JP2023105881A - Heat-sealable paper - Google Patents
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- JP2023105881A JP2023105881A JP2022006883A JP2022006883A JP2023105881A JP 2023105881 A JP2023105881 A JP 2023105881A JP 2022006883 A JP2022006883 A JP 2022006883A JP 2022006883 A JP2022006883 A JP 2022006883A JP 2023105881 A JP2023105881 A JP 2023105881A
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/22—Polyalkenes, e.g. polystyrene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/28—Presence of paper
- C09J2400/283—Presence of paper in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2425/00—Presence of styrenic polymer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paper (AREA)
Abstract
Description
本発明は、例えば食品に対する包装用紙、紙袋、紙容器、紙箱、紙カップ及び蓋材等の包装用途に使用するヒートシール性を有するヒートシール紙に関する。 TECHNICAL FIELD The present invention relates to a heat-sealing paper having heat-sealing properties, which is used for packaging applications such as food packaging paper, paper bags, paper containers, paper boxes, paper cups and lids.
食品等に対する包装用紙、紙袋、紙容器、紙箱、紙カップ及び蓋材等の包装用途に使用する紙製の包装材料は、封止及び包装形態等の加工を達成するためにヒートシール性を有する。
このような包装材料として、例えば、紙基材上にスチレンアクリル酸エステル系共重合樹脂を含有するヒートシール層を有する包装用途に好適なヒートシール紙（例えば、特許文献１参照）、紙基材の少なくとも一方の面に少なくとも２層以上の塗工層を有し、かつ前記塗工層の最表面がヒートシール層であり、前記ヒートシール層と紙基材の間に少なくとも１層のポリヒドロキシウレタンを含むバリア層を有する包装用紙（例えば、特許文献２参照）、及び紙基材上に、水蒸気バリア層及びガスバリア層を有する紙製バリア原紙の少なくとも該ガスバリア層上に、さらにヒートシール層を有する紙製バリア材料（例えば、特許文献３参照）等が公知である。
Paper packaging materials used for packaging applications such as packaging paper for foods, paper bags, paper containers, paper boxes, paper cups and lids have heat sealability in order to achieve processing such as sealing and packaging form.
Such packaging materials include, for example, heat-sealable paper suitable for packaging applications having a heat-sealable layer containing a styrene-acrylic acid ester-based copolymer resin on a paper substrate (see, for example, Patent Document 1), and a paper substrate. has at least two or more coating layers on at least one surface of the coating layer, and the outermost surface of the coating layer is a heat-sealing layer, and at least one layer of polyhydroxy is between the heat-sealing layer and the paper substrate A packaging paper having a barrier layer containing urethane (see, for example, Patent Document 2), and a paper barrier base paper having a water vapor barrier layer and a gas barrier layer on at least the gas barrier layer on the paper substrate, and further a heat seal layer. A paper barrier material (see, for example, Patent Literature 3) having
被包装物の劣化を抑制及び包装体の取り扱い易さの観点から、特に、被包装物が食品である場合に衛生的観点から、ヒートシール性だけでなく水分の浸透を抑えた透湿バリア性を有するヒートシール紙が必要である。
従来は、特許文献２に記載されるバリア層を、並びに特許文献３に記載される水蒸気バリア層及びガスバリア層のようなバリア専用の層を、ヒートシール層とは別に設ける構成が多い。しかしながら、バリア専用の層を設ける構成は、材料コスト及び製造コストを増加する。また、特許文献３に記載されるが如くの紙製バリア材料でも、例えば、水蒸気透過度が１８０ｇ／ｍ２・ｄａｙ～２００ｇ／ｍ２・ｄａｙであって、透湿バリア性は十分といえない。
特許文献１に記載されるが如くのヒートシール紙では、ヒートシール性及びリサイクル時の離解性を良好にすることが目的であるために、透湿バリア性を考慮しない。また、特許文献１に記載されるが如くのヒートシール紙では、スチレンアクリル酸エステル系共重合樹脂を含有するヒートシール層であるものの、スチレンアクリル酸エステル系共重合樹脂の単量体構成を開示しない。
特許文献２に記載されるが如くの包装用紙では、プラスチックの使用量を低減しつつ酸素バリア性を有することを目的とするために、透湿バリア性が十分といえない。特許文献２の実施例に記載する包装用紙では、水蒸気透過度が５３．８ｇ／ｍ２・ｄａｙ～２４７．８ｇ／ｍ２・ｄａｙの範囲である。
From the viewpoint of suppressing the deterioration of the package and the ease of handling of the package, especially from the hygienic point of view when the package is food, not only the heat sealability but also the moisture permeation barrier property that suppresses the penetration of moisture. A heat-sealable paper with
Conventionally, in many cases, a barrier layer described in Patent Document 2 and a layer dedicated to barrier such as a water vapor barrier layer and a gas barrier layer described in Patent Document 3 are provided separately from the heat seal layer. However, the provision of a barrier-only layer increases material and manufacturing costs. Moreover, even the paper barrier material as described in Patent Document 3 has, for example, a water vapor permeability of 180 g/m 2 ·day to 200 g/m 2 ·day, and the moisture permeability barrier property is not sufficient. .
In the heat-sealable paper as described in Patent Document 1, since the purpose is to improve the heat-sealing property and the disaggregation property during recycling, the moisture-permeable barrier property is not taken into consideration. Further, in the heat-sealable paper as described in Patent Document 1, although the heat-sealable layer contains a styrene acrylic acid ester copolymer resin, the monomer composition of the styrene acrylic acid ester copolymer resin is disclosed. do not.
The packaging paper as described in Patent Document 2 is intended to have oxygen barrier properties while reducing the amount of plastic used, so the moisture permeability barrier properties are not sufficient. The wrapping paper described in Examples of Patent Document 2 has a water vapor transmission rate in the range of 53.8 g/m 2 ·day to 247.8 g/m 2 ·day.
本発明の目的は、ヒートシール性及び透湿バリア性を有するヒートシール紙を提供することである。詳しくは、ヒートシール性を有しながら透湿バリア性を有するヒートシール性樹脂を見出し、紙基材に対して前記ヒートシール性樹脂を含有するヒートシール層を設けることによって、ヒートシール性及び透湿バリア性を有するヒートシール紙を提供することである。 An object of the present invention is to provide a heat-sealable paper having heat-sealing properties and moisture-permeable barrier properties. Specifically, a heat-sealing resin having heat-sealing properties and moisture permeability barrier properties was found, and heat-sealing properties and permeability were improved by providing a heat-sealing layer containing the heat-sealing resin on a paper substrate. An object of the present invention is to provide a heat-sealable paper having moisture barrier properties.
本発明者らは、ヒートシール性樹脂の単量体について種々検討を重ねた結果、特定の単量体から成る本発明に係るヒートシール性樹脂を見出して、本発明の完成に至った。すなわち、本発明の目的は以下によって達成される。 The inventors of the present invention have made various studies on the monomers of the heat-sealable resin, and as a result, have found the heat-sealable resin according to the present invention comprising a specific monomer, thereby completing the present invention. That is, the object of the present invention is achieved by the following.
［１］紙基材と、前記紙基材の少なくとも片面に対してヒートシール性樹脂を含有するヒートシール層を有し、前記ヒートシール性樹脂が、下記の単量体を重合して成るアクリル系樹脂であるヒートシール紙。
単量体：
（Ａ）メチルメタクリレート
（Ｂ）２－エチルヘキシルアクリレート
（Ｃ）ブチルアクリレート
（Ｄ）スチレン
[1] A paper substrate and a heat-sealing layer containing a heat-sealing resin on at least one side of the paper substrate, wherein the heat-sealing resin is acrylic obtained by polymerizing the following monomers A heat-sealing paper that is based on resin.
Monomer:
(A) methyl methacrylate (B) 2-ethylhexyl acrylate (C) butyl acrylate (D) styrene
［２］上記アクリル系樹脂が、下記の単量体を重合して成るかつ樹脂の各単量体組成が下記質量％の範囲である上記［１］に記載のヒートシール紙。
単量体組成：
（Ａ）メチルメタクリレート：２６質量％以上４６質量％以下
（Ｂ）２－エチルヘキシルアクリレート：２３質量％以上４３質量％以下
（Ｃ）ブチルアクリレート：１３質量％以上４５質量％以下
（Ｄ）スチレン：３質量％以上１６質量％以下
[2] The heat-sealable paper according to [1] above, wherein the acrylic resin is obtained by polymerizing the following monomers, and the monomer composition of the resin is within the following mass % range.
Monomer composition:
(A) Methyl methacrylate: 26% by mass or more and 46% by mass or less (B) 2-ethylhexyl acrylate: 23% by mass or more and 43% by mass or less (C) Butyl acrylate: 13% by mass or more and 45% by mass or less (D) Styrene: 3 % by mass or more and 16% by mass or less
［３］上記ヒートシール層が、パラフィンワックスを含有する上記［１］又は［２］に記載のヒートシール紙。 [3] The heat-sealable paper according to [1] or [2] above, wherein the heat-sealable layer contains paraffin wax.
［４］上記紙基材と上記ヒートシール層との間に下塗り層を有し、前記下塗り層が、板状無機顔料及び熱可塑性樹脂を含有する上記［１］～［３］のいずれかに記載のヒートシール紙。 [4] Any one of [1] to [3] above, which has an undercoat layer between the paper substrate and the heat seal layer, and wherein the undercoat layer contains a plate-like inorganic pigment and a thermoplastic resin Heat seal paper as described.
本発明のヒートシール紙は、ヒートシール性樹脂を含有するヒートシール層を紙基材に対して設けることによって、ヒートシール性及び透湿バリア性を有することができる。 The heat-sealable paper of the present invention can have heat-sealable properties and moisture-permeable barrier properties by providing a heat-sealable layer containing a heat-sealable resin on the paper substrate.
ヒートシール紙は、紙基材と、前記紙基材の少なくとも片面に対してヒートシール層を有する。いくつかの実施態様において、ヒートシール紙は、紙基材の両面にヒートシール層を有する。この理由は、表裏関係なく取り扱いに優位であるからである。いくつかの実施態様において、ヒートシール紙は、紙基材の片面に対してのみヒートシール層を有する場合、ヒートシール層を有する側に対する紙基材の反対面に印刷適性のための従来公知のコート層又は寸法安定性のための従来公知のバックコート層を有する。また、いくつかの実施態様において、ヒートシール紙は、紙基材とヒートシール層との間に、例えば特許文献３に記載されるが如くの従来公知のガスバリア層を有する。 The heat seal paper has a paper substrate and a heat seal layer on at least one side of the paper substrate. In some embodiments, the heat seal paper has heat seal layers on both sides of the paper substrate. The reason for this is that it is superior in handling regardless of the front and back. In some embodiments, the heat-sealable paper, when having a heat-sealable layer only on one side of the paper substrate, is coated with a conventionally known paper for printability on the opposite side of the paper substrate to the side having the heat-sealable layer. It has a conventionally known backcoat layer for coating layer or dimensional stability. Also, in some embodiments, the heat-sealable paper has a conventional gas barrier layer between the paper substrate and the heat-sealable layer, such as described in US Pat.
いくつかの実施態様において、ヒートシール紙は、紙基材とヒートシール層との間に下塗り層を有する。この理由は、紙基材が有する空隙を下塗り層が目止めして、結果的に紙基材の空隙に起因してヒートシール層にできる欠陥の発生を抑制できるからである。例えば、ヒートシール層に欠陥が存在する場合は、透湿バリア性が悪化する傾向を示す。また、ヒートシール層に欠陥が存在することによってヒートシール紙のヒートシール層どうしの密着に悪影響する場合は、ヒートシール性も悪化する傾向を示す。 In some embodiments, the heat seal paper has a subbing layer between the paper substrate and the heat seal layer. The reason for this is that the undercoat layer fills the voids in the paper base material, and as a result, the occurrence of defects in the heat seal layer due to the voids in the paper base material can be suppressed. For example, when defects are present in the heat seal layer, the moisture permeability barrier property tends to deteriorate. Moreover, when defects in the heat-sealing layer adversely affect the adhesion between the heat-sealing layers of the heat-sealing paper, the heat-sealing property tends to deteriorate.
下塗り層は、無機顔料及びバインダーを含有する従来公知の塗工層である。
いくつかの実施態様において、前記無機顔料は従来公知の板状無機顔料である。この理由は、紙基材の空隙に起因してヒートシール層にできる欠陥の発生をより抑制できるからである。無機顔料の例としては、軽質炭酸カルシウム、重質炭酸カルシウム、クレー、硫酸カルシウム、硫酸バリウム、二酸化チタン、酸化亜鉛、硫化亜鉛、炭酸亜鉛、サチンホワイト、珪酸アルミニウム、活性白土、珪藻土、シリカ、アルミナ、水酸化アルミニウム、リトポン、ゼオライト、炭酸マグネシウム及び水酸化マグネシウム等であって従来公知のものを挙げることができる。板状無機顔料の例としては、マイカ、カオリン、パイロフィライト、タルク、ベントナイト、モンモリロナイト、バーミキュライト、緑泥石、セプテ緑泥石、蛇紋石及びスチルプノメレーン等であって従来公知のものを挙げることができる。
The undercoat layer is a conventionally known coating layer containing an inorganic pigment and a binder.
In some embodiments, the inorganic pigment is a conventional platelet inorganic pigment. The reason for this is that the occurrence of defects in the heat seal layer due to voids in the paper substrate can be suppressed. Examples of inorganic pigments include light calcium carbonate, heavy calcium carbonate, clay, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, activated clay, diatomaceous earth, silica, and alumina. , aluminum hydroxide, lithopone, zeolite, magnesium carbonate, magnesium hydroxide and the like, which are conventionally known. Examples of plate-like inorganic pigments include mica, kaolin, pyrophyllite, talc, bentonite, montmorillonite, vermiculite, chlorite, septe chlorite, serpentine and stilpnomelane, which are conventionally known. can be done.
いくつかの実施態様において、上記バインダーは従来公知の熱可塑性樹脂である。この理由は、紙基材の空隙に起因してヒートシール層にできる欠陥の発生をより抑制できるからである。バインダーの例としては、澱粉、酸化澱粉、酵素変性澱粉、エーテル化澱粉、カチオン化澱粉、両性澱粉、ジアルデヒド化澱粉、燐酸エステル化澱粉及び尿素燐酸エステル化澱粉等のエステル化澱粉、ヒドロキシエチル化澱粉、ヒドロキシブチル化澱粉、メラミン樹脂及び尿素樹脂等の熱硬化合成樹脂、アルキド樹脂、熱硬化性ポリウレタン樹脂、熱硬化性エラストマー、カルボキシメチルセルロース、ヒドロキシエチルセルロース等のセルロース誘導体、カゼイン、ゼラチン及び大豆蛋白等の天然高分子樹脂並びにその誘導体等であって従来公知のものを挙げることができる。熱可塑性樹脂の例としては、スチレンブタジエン系共重合樹脂及びアクリロニトリルブタジエン系共重合樹脂等の共役ジエン系樹脂、アクリル酸エステル系重合樹脂及びメタクリル酸エステル系重合樹脂並びにメタクリル酸エステルブタジエン系共重合樹脂等のアクリル系樹脂、エチレン酢酸ビニル系共重合樹脂及び塩化ビニル酢酸ビニル系共重合樹脂等のビニル系樹脂、熱可塑性ポリウレタン樹脂、熱可塑性エラストマー、ポリエステル系樹脂及びこの各種共重合樹脂のカルボキシル基等の官能基含有単量体による官能基変性樹脂、ポリビニルピロリドン、ポリビニルアルコール及びその各種変性ポリビニルアルコール、ポリプロピレングリコール、並びにポリエチレングリコール等であって従来公知のものを挙げることができる。 In some embodiments, the binder is a conventional thermoplastic resin. The reason for this is that the occurrence of defects in the heat seal layer due to voids in the paper substrate can be suppressed. Examples of binders include esterified starches such as starch, oxidized starch, enzyme-modified starch, etherified starch, cationic starch, amphoteric starch, dialdehyde starch, phosphate esterified starch and urea phosphate esterified starch, and hydroxyethylated starch. Thermosetting synthetic resins such as starch, hydroxybutylated starch, melamine resins and urea resins, alkyd resins, thermosetting polyurethane resins, thermosetting elastomers, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, casein, gelatin and soy protein, etc. natural polymer resins and derivatives thereof, etc., which are conventionally known. Examples of thermoplastic resins include conjugated diene resins such as styrene-butadiene-based copolymer resins and acrylonitrile-butadiene-based copolymer resins; acrylic resins such as acrylic resins, vinyl resins such as ethylene vinyl acetate copolymer resins and vinyl chloride vinyl acetate copolymer resins, thermoplastic polyurethane resins, thermoplastic elastomers, polyester resins, and carboxyl groups of these various copolymer resins, etc. functional group-modified resins with functional group-containing monomers, polyvinylpyrrolidone, polyvinyl alcohol and its various modified polyvinyl alcohols, polypropylene glycol, polyethylene glycol, and the like, which are conventionally known.
いくつかの実施態様において、ヒートシール紙は、紙基材とヒートシール層との間に無機顔料及びバインダーを含有する下塗り層を有し、該下塗り層において無機顔料１００質量部に対してバインダーが５０質量部以上２００質量部以下である。この理由は、紙基材の空隙に起因してヒートシール層にできる欠陥の発生をより抑制できるからである。 In some embodiments, the heat-sealable paper has an undercoat layer containing an inorganic pigment and a binder between the paper substrate and the heat-sealable layer, and the undercoat layer contains a binder with respect to 100 parts by weight of the inorganic pigment. It is 50 parts by mass or more and 200 parts by mass or less. The reason for this is that the occurrence of defects in the heat seal layer due to voids in the paper substrate can be suppressed.
少なくとも一つの実施態様において、ヒートシール紙は、紙基材とヒートシール層との間に無機顔料及びバインダーを含有する下塗り層を有し、前記無機顔料が板状無機顔料及び前記バインダーが熱可塑性樹脂である。さらに、少なくとも一つの実施態様において、ヒートシール紙は、紙基材とヒートシール層との間に無機顔料及びバインダーを含有する下塗り層を有し、前記無機顔料がカオリン及び前記バインダーがスチレンブタジエン系共重合樹脂である。これらの理由は、紙基材の空隙に起因してヒートシール層にできる欠陥の発生をより抑制できるからである。 In at least one embodiment, the heat-sealable paper has an undercoat layer containing an inorganic pigment and a binder between the paper substrate and the heat-sealable layer, wherein the inorganic pigment is a platy inorganic pigment and the binder is a thermoplastic Resin. Further, in at least one embodiment, the heat-sealable paper has an undercoat layer containing an inorganic pigment and a binder between the paper substrate and the heat-sealable layer, wherein the inorganic pigment is kaolin and the binder is a styrene-butadiene-based It is a copolymer resin. The reason for these is that the generation of defects in the heat seal layer due to voids in the paper substrate can be suppressed.
いくつかの実施態様において、下塗り層は、必要に応じて、塗工紙分野で従来公知の各種添加剤を含有することができる。添加剤の例としては、界面活性剤、分散剤、増粘剤、流動性改良剤、有機顔料、カチオン化剤、滑剤、耐水化剤、消泡剤、発泡剤、浸透剤、着色剤、蛍光増白剤、紫外線吸収剤、酸化防止剤、防腐剤、防バイ剤及びバリア剤等を挙げることができる。
いくつかの実施態様において、下塗り層は、下塗り層を形成する乾燥固形分に対して無機顔料及びバインダーが８０質量％以上である。また、いくつかの実施態様において、下塗り層の塗工量は、紙基材の片面あたり乾燥固形分で６ｇ／ｍ２以上２０ｇ／ｍ２以下である。これらの理由は、材料コストを抑えながら、紙基材の空隙に起因してヒートシール層にできる欠陥の発生をより抑制できるからである。
In some embodiments, the subbing layer can optionally contain various additives conventionally known in the coated paper art. Examples of additives include surfactants, dispersants, thickeners, fluidity improvers, organic pigments, cationizing agents, lubricants, waterproofing agents, antifoaming agents, foaming agents, penetrants, coloring agents, fluorescent Whitening agents, ultraviolet absorbers, antioxidants, preservatives, anti-fungal agents, barrier agents and the like can be mentioned.
In some embodiments, the undercoat layer is 80% or more by weight inorganic pigment and binder based on the dry solids forming the undercoat layer. In some embodiments, the coating weight of the undercoat layer is 6 g/m 2 or more and 20 g/m 2 or less in terms of dry solid content per side of the paper substrate. The reason for these is that it is possible to further suppress the occurrence of defects in the heat-seal layer due to voids in the paper substrate while suppressing the material cost.
ヒートシール層のヒートシール性樹脂は、下記の単量体を重合して成るアクリル系樹脂である。
単量体：
（Ａ）メチルメタクリレート
（Ｂ）２－エチルヘキシルアクリレート
（Ｃ）ブチルアクリレート
（Ｄ）スチレン
いくつかの実施態様において、前記ヒートシール性樹脂は、下記の単量体を重合して成るかつ樹脂の各単量体組成が下記質量％の範囲であるアクリル系樹脂である。この理由は、ヒートシール性樹脂の単量体組成が前記質量％の範囲を満足すると、ヒートシール紙は、ヒートシール性及び／又は透湿バリア性が良化するからである。
単量体組成：
（Ａ）メチルメタクリレート：２６質量％以上４６質量％以下
（Ｂ）２－エチルヘキシルアクリレート：２３質量％以上４３質量％以下
（Ｃ）ブチルアクリレート：１３質量％以上４５質量％以下
（Ｄ）スチレン：３質量％以上１６質量％以下
The heat-sealing resin of the heat-sealing layer is an acrylic resin obtained by polymerizing the following monomers.
Monomer:
(A) methyl methacrylate (B) 2-ethylhexyl acrylate (C) butyl acrylate (D) styrene It is an acrylic resin having a monomer composition within the following mass % range. The reason for this is that when the monomer composition of the heat-sealing resin satisfies the above mass % range, the heat-sealing paper has improved heat-sealing properties and/or moisture-permeable barrier properties.
Monomer composition:
(A) Methyl methacrylate: 26% by mass or more and 46% by mass or less (B) 2-ethylhexyl acrylate: 23% by mass or more and 43% by mass or less (C) Butyl acrylate: 13% by mass or more and 45% by mass or less (D) Styrene: 3 % by mass or more and 16% by mass or less
ヒートシール性樹脂は、上記単量体（Ａ）～（Ｄ）を配合した単量体組成物を、所定の反応容器に入れて乳化重合及びラジカル重合等の従来公知の重合方法によって重合反応させて得ることができる。また、樹脂の単量体組成が上記であるヒートシール性樹脂は、上記単量体（Ａ）～（Ｄ）を上記質量％で配合した単量体組成物を、所定の反応容器に入れて乳化重合及びラジカル重合等の従来公知の重合方法によって重合反応させて得ることができる。 The heat-sealable resin is produced by putting a monomer composition containing the above monomers (A) to (D) into a predetermined reaction vessel and polymerizing it by a conventionally known polymerization method such as emulsion polymerization and radical polymerization. can be obtained. In addition, the heat-sealing resin having the above-described monomer composition of the resin is obtained by placing a monomer composition in which the above-described monomers (A) to (D) are blended in the above-described mass% in a predetermined reaction vessel. It can be obtained by polymerization reaction by a conventionally known polymerization method such as emulsion polymerization and radical polymerization.
いくつかの実施態様において、ヒートシール性樹脂は、上記（Ａ）～（Ｄ）の単量体以外に、これら単量体と共重合可能な他単量体を上記単量体組成物に配合してヒートシール性樹脂中に含有することができる。他単量体の例としては、上記（Ａ）、（Ｂ）及び（Ｃ）以外の（メタ）アクリレート、（メタ）アクリル酸、（メタ）アクリル酸塩、（メタ）アクリロニトリル、酢酸ビニル、塩化ビニル、塩化ビニリデン、エチレン及びプロピレン等を挙げることができる。
また、いくつかの実施態様において、ヒートシール性樹脂は、上記（Ａ）～（Ｄ）の単量体の合計が樹脂を構成する単量体に対して９５質量％以上である。少なくとも一つの実施態様において、ヒートシール性樹脂は、上記（Ａ）～（Ｄ）の単量体以外の他単量体を含有しない。これらの理由は、ヒートシール性及び透湿バリア性をバランス良く両立して有することができるからである。
In some embodiments, the heat-sealing resin comprises, in addition to the monomers (A) to (D), other monomers copolymerizable with these monomers. It can be contained in the heat-sealing resin as such. Examples of other monomers include (A), (B) and (C) other than (meth)acrylates, (meth)acrylic acid, (meth)acrylic acid salts, (meth)acrylonitrile, vinyl acetate, chloride Examples include vinyl, vinylidene chloride, ethylene and propylene.
In some embodiments, the heat-sealing resin has a total content of the above monomers (A) to (D) of 95% by mass or more based on the monomers constituting the resin. In at least one embodiment, the heat-sealable resin does not contain any monomers other than the above monomers (A) to (D). These reasons are because it is possible to have both heat-sealing properties and moisture-permeable barrier properties in a well-balanced manner.
各単量体の組成及び質量％は、例えば、ＦＴ－ＩＲ分析（フーリエ変換赤外分光光度分析）、ＧＣ－ＭＳ分析（ガスクロマトグラフィ質量分析）及びＮＭＲ分析（核磁気共鳴分析）によってヒートシール性樹脂から解析することができる。 The composition and mass% of each monomer are determined, for example, by FT-IR analysis (Fourier transform infrared spectrophotometry), GC-MS analysis (gas chromatography mass spectrometry) and NMR analysis (nuclear magnetic resonance analysis). It can be analyzed from the resin.
ヒートシール層は、上記のヒートシール性樹脂以外に、必要に応じて従来公知の各種添加剤を含有することができる。添加剤の例としては、無機顔料、上記ヒートシール性樹脂以外のヒートシール性樹脂、ヒートシール性樹脂以外の各種樹脂、澱粉類及びセルロース類等の多糖類、界面活性剤、分散剤、増粘剤、流動性改良剤、有機顔料、カチオン化剤、滑剤、耐水化剤、消泡剤、発泡剤、浸透剤、着色剤、蛍光増白剤、紫外線吸収剤、酸化防止剤、防腐剤及び防バイ剤等を挙げることができる。 The heat-sealing layer can contain conventionally known various additives, if necessary, in addition to the heat-sealable resins described above. Examples of additives include inorganic pigments, heat-sealing resins other than the above heat-sealing resins, various resins other than heat-sealing resins, polysaccharides such as starches and celluloses, surfactants, dispersants, and thickeners. agents, fluidity improvers, organic pigments, cationizing agents, lubricants, waterproofing agents, antifoaming agents, blowing agents, penetrating agents, coloring agents, fluorescent whitening agents, UV absorbers, antioxidants, preservatives and antiseptics. A binder etc. can be mentioned.
いくつかの実施態様において、ヒートシール層は、パラフィンワックスを含有する。この理由は、ヒートシール紙の透湿バリア性が良化するからである。少なくとも一つの実施態様において、ヒートシール層中のパラフィンワックスの含有量は、紙基材の片面あたりヒートシール層中のヒートシール性樹脂１００質量部に対して３質量部以上１５質量部以下である。この理由は、パラフィンワックスの含有量がこの範囲であると、ヒートシール紙のヒートシール性を阻害せずに透湿バリア性を良化することができるからである。
また、いくつかの実施態様において、ヒートシール層中のパラフィンワックスは、融点が５０℃以上である。少なくとも一つの実施態様において、ヒートシール層中のパラフィンワックスは、融点が５０℃以上８０℃以下である。これらの理由は、ヒートシール紙のヒートシール性を阻害せずに透湿バリア性が良化することができるからである。
In some embodiments, the heat seal layer contains paraffin wax. The reason for this is that the moisture permeability barrier property of the heat seal paper is improved. In at least one embodiment, the content of the paraffin wax in the heat seal layer is 3 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the heat sealable resin in the heat seal layer per one side of the paper substrate. . The reason for this is that when the content of the paraffin wax is within this range, the moisture permeability barrier property can be improved without impairing the heat sealability of the heat-sealable paper.
Also, in some embodiments, the paraffin wax in the heat seal layer has a melting point of 50° C. or higher. In at least one embodiment, the paraffin wax in the heat seal layer has a melting point of 50°C or higher and 80°C or lower. The reason for these is that the moisture permeability barrier property can be improved without impairing the heat sealability of the heat seal paper.
パラフィンワックスは、いわゆる石油ワックスに属し、石油精製において減圧蒸留留出油から分離及び精製して製造される。石油ワックスは、ＪＩＳ Ｋ２２３５：１９９１によって、パラフィンワックス、マイクロクリスタリンワックス、ペトロラタムの３種に大別される。同様に分離及び精製されるマイクロクリスタリンワックスが分子量５００～８００で炭素数３０～６０程度、大きい主鎖に側鎖を持つ分岐炭化水素（イソパラフィン）又は環状炭化水素（シクロパラフィン）が主成分であるのに対し、パラフィンワックスは、分子量が３００～５５０と狭く、直鎖状炭化水素が主成分で炭素数が大体２０～４０の範囲である。パラフィンワックスは、例えば、中京油脂社、日本精蝋社及びビックケミー・ジャパン社等から市販される。 Paraffin wax belongs to so-called petroleum waxes, and is produced by separating and refining from vacuum distilled oil in petroleum refining. According to JIS K2235:1991, petroleum waxes are roughly classified into three types: paraffin wax, microcrystalline wax, and petrolatum. Similarly, the microcrystalline wax separated and purified has a molecular weight of 500 to 800, a carbon number of about 30 to 60, and is mainly composed of branched hydrocarbons (isoparaffins) or cyclic hydrocarbons (cycloparaffins) having side chains on a large main chain. On the other hand, paraffin wax has a narrow molecular weight of 300 to 550 and is mainly composed of straight-chain hydrocarbons and has a carbon number in the range of about 20 to 40. Paraffin waxes are commercially available from, for example, Chukyo Yushi Co., Ltd., Nippon Seiro Co., Ltd., and BYK-Chemie Japan.
いくつかの実施態様において、ヒートシール層は、ヒートシール層を形成する乾燥固形分に対して上記ヒートシール性樹脂が８５質量％以上である。また、いくつかの実施態様において、ヒートシール層の塗工量は、紙基材の片面あたり乾燥固形分として５ｇ／ｍ２以上２５ｇ／ｍ２以下である。これらの理由は、ヒートシール性及び透湿バリア性が良化するからである。 In some embodiments, the heat-sealable layer contains 85% by mass or more of the heat-sealable resin with respect to the dry solid content forming the heat-sealable layer. In some embodiments, the coating amount of the heat seal layer is 5 g/m 2 or more and 25 g/m 2 or less as a dry solid content per side of the paper substrate. These reasons are because heat-sealing property and moisture-permeable barrier property improve.
ヒートシール紙の実施形態では、被包装物と対向するヒートシール紙の面がヒートシール紙のヒートシール層を有する側である。ヒートシール紙は、被包装物が食品等を包装した一次包装体であって、前記一次包装体を１つ又は２つ以上を包装する二次包装材料に好適である。 In the embodiment of the heat-sealable paper, the side of the heat-sealable paper facing the packaged item is the side having the heat-sealable layer of the heat-sealable paper. The heat-sealable paper is a primary packaging body in which the object to be packaged is food, etc., and is suitable as a secondary packaging material for packaging one or more of the primary packaging bodies.
紙基材は、木材パルプ及び／又は非木材パルプから成るスラリーに対して填料、サイズ剤、バインダー、定着剤、歩留り剤及び紙力剤等の各種添加剤を必要に応じて添加した紙料を、酸性、中性又はアルカリ性の条件で、従来公知の抄紙方法によって抄造した抄造紙、前記抄造紙をサイズプレス液でサイズプレス処理した原紙、前記抄造紙を表面処理液で表面処理した原紙、又は前記抄造紙若しくは前記原紙に対してカレンダー処理を施した普通紙である。上記紙料には、その他の添加剤として顔料分散剤、嵩高剤、増粘剤、流動性改良剤、ピッチコントロール剤、消泡剤、抑泡剤、離型剤、発泡剤、浸透剤、保湿剤、防腐剤、防バイ剤、耐水化剤、湿潤紙力増強剤及び乾燥紙力増強剤等から選ばれる一種又は二種以上を、本発明の所望の効果を損なわない範囲で、適宜添加することができる。
加えて紙基材は、例えば、前記抄造紙、前記原紙又は前記普通紙に塗工層を設けた塗工紙、クラフト紙、片艶紙及びトレーシングペーパー等を挙げることができる。
The paper base material is a paper material obtained by adding various additives such as fillers, sizing agents, binders, fixing agents, retention agents, and paper strength agents to a slurry composed of wood pulp and/or non-wood pulp as necessary. , paper made by a conventionally known papermaking method under acidic, neutral or alkaline conditions, base paper obtained by size-pressing the paper with a size press liquid, base paper obtained by surface-treating the paper with a surface treatment liquid, or It is a plain paper obtained by calendering the above paper or base paper. Other additives such as pigment dispersants, bulking agents, thickeners, fluidity improvers, pitch control agents, antifoaming agents, foam inhibitors, release agents, foaming agents, penetrating agents, moisturizing agents, and One or two or more selected from agents, preservatives, anti-baking agents, water resistance agents, wet paper strength agents, dry paper strength agents, etc. are added as appropriate to the extent that the desired effects of the present invention are not impaired. be able to.
In addition, examples of paper substrates include coated paper obtained by forming a coating layer on the above-mentioned paper, base paper, or plain paper, kraft paper, one-sided glossy paper, and tracing paper.
カレンダー処理とは、ロール間に紙を通すことによって平滑性及び厚みを平均化する処理である。カレンダー処理の装置は、例えば、マシンカレンダー、ソフトニップカレンダー、スーパーカレンダー、多段カレンダー、マルチニップカレンダー等を挙げることができる。 Calendering is a process in which smoothness and thickness are averaged by passing paper between rolls. Examples of calendering devices include machine calenders, soft nip calenders, super calenders, multi-stage calenders, and multi-nip calenders.
木材パルプは、製紙分野で従来公知のものである。木材パルプは、例えば、ＬＢＫＰ（Leaf Bleached Kraft Pulp）及びＮＢＫＰ（Needle Bleached Kraft Pulp）等の化学パルプ、ＧＰ（Groundwood Pulp）、ＰＧＷ（Pressure GroundWood pulp）、ＲＭＰ（Refiner Mechanical Pulp）、ＴＭＰ（ThermoMechanical Pulp）、ＣＴＭＰ（ChemiThermoMechanical Pulp）、ＣＭＰ（ChemiMechanical Pulp）及びＣＧＰ（ChemiGroundwood Pulp）等の機械パルプ、並びにＤＩＰ（DeInked Pulp）等の古紙パルプを挙げることができる。
非木材パルプは、製紙分野で従来公知の非木材繊維からなるパルプである。非木材繊維の原料は、例えば、コウゾ、ミツマタ及びガンピ等の木本靭皮、亜麻、***及びケナフ等の草本靭皮、マニラ麻、アバカ及びサイザル麻等の葉繊維、イネわら、ムギわら、サトウキビバカス、タケ及びエスパルト等の禾本科植物、並びにワタ及びリンター等の種毛を挙げることができる。
紙基材の木材パルプ及び／又は非木材パルプは、前記木材パルプ及び前記非木材パルプから成る群から選ばれる一種又は二種以上である。
Wood pulp is conventionally known in the papermaking arts. Wood pulp includes, for example, chemical pulps such as LBKP (Leaf Bleached Kraft Pulp) and NBKP (Needle Bleached Kraft Pulp), GP (Groundwood Pulp), PGW (Pressure GroundWood pulp), RMP (Refiner Mechanical Pulp), TMP (ThermoMechanical Pulp). ), CTMP (ChemiThermoMechanical Pulp), CMP (ChemiMechanical Pulp) and CGP (ChemiGroundwood Pulp), and waste paper pulp such as DIP (DeInked Pulp).
Non-wood pulp is pulp composed of non-wood fibers conventionally known in the paper industry. Raw materials for non-wood fibers include, for example, woody basts such as paper mulberry, mitsumata and gampi, herbaceous basts such as flax, hemp and kenaf, leaf fibers such as manila hemp, abaca and sisal hemp, rice straw, wheat straw, and sugarcane. Mention may be made of monocotyledonous plants such as bacchus, bamboo and esparto, and seed hairs such as cotton and linters.
The wood pulp and/or non-wood pulp of the paper substrate is one or more selected from the group consisting of the wood pulp and the non-wood pulp.
填料は、製紙分野で従来公知の顔料である。顔料は、例えば、軽質炭酸カルシウム、重質炭酸カルシウム、カオリン、タルク、硫酸バリウム、二酸化チタン、酸化亜鉛、硫化亜鉛、炭酸亜鉛、サチンホワイト、シリカ、珪酸アルミニウム、珪藻土、活性白土、アルミナ、アルミナ水和物、水酸化アルミニウム、リトポン、ゼオライト、炭酸マグネシウム及び水酸化マグネシウム等の無機顔料を挙げることができる。さらに、スチレン系プラスチックピグメント、アクリル系プラスチックピグメント、ポリエチレン系プラスチックピグメント、尿素樹脂、メラミン樹脂及びマイクロカプセル等の有機顔料を挙げることができる。
紙基材の填料は、前記無機顔料及び前記有機顔料から成る群から選ばれる一種又は二種以上である。
Fillers are pigments conventionally known in the papermaking arts. Pigments include, for example, light calcium carbonate, heavy calcium carbonate, kaolin, talc, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, silica, aluminum silicate, diatomaceous earth, activated clay, alumina, and alumina water. Inorganic pigments such as hydrates, aluminum hydroxide, lithopone, zeolites, magnesium carbonate and magnesium hydroxide may be mentioned. Furthermore, organic pigments such as styrene-based plastic pigments, acrylic-based plastic pigments, polyethylene-based plastic pigments, urea resins, melamine resins and microcapsules can be used.
The filler for the paper substrate is one or more selected from the group consisting of the inorganic pigments and the organic pigments.
いくつかの実施態様において、紙基材は、填料を実質的に含有しない。この理由は、ヒートシール紙の透湿バリア性が良化するからである。ここで、「填料を実質的に含有しない」とは、填料を含有することによって紙の透気性が増大する程の含有量未満を指す。例えば、填料は、紙基材中のパルプ１００質量部に対して０．５質量％未満である。 In some embodiments, the paper substrate is substantially free of fillers. The reason for this is that the moisture permeability barrier property of the heat seal paper is improved. Here, "substantially free of filler" refers to a content less than the amount of filler that increases the air permeability of the paper. For example, the filler is less than 0.5% by weight with respect to 100 parts by weight of pulp in the paper base.
いくつかの実施態様において、紙基材の灰分は３質量％以下である。この理由は、紙基材の灰分が３質量％以下であれば紙基材自身の透気性が抑えられて、得られるヒートシール紙の透湿バリア性に有利になるからである。紙基材の灰分は、ＩＳＯ１７６２：２００１「Ｐａｐｅｒ， ｂｏａｒｄ ａｎｄ ｐｕｌｐｓ － Ｄｅｔｅｒｍｉｎａｔｉｏｎ ｏｆ ｒｅｓｉｄｕｅ（ａｓｈ） ｏｎ ｉｇｎｉｔｉｏｎ ａｔ ５２５ ｄｅｇｒｅｅ Ｃ」に準拠して求められる値である。 In some embodiments, the paper substrate has an ash content of 3% by weight or less. The reason for this is that if the ash content of the paper base material is 3% by mass or less, the air permeability of the paper base material itself is suppressed, which is advantageous for the moisture permeability barrier property of the resulting heat-sealable paper. The ash content of the paper substrate is a value determined in accordance with ISO 1762:2001 "Paper, board and pulps - Determination of residue (ash) on ignition at 525 degree C".
サイズ剤は、製紙分野で従来公知の内添サイズ剤である。内添サイズ剤は、例えば、酸性紙であればロジン系サイズ剤、中性紙であればアルケニル無水コハク酸、アルキルケテンダイマー、中性ロジン系サイズ剤及びカチオン性スチレンアクリル系サイズ剤等を挙げることができる。
また、サイズプレス液に用いる表面サイズ剤は、製紙分野で従来公知のものである。表面サイズ剤は、例えば、澱粉系サイズ剤、セルロース系サイズ剤、ポリビニルアルコール系サイズ剤、スチレンアクリル系サイズ剤、オレフィン系サイズ剤、スチレンマレイン酸系サイズ剤、及びアクリルアミド系サイズ剤等を挙げることができる。
The sizing agent is an internal sizing agent conventionally known in the papermaking art. Examples of internal sizing agents include rosin-based sizing agents for acidic paper, and alkenyl succinic anhydride, alkylketene dimers, neutral rosin-based sizing agents, and cationic styrene-acrylic sizing agents for neutral paper. be able to.
Also, the surface sizing agent used in the size press liquid is conventionally known in the papermaking field. Examples of surface sizing agents include starch-based sizing agents, cellulose-based sizing agents, polyvinyl alcohol-based sizing agents, styrene-acrylic sizing agents, olefin-based sizing agents, styrene-maleic acid-based sizing agents, and acrylamide-based sizing agents. can be done.
サイズプレスは、製紙分野で従来公知のサイズプレス装置である。サイズプレス装置は、例えば、インクラインドサイズプレス、ホリゾンタルサイズプレス、フィルムトランスファー方式としてロッドメタリングサイズプレス、ロールメタリングサイズプレス、ブレードメタリングサイズプレスを、ロッドメタリングサイズプレスとしてシムサイザー、オプティサイザー、スピードサイザーを、ロールメタリングサイズプレスとしてゲートロールコーター、ビルブレードコーター、ツインブレードコーター、ベルバパコーター、タブサイズプレス、及びカレンダーサイズプレス等を挙げることができる。 A size press is a size press device conventionally known in the papermaking arts. The size press equipment includes, for example, an inclined size press, a horizontal size press, a rod metering size press, a roll metering size press, and a blade metering size press as film transfer methods, and a shim sizer, an optimizer, and a rod metering size press as rod metering size presses. A speed sizer, a roll metering size press such as a gate roll coater, a bill blade coater, a twin blade coater, a velvapa coater, a tab size press, a calender size press, and the like can be mentioned.
紙基材に対してヒートシール層を設ける方法、紙基材に対して下塗り層を設ける方法及び下塗り層に対してヒートシール層を設ける方法は、特に限定されない。設ける方法は、例えば、製紙分野で従来公知の塗工装置及び乾燥装置を用いてヒートシール層塗工液又は下塗り層塗工液を塗工及び乾燥する方法を挙げることができる。塗工装置の例としては、フィルムプレスコーター、ロッドコーター、エアーナイフコーター、ロッドブレードコーター、バーコーター、ブレードコーター、グラビアコーター、カーテンコーター、Ｅバーコーター、フィルムトランスファーコーター等を挙げることができる。乾燥装置の例としては、直線トンネル乾燥機、アーチドライヤー、エアループドライヤー、サインカーブエアフロートドライヤー等の熱風乾燥機、赤外線加熱ドライヤー、マイクロ波等を利用した乾燥機等の各種乾燥装置を挙げることができる。実験室における試作では、紙基材に対して下塗り層塗工液を、又は紙基材若しくは下塗り層に対してヒートシール層塗工液を、手塗用ワイヤーバーで塗工及び簡易熱風乾燥機で乾燥する方法を採用することができる。 The method of providing the heat-seal layer on the paper substrate, the method of providing the undercoat layer on the paper substrate, and the method of providing the heat-seal layer on the undercoat layer are not particularly limited. Examples of the method of providing include a method of applying and drying a heat seal layer coating liquid or an undercoat layer coating liquid using a conventionally known coating apparatus and drying apparatus in the field of paper manufacturing. Examples of coating equipment include film press coaters, rod coaters, air knife coaters, rod blade coaters, bar coaters, blade coaters, gravure coaters, curtain coaters, E bar coaters, and film transfer coaters. Examples of drying equipment include hot air dryers such as straight tunnel dryers, arch dryers, air loop dryers, sine curve air float dryers, infrared heating dryers, dryers using microwaves, etc. can be done. In the trial production in the laboratory, the undercoat layer coating liquid is applied to the paper base material, or the heat seal layer coating liquid is applied to the paper base material or undercoat layer with a wire bar for hand coating and a simple hot air dryer. A drying method can be adopted.
ヒートシール層塗工液がヒートシール性樹脂を含有すること並びに下塗り層塗工液が無機顔料及びバインダーを含有することによって、ヒートシール層がヒートシール性樹脂を含有並びに下塗り層が無機顔料及びバインダーを含有することができる。 The heat-sealing layer coating liquid contains a heat-sealing resin and the undercoat layer coating liquid contains an inorganic pigment and a binder, so that the heat-sealing layer contains the heat-sealing resin and the undercoat layer contains the inorganic pigment and binder. can contain
以下、実施例によって本発明をさらに詳細に説明する。なお、本発明は、これらの実施例に限定されない。ここで「質量部」及び「質量％」は、乾燥固形分量あるいは実質成分量の各々「質量部」及び「質量％」を表す。塗工層の塗工量は乾燥固形分量を表す。 The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Here, "parts by mass" and "% by mass" respectively represent "parts by mass" and "% by mass" of the amount of dry solids and the amount of substantial components. The coating amount of the coating layer represents the dry solid content.
＜紙基材＞
以下の紙料を調成した。
ＬＢＫＰ（濾水度３５０～４８０ｍｌｃｓｆ） ５０質量部
ＮＢＫＰ（濾水度３５０～４８０ｍｌｃｓｆ） ５０質量部
硫酸バンド １質量部
ロジン系サイズ剤（ＣＣ１４０４、星光ＰＭＣ社） ０．４質量部
紙力剤 ０．９質量部
<Paper substrate>
The following stock was prepared.
LBKP (freeness 350 to 480 mlcsf) 50 parts by mass NBKP (freeness 350 to 480 mlcsf) 50 parts by mass Aluminum sulfate 1 part by mass Rosin-based sizing agent (CC1404, Seiko PMC) 0.4 parts by mass Paper strength agent 0.4 parts by mass 9 parts by mass
上記配合の紙料を長網抄紙機で抄造し、表面サイズ剤として酸化澱粉をサイズプレスで片面当たり１ｇ／ｍ２付与して、坪量６５ｇ／ｍ２の原紙を得た。これに、マシンカレンダーを用いて温度６０℃・処理速度５００ｍ／分の条件でカレンダー処理して紙基材を得た。紙基材の灰分量は１．５質量％であった。 The stock having the above composition was made into paper by a Fourdrinier paper machine, and oxidized starch as a surface sizing agent was added by a size press in an amount of 1 g/m 2 per side to obtain a base paper having a basis weight of 65 g/m 2 . This was calendered using a machine calender at a temperature of 60° C. and a processing speed of 500 m/min to obtain a paper substrate. The ash content of the paper substrate was 1.5% by mass.
＜下塗り層塗工液＞
水を媒体として以下の下塗り層塗工液を調製した。
カオリン １００質量部
スチレンブタジエン系共重合樹脂 １５０質量部
<Undercoat layer coating solution>
Using water as a medium, the following undercoat layer coating solution was prepared.
Kaolin 100 parts by mass Styrene-butadiene copolymer resin 150 parts by mass
＜ヒートシール層塗工液＞
水を媒体として以下のヒートシール層塗工液を調製した。
ヒートシール性樹脂 単量体組成は表１及び２に記載／１００質量部
パラフィンワックス（ＰＷ） 配合部数は表１及び２に記載
<Heat seal layer coating solution>
Using water as a medium, the following heat seal layer coating solution was prepared.
Heat-sealing resin Monomer composition is shown in Tables 1 and 2/100 parts by mass Paraffin wax (PW) Blending parts are shown in Tables 1 and 2
各樹脂は、表１及び２に記載する各単量体を含む単量体組成物から乳化重合して調製した。 Each resin was prepared by emulsion polymerization from a monomer composition containing each monomer described in Tables 1 and 2.
＜下塗り層＞
下塗り層を設ける場合では、紙基材の片面に対して、下塗り層塗工液をエアーナイフコーターで塗工及び熱風乾燥機で乾燥した。下塗り層の塗工量は、１０ｇ／ｍ２になるようにコーター条件を調整した。
<Undercoat layer>
When providing an undercoat layer, the undercoat layer coating solution was applied to one side of the paper substrate with an air knife coater and dried with a hot air dryer. The coater conditions were adjusted so that the coating amount of the undercoat layer was 10 g/m 2 .
＜ヒートシール層＞
下塗り層を有しない場合では紙基材の片面に対して、下塗り層を有する場合では下塗り層に対して、ヒートシール層塗工液をロッドコーターで塗工及び熱風乾燥機で乾燥した。ヒートシール層の塗工量は、１０ｇ／ｍ２になるようコーター条件を調整した。
<Heat seal layer>
The heat-sealing layer coating solution was applied with a rod coater to one side of the paper base material in the case of having no undercoat layer, and to the undercoat layer in the case of having an undercoat layer, and dried with a hot air dryer. The coater conditions were adjusted so that the coating amount of the heat seal layer was 10 g/m 2 .
紙基材に対してヒートシール層を設けたヒートシール紙について、下記項目の評価を行った。 The following items were evaluated for the heat-sealable paper in which the heat-sealable layer was provided on the paper substrate.
＜透湿バリア性＞
透湿バリア性の評価は、ＪＩＳ Ｚ０２０８：１９７６「防湿包装材料の透湿度試験方法（カップ法）」に準じて実施した水蒸気の透湿度に関する測定結果から行った。測定は、ヒートシール層を有する側を内側にして測定した。温湿度の条件は、４０±０．５℃，９０±２％とした。本発明において、ヒートシール紙は、Ａ、Ｂ、Ｃ又はＤの評価であれば透湿バリア性を有するものとする。
Ａ：透湿度７ｇ／ｍ２・２４ｈ以下。
Ｂ：上記Ａより劣るものの、透湿度１５ｇ／ｍ２・２４ｈ以下。
Ｃ：上記Ｂより劣るものの、透湿度２５ｇ／ｍ２・２４ｈ以下。
Ｄ：上記Ｃより劣るものの、透湿度５０ｇ／ｍ２・２４ｈ以下。
Ｅ：上記Ｄより劣るものの、透湿度８０ｇ／ｍ２・２４ｈ以下。
Ｆ：上記Ｅより劣り、透湿度８０ｇ／ｍ２・２４ｈ超。
<Moisture permeability barrier>
The moisture permeability barrier property was evaluated from the results of measurement of water vapor permeability according to JIS Z0208:1976 "Method for testing moisture permeability of moisture-proof packaging materials (cup method)". The measurement was performed with the side having the heat seal layer facing inside. The temperature and humidity conditions were 40±0.5° C. and 90±2%. In the present invention, if the heat seal paper is evaluated as A, B, C or D, it is assumed to have moisture permeability barrier properties.
A: Moisture permeability of 7 g/m 2 ·24 h or less.
B: Poorer than A above, but moisture permeability of 15 g/m 2 ·24 h or less.
C: Poorer than B above, but moisture permeability of 25 g/m 2 ·24 h or less.
D: Poorer than C above, but moisture permeability of 50 g/m 2 ·24 h or less.
E: Poorer than D above, but moisture permeability of 80 g/m 2 ·24 h or less.
F: Inferior to E above, moisture permeability exceeding 80 g/m 2 ·24 h.
＜ヒートシール性＞
同じ構成の２枚のヒートシール紙を用いて、ヒートシール紙のヒートシール層を有する側の面どうしを対向させてヒートシーラーにより圧力０．５ＭＰａ、１３０℃、１秒間の条件によってヒートシールを施した。
ヒートシールしたヒートシール紙を１５ｍｍ幅で切り出し、温度２３℃、相対湿度５０％で２４時間静置後、引張り試験機を用い、引張り速度３００ｍｍ／分、引張り角度１８０度でヒートシール箇所の剥離強度を測定することによってヒートシール性を評価した。測定は、サンプル数５部で行い、５部の平均値とした。測定値から、ヒートシール性を下記の基準で評価した。本発明において、ヒートシール紙は、評価Ａ、Ｂ又はＣであればヒートシール性を有するものとする。
Ａ：値が、６Ｎ／１５ｍｍ以上。
Ｂ：値が、４Ｎ／１５ｍｍ以上６Ｎ／１５ｍｍ未満。
Ｃ：値が、２Ｎ／１５ｍｍ以上４Ｎ／１５ｍｍ未満。
Ｄ：値が、２Ｎ／１５ｍｍ未満。
<Heat sealability>
Using two sheets of heat-sealing paper having the same structure, the surfaces of the heat-sealing paper having the heat-sealing layer are opposed to each other, and heat-sealed with a heat sealer under the conditions of a pressure of 0.5 MPa, 130° C., and 1 second. bottom.
Cut out the heat-sealed heat-sealed paper to a width of 15 mm, leave it at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, then use a tensile tester to measure the peel strength at the heat-sealed portion at a tensile speed of 300 mm / min and a tensile angle of 180 degrees. The heat-sealability was evaluated by measuring the The measurement was performed with 5 samples, and the average value of the 5 samples was taken. From the measured values, the heat sealability was evaluated according to the following criteria. In the present invention, if the heat-sealable paper is rated A, B or C, it is assumed to have heat-sealable properties.
A: The value is 6N/15mm or more.
B: The value is 4N/15mm or more and less than 6N/15mm.
C: The value is 2 N/15 mm or more and less than 4 N/15 mm.
D: The value is less than 2N/15mm.
評価結果を表１及び２に示す。 Evaluation results are shown in Tables 1 and 2.
表１及び２から、本発明のヒートシール紙に該当する実施例１～２２は、ヒートシール性及び透湿バリア性を有すると分かる。一方、本発明のヒートシール紙の構成を満足しない比較例１～３は、ヒートシール性及び／又は透湿バリア性を満足できないと分かる。 From Tables 1 and 2, it can be seen that Examples 1 to 22, which correspond to the heat-sealable papers of the present invention, have heat-sealing properties and moisture-permeable barrier properties. On the other hand, Comparative Examples 1 to 3, which do not satisfy the constitution of the heat-sealable paper of the present invention, cannot satisfy the heat-sealing property and/or the moisture-permeable barrier property.
主に、実施例２、３、４、７、８、１１、１２、１５及び１６と実施例１、５、６、９、１０、１３、１４及び１７との対比から、ヒートシール性樹脂の単量体組成が、（Ａ）メチルメタクリレート：２６質量％以上４６質量％以下、（Ｂ）２－エチルヘキシルアクリレート：２３質量％以上４３質量％以下、（Ｃ）ブチルアクリレート：１３質量％以上４５質量％以下及び（Ｄ）スチレン：３質量％以上１６質量％以下の範囲であると、ヒートシール紙は、ヒートシール性及び／又は透湿バリア性が良化すると分かる。 Mainly from the comparison between Examples 2, 3, 4, 7, 8, 11, 12, 15 and 16 and Examples 1, 5, 6, 9, 10, 13, 14 and 17, the heat-sealing resin The monomer composition is (A) methyl methacrylate: 26% by mass or more and 46% by mass or less, (B) 2-ethylhexyl acrylate: 23% by mass or more and 43% by mass or less, (C) butyl acrylate: 13% by mass or more and 45% by mass. % or less and (D) styrene: in the range of 3% to 16% by mass, the heat-sealable paper has improved heat-sealing properties and/or moisture-permeable barrier properties.
主に、実施例３と実施例１８との対比から、ヒートシール層がパラフィンワックスを含有すると、ヒートシール紙は、透湿バリア性が良化すると分かる。 Mainly from the comparison between Example 3 and Example 18, it can be seen that the moisture permeability barrier property of the heat seal paper is improved when the heat seal layer contains paraffin wax.
主に、実施例３と実施例１９との対比から、板状無機顔料及び熱可塑性樹脂を含有する下塗り層を有すると、ヒートシール紙は、透湿バリア性及びヒートシール性が良化すると分かる。 Mainly from the comparison between Example 3 and Example 19, it can be seen that the heat-sealable paper has improved moisture permeability barrier properties and heat-sealability when it has an undercoat layer containing a plate-like inorganic pigment and a thermoplastic resin. .
Claims (4)
単量体：
（Ａ）メチルメタクリレート
（Ｂ）２－エチルヘキシルアクリレート
（Ｃ）ブチルアクリレート
（Ｄ）スチレン A paper substrate and a heat-sealing layer containing a heat-sealing resin on at least one side of the paper substrate, wherein the heat-sealing resin is an acrylic resin obtained by polymerizing the following monomers: some heat seal paper.
Monomer:
(A) methyl methacrylate (B) 2-ethylhexyl acrylate (C) butyl acrylate (D) styrene
単量体組成：
（Ａ）メチルメタクリレート：２６質量％以上４６質量％以下
（Ｂ）２－エチルヘキシルアクリレート：２３質量％以上４３質量％以下
（Ｃ）ブチルアクリレート：１３質量％以上４５質量％以下
（Ｄ）スチレン：３質量％以上１６質量％以下 2. The heat-sealable paper according to claim 1, wherein the acrylic resin is obtained by polymerizing the following monomers, and each monomer composition of the resin is within the following mass % range.
Monomer composition:
(A) Methyl methacrylate: 26% by mass or more and 46% by mass or less (B) 2-ethylhexyl acrylate: 23% by mass or more and 43% by mass or less (C) Butyl acrylate: 13% by mass or more and 45% by mass or less (D) Styrene: 3 % by mass or more and 16% by mass or less
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022006883A JP2023105881A (en) | 2022-01-20 | 2022-01-20 | Heat-sealable paper |
| DE102023100601.0A DE102023100601A1 (en) | 2022-01-20 | 2023-01-12 | HEAT SEAL PAPER |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2022006883A JP2023105881A (en) | 2022-01-20 | 2022-01-20 | Heat-sealable paper |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2020163675A (en) | 2019-03-29 | 2020-10-08 | 日本製紙株式会社 | Paper-made barrier material |
| JP2021070171A (en) | 2019-10-29 | 2021-05-06 | 日本製紙株式会社 | Heat seal paper |
| JP2021138434A (en) | 2020-03-09 | 2021-09-16 | 北越コーポレーション株式会社 | Packaging paper |
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