層表面を指先で撫でた際の焼成前に比べてのざらつきの増加）、ポリマー臭（容器自体及びケーキ表面のテトラヒドロフラン臭）を評価したところ、容器表面の艶と平滑性については変化せず、また、容器自体及びケーキ表面へのテトラヒドロフラン臭も生じず、いずれも良好な結果であった。 In addition, for each of the heat-resistant paper containers of Examples, Comparative Examples, and Reference Examples, those filled with the cake dough used for evaluation of shape retention were baked at 200 ° C. for 18 minutes according to the cooking instructions for the cake dough, Gloss on the surface of the container (loss of gloss on the surface of the polybutylene terephthalate resin layer compared to before firing), smoothness on the surface of the container (roughness compared to before firing when the surface of the polybutylene terephthalate resin layer is stroked with a fingertip) Increase), polymer odor (tetrahydrofuran odor on the container itself and the cake surface), the gloss and smoothness of the container surface did not change, and neither tetrahydrofuran odor on the container itself nor the cake surface was generated. Good results.
　従って、本発明によれば、ポリエステルと基材である紙との密着性に優れ、また、取扱性及び成形性に優れた耐熱性紙材を得られることや、容器の形状保持性、表面性状の保持性に優れ、内容物へのポリマー臭の移行がなく、高温での熱処理用の耐熱性容器として好適な、耐熱性紙容器を得られることが推察される。 Therefore, according to the present invention, it is possible to obtain a heat-resistant paper having excellent adhesion between the polyester and the paper as the base material, and also excellent in handleability and moldability, and in maintaining the shape of the container and the surface properties. It is presumed that a heat-resistant paper container which is excellent in the retention of polymer, does not transfer polymer odor to the contents, and is suitable as a heat-resistant container for heat treatment at a high temperature can be obtained.

Claims (13)

  1. 　ポリブチレンテレフタレート樹脂が耐熱紙にラミネートされており、ラミネート後のポリブチレンテレフタレート樹脂の結晶化割合を１０～３０％となるようにした積層体が成形されてなる、電子レンジ及び１６０～２２０℃に達する熱処理で使用可能な耐熱性紙容器であって、
    　前記耐熱紙は、ラミネート面のＪＩＳ　Ｐ８１１９に規定される平滑度が５０秒未満であり、秤量が１００ｇ／ｍ２以上である、耐熱性紙容器。     A polybutylene terephthalate resin is laminated on heat-resistant paper, and a laminate is formed in which the crystallization ratio of the polybutylene terephthalate resin after lamination is 10 to 30%. A heat-resistant paper container that can be used in heat treatment
    The heat-resistant paper container, wherein the heat-resistant paper has a smoothness specified by JIS P8119 of a laminate surface of less than 50 seconds and a weighing of 100 g / m 2 or more.
  2. 　前記ポリブチレンテレフタレート樹脂は、末端カルボキシル基含有量が６０ミリ当量／ｋｇ未満であり、
    　前記耐熱性紙容器は、加熱調理に用いられる、請求項１に記載の耐熱性紙容器。     The polybutylene terephthalate resin has a terminal carboxyl group content of less than 60 meq / kg,
    The heat-resistant paper container according to claim 1, wherein the heat-resistant paper container is used for cooking.
  3. 　前記耐熱紙は、ラミネート面のＪＩＳ　Ｐ８１１９に規定される平滑度が３０秒未満である、請求項１又は２に記載の耐熱性紙容器。 3. The heat-resistant paper container according to claim 1, wherein the heat-resistant paper has a smoothness defined by JIS P8119 of a laminate surface of less than 30 seconds. 4.
  4. 　［内容物重量（ｇ）÷容積（ｃｍ３）］÷［秤量（ｇ／ｍ２）］が０．００１以上となる用途に用いられる、請求項１から３のいずれかに記載の耐熱性紙容器。 The heat-resistant paper according to any one of claims 1 to 3, which is used for applications where [content weight (g) ÷ volume (cm 3 )] ÷ [weight (g / m 2 )] is 0.001 or more. container.
  5. 　ポリブチレンテレフタレート樹脂が耐熱紙にラミネートされており、ラミネート後のポリブチレンテレフタレート樹脂の結晶化割合が１０～３０％となるようにした積層体からなる、電子レンジ及び１６０～２２０℃に達する熱処理で使用可能な耐熱性紙材であって、
    　前記耐熱紙は、ラミネート面のＪＩＳ　Ｐ８１１９に規定される平滑度が５０秒未満であり、秤量が１００ｇ／ｍ２以上である、耐熱性紙材。     A polybutylene terephthalate resin is laminated on heat-resistant paper, and the laminate is made so that the crystallization ratio of the polybutylene terephthalate resin after lamination is 10 to 30%. A heat-resistant paper material that can be used,
    A heat-resistant paper material, wherein the heat-resistant paper has a smoothness defined by JIS P8119 of a laminate surface of less than 50 seconds and a weighing of 100 g / m 2 or more.
  6. 　前記ポリブチレンテレフタレート樹脂は、末端カルボキシル基含有量が６０ミリ当量／ｋｇ未満であり、
    　前記耐熱性紙材が加熱調理に用いられる、請求項５に記載の耐熱性紙材。     The polybutylene terephthalate resin has a terminal carboxyl group content of less than 60 meq / kg,
    The heat-resistant paper material according to claim 5, wherein the heat-resistant paper material is used for cooking.
  7. 　前記耐熱紙は、ラミネート面のＪＩＳ　Ｐ８１１９に規定される平滑度が３０秒未満である、請求項５又は６に記載の耐熱性紙材。 7. The heat-resistant paper material according to claim 5, wherein the heat-resistant paper has a smoothness specified in JIS P8119 of a laminate surface of less than 30 seconds.
  8. 　［内容物重量（ｇ）÷容積（ｃｍ３）］÷［秤量（ｇ／ｍ２）］が０．００１以上となる容器の用途に用いられる、請求項５から７のいずれかに記載の耐熱性紙材。 The heat resistance according to any one of claims 5 to 7, which is used for a container having a content weight (g) ÷ volume (cm 3 ) ÷ [weight (g / m 2 )] of 0.001 or more. Paper material.
  9. 　ポリブチレンテレフタレート樹脂を耐熱紙にラミネートし、ラミネート後のポリブチレンテレフタレート樹脂の結晶化割合を１０～３０％となるようにする、電子レンジ及び１６０～２２０℃に達する熱処理で使用可能な耐熱性紙材の製造方法であって、
    　前記耐熱紙として、ラミネート面におけるＪＩＳ　Ｐ８１１９に規定される平滑度が５０秒未満であり、秤量が１００ｇ／ｍ２以上であるものを用いる、耐熱性紙材の製造方法。     Laminated polybutylene terephthalate resin on heat-resistant paper, so that the crystallization ratio of the polybutylene terephthalate resin after lamination is 10 to 30%. Heat-resistant paper usable in a microwave oven and heat treatment reaching 160 to 220 ° C. A method of manufacturing a material,
    A method for producing a heat-resistant paper material, wherein the heat-resistant paper has a smoothness of less than 50 seconds specified in JIS P8119 on a laminate surface and a weighing of 100 g / m 2 or more.
  10. 　前記ポリブチレンテレフタレート樹脂として、末端カルボキシル基含有量が６０ミリ当量／ｋｇ未満であるものを用い、
    　前記耐熱性紙材が加熱調理に用いられる、請求項９に記載の耐熱性紙材の製造方法。     As the polybutylene terephthalate resin, a resin having a terminal carboxyl group content of less than 60 meq / kg is used,
    The method for producing a heat-resistant paper material according to claim 9, wherein the heat-resistant paper material is used for cooking.
  11. 　前記耐熱紙として、ラミネート面のＪＩＳ　Ｐ８１１９に規定される平滑度が３０秒未満であるものを用いる、請求項９又は１０に記載の耐熱性紙材の製造方法。 11. The method for producing a heat-resistant paper material according to claim 9, wherein the heat-resistant paper has a smoothness specified in JIS P8119 of a laminate surface of less than 30 seconds.
  12. 　請求項９から１１のいずれかに記載の製造方法によって得られる耐熱性紙材を用いて、前記耐熱性紙材を成形する工程を有する、耐熱性紙容器の製造方法。 A method for manufacturing a heat-resistant paper container, comprising a step of forming the heat-resistant paper material using the heat-resistant paper material obtained by the manufacturing method according to any one of claims 9 to 11.
  13. 　前記成形によって、［内容物重量（ｇ）÷容積（ｃｍ３）］÷［秤量（ｇ／ｍ２）］が０．００１以上となる容器を成形する、請求項１２に記載の耐熱性紙容器の製造方法。 By the molding, [content weight (g) ÷ volume (cm 3)] ÷ [weighing (g / m 2)] is molded container comprising a 0.001 or more, the heat resistance paper container according to claim 12 Manufacturing method.
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JP2003266512A (en) * 2002-12-11 2003-09-24 Polyplastics Co Method for manufacturing heat-resistant paper container for heat cooking
JP2006111007A (en) * 2004-09-17 2006-04-27 Mitsubishi Engineering Plastics Corp Manufacturing method of paper laminated by laminated polyester and container made of paper laminated with polyester
JP2007015160A (en) * 2005-07-06 2007-01-25 Mitsubishi Engineering Plastics Corp Polybutylene terephthalate-laminated paper and paper container using it
JP2007062084A (en) * 2005-08-30 2007-03-15 Toyobo Co Ltd Laminate for molding container
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JP2016150210A (en) * 2015-02-19 2016-08-22 花王株式会社 Microwave oven cooking container

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