JP5640698B2 - Laminated body and method for producing the same - Google Patents

Description

  The present invention relates to a laminate and a method for producing the same.

  Containers and packaging materials such as food, toiletry products, medicines, medical products, and electronic materials are required to have high gas barrier properties in order to protect the contents. Most of the gas barrier agents currently used are manufactured from chlorinated materials such as polyvinylidene chloride and those manufactured by vapor deposition of inorganic substances, so a huge amount of carbon dioxide and heat are generated during manufacturing and disposal. It has been discharged. In addition, chlorine-based materials have the problem of generating dioxins, and inorganic vapor-deposited films have problems such as damaging the incinerator during incineration or peeling the film during recycling. . For this reason, gas barrier materials are being converted to environmentally friendly materials that suppress these problems.

  Cellulose is a material that is attracting attention as an environmentally friendly type. Cellulose is contained in plant cell walls, microbial exocrine secretions, and sea squirt mantles, and is the most abundant polysaccharide on earth, biodegradable, highly crystalline, stable and safe. Excellent in properties. Therefore, application development is expected in various fields.

  Cellulose has strong intramolecular hydrogen bonds and high crystallinity, so it is almost insoluble in water and common solvents, but research has been actively conducted to improve solubility. Among them, among the three hydroxyl groups of cellulose using a TEMPO catalyst system, the method of oxidizing only the primary hydroxyl group at the C6 position and converting it to a carboxyl group via an aldehyde group or a ketone group selectively oxidizes only the primary hydroxyl group. In recent years, it has attracted a great deal of attention because it is possible to carry out the reaction under mild conditions such as aqueous systems and room temperature. In addition, when TEMPO oxidation is performed using natural cellulose, only the nano-order crystal surface can be oxidized while maintaining the crystallinity of cellulose, and fine cellulose can be dispersed in water simply by applying a slight mechanical treatment. It is known that Furthermore, it is known that a film formed by drying this water-dispersed fine cellulose has gas barrier properties due to its fine structure and high crystallinity.

  Patent Document 1 discloses a production method in which the surface of a base material made of biomass plastic such as polylactic acid and a biodegradable resin is subjected to plasma treatment with nitrogen gas to improve its coating property.

JP 2010-179579 A

However, in the invention described in Patent Document 1, the cellulose surface is the outermost surface, and there is a possibility that the cellulose surface is deteriorated due to scratches or swelling due to water vapor. For example, a fine cellulose film has a high hygroscopic property and absorbs moisture over time, and there is a problem that the gas barrier property deteriorates due to swelling. Also, when the plasma gas species is only nitrogen, depending on the substrate used, the hydrophilic functional group cannot be sufficiently introduced, and the intended effect may not be obtained. Furthermore, if plasma treatment at atmospheric pressure is not performed at any time, plasma treatment of the substrate, coating of fine cellulose, and lamination of thermoplastic resin cannot be performed continuously in-line. May cause various problems such as inactivation, deterioration of the fine cellulose layer, and increase in production costs.
Furthermore, in the invention described in Patent Document 1, there is still room for improvement in the coating property of the fine cellulose aqueous dispersion on the substrate, and problems such as repelling have not been solved.

The present invention has been made in view of the above circumstances, and can be improved in hydrophilicity in any base material, and a laminate capable of suppressing various adverse effects by continuously treating each step and its production It is an object to provide a method.
Specifically, the present invention provides a laminate having good coating properties of a fine cellulose aqueous dispersion on a substrate, suppressing deterioration with time of a layer made of fine cellulose, and improving gas barrier properties, and a method for producing the same It is an issue to provide.

The invention according to claim 1 is a thermoplastic resin that can be heat-sealed with a base material having a surface plasma-treated at least under atmospheric pressure , a fine cellulose layer containing fine cellulose having a carboxyl group , and provided on the treated surface. a laminate ing by stacking three layers of the layers,
The gas species of the plasma treatment is one of a composite gas of nitrogen gas and oxygen gas, a composite gas of nitrogen gas and hydrogen gas,
The laminate according to claim 1, wherein the fine cellulose layer contains an inorganic layered mineral, and the content of the inorganic layered mineral is 0.1 to 50% by mass with respect to the fine cellulose .
According to a second aspect of the invention, the base material is polyester, polyolefin, cellulose, polyamide, acrylic, polystyrene, polyimide, polycarbonate, polyvinyl chloride, polyurethane, polyvinyl alcohol, paper The laminate according to claim 1, wherein the laminate is any one of the systems or a derivative or composite material thereof.
According to a third aspect of the present invention, the fine cellulose has a carboxyl group introduced to the crystal surface by an oxidation reaction using an N-oxyl compound, and the amount of the carboxyl group of the fine cellulose is 0.1 mmol / g or more. It is 0 mmol / g or less, It is a laminated body of Claim 1 or 2 characterized by the above-mentioned.
The invention according to claim 4 is characterized in that the fine cellulose has a number average fiber width of 1 nm to 50 nm and a number average fiber length of 100 times to 10000 times the number average fiber width. It is a laminated body in any one of claim | item 1-3.
The invention according to claim 5 includes a step of plasma-treating a substrate under atmospheric pressure, a step of coating a fine cellulose layer containing fine cellulose having a carboxyl group on the treated surface, and heat on the fine cellulose layer. And laminating a plastic resin layer,
The gas species of the plasma treatment is one of a composite gas of nitrogen gas and oxygen gas, a composite gas of nitrogen gas and hydrogen gas,
The fine cellulose layer contains an inorganic layered mineral, and the content of the inorganic layered mineral is 0.1 to 50% by mass with respect to the fine cellulose.
It is a method of manufacturing the laminated body in any one of Claims 1-4 characterized by the above-mentioned.
The invention described in claim 6 includes a step of plasma-treating a substrate under atmospheric pressure, a step of coating a fine cellulose layer containing fine cellulose having a carboxyl group on the treated surface, and heat on the fine cellulose layer. A method for producing a laminate comprising the steps of laminating a plastic resin layer, wherein all the steps are performed in-line.

Since the laminated body of the present invention can continuously process the plasma treatment of the substrate, the application of fine cellulose, and the lamination of the thermoplastic resin, it is possible to suppress various deteriorations.
ADVANTAGE OF THE INVENTION According to this invention, the coating property of the fine cellulose aqueous dispersion with respect to a base material is favorable, the laminated body which suppressed deterioration with time of the layer which consists of fine cellulose, and improved gas barrier property is provided.
Further, according to the present invention, since the plasma treatment of the substrate, the application of fine cellulose, and the lamination of the thermoplastic resin can be continuously performed, it is possible to suppress the above-described various deteriorations.

Details of the present invention will be described below.

(About the base material of the laminate)
The base material in the laminate of the present invention is polyester (polyethylene terephthalate, polyethylene naphthalate, polylactic acid, etc.), polyolefin (polyethylene, polypropylene, etc.), cellulose (cellulose, triacetyl cellulose, etc.), polyamide (nylon, etc.) , Acrylic (polyacrylonitrile, etc.), polystyrene, polyimide, polycarbonate, polyvinyl chloride, polyurethane, polyvinyl alcohol, paper, or derivatives or composite materials thereof.

  The shape of the substrate is not particularly limited, and when used as a film or sheet, the thickness may be 10 μm or more and 1000 μm or less. In particular, when used as a packaging material, it is preferably 10 μm or more and 100 μm or less.

(About substrate surface treatment)
The plasma treatment on the substrate surface of the present invention is performed under atmospheric pressure. The substrate surface here is a coated surface on which a layer made of fine cellulose (hereinafter referred to as a fine cellulose layer) is formed. By performing the plasma treatment under atmospheric pressure, a large-scale vacuum system is unnecessary, and the equipment cost can be reduced. Furthermore, since it becomes possible to continuously process in-line with the subsequent coating process and laminating process, the manufacturing cost can be reduced.

  As the treatment gas, nitrogen gas, a composite gas of nitrogen gas and oxygen gas, or a composite gas of nitrogen gas and hydrogen gas is preferable. These gas types and compounding ratios can be arbitrarily selected depending on the target base material, the gap between the base material surface and the discharge part, or the like. Since processing is performed under atmospheric pressure, air is likely to enter from the periphery of the processing unit. Therefore, when it is desired to introduce a large number of functional groups of the nitrogen compound on the surface, a composite gas of nitrogen gas and hydrogen gas is preferable. As a blending ratio, nitrogen gas is preferably 80% or more. Moreover, when it is desired to introduce a large number of functional groups of the oxygen compound on the surface, a composite gas of nitrogen gas and oxygen gas is preferable. As a blending ratio, nitrogen gas is preferably 70% or more.

  The gap between the substrate and the discharge part needs to be determined depending on the type, flow rate, and output of the gas, but is generally preferably 0.5 mm or more and 50 mm or less. In consideration of air mixing and the like, 0.5 mm or more and 10 mm or less is more preferable.

    The treatment output needs to be determined depending on the structure of the substrate, heat resistance, etc., but is preferably 0.01 kW or more and 100 kW or less. In consideration of damage to the base material, 0.1 kW or more and 10 kW or less is more preferable.

(The fine cellulose layer of the laminate and its production method)
The fine cellulose of the present invention preferably has a carboxyl group content of 0.1 mmol / g or more and 3.0 mmol / g or less. 0.5 mmol / g or more and 2.0 mmol / g or less is more preferable. When the carboxyl group amount is less than 0.1 mmol / g, it is difficult to uniformly disperse the fine cellulose without causing electrostatic repulsion. Moreover, when it exceeds 3.0 mmol / g, there exists a possibility that the crystallinity of a fine cellulose may fall. The fine cellulose of the present invention preferably has a number average fiber width of 1 nm to 50 nm and a number average fiber length of 100 times to 10,000 times the number average fiber width. If the number average fiber width is less than 1 nm, the cellulose will not be in a nanofiber state, and if it exceeds 50 nm, the transparency of the dispersion will be impaired. In addition, when the number average fiber length is less than 100 times the number average fiber width, the strength of the cellulose film may be lowered. When the number average fiber length exceeds 10,000 times, the viscosity of the dispersion becomes very high, and there is a problem in coating properties. May occur.

  The method for producing the fine cellulose layer having a carboxyl group of the present invention will be described.

  The fine cellulose having a carboxyl group used in the present invention is obtained by a step of oxidizing cellulose, a step of refining, and a step of coating.

(Step of oxidizing cellulose)
As raw materials for cellulose to be oxidized, wood pulp, non-wood pulp, waste paper pulp, cotton, bacterial cellulose, valonia cellulose, squirt cellulose, fine cellulose, microcrystalline cellulose, and the like can be used.

  As a method for modifying cellulose, a co-oxidant was used in the presence of an N-oxyl compound having high selectivity to oxidation of a primary hydroxyl group while maintaining the structure as much as possible under relatively mild conditions in an aqueous system. Method is desirable. Examples of the N-oxyl compound include TEMPO, 2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,6,6-tetramethyl-4-hydroxy as the N-oxyl compound. Piperidine-1-oxyl, 2,2,6,6-tetramethyl-4-phenoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-benzylpiperidine-1-oxyl, 2,2, 6,6-tetramethyl-4-acryloyloxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-methacryloyloxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4 -Benzoyloxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-cinnamoyloxypiperidine-1-oxyl, 2,2,6, -Tetramethyl-4-acetylaminopiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-acryloylaminopiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-methacryloylamino Piperidine-1-oxyl, 2,2,6,6-tetramethyl-4-benzoylaminopiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-cinnamoylaminopiperidine-1-oxyl, 4 -Propionyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-ethoxy-2,2,6, 6-tetramethylpiperidine-N-oxyl, 4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-o So-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,4,4-tetramethylazetidine-1-oxyl, 2,2-dimethyl-4,4-dipropylazetidine- 1-oxyl, 2,2,5,5-tetramethylpyrrolidine-N-oxyl, 2,2,5,5-tetramethyl-3-oxopyrrolidine-1-oxyl, 2,2,6,6-tetramethyl -4-acetoxypiperidine-1-oxyl, ditert-butylamine-N-oxyl, poly [(6- [1,1,3,3-tetramethylbutyl] amino) -s-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino and the like. 2,2,6,6-tetramethyl-1-piperidine-N-oxyl and the like are preferably used.

  The co-oxidant may promote an oxidation reaction such as halogen, hypohalous acid, halous acid or perhalogen acid, or a salt thereof, halogen oxide, nitrogen oxide, or peroxide. Any oxidant can be used if possible. Sodium hypochlorite is preferred because of its availability and reactivity.

  Furthermore, when carried out in the presence of bromide or iodide, the oxidation reaction can proceed smoothly, and the introduction efficiency of the carboxyl group can be improved.

  As the N-oxyl compound, TEMPO is preferable, and an amount that functions as a catalyst is sufficient. As the bromide, a system using sodium bromide or lithium bromide is preferable, and sodium bromide is more preferable from the viewpoint of cost and stability. The amount of the co-oxidant, bromide or iodide used is sufficient if there is an amount capable of promoting the oxidation reaction. The reaction is more preferably pH 9 to 11, but as the oxidation proceeds, carboxyl groups are generated and the pH in the system is lowered, so the inside of the system needs to be maintained at pH 9 to 11.

  In order to keep the inside of the system alkaline, it can be prepared by adding an alkaline aqueous solution while keeping the pH constant. Examples of the alkaline aqueous solution include sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia solution, and organic alkalis such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide. Although used, sodium hydroxide is preferred in view of cost.

  In order to complete the oxidation reaction, it is necessary to add the other alcohol while maintaining the pH in the system and complete the reaction of the co-oxidant. As the alcohol to be added, a low molecular weight alcohol such as methanol, ethanol or propanol is desirable in order to quickly terminate the reaction. Ethanol is more preferable from the viewpoint of safety of by-products generated by the reaction.

  Cleaning methods for oxidized pulp after oxidation include a method of cleaning while forming an alkali and salt, a method of cleaning by adding an acid to a carboxylic acid, a method of cleaning by adding an organic solvent and making it unnecessary. is there. In view of handling properties and yield, a method of adding an acid to obtain a carboxylic acid and washing it is preferred. The washing solvent is preferably water.

(Process to refine cellulose)
As a method for refining oxidized cellulose, first, the pH of the dispersion is adjusted after immersing in oxidized water using oxidized cellulose as a dispersion medium. For example, when acid-washed oxidized pulp is dispersed in water, the pH of the dispersion is about 4-6, so the pH is adjusted to 4-12 using alkali. When the pH is lowered, the molecular weight of the obtained cellulose nanofiber is increased, and when the pH is raised, the molecular weight of the obtained cellulose nanofiber is decreased. Examples of the alkaline aqueous solution used include sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia aqueous solution, and organic alkalis such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide. Etc. Sodium hydroxide is preferred because of cost and availability.

  Subsequent physical defibrating methods include high pressure homogenizer, ultra high pressure homogenizer, ball mill, roll mill, cutter mill, planetary mill, jet mill, attritor, grinder, juicer mixer, homomixer, ultrasonic homogenizer, nanogenizer, underwater It can be miniaturized by using an opposing collision or the like. A modified fine cellulose-dispersed aqueous solution having a carboxyl group at the C6 position can be obtained by performing such a micronization treatment for an arbitrary time or number of times.

  If necessary, the fine cellulose dispersion may contain cellulose and other components other than those used for pH adjustment as long as the effects of the present invention are not impaired. The other components are not particularly limited, and can be appropriately selected from known additives according to the use of the fine cellulose layer. Specifically, organometallic compounds such as alkoxysilanes or hydrolysates thereof, inorganic layered compounds, inorganic needle minerals, leveling agents, antifoaming agents, water-soluble polymers, synthetic polymers, inorganic particles, organic particles , Lubricants, antistatic agents, ultraviolet absorbers, dyes, pigments, stabilizers, magnetic powders, orientation promoters, plasticizers, crosslinking agents and the like. Of these, inorganic layered compounds are preferred because they promote surface orientation of the film and improve water resistance, moisture resistance, gas barrier properties, and the like.

The inorganic layered compound refers to a crystalline inorganic compound having a layered structure, and as long as it is an inorganic layered compound, its type, particle size, aspect ratio, etc. are not particularly limited, and should be appropriately selected according to the purpose of use and the like. Can do. Specific examples of the inorganic layered compound include clay minerals represented by the kaolinite group, smectite group, mica group and the like. Among these, montmorillonite, hectorite, saponite, etc. are mentioned as the smectite group inorganic layered compound. Among these, montmorillonite is preferable from the viewpoints of dispersion stability in the composition, coating properties of the composition, and the like.
The inorganic layered compound may be blended directly in the aqueous dispersion, or may be blended after being previously dispersed in an aqueous medium such as water.
The inorganic layered mineral is preferably added in the range of 0.1 to 50% by mass with respect to fine cellulose.

(Process to apply fine cellulose)
As a coating method of the cellulose dispersion of the present invention, a comma coater, roll coater, reverse roll coater, direct gravure coater, reverse gravure coater, offset gravure coater, roll kiss coater, reverse kiss coater, micro gravure coater, air doctor coater, A coating method using a knife coater, bar coater, wire bar coater, die coater, dip coater, blade coater, brush coater, curtain coater, die slot coater or the like can be used.
The fine cellulose layer preferably has a dry film thickness of 0.1 μm to 30 μm.

(Process of laminating thermoplastic resin)
Examples of the heat-sealable thermoplastic resin of the present invention include a polypropylene film such as an unstretched polypropylene film, a polyethylene film such as a low-density polyethylene film, a linear low-density polyethylene film, and the like. The thermoplastic resin is usually laminated via an adhesive layer.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, the technical scope of this invention is not limited to these embodiment.
<TEMPO oxidation of cellulose>

  30 g of softwood bleached kraft pulp was suspended in 1800 g of distilled water, a solution of 0.3 g of TEMPO and 3 g of sodium bromide was added to 200 g of distilled water and cooled to 15 ° C. To this, 172 g of a sodium hypochlorite aqueous solution having a concentration of 2 mol / l and a density of 1.15 g / ml was added dropwise to initiate an oxidation reaction. The temperature in the system was always kept at 20 ° C., and the decrease in pH during the reaction was kept at pH 10 by adding a 0.5N aqueous sodium hydroxide solution. When sodium hydroxide reached 2.85 mmol / g based on the mass of cellulose, a sufficient amount of ethanol was added to stop the reaction. Thereafter, hydrochloric acid was added until the pH reached 3, and washing was sufficiently repeated with distilled water to obtain oxidized pulp.

-Measurement of carboxyl group of oxidized pulp 0.1 g of oxidized pulp and re-oxidized pulp obtained by the above TEMPO oxidation were weighed and dispersed in water at a concentration of 1%, and hydrochloric acid was added to adjust the pH to 3. Thereafter, the amount of carboxyl groups (mmol / g) was determined by conductometric titration using a 0.5N aqueous sodium hydroxide solution. The result was 1.6 mmol / g.
<Refining of oxidized pulp>
(Production Example 1)

1 g of oxidized pulp obtained by the TEMPO oxidation was dispersed in 99 g of distilled water and adjusted to pH 10 using an aqueous sodium hydroxide solution. The prepared dispersion was refined with a juicer mixer for 60 minutes to obtain a 1% fine cellulose aqueous dispersion.
(Production Example 2)

  0.7 g of oxidized pulp obtained by the TEMPO oxidation and 0.3 g of inorganic layered mineral (montmorillonite) were dispersed in 99 g of distilled water, and adjusted to pH 10 using an aqueous sodium hydroxide solution. The prepared dispersion was refined with a juicer mixer for 60 minutes to obtain a 1% fine cellulose + inorganic layered mineral aqueous dispersion.

-Shape observation The shape observation of the said fine cellulose was observed using atomic force microscope (AFM). A 1% fine cellulose aqueous dispersion diluted 1000 times was cast on a cleaved surface of mica, dried, observed with a tapping AFM, the fiber height was measured at 10 points, and the average was taken as the number average fiber width. Further, the fiber length was similarly observed by tapping AFM, the length in the longitudinal direction of the fiber was measured at 10 points, and the average was taken as the number average fiber length. The number average fiber width was 3.5 nm, and the number flat fiber length was 1.3 μm.
(Examples 1-9)

A polylactic acid biaxially stretched film (PLA) was used as a substrate, and surface treatment was performed using an atmospheric pressure plasma treatment apparatus (ADMASTER-350d manufactured by E-Square Co., Ltd.). Next, the aqueous dispersion produced in Production Example 1 or 2 was applied on the surface-treated substrate with a bar coater so as to have a dry film thickness of 1 μm and sufficiently dried. Thereafter, an unstretched polypropylene film (CPP) having a thickness of 70 μm was bonded to the coated surface side by dry lamination using a urethane polyol-based adhesive to prepare a laminate. Detailed conditions for each example are shown in Table 1. For Examples 3, 6, and 9, three-layer lamination was performed in-line and continuously.
(Comparative Examples 1-3)

Using PLA as a base material, without applying surface treatment, apply the aqueous dispersion prepared in Production Example 1 or 2 on the base material to a dry film thickness of 1 μm with a bar coater and dry it sufficiently. It was. Thereafter, an unstretched polypropylene film (CPP) having a thickness of 70 μm was bonded to the coated surface side by dry lamination using a urethane polyol-based adhesive to prepare a laminate. Detailed conditions of each comparative example are shown in Table 1. For Comparative Example 3, three-layer lamination was performed in-line and continuously.
(Comparative Examples 4-6)

  PLA was used as the substrate, and surface treatment was performed under the treatment conditions described in Table 1 using a corona discharge treatment apparatus (CG-102 type manufactured by Kasuga Electric Co., Ltd.). Next, the aqueous dispersion produced in Production Example 1 or 2 was applied on the surface-treated substrate with a bar coater so as to have a dry film thickness of 1 μm and sufficiently dried. Thereafter, an unstretched polypropylene film (CPP) having a thickness of 70 μm was bonded to the coated surface side by dry lamination using a urethane polyol-based adhesive to prepare a laminate. Detailed conditions of each comparative example are shown in Table 1. For Comparative Example 6, three-layer lamination was performed in-line and continuously.

-Contact angle measurement of base material treatment surface The contact angle before and after surface treatment in each base material was measured with distilled water using an automatic contact angle meter (Kyowa Interface Science Co., Ltd. CA-V). In addition, the value of the contact angle was a value 20 seconds after dropping distilled water. The results are shown in Table 2.

-Evaluation of coatability On the surface of each substrate, the applicability of the fine cellulose aqueous dispersion was evaluated by the number of repellant holes after the fine cellulose application. The results are shown in Table 2.

-Measurement of oxygen permeability Oxygen permeability was measured for each of the laminates produced in Examples 1 to 9 and Comparative Examples 1 to 6 using an oxygen permeability measuring device (MOCON OX-TRAN 2/21 manufactured by Modern Control). (Cm < ³ > / m < ² > * day) was measured in 30 degreeC-70% RH atmosphere. The results are shown in Table 2.

From the result of Table 2, it became possible to improve the coating property of the fine cellulose aqueous dispersion by applying the atmospheric pressure nitrogen plasma treatment on the base material. In addition, it becomes possible to improve the coatability by changing the gas type to nitrogen + oxygen or nitrogen + hydrogen, and further suppress the moisture absorption of the fine cellulose layer by producing a layer structure continuously. As a result, the gas barrier properties can be improved. In addition, Examples 1-4, 7 are reference examples.

Claims (6)

At least three layers of a base material plasma-treated on the surface under atmospheric pressure , a fine cellulose layer containing fine cellulose having a carboxyl group and a heat-sealable thermoplastic resin layer provided on the treated surface are laminated. A laminate,
The gas species of the plasma treatment is one of a composite gas of nitrogen gas and oxygen gas, a composite gas of nitrogen gas and hydrogen gas,
The laminate, wherein the fine cellulose layer contains an inorganic layered mineral, and the content of the inorganic layered mineral is 0.1 to 50% by mass with respect to the fine cellulose . The base material is polyester, polyolefin, cellulose, polyamide, acrylic, polystyrene, polyimide, polycarbonate, polycarbonate, polyvinyl chloride, polyurethane, polyvinyl alcohol, paper, or derivatives thereof. the laminate according to claim 1, characterized in that a composite material. The fine cellulose has a carboxyl group introduced to the crystal surface by an oxidation reaction using an N-oxyl compound, and the amount of the carboxyl group of the fine cellulose is from 0.1 mmol / g to 3.0 mmol / g. The laminate according to claim 1 or 2 . The fine cellulose is less than 50nm number average fiber width is 1nm or more, and according to any one of claims 1 to 3, wherein the number average fiber length is less than 10000 times more than 100 times the number average fiber width Laminated body. Plasma treatment of the substrate under atmospheric pressure, coating of a fine cellulose layer containing fine cellulose having a carboxyl group on the treated surface , and laminating a thermoplastic resin layer on the fine cellulose layer Equipped ,
The gas species of the plasma treatment is one of a composite gas of nitrogen gas and oxygen gas, a composite gas of nitrogen gas and hydrogen gas,
The fine cellulose layer contains an inorganic layered minerals, and the content of the inorganic layered mineral, according to claim 1-4, characterized in <br/> be 0.1 to 50 wt% with respect to the fine cellulose A method for producing the laminate according to any one of the above. Plasma treatment of the substrate under atmospheric pressure, coating of a fine cellulose layer containing fine cellulose having a carboxyl group on the treated surface , and laminating a thermoplastic resin layer on the fine cellulose layer The manufacturing method of the laminated body which comprises, Comprising: All the processes are performed in-line. The manufacturing method of Claim 5 characterized by the above-mentioned.