JP2017100370A - Laminate and method for manufacturing the same - Google Patents

Laminate and method for manufacturing the same Download PDF

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JP2017100370A
JP2017100370A JP2015235855A JP2015235855A JP2017100370A JP 2017100370 A JP2017100370 A JP 2017100370A JP 2015235855 A JP2015235855 A JP 2015235855A JP 2015235855 A JP2015235855 A JP 2015235855A JP 2017100370 A JP2017100370 A JP 2017100370A
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base material
atmospheric pressure
material sheet
pressure plasma
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JP6748420B2 (en
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俊逸 米内山
Shunitsu Yoneuchiyama
俊逸 米内山
植松　武彦
Takehiko Uematsu
武彦 植松
後藤　実
Minoru Goto
実 後藤
祥悟 千葉
Shogo Chiba
祥悟 千葉
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Kao Corp
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Abstract

PROBLEM TO BE SOLVED: To provide a laminate which is flexible, is excellent in air permeability, and reduces a load on the environment.SOLUTION: A laminate has a laminated structure formed by directly joining a first substrate and a second substrate that have different kinds and have sheet shapes, the first substrate is a film mainly containing a thermoplastic resin or a nonwoven fabric, and the second substrate is a fiber assembly mainly containing a cellulose-based resin. A method for manufacturing a laminate includes: an atomospheric plasma treatment step of subjecting one surface of a rolled sheet for a first substrate to atomospheric plasma treatment of bringing atomospheric plasma generated by a plasma device using gas for treatment under atomospheric pressure into contact with the one surface; and an integration step of overlapping a rolled sheet for a second substrate on one surface of the rolled sheet for the first substrate subjected to the atomospheric plasma treatment, heating and pressurizing the overlapped body, and integrating both of the sheets.SELECTED DRAWING: None

Description

本発明は、水に対する親和性が異なる異種材料どうしの積層体に関する。   The present invention relates to a laminate of different materials having different affinity for water.

従来、包装材料等の種々の用途において、各種材料からなる複数の基材どうしを積層一体化してなる積層体が利用されている。例えば、包装材料用積層体としては、ポリアミド樹脂フィルムとポリエチレン樹脂フィルムとの積層体のような、疎水性樹脂どうしの積層体が多用されている。このような積層体における層間の接合には、ホットメルト型接着剤のような化学系接着剤が用いられる場合が多い。しかし、接着剤の使用は、環境対策や省エネルギー対策の点で問題がある。また、接着剤が塗布された部分は、比較的硬く、さらには通気性が低いため、例えば衛生品の如き、柔軟性や通気性の高さが要求される用途では、接着剤を用いずに、必要とされる接合強度を有する積層体を製造し得る技術が要望されている。   Conventionally, in various applications such as packaging materials, a laminate formed by laminating and integrating a plurality of base materials made of various materials has been used. For example, as a laminate for packaging material, a laminate of hydrophobic resins such as a laminate of a polyamide resin film and a polyethylene resin film is frequently used. In many cases, a chemical adhesive such as a hot-melt adhesive is used for joining the layers in such a laminate. However, the use of adhesives has problems in terms of environmental measures and energy saving measures. In addition, since the part where the adhesive is applied is relatively hard and has a low air permeability, for example in sanitary products where flexibility and high air permeability are required, an adhesive is not used. Therefore, there is a demand for a technique capable of producing a laminated body having a required bonding strength.

このような要望に対して、熱可塑性樹脂からなる材料どうしの積層体の製造において、プラズマ処理を用いて層間の接合を行うことが提案されている。
例えば特許文献１には、アラミド繊維を湿式抄紙してなるアラミド紙とポリエチレンテレフタレート製樹脂フィルムとを接着剤無しで接合する方法として、アラミド紙の表面に対して低温プラズマ処理を施して該表面の改質を行う方法が記載されている。
また特許文献２には、熱可塑性樹脂フィルムからなる第１基材の両面に、該第１基材用原反シートと異なる種類の熱可塑性樹脂フィルムであってヒートシール性を有する第２基材用原反シートを接合してなる包装材料積層体の製造方法において、両基材用原反シートの接合に大気圧プラズマ処理を用いることが記載されている。 In response to such demands, it has been proposed to perform interlayer bonding using plasma treatment in the manufacture of a laminate of materials made of thermoplastic resin.
For example, in Patent Document 1, as a method of joining aramid paper formed by wet papermaking of aramid fibers and a polyethylene terephthalate resin film without using an adhesive, the surface of the aramid paper is subjected to low-temperature plasma treatment. A method of modifying is described.
Further, Patent Document 2 discloses a second base material that is a thermoplastic resin film of a type different from the first base material sheet on both surfaces of a first base material made of a thermoplastic resin film and has heat sealability. In the manufacturing method of the packaging material laminated body formed by joining the original fabric sheets for use, it is described that atmospheric pressure plasma treatment is used for joining the original fabric sheets for both substrates.

特開２００９−１３８３１２号公報JP 2009-138312 A 特開２０１１−１４３５８６号公報JP 2011-143586 A

使い捨ておむつ等の衛生品においては、例えば、ポリエチレン等の疎水性樹脂製フィルムからなる構成部材（例えば防漏材）と親水性であるセルロース繊維を主体とする構成部材（例えば吸水性ポリマー等の吸収性材料を包む台紙）とからなる積層体の如き、水に対する親和性が異なる異種材料どうしの積層体が用いられている。このような異種材料の積層体には、柔軟性や通気性の確保等の観点から、層間の接合を接着剤無しで行うことが要望されているが、斯かる要望に十分に応え得る技術は未だ提供されていない。   In sanitary goods such as disposable diapers, for example, a component made of a hydrophobic resin film such as polyethylene (for example, a leak-proof material) and a component mainly composed of hydrophilic cellulose fibers (for example, absorption of a water-absorbing polymer or the like) For example, a laminate of different materials having different affinity for water is used, such as a laminate made of a base material that wraps a functional material. In such a laminate of different materials, it is demanded to perform interlayer bonding without an adhesive from the viewpoint of ensuring flexibility and air permeability, etc., but a technology that can sufficiently meet such a demand is provided. Not yet provided.

本発明の課題は、柔軟で通気性に優れ、且つ環境に対する負荷が低減されている積層体を提供することに関する。   The subject of this invention is related with providing the laminated body which is flexible, excellent in air permeability, and the load with respect to the environment is reduced.

本発明は、互いに異種のシート状の第１基材と第２基材とが直接接合されてなる積層構造を有し、前記第１基材は、熱可塑性樹脂を主体とするフィルム又は不織布であり、前記第２基材は、セルロース系繊維を主体とする繊維集合体である積層体である。   The present invention has a laminated structure in which a sheet-like first base material and a second base material, which are different from each other, are directly joined, and the first base material is a film or nonwoven fabric mainly composed of a thermoplastic resin. In addition, the second base material is a laminate that is a fiber assembly mainly composed of cellulosic fibers.

また本発明は、第１基材用原反シートの片面に、処理用ガスを用いてプラズマ装置により大気圧下で生成した大気圧プラズマを接触させる大気圧プラズマ処理を施す大気圧プラズマ処理工程と、前記大気圧プラズマ処理が施された前記第１基材用原反シートの片面に第２基材用原反シートを重ね合わせ、その重ね合わせ体を加熱加圧して両シートを一体化する一体化工程とを有する積層体の製造方法である。   The present invention also includes an atmospheric pressure plasma treatment step of performing an atmospheric pressure plasma treatment in which one side of the first base material sheet is brought into contact with atmospheric pressure plasma generated at atmospheric pressure by a plasma apparatus using a treatment gas. Integrating the second base material sheet on one side of the first base material sheet that has been subjected to the atmospheric pressure plasma treatment, and heating and pressing the superposed body to integrate the two sheets It is a manufacturing method of the laminated body which has a formation process.

本発明によれば、柔軟で通気性に優れ、且つ環境に対する負荷が低減されている積層体が提供される。   ADVANTAGE OF THE INVENTION According to this invention, the laminated body which is flexible, is excellent in air permeability, and the load with respect to the environment is reduced is provided.

図１は、本発明の積層体の製造方法における大気圧プラズマ処理工程の一実施態様の概略図である。FIG. 1 is a schematic view of one embodiment of an atmospheric pressure plasma treatment step in the method for producing a laminate of the present invention.

本発明の積層体は、互いに異種のシート状の第１基材と第２基材とが直接接合されてなる積層構造を有する。ここでいう「互いに異種」とは、主として、第１基材及び第２基材それぞれの主成分どうし（即ち、熱可塑性樹脂、セルロース系繊維）の比較からも明らかなように、第１基材と第２基材とで基本特性が全く異なることを意味し、特許文件１及び２に記載されているような、同種又は異種の熱可塑性樹脂どうしの接合は含まない。この「基本特性」としては、具体的には例えば「水に対する親和性」が挙げられる。即ち、熱可塑性樹脂を主体とする第１基材は、基本的に疎水性であるのに対し、セルロース系繊維を主体とする第２基材は、基本的に親水性であり、両基材は水に対する親和性が異なり、それ故に互いに異種である。   The laminated body of the present invention has a laminated structure in which different types of sheet-like first base material and second base material are directly joined. As used herein, the term “different from each other” mainly refers to the first base material, as is clear from the comparison of the main components of the first base material and the second base material (that is, thermoplastic resin and cellulosic fiber). This means that the basic characteristics are completely different between the second base material and the joining of the same or different thermoplastic resins as described in Patent Documents 1 and 2 is not included. Specific examples of the “basic characteristics” include “affinity with water”. That is, the first base material mainly composed of thermoplastic resin is basically hydrophobic, whereas the second base material mainly composed of cellulosic fibers is basically hydrophilic, and both base materials Have different affinities for water and are therefore different from each other.

本発明に係る第１基材は、熱可塑性樹脂を主体とするフィルム又は不織布である。ここでいう「熱可塑性樹脂を主体とする」とは、第１基材における熱可塑性樹脂の含有量が５０質量％以上である場合を意味する。第１基材における熱可塑性樹脂の含有量は、好ましくは６５質量％以上、さらに好ましくは７０質量％以上であり、１００質量％でも良い。熱可塑性樹脂としては、衛生品や包装材料をはじめとする各種用途に用いられているものを特に制限なく用いることができ、例えば、ポリエチレン（略してＰＥ）、ポリプロピレン（略してＰＰ）等のポリオレフィン系樹脂；ポリエチレンテレフタレート（略してＰＥＴ）、ポリブチレンテレフタレート（略してＰＢＴ）、ポリ乳酸系樹脂等のポリエステル系樹脂；ナイロン６等のポリアミド系樹脂；ポリアクリル酸エチル等のポリアクリル系樹脂；ポリ塩化ビニル系樹脂；ポリウレタン系樹脂；セルロース誘導体系樹脂等が挙げられ、これらの１種を単独で又は２種以上を組み合わせて用いることができる。これらの熱可塑性樹脂の中でも特に、ガラス転移温度が一般に１００℃以下という観点から、ポリオレフィン系樹脂及びポリエステル系樹脂が好ましい。   The first substrate according to the present invention is a film or nonwoven fabric mainly composed of a thermoplastic resin. Here, “mainly composed of a thermoplastic resin” means that the content of the thermoplastic resin in the first base material is 50% by mass or more. The content of the thermoplastic resin in the first substrate is preferably 65% by mass or more, more preferably 70% by mass or more, and may be 100% by mass. As the thermoplastic resin, those used in various applications including sanitary goods and packaging materials can be used without any particular limitation. For example, polyolefins such as polyethylene (abbreviated PE) and polypropylene (abbreviated PP) Polyester resins such as polyethylene terephthalate (abbreviated PET), polybutylene terephthalate (abbreviated PBT) and polylactic acid resins; polyamide resins such as nylon 6; polyacrylic resins such as ethyl polyacrylate; Examples thereof include a vinyl chloride resin; a polyurethane resin; a cellulose derivative resin, and the like. These can be used alone or in combination of two or more. Among these thermoplastic resins, polyolefin resins and polyester resins are preferred from the viewpoint that the glass transition temperature is generally 100 ° C. or lower.

熱可塑性樹脂を主体とするフィルム（即ち第１基材）は、典型的には、樹脂又は樹脂組成物の膜状物であって貫通孔の無い無孔平坦な形状のものであるが、特にこれに限定されず、熱可塑性樹脂フィルムとして種々の用途で使用されているものを特に制限なく用いることができる。具体的には例えば、低密度ＰＥフィルム、二軸延伸ＰＥＴフィルム等が挙げられる。フィルムの厚みは特に制限されず、積層体の用途等に応じて適宜設定すれば良い。例えば、積層体の用途が使い捨ておむつの防漏材である場合、第１基材としてのフィルムの厚みは、好ましくは０．５μｍ以上、さらに好ましくは５μｍ以上、そして、好ましくは５０μｍ以下、さらに好ましくは３０μｍ以下である。   A film mainly composed of a thermoplastic resin (that is, the first base material) is typically a film of a resin or a resin composition and has a non-porous flat shape having no through holes. It is not limited to this, What is used for various uses as a thermoplastic resin film can be especially used without a restriction | limiting. Specific examples include a low-density PE film and a biaxially stretched PET film. The thickness in particular of a film is not restrict | limited, What is necessary is just to set suitably according to the use etc. of a laminated body. For example, when the use of the laminate is a leakproof material for disposable diapers, the thickness of the film as the first substrate is preferably 0.5 μm or more, more preferably 5 μm or more, and preferably 50 μm or less, more preferably Is 30 μm or less.

熱可塑性樹脂を主体とする不織布（即ち第１基材）は、典型的には、熱可塑性樹脂繊維からなる不織布である。不織布の種類は特に制限されず、例えば、スパンボンド不織布、スパンレース不織布、メルトブローン不織布、エアスルー不織布、サーマルボンド不織布、ニードルパンチ不織布等の各種製法による不織布を用いることができ、あるいは２種以上の不織布の積層体、例えば、スパンボンド−メルトブローン−スパンボンド（略してＳＭＳ）不織布を用いることもできる。但し、エアスルー不織布、サーマルボンド不織布、ニードルパンチ不織布については、水洗又は湯洗をし、繊維表面より工程油剤が除去されているものを用いた方が良い。第１基材としての不織布の坪量は特に制限されず、積層体の用途等に応じて適宜設定すれば良い。例えば、積層体の用途が使い捨ておむつの防漏材である場合、第１基材としての不織布の坪量は、好ましくは３ｇ／ｍ2 以上、さらに好ましくは５ｇ／ｍ2 以上、そして、好ましくは７０ｇ／ｍ2 以下、さらに好ましくは２５ｇ／ｍ2 以下である。 The nonwoven fabric (that is, the first base material) mainly composed of a thermoplastic resin is typically a nonwoven fabric made of thermoplastic resin fibers. The type of the nonwoven fabric is not particularly limited. For example, a nonwoven fabric produced by various production methods such as a spunbond nonwoven fabric, a spunlace nonwoven fabric, a meltblown nonwoven fabric, an air-through nonwoven fabric, a thermal bond nonwoven fabric, a needle punch nonwoven fabric, or two or more types of nonwoven fabrics can be used. For example, a spunbond-meltblown-spunbond (abbreviated as SMS) nonwoven fabric can be used. However, about an air through nonwoven fabric, a thermal bond nonwoven fabric, and a needle punch nonwoven fabric, it is better to use what wash | cleaned with water or hot water, and the process oil agent was removed from the fiber surface. The basis weight of the nonwoven fabric as the first substrate is not particularly limited, and may be set as appropriate according to the use of the laminate. For example, when the use of the laminate is a leakproof material for disposable diapers, the basis weight of the nonwoven fabric as the first substrate is preferably 3 g / m 2 or more, more preferably 5 g / m 2 or more, and preferably It is 70 g / m 2 or less, more preferably 25 g / m 2 or less.

熱可塑性樹脂を主体とする不織布（即ち第１基材）の構成繊維としては、１種類の熱可塑性樹脂からなる単一繊維でも良く、融点の異なる２種類以上の熱可塑性樹脂を含む複合繊維でも良い。複合繊維としては、相対的に融点の低い樹脂（即ち低融点樹脂）を鞘部、相対的に融点の高い樹脂（即ち高融点樹脂）を芯部とした芯鞘型；低融点樹脂と高融点樹脂とが所定方向に並列したサイドバイサイド型等が挙げられ、本発明では何れも使用できる。具体的には例えば、ＰＥＴを芯部、ＰＥを鞘部とする芯鞘型複合繊維が挙げられる。不織布の構成繊維の平均繊維径は、特に制限されないが、通常０．１〜３０μｍの範囲である。   The constituent fiber of the nonwoven fabric (ie, the first substrate) mainly composed of thermoplastic resin may be a single fiber made of one kind of thermoplastic resin, or a composite fiber containing two or more kinds of thermoplastic resins having different melting points. good. As the composite fiber, a core-sheath type in which a resin having a relatively low melting point (that is, a low melting point resin) is used as a sheath part and a resin having a relatively high melting point (that is, a high melting point resin) is used as a core part; Examples include a side-by-side type in which a resin is aligned in a predetermined direction, and any of them can be used in the present invention. Specifically, for example, a core-sheath type composite fiber having PET as a core part and PE as a sheath part may be mentioned. The average fiber diameter of the constituent fibers of the nonwoven fabric is not particularly limited, but is usually in the range of 0.1 to 30 μm.

一方、本発明に係る第２基材は、セルロース系繊維を主体とする繊維集合体である。繊維集合体は、セルロース系繊維の如き繊維材料を積繊してなる繊維集合体であり、繊維集合体においては通常、各繊維材料が本来有する繊維形状（又は紐状）が実質的に維持されており多数の繊維間空隙を有している。ここでいう「セルロース系繊維を主体とする」とは、第２基材におけるセルロース系繊維の含有量が５０質量％以上である場合を意味する。第２基材におけるセルロース系繊維の含有量は、好ましくは６５質量％以上、さらに好ましくは７０質量％以上であり、１００質量％でも良い。   On the other hand, the second substrate according to the present invention is a fiber assembly mainly composed of cellulosic fibers. The fiber aggregate is a fiber aggregate obtained by stacking fiber materials such as cellulosic fibers. In the fiber aggregate, the fiber shape (or string shape) inherent to each fiber material is generally substantially maintained. And has many interfiber spaces. Here, “mainly composed of cellulosic fibers” means that the content of cellulosic fibers in the second substrate is 50% by mass or more. The content of cellulosic fibers in the second substrate is preferably 65% by mass or more, more preferably 70% by mass or more, and may be 100% by mass.

セルロース系繊維としては、衛生品をはじめとする各種用途に用いられているものを特に制限なく用いることができ、例えば、天然セルロース繊維、マーセル化セルロース繊維、溶解セルロース繊維及びセルロース繊維誘導体が挙げられ、これらの１種を単独で又は２種以上を組み合わせて用いることができる。天然セルロース繊維としては、例えば、針葉樹パルプ、広葉樹パルプ等の木材パルプ；コットンリンター、コットンリント等の綿パルプ；麦わらパルプ、バガスパルプ、麻パルプ等の非木材パルプ；古紙パルプ等が挙げられる。マーセル化セルロース繊維は、周知の通り、濃アルカリ処理によってアルカリ変性（いわゆるマーセル化）されているセルロース繊維である。溶解セルロース繊維としては、例えば、リヨセル（登録商標）、テンセル（登録商標）、ベンベルグ（登録商標）、ビスコースレーヨン、ベンリーゼ（登録商標）等が挙げられる。セルロース繊維誘導体としては、例えば、カルボキシメチルセルロース、カルボキシエチルセルロース、ＴＥＭＰＯ触媒酸化セルロース、メチルセルロース、エチルセルロース等が挙げられる。   As the cellulosic fibers, those used in various applications including sanitary products can be used without particular limitation, and examples thereof include natural cellulose fibers, mercerized cellulose fibers, dissolved cellulose fibers, and cellulose fiber derivatives. These 1 type can be used individually or in combination of 2 or more types. Examples of natural cellulose fibers include wood pulp such as softwood pulp and hardwood pulp; cotton pulp such as cotton linter and cotton lint; non-wood pulp such as straw pulp, bagasse pulp and hemp pulp; waste paper pulp and the like. As is well known, mercerized cellulose fibers are cellulose fibers that have been alkali-modified (so-called mercerized) by concentrated alkali treatment. Examples of the dissolved cellulose fiber include lyocell (registered trademark), tencel (registered trademark), Bemberg (registered trademark), viscose rayon, and Benlyse (registered trademark). Examples of the cellulose fiber derivative include carboxymethyl cellulose, carboxyethyl cellulose, TEMPO-catalyzed oxidized cellulose, methyl cellulose, ethyl cellulose and the like.

本発明に係る第２基材は、典型的には、公知の湿式抄紙法によって製造された紙、又は不織布である。第２基材としての紙又は不織布の坪量は特に制限されず、積層体の用途等に応じて適宜設定すれば良い。例えば、積層体の用途が使い捨ておむつの防漏材である場合、第２基材としての紙又は不織布の坪量は、好ましくは１０ｇ／ｍ2 以上、さらに好ましくは１２ｇ／ｍ2 以上、そして、好ましくは５０ｇ／ｍ2 以下、さらに好ましくは３０ｇ／ｍ2 以下である。 The second substrate according to the present invention is typically paper or non-woven fabric produced by a known wet papermaking method. The basis weight of the paper or nonwoven fabric as the second base material is not particularly limited, and may be set as appropriate according to the use of the laminate. For example, when the use of the laminate is a leakproof material for disposable diapers, the basis weight of the paper or nonwoven fabric as the second substrate is preferably 10 g / m 2 or more, more preferably 12 g / m 2 or more, and Preferably it is 50 g / m 2 or less, more preferably 30 g / m 2 or less.

本発明の積層体の主たる特徴の１つとして、互いに異種の第１基材と第２基材とが直接接合されている点が挙げられる。本発明でいう「直接接合」とは、第１基材と第２基材とが、接着成分を介さずに直に重なり合って互いに接合されている状態を意味する。また、ここでいう「接着成分」には、両基材とは別体の接着剤、及び、両基材に含有されている成分で加熱により接着成分となり得る物質（典型的には第１基材の熱可塑性樹脂）が含まれる。従って、本発明でいう「直接接合」には、ｉ）第１基材と第２基材とが接着剤を介して互いに接合されている形態、及びｉｉ）両基材の何れか一方又は両方（通常は熱可塑性樹脂を主体とする第１基材）が加熱により熱融着性を帯びることに起因して両基材が互いに接合されている形態（いわゆる熱融着）は含まれない。   One of the main features of the laminate of the present invention is that the first and second substrates different from each other are directly joined. The term “direct bonding” as used in the present invention means a state in which the first base material and the second base material are directly overlapped and joined to each other without using an adhesive component. In addition, the “adhesive component” referred to herein includes an adhesive separate from both base materials, and a substance (typically the first group) that can be converted into an adhesive component by heating with components contained in both base materials. Material thermoplastic resin). Therefore, in the “direct bonding” in the present invention, i) a form in which the first substrate and the second substrate are bonded to each other through an adhesive, and ii) either one or both of the substrates. It does not include a form (so-called heat fusion) in which both base materials are joined to each other due to the fact that (usually the first base material mainly composed of a thermoplastic resin) is heat-fusible by heating.

このような、第１基材と第２基材との接着成分を介さない「直接接合」は、熱可塑性樹脂を主体とする第１基材用原反シートに対し、前処理として大気圧プラズマ処理を施した後、その大気圧プラズマ処理面に第２基材用原反シートを重ね合わせて加熱加圧することによって実現可能である。即ち、本発明の積層体は、１）第１基材用原反シートの片面に、処理用ガスを用いてプラズマ装置により大気圧下で生成した大気圧プラズマを接触させる大気圧プラズマ処理を施す大気圧プラズマ処理工程と、２）前記大気圧プラズマ処理が施された第１基材用原反シートの片面に第２基材用原反シートを重ね合わせ、その重ね合わせ体を加熱加圧して両シートを一体化する一体化工程とを経て、製造され得る。   Such “direct joining” without using an adhesive component between the first base material and the second base material is an atmospheric pressure plasma as a pretreatment for the first base material sheet mainly composed of a thermoplastic resin. After the treatment, it can be realized by superposing the second base material sheet on the atmospheric pressure plasma treatment surface and heating and pressing. That is, the laminate of the present invention is subjected to 1) atmospheric pressure plasma treatment in which one side of the first base material sheet is brought into contact with atmospheric pressure plasma generated under atmospheric pressure by a plasma apparatus using a processing gas. An atmospheric pressure plasma treatment step, and 2) superimposing a second base material sheet on one side of the first base material sheet that has been subjected to the atmospheric pressure plasma treatment, and heating and pressing the superposed body. It can be manufactured through an integration step of integrating both sheets.

ここでいう「第１基材用原反シート」とは、本発明の積層体を構成する第１基材の主原材料であり、この原反シートに大気圧プラズマ処理前を施すことで第１基材が得られる。また、「第２基材用原反シート」とは、本発明の積層体を構成する第２基材の主原材料である。本発明の積層体の製造方法には、第２基材用原反シートに対して、大気圧プラズマ処理を施す態様と、大気圧プラズマ処理のような改質処理を施さない態様とが含まれるところ、前者の態様では、第２基材用原反シートと第２基材とは実質的に同じであり、後者の態様では、第２基材用原反シートに大気圧プラズマ処理前を施すことで第２基材が得られる。   The “raw material sheet for the first base material” referred to here is a main raw material of the first base material constituting the laminate of the present invention, and the first raw material sheet is subjected to the atmospheric pressure plasma treatment before the first. A substrate is obtained. The “second base material sheet” is a main raw material of the second base material constituting the laminate of the present invention. The production method of the laminate of the present invention includes an aspect in which the second base material sheet is subjected to an atmospheric pressure plasma treatment and an aspect in which a modification treatment such as an atmospheric pressure plasma treatment is not performed. However, in the former mode, the second base material sheet and the second base material are substantially the same. In the latter mode, the second base material sheet is subjected to the atmospheric pressure plasma treatment. Thus, the second base material is obtained.

尚、熱可塑性樹脂を主体とするフィルム又は不織布である第１基材とセルロース系繊維を主体とする繊維集合体である第２基材との積層体において、両基材が「直接接合」されているか否かは、第１基材における第２基材との接合面について、水に対する接触角又は濡れ張力を測定することで判断が可能である。また、ある「熱可塑性樹脂を主体とするフィルム又は不織布」（即ち第１基材用原反シート）が「セルロース系繊維を主体とする繊維集合体」（即ち、第２基材用原反シート又は第２基材）に「直接接合」し得るものであるか否かは、第１基材用原反シートにおける第２基材用原反シートとの接合予定面について、水に対する接触角又は濡れ張力を測定することで判断が可能である。また前述した通り、「直接接合」は第１基材用原反シートの大気圧プラズマ処理によって実現可能であることから、第１基材又は第１基材用原反シートについて、水に対する接触角又は濡れ張力を測定することで、それが大気圧プラズマ処理されたものであるか否かを判断することが可能である。   In the laminate of the first base material, which is a film or nonwoven fabric mainly composed of thermoplastic resin, and the second base material, which is a fiber aggregate mainly composed of cellulosic fibers, both base materials are “directly joined”. It can be judged by measuring the contact angle or the wet tension with respect to water about the joint surface with the 2nd base material in a 1st base material. Further, a certain “film or nonwoven fabric mainly composed of a thermoplastic resin” (that is, a first base material sheet) is “a fiber assembly mainly composed of cellulose fibers” (that is, a second material sheet). Whether or not it can be “directly bonded” to the second base material) is determined based on the contact angle with water or the surface to be joined with the second base material sheet in the first base material sheet or Judgment is possible by measuring the wetting tension. Further, as described above, since “direct bonding” can be realized by atmospheric pressure plasma treatment of the first base material sheet, the contact angle with water for the first base material or the first base material sheet is as follows. Alternatively, by measuring the wetting tension, it is possible to determine whether or not it has been subjected to atmospheric pressure plasma treatment.

即ち、第１基材がフィルムの場合において、該第１基材即ちフィルムにおける第２基材との接合面の水に対する接触角が６０°以下である場合には、該第１基材即ちフィルムは、接着成分を介さずに第２基材と直に重なって接合し得ると判断でき、あるいは、大気圧プラズマ処理されたものであると判断できる。尚、第１基材即ちフィルムにおける第２基材との接合面の水に対する接触角については、特に下限は設けないが、０°に近いほど好ましい。水に対する接触角はＪＩＳ Ｒ ３２５７：１９９９に従って測定される。   That is, in the case where the first substrate is a film, when the contact angle with respect to water of the bonding surface with the second substrate in the first substrate, that is, the film is 60 ° or less, the first substrate, that is, the film It can be judged that it can be directly joined to the second base material without using an adhesive component, or it can be judged that it has been subjected to atmospheric pressure plasma treatment. In addition, about the contact angle with respect to the water of the joint surface with the 2nd base material in a 1st base material, ie, a film, although a minimum is not provided, it is so preferable that it is close to 0 degree. The contact angle for water is measured according to JIS R 3257: 1999.

また、第１基材が不織布の場合において、該第１基材即ち不織布における第２基材との接合面の濡れ張力が５５ｍＮ／ｍ以上である場合には、該第１基材即ち不織布は、接着成分を介さずに第２基材と直に重なって接合し得ると判断でき、あるいは、大気圧プラズマ処理されたものであり、本来的に疎水性の熱可塑性繊維を主体とし且つ界面活性剤が付与されていないものであるにもかかわらず、大気圧プラズマ処理により濡れ張力が向上したと判断できる。尚、第１基材即ち不織布における第２基材との接合面の水に対する濡れ張力については、特に上限はなく、７３ｍＮ／ｍを超えてもかまわない（但し、水銀の表面張力相当の４２７ｍＮ／ｍまでもの濡れ張力を有する必要はない）。不織布の濡れ張力は下記方法で測定される。   In the case where the first base material is a non-woven fabric, when the wetting tension of the first base material, that is, the non-woven fabric, on the joint surface with the second base material is 55 mN / m or more, the first base material, ie, the non-woven fabric, It can be judged that it can be bonded directly to the second base material without using an adhesive component, or has been subjected to atmospheric pressure plasma treatment, and is essentially composed of hydrophobic thermoplastic fibers and has surface activity. Although the agent is not applied, it can be determined that the wet tension is improved by the atmospheric pressure plasma treatment. In addition, there is no upper limit in particular about the wet tension | tensile_strength with respect to the water of the joint surface with the 2nd base material in the 1st base material, ie, a nonwoven fabric, and it may exceed 73 mN / m (however, 427 mN / m equivalent to the surface tension of mercury) m need not have a wetting tension up to m). The wetting tension of the nonwoven fabric is measured by the following method.

＜不織布の濡れ張力の測定方法＞
雰囲気温度２０℃の環境領域で、測定対象の不織布を空中に水平に張設し、該不織布の上面に濡れ張力試験液を１５μＬ滴下し、試験液の滴下から２０秒経過後に、該上面における該試験液の状態を目視観察する。その観察において、試験液が不織布の厚み方向に透過又は面方向に拡散した場合は、表面張力のより大きな試験液に変更して同様の操作を行う。そして、試験液が不織布を透過できずにその液滴が不織布の上面に残った場合、又は面方向に拡散せずに該上面に濡れがほとんど認められない場合、斯かる場合の直前の滴下操作に使用した試験液、即ち、不織布を透過又は拡散できた試験液のうち表面張力が最大のものの表面張力を、当該不織布の雰囲気温度２０℃における濡れ張力とする。濡れ張力試験液としては、ＪＩＳ Ｋ ６７６８：１９９９に従い調製した、エチレングリコールモノエチルエーテル、ホルムアミド、メタノール及び水の混合液を用い、各成分の混合比を適宜変更して表面張力を調整する。尚、このような濡れ張力試験液は例えば和光純薬より、ぬれ張力試験用混合液という商品名で市販されている。 <Method for measuring wet tension of nonwoven fabric>
In an environmental region with an atmospheric temperature of 20 ° C., a nonwoven fabric to be measured is horizontally stretched in the air, 15 μL of a wet tension test solution is dropped on the upper surface of the nonwoven fabric, and 20 seconds after the test solution is dropped, The state of the test solution is visually observed. In the observation, when the test solution permeates in the thickness direction of the nonwoven fabric or diffuses in the surface direction, the test solution is changed to a test solution having a larger surface tension and the same operation is performed. And, when the test liquid cannot penetrate the nonwoven fabric and the droplet remains on the upper surface of the nonwoven fabric, or when the upper surface is hardly diffused and does not diffuse in the surface direction, the dripping operation immediately before such case The surface tension of the test liquid used in the above, that is, the test liquid having the maximum surface tension among the test liquids that can permeate or diffuse through the nonwoven fabric is defined as the wetting tension at an ambient temperature of 20 ° C. of the nonwoven fabric. As the wetting tension test solution, a mixed solution of ethylene glycol monoethyl ether, formamide, methanol and water prepared according to JIS K 6768: 1999 is used, and the surface tension is adjusted by appropriately changing the mixing ratio of each component. Such a wet tension test solution is commercially available, for example, from Wako Pure Chemicals under the trade name of a wet tension test mixture.

図１には、前記プラズマ処理工程の一実施態様の概略が示されている。本実施態様で用いるプラズマ装置１０は、電極１２，１２間で生成した大気圧プラズマＧを、一対の電極１２，１２間の外に配された処理対象物に向けて吹き出すいわゆるリモート式のプラズマ装置である。プラズマ装置１０は、処理対象物に対向配置された処理ヘッド１１を具備し、その処理ヘッド１１の内部に一対の電極１２，１２が相対向して配置され、各電極１２の対向面には図示しない固体誘電体層が形成されている。両電極１２，１２のうちの一方が電源１３に接続され、他方が電気的に接地されており、電源１３からの電圧供給によって、両電極１２，１２間の空間が大気圧又はその近傍の放電空間１４になる。放電空間１４における処理用ガスの導入口１５側は、処理用ガスＧ’の供給源１６と連通している。斯かる構成のプラズマ装置１０においては、供給源１６から放電空間１４に処理用ガスＧ’を導入して大気圧プラズマＧ（即ちプラズマ化された処理用ガスＧ’）を生成し、その大気圧プラズマＧを処理ヘッド１１の下端のガス吹き出し口１７から吹き出し、ガス吹き出し口１７の下方を搬送中の第１基材用原反シート２０（即ち処理対象物）の一面（即ち上面）に吹き付けるようになされている。図示の態様における第１基材用原反シート２０は連続帯状をなし、その長手方向を搬送方向ＭＤに一致させて、搬送コンベア１９によって処理ヘッド１１の下方を搬送される。処理用ガスＧ’としては、窒素及び酸素からなる群から選択される１種以上又は大気を用いることができる。   FIG. 1 shows an outline of one embodiment of the plasma processing step. The plasma apparatus 10 used in the present embodiment is a so-called remote type plasma apparatus that blows out atmospheric pressure plasma G generated between the electrodes 12 and 12 toward a processing object disposed outside the pair of electrodes 12 and 12. It is. The plasma apparatus 10 includes a processing head 11 disposed to face a processing object, and a pair of electrodes 12 and 12 are disposed inside the processing head 11 so as to face each other. A solid dielectric layer is formed. One of the electrodes 12, 12 is connected to the power source 13 and the other is electrically grounded, and the voltage supply from the power source 13 causes the space between the electrodes 12, 12 to discharge at atmospheric pressure or in the vicinity thereof. It becomes space 14. The processing gas inlet 15 side in the discharge space 14 communicates with the supply source 16 of the processing gas G ′. In the plasma apparatus 10 having such a configuration, the processing gas G ′ is introduced from the supply source 16 into the discharge space 14 to generate the atmospheric pressure plasma G (that is, the plasma processing gas G ′), and the atmospheric pressure thereof. The plasma G is blown out from the gas blowing port 17 at the lower end of the processing head 11, and the lower side of the gas blowing port 17 is blown onto one surface (that is, the upper surface) of the first base material sheet 20 (that is, the processing target) that is being conveyed. Has been made. In the illustrated embodiment, the first base material sheet 20 has a continuous belt shape, and the longitudinal direction thereof coincides with the transport direction MD, and is transported below the processing head 11 by the transport conveyor 19. As the processing gas G ′, one or more selected from the group consisting of nitrogen and oxygen, or the atmosphere can be used.

図１に示す如き態様で大気圧プラズマ処理が施された第１基材用原反シート２０は、その大気圧プラズマ処理面即ち大気圧プラズマが吹き付けられた面（即ち図１の第１基材用原反シート２０においては上面、即ち搬送コンベア１９側とは反対側の面）が改質され、本来的に化学的には第２基材（又は第２基材用原反シート）と接合し得ない状態から接合可能な状態に変化する。即ち第１基材用原反シート２０は、大気圧プラズマ処理によって第１基材となる。このような大気圧プラズマ処理による第１基材用原反シート２０の表面改質のメカニズムは定かではないが、例えば第１基材用原反シート２０がポリエチレンフィルムの場合、その表面は水素原子で占められていて本来的に疎水性（即ち水との接触角が約９０°）であるが、大気圧プラズマ処理によって該表面の水素原子の一部がケトンや水酸基等の極性基に置換されることで、該表面が親水化される（即ち水との接触角が約５０°になる）ことに起因するものと推察される。そして、こうして親水化された第１基材用原反シート２０即ち第１基材の大気圧プラズマ処理面に、セルロース系繊維を主体とする繊維集合体である第２基材用原反シート即ち第２基材を重ね合わせて加熱加圧することで、第１基材の大気圧プラズマ処理面に存するケトンや水酸基等の極性基と、第２基材の表面に本来的に存する水酸基等の極性基とが、脱水縮合反応等により化学的に結合、あるいは水素結合により物理的に結合し、その結果として、第１基材と第２基材との「直接接合」がなされると推察される。   The first base material sheet 20 that has been subjected to the atmospheric pressure plasma treatment in the mode shown in FIG. 1 has its atmospheric pressure plasma treatment surface, that is, the surface on which atmospheric pressure plasma is sprayed (that is, the first substrate of FIG. 1). In the original sheet 20, the upper surface, that is, the surface opposite to the conveyor 19 side) is modified, and chemically bonded to the second base material (or the second base material sheet). It changes from the state which cannot do to the state which can be joined. That is, the first base material sheet 20 becomes the first base material by the atmospheric pressure plasma treatment. The mechanism of surface modification of the first base material sheet 20 by such atmospheric pressure plasma treatment is not clear, but for example, when the first base material sheet 20 is a polyethylene film, the surface is a hydrogen atom. Is inherently hydrophobic (ie, the contact angle with water is about 90 °), but atmospheric pressure plasma treatment replaces some of the hydrogen atoms on the surface with polar groups such as ketones and hydroxyl groups. This is presumably due to the surface being hydrophilized (that is, the contact angle with water is about 50 °). And, the first base material sheet 20 made hydrophilic in this way, that is, the second base material sheet, which is a fiber aggregate mainly composed of cellulosic fibers, on the atmospheric pressure plasma treated surface of the first base material, By superposing and heating the second substrate, polar groups such as ketones and hydroxyl groups existing on the atmospheric pressure plasma treated surface of the first substrate and polarities such as hydroxyl groups originally existing on the surface of the second substrate It is presumed that the group is chemically bonded by a dehydration condensation reaction or the like, or physically bonded by a hydrogen bond, and as a result, “direct bonding” between the first substrate and the second substrate is performed. .

大気圧プラズマ処理には、図１に示す如きリモート式のプラズマ処理の他に、処理対象物を放電空間（即ち一対の電極間）に配置して処理を行なういわゆるダイレクト式があり、本発明では何れの方法も利用できる。リモート式プラズマ処理は、プラズマ生成領域（放電空間）と処理対象物処理領域とが分離されているため、ダイレクト式プラズマ処理のように、放電空間に存する電子が処理対象物に衝突することがなく、処理対象物が放電損傷や熱損傷等の電界ダメージを受けないという利点を有する。また、リモート式プラズマ処理は、図１に示す如く、処理対象物に対して連続的に処理を施すことが可能であるため、バッチ式の処理方法に比して、製造効率が高いという利点も有している。以上の点から、本発明に係る大気圧プラズマ処理としては、リモート式プラズマ処理が好ましい。   In addition to the remote plasma treatment as shown in FIG. 1, the atmospheric pressure plasma treatment includes a so-called direct method in which a treatment object is disposed in a discharge space (that is, between a pair of electrodes). Either method can be used. In remote plasma processing, the plasma generation region (discharge space) and the processing object processing region are separated from each other, so that electrons existing in the discharge space do not collide with the processing target as in direct plasma processing. This has the advantage that the object to be treated is not subject to electric field damage such as electric discharge damage or heat damage. In addition, as shown in FIG. 1, the remote plasma processing can continuously process the object to be processed, and therefore has an advantage that the manufacturing efficiency is higher than that of the batch processing method. Have. From the above points, remote plasma processing is preferable as the atmospheric pressure plasma processing according to the present invention.

本実施態様の大気圧プラズマ処理工程においては、搬送コンベア１９が具備する図示しない吸引手段によって、搬送中の第１基材用原反シート２０（即ち処理対象物）の他面側、即ち大気圧プラズマＧが吹き付けられる面とは反対側から第１基材用原反シート２０の吸引を実施する。斯かる吸引の主たる目的は、処理対象物である第１基材用原反シート２０の固定であり、斯かる吸引により、第１基材用原反シート２０が搬送コンベア１９に固定され、例えば第１基材用原反シート２０の搬送時のめくれや蛇行が防止され、それによって大気圧プラズマＧによる第１基材用原反シート２０の改質効率が向上し、第２基材との直接接合の実現がより一層確実なものとなり得る。第１基材用原反シート２０の吸引は、少なくとも、第１基材用原反シート２０にプラズマＧを吹き付ける時点の前後にわたって実施することが好ましく、つまり、大気圧プラズマＧの吹き出し口１７から搬送方向ＭＤ及びそれとは逆方向それぞれに所定距離離間した位置にわたって実施することが好ましい。第１基材用原反シート２０を吸引するための手段としては、各種のシートを吸引可能な公知の吸引手段を用いることができる。   In the atmospheric pressure plasma treatment process of the present embodiment, the other side of the first base material sheet 20 (that is, the object to be processed) being conveyed by the suction means (not shown) included in the conveyance conveyor 19, that is, the atmospheric pressure. The first base material sheet 20 is sucked from the side opposite to the surface to which the plasma G is sprayed. The main purpose of the suction is to fix the first base material sheet 20 that is the object to be processed. By such suction, the first base material sheet 20 is fixed to the transport conveyor 19, for example, Turning over and meandering during conveyance of the first base material sheet 20 are prevented, thereby improving the reforming efficiency of the first base material sheet 20 by the atmospheric pressure plasma G, and the second base material. Realization of direct joining can be made even more reliable. The suction of the first base material sheet 20 is preferably performed at least before and after the time point when the plasma G is sprayed on the first base material sheet 20, that is, from the outlet 17 of the atmospheric pressure plasma G. It is preferable to carry out over a position separated by a predetermined distance in each of the transport direction MD and the opposite direction. As means for sucking the first base material sheet 20, known suction means capable of sucking various sheets can be used.

また、本実施態様においては、図１に示すように、第１基材用原反シート２０（即ち処理対象物）に大気圧プラズマを接触させる前に、加熱手段１８を用いて第１基材用原反シート２０を加熱する。本実施態様における加熱手段１８は熱風（いわゆる加熱エアー）の吹き付け装置であり、大気圧プラズマＧの吹き出し口１７よりも搬送方向ＭＤの上流側にて、第１基材用原反シート２０における大気圧プラズマＧが吹き付けられる面（即ち大気圧プラズマ処理面）に対向配置されており、該大気圧プラズマ処理面に熱風を直接吹き付けてこれを加熱するようになされている。斯かる第１基材用原反シート２０の加熱処理により、その後の大気圧プラズマ吹き付けによる第１基材用原反シート２０の改質効率が向上し、第２基材用原反シート（又は第２基材）との直接接合の実現がより一層確実なものとなり得る。尚、第１基材用原反シート２０の加熱方法は、図１に示す如き、大気圧プラズマ処理手段と加熱手段（即ち熱風吹き付け装置）とが一体となった装置を用いた形態での熱風の吹き付けに制限されず、例えば、大気圧プラズマ処理手段とこれとは別体の乾燥機とを用い、大気圧プラズマ接触前に第１基材用原反シート２０を乾燥機に搬送して乾燥機中での熱風の吹き付けを行うこともできる。   Moreover, in this embodiment, as shown in FIG. 1, before making atmospheric pressure plasma contact the raw fabric sheet 20 for 1st base materials (namely, process target object), the 1st base material is used. The raw fabric sheet 20 is heated. The heating means 18 in this embodiment is a blowing device for hot air (so-called heated air), and is larger in the first base material sheet 20 on the upstream side in the conveying direction MD than the blowing port 17 of the atmospheric pressure plasma G. A surface to which the atmospheric pressure plasma G is sprayed (that is, an atmospheric pressure plasma processing surface) is disposed oppositely, and hot air is directly blown onto the atmospheric pressure plasma processing surface to heat it. By such heat treatment of the first base material sheet 20, the reforming efficiency of the first base material sheet 20 by subsequent atmospheric pressure plasma spraying is improved, and the second base material sheet (or Realization of direct bonding with the second base material) can be further ensured. In addition, the heating method of the raw material sheet | seat 20 for 1st base materials is the hot air in the form using the apparatus which integrated the atmospheric pressure plasma processing means and the heating means (namely, hot air spraying apparatus) as shown in FIG. For example, the atmospheric pressure plasma processing means and a separate dryer are used, and the first base material sheet 20 is conveyed to the dryer and dried before the atmospheric pressure plasma contact. Hot air can be blown in the machine.

斯かる大気圧プラズマ接触前の第１基材用原反シート２０の加熱温度は、加熱処理による改質効果をより一層確実に奏させるようにする観点から、例えば搬送速度２５ｍ／ｍｉｎの場合、第１基材用原反シート２０に含まれる熱可塑性樹脂のガラス転移温度プラス７０℃以上で且つ該熱可塑性樹脂の融点プラス５０℃未満とすることが好ましい。尚、ここでいう「第１基材用原反シートの加熱温度」とは、加熱されている第１基材用原反シート２０自体の温度（いわゆる品温）ではなく、加熱手段自体あるいは加熱手段による加熱設定温度を意味し、例えば加熱手段が図１に示す如き熱風の場合は、第１基材用原反シート２０の表面（即ち大気圧プラズマ処理予定面）位置での熱風の温度を意味する。また、第１基材用原反シート２０にガラス転移温度の異なる複数種の熱可塑性樹脂が含有されている場合における、前記「第１基材用原反シートに含まれる熱可塑性樹脂」は、芯鞘繊維が配合されている場合にはその鞘成分の樹脂とし、複数種類の繊維が配合されている場合には、第１基材用原反シート２０における配合割合の質量％で最も割合の大きい樹脂を意味する。前記融点についてもガラス転移温度と同様に考えることができる。第１基材用原反シート２０の加熱温度をそれに含まれる熱可塑性樹脂のガラス転移温度以上とする理由は、主として、第２基材用原反シート（又は第２基材）との密着性を向上させるためであり、また、該加熱温度を該熱可塑性樹脂の融点プラス５０℃未満とする理由は、第１基材用原反シート２０の形状を保持するためである。   The heating temperature of the first base material sheet 20 before the atmospheric pressure plasma contact is, for example, in the case of a conveyance speed of 25 m / min, from the viewpoint of more reliably achieving the modification effect by the heat treatment, It is preferable that the glass transition temperature of the thermoplastic resin contained in the first base material sheet 20 plus 70 ° C. or more and the melting point of the thermoplastic resin plus less than 50 ° C. The “heating temperature of the first base material sheet” is not the temperature of the heated first base material sheet 20 itself (so-called product temperature), but the heating means itself or the heating temperature. For example, when the heating means is hot air as shown in FIG. 1, the temperature of the hot air at the position of the surface of the first base material sheet 20 (ie, the atmospheric pressure plasma processing scheduled surface) is set. means. Further, in the case where a plurality of types of thermoplastic resins having different glass transition temperatures are contained in the first base material sheet 20, the "thermoplastic resin contained in the first base material sheet" When the core-sheath fiber is blended, the resin of the sheath component is used, and when a plurality of types of fibers are blended, the ratio is the highest in mass% of the blend ratio in the first base material sheet 20. Means a large resin. The melting point can be considered in the same manner as the glass transition temperature. The reason why the heating temperature of the first base material sheet 20 is equal to or higher than the glass transition temperature of the thermoplastic resin contained in the first base material sheet 20 is mainly the adhesion to the second base material sheet (or the second base material). The reason why the heating temperature is set to the melting point of the thermoplastic resin plus less than 50 ° C. is to maintain the shape of the first base material sheet 20.

本発明者らの知見によれば、第１基材用原反シート２０に対する大気圧プラズマの接触回数（即ちプラズマ処理回数）が多いほど、第１基材用原反シート２０の表面改質効果が高まり、第２基材用原反シート（又は第２基材）との直接接合がより強力なものとなり得る。従って、例えば図１に示す如く、第１基材用原反シート２０の一面に大気圧プラズマＧを吹き付けた後、再度、第１基材用原反シート２０の一面に対して同様の方法で大気圧プラズマＧを吹き付けることで、第１基材用原反シート２０の一面に対して合計２回の大気圧プラズマ処理を行っても良い。第１基材用原反シート２０の一面のプラズマ処理回数は３回以上でも良い。つまり、本発明の積層体の製造方法には、第１基材用原反シートの片面（即ち第２基材用原反シートとの接合予定面）に対し大気圧プラズマを１回以上接触させる態様が含まれる。尚、第１基材用原反シート２０の両面それぞれに大気圧プラズマを１回以上接触させても良い。   According to the knowledge of the present inventors, the surface modification effect of the first base material sheet 20 increases as the number of contact times of the atmospheric pressure plasma with the first base material sheet 20 (that is, the number of plasma treatments) increases. And the direct bonding with the second base material sheet (or the second base material) can be stronger. Therefore, for example, as shown in FIG. 1, after atmospheric pressure plasma G is sprayed on one surface of the first base material sheet 20, the same method is performed again on one surface of the first base material sheet 20. By blowing the atmospheric pressure plasma G, a total of two atmospheric pressure plasma treatments may be performed on one surface of the first base material sheet 20. The number of plasma treatments on one surface of the first base material sheet 20 may be three or more. That is, in the method for producing a laminate of the present invention, atmospheric pressure plasma is contacted once or more with respect to one side of the first base material sheet (that is, the surface to be bonded to the second base material sheet). Embodiments are included. Note that atmospheric pressure plasma may be brought into contact with both surfaces of the first base material sheet 20 one or more times.

一方、第２基材用原反シートについては、その表面に本来的に水酸基等の極性基を有していて表面改質を必要としないため、大気圧プラズマ処理を施さなくても良く、第２基材用原反シートはそのまま第２基材として使用できる。但し、第２基材用原反シートに対しても第１基材用原反シートと同様に大気圧プラズマ処理を施すことによって、第１基材と第２基材との直接接合がより強固なものとなり得る等、好ましい結果が得られる可能性はある。本発明の積層体の製造方法には、第２基材用原反シートには大気圧プラズマ処理を施さないか、又は第２基材用原反シートにおける第１基材との対向面に大気圧プラズマを１回以上接触させる態様が含まれ、また、第２基材用原反シートの両面それぞれに大気圧プラズマを１回以上接触させても良い。   On the other hand, the second base material sheet has a polar group such as a hydroxyl group on its surface and does not require surface modification. The two-substrate raw sheet can be used as it is as the second substrate. However, the direct bonding between the first base material and the second base material is made stronger by applying the atmospheric pressure plasma treatment to the second base material raw sheet in the same manner as the first base material raw sheet. There is a possibility that a favorable result can be obtained. In the method for producing a laminate of the present invention, the second base material sheet is not subjected to atmospheric pressure plasma treatment, or the second base material sheet has a large surface facing the first base material. A mode in which atmospheric pressure plasma is contacted once or more is included, and atmospheric pressure plasma may be contacted once or more on both surfaces of the second base material sheet.

本発明の積層体の製造方法においては、前述した大気圧プラズマ処理が施された第１基材用原反シート２０即ち第１基材の片面に第２基材用原反シート（又は第２基材）を重ね合わせて重ね合わせ体を得、該重ね合わせ体を加熱加圧して両シート即ち両基材を一体化する（即ち一体化工程）。前記大気圧プラズマ処理工程のみを実施し、斯かる一体化工程を実施しない場合には、両基材の直接接合は困難であり、両工程が必須である。一体化工程は、公知の加熱加圧装置を用いて行うことができ、例えば、一対の加熱加圧ロール間に前記重ね合わせ体を通すことで行うことができる。また、別の手段として手動式熱プレス装置を用いて行うこともでき、この場合の加熱加圧条件は、積層体の用途等に応じて適宜設定可能であり、特に制限されないが、前記重ね合わせ体の加熱温度は、好ましくは８０℃以上、さらに好ましくは９０℃以上、そして、好ましくは１２０℃以下、さらに好ましくは１１０℃以下である。また、前記重ね合わせ体にかける圧力は、好ましくは０．１ＭＰａ以上、さらに好ましくは５ＭＰａ以上、そして、好ましくは３０ＭＰａ以下、さらに好ましくは２５ＭＰａ以下である。前記重ね合わせ体の加熱温度、圧力が低すぎると、第１基材と第２基材との直接接合が困難になるおそれがあり、前記重ね合わせ体の加熱温度、圧力が高すぎると、望ましくない第１基材の融解あるいは風合いの著しい変化につながるおそれがある。前記手動式熱プレス装置は、相対向する一対の平板状の加熱加圧部材を備え、両部材間に載置された処理対象物（即ち前記重ね合わせ体）を両部材で圧縮しつつ加熱する装置である。   In the method for producing a laminate of the present invention, the first base material sheet 20 that has been subjected to the atmospheric pressure plasma treatment described above, that is, the second base material sheet (or second material) on one side of the first base material. The base material is superposed to obtain a superposed body, and the superposed body is heated and pressed to integrate both sheets, that is, both base materials (that is, integration step). When only the atmospheric pressure plasma treatment process is performed and such an integration process is not performed, it is difficult to directly bond both substrates, and both processes are essential. The integration step can be performed using a known heating and pressing apparatus, for example, by passing the overlapped body between a pair of heating and pressing rolls. Further, as another means, it can also be performed using a manual hot press apparatus, and the heating and pressing conditions in this case can be appropriately set according to the use of the laminated body, and are not particularly limited. The body heating temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and preferably 120 ° C. or lower, more preferably 110 ° C. or lower. The pressure applied to the superposed body is preferably 0.1 MPa or more, more preferably 5 MPa or more, and preferably 30 MPa or less, more preferably 25 MPa or less. If the heating temperature and pressure of the superposed body are too low, direct bonding between the first base material and the second base material may be difficult, and if the heating temperature and pressure of the superposed body is too high, it is desirable. There is a possibility that it may lead to a significant change in the melting or texture of the first base material. The manual heat press apparatus includes a pair of opposed flat plate-like heating and pressing members, and heats a processing object (that is, the overlapped body) placed between the two members while compressing the processing object with both members. Device.

前述したように大気圧プラズマ処理及び加熱加圧処理を経て製造される本発明の積層体は、第１基材と第２基材とが接着剤無しで直接接合されているため、例えばホットメルト型接着剤の如き化学系接着剤を用いて製造された従来の積層体に比して、柔軟で通気性に優れ、且つ環境に対する負荷が低減されているという利点を有しつつも、実用上十分な接合強度を有している。本発明の積層体において直接接合している第１基材と第２基材との接合強度は、基材の種類等によって異なるため設定可能な範囲は広範囲にわたるが、通常、０．５〜１５０ｃＮ／１０ｍｍの範囲である。例えば、第１基材（又は第１基材用原反シート）が熱可塑性樹脂を主体とするフィルム、第２基材（又は第２基材用原反シート）がセルロース系繊維を主体とする紙である場合、両基材の接合強度は、好ましくは１ｃＮ／１０ｍｍ以上、さらに好ましくは２ｃＮ／１０ｍｍ以上である。また、第１基材（又は第１基材用原反シート）が熱可塑性樹脂を主体とする不織布、第２基材（又は第２基材用原反シート）がセルロース系繊維を主体とする紙である場合、両基材の接合強度は、好ましくは１ｃＮ／１０ｍｍ以上、さらに好ましくは２ｃＮ／１０ｍｍ以上である。接合強度の調整は、大気圧プラズマ処理及び／又は加熱加圧処理の条件を適宜調整することで実施可能である。接合強度は下記方法により測定される。   As described above, the laminate of the present invention produced through the atmospheric pressure plasma treatment and the heating and pressurizing treatment is such that the first base material and the second base material are directly joined without an adhesive. Compared to conventional laminates manufactured using chemical adhesives such as mold adhesives, it has the advantages of being flexible, breathable and reducing the burden on the environment. It has sufficient bonding strength. The bonding strength between the first base material and the second base material that are directly bonded in the laminate of the present invention varies depending on the type of the base material and the like, and thus the settable range is wide, but usually 0.5 to 150 cN. The range is / 10 mm. For example, the first base material (or the first base material sheet) is a film mainly composed of a thermoplastic resin, and the second base material (or the second base material sheet) is mainly composed of cellulosic fibers. In the case of paper, the bonding strength between the two substrates is preferably 1 cN / 10 mm or more, more preferably 2 cN / 10 mm or more. Further, the first base material (or the first base material sheet) is a nonwoven fabric mainly composed of a thermoplastic resin, and the second base material (or the second base material sheet) is mainly composed of cellulosic fibers. In the case of paper, the bonding strength between the two substrates is preferably 1 cN / 10 mm or more, more preferably 2 cN / 10 mm or more. The bonding strength can be adjusted by appropriately adjusting the conditions of the atmospheric pressure plasma treatment and / or the heat and pressure treatment. The bonding strength is measured by the following method.

＜積層体の接合強度の測定方法＞
ＪＩＳ Ｚ ０２３７：２００９に規定する１８０°引きはがし（Ｔ型剥離）粘着力の測定法に準じて測定する。測定対象の積層体から幅１００ｍｍ×長さ２０ｍｍ以上の帯状物をサンプリングして試験片とする。２０℃、６５％ＲＨの環境下にて、引張試験機（島津製作所製、オートグラフ（登録商標）ＡＧ−ＩＳ １００Ｎ）チャック間に試験片の長手方向両端部を挟み、その状態で剥離速度３００ｍｍ／分ｍｉｎで１８０°方向に引き剥がし（剥離長さ１００ｍｍ）、剥離強度を測定する。測定結果を試験片の幅（単位はｍｍ）で割って、１０ｍｍ幅当り接合強度（単位はｃＮ／１０ｍｍ）とする。 <Measurement method of bonding strength of laminate>
It is measured according to the measuring method of 180 ° peeling (T-type peeling) adhesive strength defined in JIS Z 0237: 2009. A strip having a width of 100 mm and a length of 20 mm or more is sampled from the laminate to be measured to obtain a test piece. In an environment of 20 ° C. and 65% RH, both ends in the longitudinal direction of the test piece are sandwiched between tensile tester (manufactured by Shimadzu Corporation, Autograph (registered trademark) AG-IS 100N) chuck, and the peeling speed is 300 mm in that state. Peel at 180 ° / min (min. Peel length 100 mm) and measure peel strength. The measurement result is divided by the width of the test piece (unit: mm) to obtain the bonding strength per 10 mm width (unit: cN / 10 mm).

本発明の積層体が有する積層構造は、少なくとも第１基材及び第２基材をそれぞれ１層有する二層構造であればよく、斯かる二層構造にさらに１層以上の第１基材及び／又は第２基材が積層された三層以上の積層構造であっても良い。例えば、１層の第１基材の両面それぞれに１層の第２基材が直接接合されてなる三層構造でも良く、斯かる三層構造の製造時には、三層構造の中間層となる第１基材用原反シートの両面それぞれに大気圧プラズマ処理を施すことが好ましい。   The laminated structure of the laminate of the present invention may be a two-layer structure having at least one first base material and one second base material, and the two-layer structure further includes one or more first base materials and A laminated structure of three or more layers in which the second base material is laminated may be used. For example, a three-layer structure in which one layer of a second base material is directly bonded to both surfaces of one layer of the first base material may be used. It is preferable to perform atmospheric pressure plasma treatment on each of both surfaces of the raw sheet for one substrate.

以下、本発明を実施例により更に具体的に説明するが、本発明は斯かる実施例に限定されるものではない。   EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to such examples.

〔実施例１〕
第１基材用原反シートとして市販の低密度ＰＥフィルム（商品名「ノバテック（登録商標）」、三菱化学（株）製、厚み２２μｍ）を用い、第２基材用原反シートとして坪量２０ｇ／ｍ2 の天然セルロース繊維からなる紙を用いた。第２基材用原反シートとして用いた紙は、原料として針葉樹晒しクラフトパルプ１００％を用い、これをＪＩＳ Ｐ ８２２０：１９９８に従って離解した後、ＪＩＳ Ｐ ８１２１：２０１２に従ってカナダ標準濾水度５６０ｍＬになるまで叩解し、ＪＩＳ Ｐ ８２２３：２００５に従って湿式抄紙して製造した。
第１基材用原反シートの片面に対し、図１に示すリモート式プラズマ装置１０と基本構成が同様の装置を用いて、大気圧プラズマ処理を施した（即ち大気圧プラズマ処理工程）。大気圧プラズマ処理工程における諸条件の詳細は下記の通りである。
次いで、大気圧プラズマ処理が施された第１基材用原反シート即ち第１基材の片面に第２基材用原反シート（又は第２基材）を重ね合わせ、その重ね合わせ体を加熱加圧して両シート（即ち基材）を一体化して、目的とする積層体を得た（即ち一体化工程）。一体化工程における諸条件の詳細は下記の通りである。 [Example 1]
A commercially available low density PE film (trade name “NOVATEC (registered trademark)”, manufactured by Mitsubishi Chemical Corporation, thickness 22 μm) is used as the first base material sheet, and the basis weight is used as the second base material sheet. Paper made of 20 g / m 2 natural cellulose fiber was used. The paper used as the second base material sheet is 100% softwood bleached kraft pulp as a raw material, which is disaggregated according to JIS P 8220: 1998, and then to Canadian standard freeness of 560 mL according to JIS P 8121: 2012. It was beaten until it was, and was made by wet papermaking according to JIS P 8223: 2005.
An atmospheric pressure plasma treatment was performed on one side of the first base material sheet using an apparatus having the same basic configuration as the remote plasma apparatus 10 shown in FIG. 1 (that is, an atmospheric pressure plasma treatment step). Details of various conditions in the atmospheric pressure plasma treatment process are as follows.
Next, the first base material sheet that has been subjected to the atmospheric pressure plasma treatment, that is, the second base material sheet (or the second base material) is superposed on one side of the first base material, Both sheets (namely, base materials) were integrated by heating and pressurizing to obtain a target laminate (namely, integration step). Details of various conditions in the integration process are as follows.

（プラズマ処理工程における諸条件）
・リモート式プラズマ装置：Tough Plasma（登録商標） FPE20（富士機械製造（株）製）
・プラズマ吹き出し口と第１基材用原反シート（即ち処理対象物）との距離：５ｍｍ
・大気圧プラズマ処理時における第１基材用原反シート（即ち処理対象物）の搬送速度：２５ｍ／ｍｉｎ
・処理制御方法：二軸ロボット（（株）ＩＡＩ製）で制御（ここではＡ４判にわたり処理）
・処理用ガスとして窒素（純度９９．９％以上、酸素含有量０．１％以下）を用い、処理用ガスの流量を３０Ｌ／ｍｉｎとした。
・加熱エアーを用い、大気圧プラズマ吹き付け前の処理対象物を加熱処理した。加熱エアーには大気を用いた。加熱エアーの流量２０Ｌ／ｍｉｎ、加熱温度（即ち加熱エアーの処理対象物の表面位置での温度）１５０℃とした。
・大気圧プラズマ処理時に、処理対象物における大気圧プラズマが吹き付けられる面とは反対側から処理対象物の吸引を実施した。 (Various conditions in the plasma treatment process)
-Remote type plasma equipment: Tough Plasma (registered trademark) FPE20 (Fuji Machinery Manufacturing Co., Ltd.)
The distance between the plasma outlet and the first base material sheet (that is, the object to be processed): 5 mm
-Conveying speed of the first base material sheet (that is, the object to be treated) during the atmospheric pressure plasma treatment: 25 m / min
・ Processing control method: Controlled by a two-axis robot (manufactured by IAI Co., Ltd.)
-Nitrogen (purity 99.9% or more, oxygen content 0.1% or less) was used as the processing gas, and the flow rate of the processing gas was 30 L / min.
-Heated air was used to heat the object to be treated before atmospheric pressure plasma spraying. Air was used as the heated air. The flow rate of heated air was 20 L / min, and the heating temperature (that is, the temperature at the surface position of the object to be treated with heated air) was 150 ° C.
-During the atmospheric pressure plasma treatment, the object to be treated was sucked from the side opposite to the surface to which the atmospheric pressure plasma was sprayed.

（一体化工程における諸条件）
・装置：東洋精機（株）製 Mini Test Press−１０
・重ね合わせ体の加熱温度：１００℃
・重ね合わせ体への圧力：２５ＭＰａ
・加熱加圧時間：１０秒間 (Various conditions in the integration process)
・ Device: Mini Test Press-10 manufactured by Toyo Seiki Co., Ltd.
-Heating temperature of the stacked body: 100 ° C
-Pressure on the stacked body: 25 MPa
-Heating and pressing time: 10 seconds

〔実施例２〕
第１基材用原反シートとして、市販の二軸延伸ＰＥＴフィルム（商品名「テトロン（登録商標）Ｇ２Ｃ」、帝人（株）製、厚み２５μｍ）を用いた以外は、実施例１と同様にして積層体を得た。 [Example 2]
As in Example 1, except that a commercially available biaxially stretched PET film (trade name “Tetron (registered trademark) G2C”, manufactured by Teijin Ltd., thickness 25 μm) was used as the first base material sheet. To obtain a laminate.

〔実施例３〕
第２基材用原反シートとして、市販のコピー用紙（商品名「リサイクルカット判Ｇ８０（型番Ｇ８０Ａ４Ｗ）、トッパン・フォームズ（株）製、古紙パルプ配合率７０質量％、森林認証材パルプ配合率３０質量％、坪量６４ｇ／ｍ2）を用いた以外は、実施例１と同様にして積層体を得た。 Example 3
As a raw material sheet for the second base material, commercially available copy paper (trade name “recycled cut size G80 (model number G80A4W), manufactured by Toppan Foams Co., Ltd., recycled paper pulp content 70 mass%, forest certified material pulp content 30 A laminate was obtained in the same manner as in Example 1 except that mass% and basis weight 64 g / m 2 ) were used.

〔実施例４〕
第１基材用原反シートとして、実施例１で用いたＰＥＴフィルムと同じものを用いた以外は、実施例３と同様にして積層体を得た。 Example 4
A laminate was obtained in the same manner as in Example 3 except that the same material as the PET film used in Example 1 was used as the first base material sheet.

〔実施例５〕
第１基材用原反シートとして、ＰＥＴを芯部、ＰＥを鞘部とする芯鞘型複合繊維から構成されるスパンボンド不織布（商品名「エルベス（登録商標）」（型番Ｓ２０Ｓ０２０３ＷＤＯ）、ユニチカ（株）製、坪量２０ｇ／ｍ2）を用いた以外は、実施例１と同様にして積層体を得た。 Example 5
A spunbonded nonwoven fabric (trade name “Elves (registered trademark)” (model number S20S0203WDO), unitica (unit name: A laminated body was obtained in the same manner as in Example 1 except that the product manufactured by the same company, with a basis weight of 20 g / m 2 ) was used.

〔実施例６〕
第２基材として、実施例３で用いたコピー用紙と同じものを用いた以外は、実施例５と同様にして積層体を得た。 Example 6
A laminate was obtained in the same manner as in Example 5 except that the same copy paper as used in Example 3 was used as the second substrate.

〔実施例７〕
第２基材用原反シートとして、市販の板紙（商品名「色上質紙 超厚口黒」、北越紀州製紙（株）製、坪量２０４．５ｇ／ｍ2）を用いた以外は、実施例５と同様にして積層体を得た。 Example 7
Implemented except that a commercially available paperboard (trade name “color quality paper ultra-thick black”, manufactured by Hokuetsu Kishu Paper Co., Ltd., basis weight 204.5 g / m 2 ) was used as the second base material sheet. A laminate was obtained in the same manner as in Example 5.

〔比較例１〜７〕
第１基材用原反シートに大気圧プラズマ処理を施さずに、第１基材用原反シートと第２基材用原反シートとの一体化工程を行った以外は、実施例１〜７と同様にして積層体を得た。 [Comparative Examples 1-7]
Examples 1 to 1 were performed except that the first base material sheet and the second base material sheet were integrated without subjecting the first base material sheet to atmospheric pressure plasma treatment. In the same manner as in Example 7, a laminate was obtained.

〔評価試験〕
各実施例及び比較例の積層体について、前記方法により第１基材と第２基材との接合強度（即ちＴ型剥離強度）を測定した。その結果を下記表１に示す。 〔Evaluation test〕
About the laminated body of each Example and the comparative example, the joint strength (namely, T-type peeling strength) of a 1st base material and a 2nd base material was measured by the said method. The results are shown in Table 1 below.

Figure 2017100370
Figure 2017100370

１０ リモート式プラズマ装置
１１ 処理ヘッド
１２ 電極
１３ 電源
１４ 放電空間
１５ 処理用ガスの導入口
１６ 処理用ガスの供給源
１７ ガス吹き出し口
１８ 加熱手段
１９ 搬送コンベア
２０ 第１基材用原反シート（即ち処理対象物）
Ｇ’ 処理用ガス
Ｇ 大気圧プラズマ DESCRIPTION OF SYMBOLS 10 Remote type plasma apparatus 11 Processing head 12 Electrode 13 Power supply 14 Discharge space 15 Processing gas introduction port 16 Processing gas supply source 17 Gas blowing port 18 Heating means 19 Conveyor 20 First base material sheet (i.e. Processing object)
G 'processing gas G atmospheric pressure plasma

Claims (11)

互いに異種のシート状の第１基材と第２基材とが直接接合されてなる積層構造を有し、
前記第１基材は、熱可塑性樹脂を主体とするフィルム又は不織布であり、前記第２基材は、セルロース系繊維を主体とする繊維集合体である積層体。 Having a laminated structure in which a first base material and a second base material, which are different from each other, are directly joined,
The first base material is a film or non-woven fabric mainly composed of a thermoplastic resin, and the second base material is a laminate composed of a fiber aggregate mainly composed of cellulosic fibers. 前記第１基材の熱可塑性樹脂は、ポリオレフィン系及びポリエステル系からなる群から選択される１種以上である請求項１に記載の積層体。   The laminate according to claim 1, wherein the thermoplastic resin of the first base material is at least one selected from the group consisting of polyolefins and polyesters. 前記第１基材がフィルムの場合、該第１基材における前記第２基材との接合面の水に対する接触角が６０°以下である請求項１又は２に記載の積層体。   3. The laminate according to claim 1, wherein, when the first substrate is a film, a contact angle with respect to water of a bonding surface of the first substrate with the second substrate is 60 ° or less. 前記第１基材が不織布の場合、該第１基材における前記第２基材との接合面の濡れ張力が５５ｍＮ／ｍ以上である請求項１〜３の何れか一項に記載の積層体。   The laminate according to any one of claims 1 to 3, wherein when the first base material is a nonwoven fabric, the wetting tension of the joint surface of the first base material with the second base material is 55 mN / m or more. . 前記第２基材のセルロース系繊維は、天然セルロース繊維、マーセル化セルロース繊維、溶解セルロース繊維及びセルロース繊維誘導体からなる群から選択される１種以上である請求項１〜４の何れか一項に記載の積層体。   The cellulosic fiber of the second substrate is at least one selected from the group consisting of natural cellulose fiber, mercerized cellulose fiber, dissolved cellulose fiber, and cellulose fiber derivative. The laminated body of description. 請求項１〜５の何れか一項に記載の積層体の製造方法であって、
第１基材用原反シートの片面に、処理用ガスを用いてプラズマ装置により大気圧下で生成した大気圧プラズマを接触させる大気圧プラズマ処理を施す大気圧プラズマ処理工程と、
前記大気圧プラズマ処理が施された前記第１基材用原反シートの片面に第２基材用原反シートを重ね合わせ、その重ね合わせ体を加熱加圧して両シートを一体化する一体化工程とを有する積層体の製造方法。 It is a manufacturing method of the layered product according to any one of claims 1 to 5,
An atmospheric pressure plasma treatment step of performing an atmospheric pressure plasma treatment in which an atmospheric pressure plasma generated under atmospheric pressure by a plasma apparatus using a treatment gas is brought into contact with one side of the first base material sheet;
An integration in which the second base material sheet is superposed on one side of the first base material sheet which has been subjected to the atmospheric pressure plasma treatment, and the two sheets are integrated by heating and pressing the superposed body. The manufacturing method of the laminated body which has a process. 前記処理用ガスは、窒素及び酸素からなる群から選択される１種以上又は大気である請求項６に記載の積層体の製造方法。   The method for producing a laminate according to claim 6, wherein the processing gas is one or more selected from the group consisting of nitrogen and oxygen, or air. 前記第１基材用原反シートの片面に前記大気圧プラズマを接触させる前に、該第１基材用原反シートを加熱する請求項６又は７に記載の積層体の製造方法。   The manufacturing method of the laminated body of Claim 6 or 7 which heats this raw material sheet | seat for 1st base materials before making the said atmospheric pressure plasma contact the single side | surface of the said raw material sheet for 1st base materials. 前記第１基材用原反シートの加熱温度が、該第１基材用原反シートに含まれる熱可塑性樹脂のガラス転移温度以上で且つ該熱可塑性樹脂の融点未満である請求項８に記載の積層体の製造方法。   The heating temperature of the first base material sheet is equal to or higher than the glass transition temperature of the thermoplastic resin contained in the first base material sheet and lower than the melting point of the thermoplastic resin. The manufacturing method of the laminated body. 前記第１基材用原反シートの片面に前記大気圧プラズマを１回以上接触させ、且つ
前記第２基材用原反シートには前記大気圧プラズマ処理を施さないか、又は前記第２基材用原反シートにおける前記第１基材用原反シートとの対向面に前記大気圧プラズマを１回以上接触させる請求項６〜９の何れか一項に記載の積層体の製造方法。 The atmospheric pressure plasma is brought into contact with one side of the first base material sheet one or more times, and the second base material sheet is not subjected to the atmospheric pressure plasma treatment, or the second group The manufacturing method of the laminated body as described in any one of Claims 6-9 which makes the said atmospheric pressure plasma contact the surface facing the said original fabric sheet for 1st base materials at least once in the raw fabric sheet for materials. 前記一体化工程において、前記重ね合わせ体の加熱温度が８０℃以上、前記重ね合わせ体にかける圧力が０．１ＭＰａ以上３０ＭＰａ以下である請求項６〜１０の何れか一項に記載の積層体の製造方法。   In the said integration process, the heating temperature of the said laminated body is 80 degreeC or more, The pressure applied to the said laminated body is 0.1 MPa or more and 30 MPa or less, The laminated body as described in any one of Claims 6-10. Production method.
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