JP2019116068A - Laminate and method for manufacturing the same - Google Patents

Abstract

To provide a laminate having a structure which is excellent in adhesion between an upper layer body and a lower layer body constituting a laminate and is also excellent in performance (durability of upper layer body) that can maintain performance of the upper layer body.SOLUTION: A laminate is formed by laminating an upper layer body and a lower layer body, in which the upper layer body is a film having a hydrophobic modified cellulose fiber formed by bonding a modification group to one or more selected from a carboxy group and a hydroxyl group of a carboxy group-containing cellulose fiber and an organic medium having an SP value of 10 or less, and the lower layer body is a layer body containing a resin having a hydrogen bond group.SELECTED DRAWING: None

Description

  The present invention relates to a laminate and a method of manufacturing the same.

  2. Description of the Related Art Conventionally, in the field of packaging containers for cosmetics and food, an object that can come in contact with a container, tray, etc. (for example, an object to be filled in a container or packaged with a film, such as cosmetics or food itself) Surface films have been developed to prevent the adhesion of fluids such as water and dirt. Recently, a fibrous polymer forms a skeleton of a network structure in which fibrous polymers are intertwined in a three-dimensional direction, and a porous polymer membrane having a continuous pore structure as its voids, and the inside of the pores of the porous polymer membrane And a lubricant liquid impregnated therein are known (Patent Document 1), and in Patent Document 1, a fluorinated oil or silicone oil is exemplified as the lubricant liquid. (Claim 7).

JP, 2016-011375, A

  However, in the technology of Patent Document 1, the adhesion between the surface film and the base material such as the packaging container is not sufficient, and there is also a problem in the durability of the surface film.

  Therefore, the present invention relates to a laminate having a structure excellent in the adhesion between the upper layer and the lower layer constituting the laminate and capable of maintaining the performance of the upper layer (the durability of the upper layer). The invention further relates to a method of manufacturing such a laminate.

The present invention relates to the following [1] to [2].
[1] A laminate in which an upper layer body and a lower layer body are laminated, wherein the upper layer body is a hydrophobic group in which a modifying group is bonded to at least one selected from carboxy group and hydroxy group of carboxy group-containing cellulose fiber A laminate comprising a modified cellulose fiber and an organic medium having an SP value of 10 or less, wherein the lower layer body is a lower layer body containing a resin having a hydrogen bonding group.
[2] A coating liquid containing a hydrophobic modified cellulose fiber in which a modifying group is bonded to one or more selected from carboxy group and hydroxyl group of carboxy group-containing cellulose fiber, and an organic medium having an SP value of 10 or less is hydrogen The manufacturing method of a laminated body including the process of applying to the lower layer body containing resin which has a coupling group.

  According to the present invention, a laminate having a structure excellent in adhesion between the upper layer and the lower layer, and also excellent in performance (durability of the upper layer) capable of maintaining the performance of the upper layer, and the laminate A method of manufacture is provided.

FIG. 1 is a schematic view showing the cross-sectional structure of one aspect of the laminate of the present invention. FIG. 2 is a schematic view showing a cross-sectional structure of another embodiment of the laminate of the present invention, that is, a laminate in which a base material is further laminated on the lower surface of the lower layer.

[Laminate]
The laminate of the present invention is a laminate in which an upper layer body and a lower layer body are laminated.
A preferred embodiment of the laminate of the present invention is a laminate in which the upper layer is laminated on the upper surface of the lower layer, a cross-sectional view of which is schematically shown in FIG. As shown in FIG. 1, the structure of this embodiment is a structure in which the upper layer 1 is laminated on the upper surface which is one surface of the lower layer 2.
Another preferable embodiment of the laminate of the present invention is a laminate obtained by further laminating a base on the laminate of the above aspect, for example, an upper layer is laminated on the upper surface of the lower layer, and the lower surface of the lower layer Is a laminate further laminated, the cross-sectional view of which is schematically shown in FIG. As shown in FIG. 2, the structure of this embodiment is a structure in which the upper layer 1 is laminated on the upper surface of the lower layer 2 and the base material 3 is laminated on the lower surface which is the other surface of the lower layer 2. The upper layer is at a position not in direct contact with the substrate, the lower layer is positioned between the upper layer and the substrate, and the lower layer is in contact with the substrate. In the present embodiment, the lower layer 2 serves as an adhesive between the upper layer 1 and the base 3.

  The laminate of the present invention may contain layers or films other than the upper layer, lower layer and substrate, such as a printing layer, a gas barrier layer, an adhesive layer, a sealant layer and the like. Such a layer or film is usually laminated on the side of the substrate not in contact with the lower layer body.

  The thickness of the laminate of the present invention is preferably 0.6 μm or more, more preferably 2 μm or more, and still more preferably 13 μm or more, from the viewpoint of securing the mechanical strength as the laminate. On the other hand, from the viewpoint of securing the flexibility as a laminate, it is preferably 240 μm or less, more preferably 170 μm or less, and still more preferably 125 μm or less.

  The thickness of the upper layer in the laminate is preferably 0.5 μm or more, more preferably 1 μm or more, and still more preferably 10 μm or more, from the viewpoint of securing the surface property of the synovial fluid. On the other hand, from the viewpoint of economy, it is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 60 μm or less.

  The thickness of the lower layer in the laminate is preferably 0.1 μm or more, more preferably 1 μm or more, and still more preferably 3 μm or more from the viewpoint of securing adhesiveness and durability. On the other hand, it is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less from the viewpoint of economy.

  The thickness of the substrate in the laminate is preferably 8 μm or more, more preferably 20 μm or more, and still more preferably 50 μm or more from the viewpoint of securing the mechanical strength as the laminate. On the other hand, from the viewpoint of securing the flexibility as a laminate, it is preferably 120 μm or less, more preferably 80 μm or less, and still more preferably 60 μm or less.

  The mechanism by which the laminate of the present invention is excellent in adhesiveness and durability is not clear, but by using a resin having a hydrogen bonding group for the lower layer, the adhesiveness is due to the interaction between the upper layer and the lower layer. As a result that the lower layer body hardly absorbs the organic medium which is a component of the upper layer body, it is presumed that the performance (the durability of the upper layer body) capable of maintaining the performance of the upper layer body is improved.

  The laminate of the present invention is used as a packaging material for various purposes, for example, as a packaging material for daily necessities, cosmetics, household appliances, etc., for transportation and protection of packaging containers such as blister packs and trays, lids for lunch boxes, food containers and industrial parts. It can be suitably used for industrial trays and the like to be used.

[Upper body]
The upper layer is a membrane comprising hydrophobic modified cellulose fiber and an organic medium having an SP value of 10 or less.

  Here, the membrane refers to a membrane that does not flow at room temperature and retains its shape.

As the surface hardness of the film, for example, when measured with a microhardness tester, the Martens hardness (HM) calculated by the following equation is preferably 0.1 (N / mm ² ) or more. Specifically, the Martens hardness of the film is measured by the method described in the below-mentioned Examples.
HM = F / (26.43 × hmax ² )
F: Test force (N)
hmax: Maximum indentation depth (mm)

  The laminate of the present invention is shown in the literature (technology of super-water-repellent, super-oil-repellent, and synovial surface / issuer: Hiroshi Motoki / issuer: Science & Technology Co., Ltd./issued on January 28, 2016) It is preferable to show the surface properties of the synovial fluid. The synovial fluid surface property is expressed by the upper layer which is the upper layer surface of the laminate, and can be evaluated by the method described in the examples below.

  The synovial fluid surface property can be measured, for example, by the method described in the paper (Nature 2011, vol 477, p 443-447). Specifically, the surface property of the synovial fluid was determined by dropping 2 μL droplets (20 ° C.) onto the membrane surface at room temperature of 20 ° C., leaving the surface at a speed of 1 ° / s after standing for 10 seconds. The tilt can be evaluated by measuring the angle at which the droplet starts to flow (hereinafter also referred to as sliding angle) (sliding angle measurement test). For example, when dodecane is used as a droplet in the measurement method, the sliding angle of the membrane is preferably 80 ° or less, more preferably 50 ° or less, still more preferably 40 ° or less from the viewpoint of developing synovial fluid surface properties. It is.

  The arithmetic mean roughness of the upper layer in the laminate of the present invention is preferably 0.5 μm or more, more preferably 0.7 μm or more, and still more preferably, from the viewpoint of securing the surface property of the lubricant to the laminate. It is 1.0 μm or more. On the other hand, from the viewpoint of economy, it is preferably 10.0 μm or less, more preferably 5.0 μm or less, and still more preferably 2.0 μm or less. The arithmetic mean roughness of the upper layer surface of the laminate is determined by the method described in the examples below.

  The upper layer in the present invention is, for example, a membrane for reforming the solid surface of various materials into a synovial fluid surface. By modifying the surface of the synovial fluid, it is possible to impart an effect (adhesion suppression effect) to the solid surface to suppress the adhesion of the fluid.

  One feature of the membrane of the present invention is that the effect of suppressing the adhesion of the fluid contacting the membrane is high. Specifically, the sliding speed is preferably 1.5 cm / min or more, more preferably 2.0 cm / min or more, and still more preferably 2.5 cm / min or more. In addition, sliding speed can be measured according to the method as described in the below-mentioned Example.

  The amount of hydrophobically modified cellulose fiber in the upper layer is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 6% by mass or more, from the viewpoint of adhesion and durability. The content is more preferably 10% by mass or more, and from the same viewpoint, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less.

  The content of the organic medium having an SP value of 10 or less in the upper layer is not particularly limited, but is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably from the viewpoint of adhesion and durability. It is 50% by mass or more, more preferably 55% by mass or more. Moreover, from the same viewpoint, it is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, and further preferably 75% by mass or less. When the organic medium is two or more, the amount of the organic medium is the total amount of each organic medium.

  The upper layer may contain components other than the hydrophobic modified cellulose fiber and the organic medium having an SP value of 10 or less, for example, additives such as a polymer, a low molecular weight surfactant, a filler, and a plasticizer. A polyamide resin etc. are mentioned as a specific example of a polymer. The content of these additives in the upper layer is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less from the viewpoint of exhibiting the effects of the present invention. It is more preferably 1% by mass or less.

<Hydrophobic Modified Cellulose Fiber>
The hydrophobically modified cellulose fiber in the present invention is obtained by bonding a modifying group to one or more groups selected from the carboxy group and the hydroxyl group of a carboxy group-containing cellulose fiber.

(Cellulose fiber)
Cellulose fibers as the raw material are preferably natural cellulose fibers from the environmental point of view; for example, wood pulp such as softwood pulp and hardwood pulp; cotton lumber such as cotton linters and cotton lint; straw pulp, bagasse pulp and the like Non-wood-based pulp; bacterial cellulose etc. may be mentioned, and one of these may be used alone or in combination of two or more.

(Oxidized cellulose fiber)
A carboxyl group-containing cellulose fiber (hereinafter, also referred to as oxidized cellulose fiber) is obtained by oxidizing the raw material cellulose fiber by a known method.
Oxidized cellulose fiber uses, for example, 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) as a catalyst, and an oxidizing agent such as sodium hypochlorite, sodium bromide, etc. It is possible to apply the method of oxidation using bromide in combination. In more detail, the method of Unexamined-Japanese-Patent No. 2011-140632 can be referred, Furthermore, by performing an additional oxidation process or a reduction process, it can prepare as an oxidized cellulose fiber which removed the aldehyde.

By oxidizing cellulose fibers using TEMPO as a catalyst, the C6-position group (-CH ₂ OH) of the cellulose structural unit is selectively converted to a carboxy group. Therefore, a preferred embodiment of the oxidized cellulose fiber in the present invention is a cellulose fiber in which the C6 position of the cellulose structural unit is a carboxy group.

(Carboxyl group content)
The carboxy group content of the oxidized cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.4 mmol / g or more, still more preferably 0.6 mmol / g or more, further preferably from the viewpoint of introducing a modifying group. It is 0.8 mmol / g or more. Also, from the viewpoint of improving the handleability, it is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, and still more preferably 1.8 mmol / g or less. In addition, "carboxy group content" means the total amount of the carboxy group in the cellulose which comprises hydrophobic modified cellulose fiber or oxidized cellulose fiber, and, specifically, it measures by the method as described in the below-mentioned Example.

  In addition, the preferable range of the average fiber diameter, average fiber length and average aspect ratio of the oxidized cellulose fiber is the same as that of the hydrophobic modified cellulose fiber described later, and is determined by the same measuring method as the hydrophobic modified cellulose fiber described later. Can.

(Modification group)
In the present specification, the bonding of the modifying group in the hydrophobic modified cellulose fiber means that the modifying group is ionically bonded to at least one group selected from the group consisting of a carboxy group and a hydroxy group on the oxidized cellulose fiber surface. And / or a state of being linked via a covalent bond. The manner of bonding to a carboxy group includes ionic bonding and covalent bonding. Examples of the covalent bond here include an amide bond, an ester bond, and a urethane bond, and among them, from the viewpoint of adhesion and durability, an amide bond is preferable. Further, the manner of bonding to a hydroxyl group includes a covalent bond, and specifically, an ester bond; an ether bond such as carboxymethylation and carboxyethylation; and a urethane bond. From the viewpoint of adhesion and durability, as the hydrophobically modified cellulose fiber in the present invention, a compound for introducing a modifying group is ionically bonded and / or amide bonded to a carboxy group already present on the surface of oxidized cellulose fiber. What is obtained is preferable.

(Compound for introducing modification group)
As a compound for introducing a modifying group, any one which can introduce a modifying group described later may be used, and for example, the following can be used depending on the binding mode. In the case of ionic bonding, any of primary amines, secondary amines, tertiary amines, quaternary ammonium compounds, and phosphonium compounds may be used. Among these, from the viewpoint of adhesion and durability, preferred are primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds. Further, as the anion component of the above ammonium compound or phosphonium compound, from the viewpoint of reactivity, preferably, a halogen ion such as chlorine ion or bromine ion, hydrogen sulfate ion, perchlorate ion, tetrafluoroborate ion, hexa ion Fluorophosphate ion, trifluoromethanesulfonate ion, hydroxy ion are mentioned, More preferably, hydroxy ion is mentioned. In the case of covalent bonding, the following can be used depending on the functional group to be substituted.

  In the case of modification to a carboxy group, in the case of an amide bond, any of a primary amine and a secondary amine may be used. In the case of an ester bond, an alcohol is preferable, and examples thereof include butanol, octanol and dodecanol. In the case of a urethane bond, an isocyanate compound is preferable.

  In the case of modification to a hydroxyl group, in the case of an ester bond, an acid anhydride is preferable, and examples thereof include acetic anhydride, propionic anhydride and succinic anhydride. In the case of the ether bond, epoxy compounds (for example, alkylene oxide and alkyl glycidyl ether), alkyl halides and derivatives thereof (for example, methyl chloride, ethyl chloride and monochloroacetic acid) are exemplified.

  As the modifying group in the present invention, a hydrocarbon group or the like can be used. These may be bonded (introduced) to the oxidized cellulose fiber alone or in combination of two or more.

(Hydrocarbon group)
The hydrocarbon group includes, for example, a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, a cyclic saturated hydrocarbon group, and an aromatic hydrocarbon group, and from the viewpoint of suppressing side reactions and stability From the viewpoint, a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, and an aromatic hydrocarbon group are preferable.

  The chain saturated hydrocarbon group may be linear or branched. The carbon number of the chain saturated hydrocarbon group is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, still more preferably 6 or more, from the viewpoint of adhesiveness and durability. More preferably, it is 8 or more. Moreover, from the same viewpoint, it is preferably 30 or less, more preferably 24 or less, still more preferably 18 or less, and further preferably 16 or less. In addition, carbon number of a hydrocarbon group means the thing of carbon number in one modifying group hereafter.

  Specific examples of the chain saturated hydrocarbon group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, pentyl group, tert-pentyl group, Isopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, octadecyl group, docosyl group, octacosanyl group, etc. And from the viewpoint of durability, preferably propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, tert-pentyl, isopentyl, hexyl, isohexyl and heptyl groups , Octyl group, 2-ethylhexyl group, nonyl group, decyl group, And decyl, tridecyl, tetradecyl, octadecyl, docosyl and octacosanyl groups. These may be introduced singly or in combination of two or more in any proportion.

  The chain unsaturated hydrocarbon group may be linear or branched. The carbon number of the chain unsaturated hydrocarbon group is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more from the viewpoint of handleability. In addition, from the viewpoint of easy availability, it is preferably 30 or less, more preferably 18 or less, still more preferably 12 or less, and further preferably 8 or less.

  Specific examples of the chain unsaturated hydrocarbon group include, for example, ethylene group, propylene group, butene group, isobutene group, isoprene group, pentene group, hexene group, heptene group, octene group, octene group, nonene group, decene group, dodecene group And tridecene groups, tetradecene groups and octadecene groups, and from the viewpoint of adhesion and durability, preferably ethylene, propylene, butene, isobutene, isoprene, pentene, hexene, heptene, octene groups , Nonene group, decene group, dodecene group. These may be introduced singly or in combination of two or more in any proportion.

  The carbon number of the cyclic saturated hydrocarbon group is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more from the viewpoint of adhesion and durability. Also, from the viewpoint of easy availability, it is preferably 20 or less, more preferably 16 or less, still more preferably 12 or less, and still more preferably 8 or less.

  The carbon number of the aromatic hydrocarbon group is, in terms of adhesion and durability, the carbon number of one modifying group is 6 or more, and from the same viewpoint, preferably 30 or less, more preferably 24 or less. More preferably, it is 18 or less, more preferably 14 or less, still more preferably 10 or less.

  When the modifying group is a hydrocarbon group and the hydrocarbon group has a substituent, the substituent may be, for example, a straight chain having 1 to 6 carbon atoms, provided that the number of carbons in the modifying group satisfies the above range. Or a branched alkoxy group; a linear or branched alkoxycarbonyl group having 1 to 6 carbon atoms of the alkoxy group; a halogen atom such as a bromine atom or an iodine atom; an acyl group having 1 to 6 carbon atoms; an aralkyl group; Group: an alkylamino group having 1 to 6 carbon atoms; a dialkylamino group having 1 to 6 carbon atoms in an alkyl group, a hydroxyl group, an ether, an amide or the like may be used. In addition, the various hydrocarbon groups described above may be bonded to another hydrocarbon group as a substituent.

  The primary amine, secondary amine, tertiary amine, quaternary ammonium compound, phosphonium compound, acid anhydride, isocyanate compound for introducing the above-mentioned hydrocarbon group may be commercially available products or known methods. It can be prepared according to

  As the primary to tertiary amines, the carbon number is preferably 2 or more, more preferably 6 or more from the viewpoint of adhesiveness and durability, and from the same viewpoint, the carbon number is preferably 30 or less. More preferably, it is 24 or less, more preferably 18 or less (except for the amino-modified silicone compound). Specific examples of the primary to tertiary amines include, for example, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, dibutylamine, hexylamine, dihexylamine, octylamine, dioctylamine, trioctylamine And dodecylamine, didodecylamine, stearylamine, distearylamine, monoethanolamine, diethanolamine, triethanolamine, aniline, and benzylamine, amino-modified silicone compounds, and the like. Examples of quaternary ammonium compounds include tetramethyl ammonium hydroxide (TMAH), tetraethyl ammonium hydroxide (TEAH), tetraethyl ammonium chloride, tetrapropyl ammonium hydroxide (TPAH), tetrabutyl ammonium hydroxide (TBAH), and tetrabutyl ammonium hydroxide (TBAH). Examples include butyl ammonium chloride, lauryl trimethyl ammonium chloride, dilauryl dimethyl chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, cetyl trimethyl ammonium chloride, and alkyl benzyl dimethyl ammonium chloride. Among these, from the viewpoint of adhesion and durability, preferably propylamine, dipropylamine, butylamine, dibutylamine, hexylamine, hexylamine, dihexylamine, octylamine, dioctylamine, trioctylamine, dodecylamine, didodecyl Amine, distearylamine, amino-modified silicone compound, tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), tetrapropylammonium hydroxide (TPAH), aniline, more preferably propylamine, dodecylamine, amino-modified It is a silicone compound, tetrabutyl ammonium hydroxide (TBAH), aniline, more preferably an amino-modified silicone compound.

  Among these compounds, hydrophobically modified cellulose fibers obtained using, among others, amino-modified silicone compounds are useful as raw materials for the upper layer. Therefore, as one aspect of the hydrophobic modified cellulose fiber, provided is a hydrophobic modified cellulose fiber in which a modifying group introduced by an amino-modified silicone compound is bonded to one or more groups selected from a carboxy group and a hydroxyl group of oxidized cellulose fiber. Be done. When such a hydrophobically modified cellulose fiber is used as a raw material of the upper layer, the effect of excellent surface property of synovial fluid and the ability to suppress the transfer of the organic medium to the fluid can be exhibited.

(Amino-modified silicone compound)
Preferred amino-modified silicone compounds are amino-modified silicone compounds having a kinematic viscosity of 10 to 20,000 mm ² / s at 25 ° C. and an amino equivalent weight of 400 to 8,000 g / mol.

The kinematic viscosity at 25 ° C. can be determined with an Ostwald viscometer, and from the viewpoint of adhesion and durability, more preferably 200 to 10,000 mm ² / s, still more preferably 500 to 5,000 mm ² / s. is there.

  The amino equivalent is preferably 400 to 8,000 g / mol, more preferably 600 to 5,000 g / mol, and still more preferably 800 to 3,000 g / mol from the viewpoint of adhesion and durability. The amino equivalent is a molecular weight per nitrogen atom, and is determined by amino equivalent (g / mol) = mass average molecular weight / number of nitrogen atoms per molecule. Here, the mass average molecular weight is a value determined by gel permeation chromatography using polystyrene as a standard substance, and the number of nitrogen atoms can be determined by elemental analysis.

  As a specific example of the amino-modified silicone compound, a compound represented by general formula (a1) can be mentioned.

[Wherein, R ^1a represents a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom, preferably a methyl group from the viewpoint of adhesion and durability. Or a hydroxy group. R ^2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group or a hydrogen atom, and is preferably a methyl group or a hydroxy group from the viewpoint of adhesion and durability. B represents a side chain having at least one amino group, and R ^3a represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Each of x and y represents an average degree of polymerization, and is selected so that the kinematic viscosity at 25 ° C. and the amino equivalent of the compound fall within the above ranges. R ^1a , R ^2a and R ^3a may be the same or different, and a plurality of R ^2a may be the same or different. ]

  In the compound of the general formula (a1), in view of adhesion and durability, x is preferably a number of 10 to 10,000, more preferably a number of 20 to 5,000, still more preferably 30 to 3,000. It is a number. y is preferably a number of 1 to 1,000, more preferably a number of 1 to 500, still more preferably a number of 1 to 200. The weight average molecular weight of the compound of the general formula (a1) is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000, and still more preferably 8,000 to 50,000.

In the general formula (a1), examples of the side chain B having an amino group include the following.
-C ₃ H ₆ -NH _{2
-C 3 H 6 -NH-C 2} H 4 -NH 2
_{-C 3 H 6 -NH- [C 2} H 4 -NH] e -C 2 H 4 -NH 2
_{-C 3 H 6 -NH (CH 3} )
_{-C 3 H 6 -NH-C 2} H 4 -NH (CH 3)
_{-C 3 H 6 -NH- [C 2} H 4 -NH] f -C 2 H 4 -NH (CH 3)
_{-C 3 H 6 -N (CH 3} ) 2
_{-C 3 H 6 -N (CH 3} ) -C 2 H 4 -N (CH 3) 2
_{-C 3 H 6 -N (CH 3} ) - [C 2 H 4 -N (CH 3)] g -C 2 H 4 -N (CH 3) 2
_{-C 3 H 6 -NH-cyclo-} C 5 H 11
(Here, e, f and g are each a number of 1 to 30.)

The amino-modified silicone compound used in the present invention is, for example, a hydrolyzate obtained by hydrolyzing an organoalkoxysilane represented by the general formula (a2) with an excess of water, and sodium hydroxide with dimethylcyclopolysiloxane. The reaction is equilibrated by heating to 80 to 110 ° C. using a basic catalyst such as, and produced by neutralizing the basic catalyst using an acid when the reaction mixture reaches a desired viscosity (See JP-A-53-98499).
_{H 2 N (CH 2) 2} NH (CH 2) 3 Si (CH 3) (OCH 3) 2 (a2)

In addition, as the amino-modified silicone compound, from the viewpoint of adhesion and durability, preferably a mono-amino-modified silicone having one amino group in one side chain B and an amino group in one side chain B Is a compound selected from the group consisting of diamino-modified silicones having two, more preferably a compound in which the side chain B having an amino group is represented by —C ₃ H ₆ —NH ₂ [hereinafter, referred to as (a1-1) And a side chain B having an amino group is selected from the group consisting of compounds represented by -C ₃ H ₆ -NH-C ₂ H ₄ -NH ₂ [hereinafter referred to as component (a1-2)]. One or more.

As the amino-modified silicone compound in the present invention, from the viewpoint of performance, TSF 4703 (kinematic viscosity: 1000, amino equivalent: 1600), TSF 4708 (kinematic viscosity: 1000, amino equivalent: 2800) manufactured by Momentive Performance Materials, Inc. Toray Dow Corning Silicone Co., Ltd. SS-3551 (Kinematic viscosity: 1000, Amino equivalent: 1600), SF8457C (Kinematic viscosity: 1200, Amino equivalent: 1800), SF8417 (Kinematic viscosity: 1200, Amino equivalent: 1700) ), BY16-209 (Kinematic viscosity: 500, Amino equivalent: 1800), BY16-892 (Kinematic viscosity: 1500, Amino equivalent: 2000), BY 16-898 (Kinematic viscosity: 2000, Amino equivalent: 2900), FZ-3760 (Kinematic viscosity: 220, amino equivalent: 600), Shin-Etsu Chemical Co., Ltd. KF 8002 (Kinematic viscosity: 1100, Amino equivalent: 1700), KF 867 (Kinematic viscosity: 1300, Amino equivalent: 1700), KF-864 (Kinematic viscosity: 1700, Amino equivalent: 3800) ), BY16-213 (kinetic viscosity: 55, amino equivalent: 2700), BY16-853U (kinetic viscosity: 14, amino equivalent: 450) are preferable. In (), the kinematic viscosity shows a measured value at 25 ° C. (unit: mm ² / s), and the unit of amino equivalent is g / mol.

  As the component (a1-1), BY16-213 and BY16-853U are more preferable. As the component (a1-2), SF8417, BY16-209 and FZ-3760 are more preferable.

  The average bonding amount of the modifying group in the hydrophobically modified cellulose fiber, preferably one or more groups selected from the group consisting of a hydrocarbon group and a silicone group, is from the viewpoint of adhesion and durability per hydrophobically modified cellulose fiber, It is preferably 0.01 mmol / g or more, more preferably 0.05 mmol / g or more, further preferably 0.1 mmol / g or more, still more preferably 0.3 mmol / g or more, further preferably 0.5 mmol / g or more . Further, from the viewpoint of reactivity, it is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less, still more preferably 2 mmol / g or less, still more preferably 1.8 mmol / g or less, still more preferably 1.5 mmol / g. g or less. Here, when a hydrocarbon group selected from a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, and a cyclic saturated hydrocarbon group as a modifying group and an aromatic hydrocarbon group are simultaneously introduced. Even if the average binding amount of each individual is preferably within the above range.

  In addition, the introduction rate of the modifying group in the hydrophobically modified cellulose fiber is preferably 5% or more, more preferably 10% or more, and still more preferably 15% or more from the viewpoint of adhesion and durability for any of the modifying groups. From the viewpoint of reactivity, it is preferably 70% or less, more preferably 60% or less, and still more preferably 50% or less.

  In the present specification, the average bonding amount of the modifying group is adjusted by the addition amount of the compound for introducing the modifying group, the kind of the compound for introducing the modifying group, the reaction temperature, the reaction time, the solvent and the like. Can. Moreover, the average bonding amount (mmol / g) and introduction ratio (%) of the modifying group in the hydrophobic modified cellulose fiber are the amount and ratio of the modifying group introduced to the carboxy group or hydroxyl group of the hydrophobic modified cellulose fiber surface. The carboxy group content of the hydrophobically modified cellulose fiber can be calculated according to a known method (for example, titration, IR measurement, etc.), specifically, by measurement according to the method described in the examples described later, and is hydrophobic. The hydroxyl group content of the modified cellulose fiber can be calculated by measurement according to a known method (for example, titration, IR measurement, etc.).

<Method for producing hydrophobically modified cellulose fiber>
The hydrophobically modified cellulose cellulose fiber used in the present invention can be produced according to a known method without particular limitation as long as it can introduce a modifying group into the above-mentioned oxidized cellulose fiber. For example, the method of implementing the process of introduce | transducing a modifying group to an oxidized cellulose fiber, and the process of refine | miniaturizing the object cellulose fiber is implemented without restriction | limiting to an order. The oxidized cellulose fiber referred to here is a known method, for example, an oxidized cellulose fiber obtained with reference to the explanation of the oxidation reaction step described in JP-A-2011-140632, or additionally, additional oxidation treatment Alternatively, by performing reduction treatment, it can be prepared as oxidized cellulose fiber from which aldehyde is removed.

(Step of introducing modifying group)
Specific steps include an aspect (aspect A) in which the modifying group is bound to the oxidized cellulose fiber by ionic bond, and an aspect (aspect B) in which the modifying group is bound to the oxidized cellulose fiber by covalent bond. In addition, as a covalent bond, the case of an amide bond is shown below.
(Aspect A)
Mixing the oxidized cellulose fiber with the compound having a modifying group.
(Aspect B)
A process of amidating the oxidized cellulose fiber with a compound having a modifying group.
As a specific method, Embodiment A refers to the method described in step (B) of JP-A-2015-143336, and Embodiment B refers to the method described in step (B) of JP-A-2015-143337. Can be implemented. In addition, "the amine which has an EO / PO copolymerized part" in process (B) of both gazettes corresponds in the "compound for introduce | transducing a modifying group" in this invention.

(Micronization process)
This step is a step of refining the oxidized cellulose fiber (or the oxidized cellulose fiber into which the modifying group is introduced), and a fine oxidized cellulose fiber can be obtained. In the refining step, it is preferable to disperse the oxidized cellulose fiber which has been subjected to the refining step in a solvent to carry out a refining treatment. Specifically, it can carry out with reference to description of the refinement | miniaturization process of Unexamined-Japanese-Patent No. 2013-151661.

  The average fiber diameter of the obtained hydrophobically modified cellulose fiber is preferably 0.1 nm or more, more preferably 0.5 nm or more, still more preferably 1 nm or more, still more preferably 2 nm or more, from the viewpoint of adhesion and durability. More preferably, it is 3 nm or more. From the same point of view, it is preferably 100 nm or less, more preferably 50 nm or less, still more preferably 20 nm or less, still more preferably 10 nm or less, further preferably 6 nm or less, still more preferably 5 nm or less.

  The length (average fiber length) of the obtained hydrophobically modified cellulose fiber is preferably 150 nm or more, more preferably 200 nm or more, from the viewpoint of adhesion and durability. In addition, from the same viewpoint, it is preferably 1000 nm or less, more preferably 750 nm or less, still more preferably 500 nm or less, and further preferably 400 nm or less.

The average aspect ratio (fiber length / fiber diameter) of the obtained hydrophobically modified cellulose fiber is preferably 1 or more, more preferably 10 or more, still more preferably 20 or more, further preferably from the viewpoint of adhesion and durability. Is 40 or more, more preferably 50 or more, and from the same viewpoint, preferably 150 or less, more preferably 140 or less, still more preferably 130 or less, still more preferably 100 or less, still more preferably 95 or less, more preferably 90 It is below. In addition, when the average aspect ratio is within the above range, the standard deviation of the aspect ratio is preferably 60 or less, more preferably 50 or less, and still more preferably 45 or less, from the viewpoint of adhesion and durability. Is not particularly set, but is preferably 4 or more from the viewpoint of economy. The low aspect ratio hydrophobic modified cellulose fiber is excellent in the dispersibility in the dispersion, so that a highly uniform film can be obtained.
The average fiber diameter, average fiber length and average aspect ratio of the hydrophobically-modified cellulose fiber can be determined by the method described in the examples below.

<Organic media with an SP value of 10 or less>
In the present invention, an organic medium having an SP value of 10 or less defined as described above is used as a lubricating oil constituting the upper layer.

The SP value in the present specification indicates the solubility parameter (unit: (cal / cm ³ ) ^1/2 ) calculated by the Fedors method, and, for example, the reference document “SP value basic / application and calculation method” (information mechanism (2005), Polymer handbook Third edition (A Wiley-Interscience publication, 1989), and the like.

  The mass average molecular weight of the organic medium having an SP value of 10 or less is not particularly limited, but is preferably 100 or more, and preferably 100,000 or less, more preferably 50,000 or less, still more preferably 20,000. It is below.

  As an organic medium having an SP value of 10 or less used in the present invention, for example, oleic acid (SP value: 9.2), D-limonene (SP value: 9.4), PEG 400 (SP value: 9.4) ), Dimethyl succinate (SP value: 9.9), neopentyl glycol dicaprate (SP value: 8.9), hexyl laurate (SP value: 8.6), isopropyl laurate (SP value 8.5) , Isopropyl myristate (SP value 8.5), isopropyl palmitate (SP value 8.5), isopropyl oleate (SP value: 8.6), hexadecane (SP value: 8.0), olive oil (SP value: 9.3), jojoba oil (SP value: 8.6), squalane (SP value: 7.9), liquid paraffin (SP value: 7.9), Fluorinert FC-40 (manufactured by 3M, SP value: 6) .1), Florinator FC-43 (manufactured by 3M, SP: 6.1) Florinert FC-72 (manufactured by 3M, SP: 6.1), Florinert FC-770 (manufactured by 3M, SP: 6.1), KF96 -1cs (Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-10 cs (Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-50 cs (Shin-Etsu Chemical Co., Ltd., SP value: 7) .3), KF-96-100cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-1000 cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), and the like. Among these, from the viewpoint of adhesion and durability, the SP value of the organic medium is preferably 9.5 or less, more preferably 9.0 or less, and still more preferably 8.5 or less.

<Method of forming upper body>
As an example of the method of forming the upper layer, a coating liquid containing at least the hydrophobic modified cellulose fiber which is a component of the upper layer and the organic medium is prepared, and then the coating liquid is applied to the lower layer. The method of working is mentioned.

(Preparation of coating solution)
The coating liquid can be prepared by mixing the hydrophobic modified cellulose fiber and the organic medium, preferably from the viewpoint of adhesiveness and durability, by mixing together with an organic solvent.

  The amount of hydrophobically modified cellulose fiber in the coating liquid is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and still more preferably 1 from the viewpoint of adhesion and durability. .5% by mass or more, and from the same viewpoint, preferably 5.0% by mass or less, more preferably 4.5% by mass or less, and still more preferably 4.0% by mass or less.

  The amount of the organic medium having an SP value of 10 or less in the coating liquid is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, from the viewpoint of adhesion and durability. More preferably, it is 1.5% by mass or more, and from the same viewpoint, it is preferably 5.0% by mass or less, more preferably 4.5% by mass or less, still more preferably 4.0% by mass or less is there.

  Examples of the organic solvent include isopropyl alcohol, ethanol, methyl ethyl ketone, toluene and the like.

  The amount of the organic solvent in the coating liquid is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more from the viewpoint of adhesion and durability. From the same viewpoint, it is preferably 99% by mass or less, more preferably 98% by mass or less, and still more preferably 97% by mass or less.

  The coating liquid may contain components other than these.

  As mixing conditions of these components, 15-35 degreeC is preferable, for example. Furthermore, as mixing time, 10 minutes-36 hours are preferable.

(Coating to lower layer)
Examples of the coating method for applying the coating liquid to the lower layer body include a method using an applicator, a bar coater and a roll coater, and various coating methods such as gravure coating, dip coating, spray coating and spin coating. Be

  The thickness of the coating liquid when the coating liquid is applied to the lower layer is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 30 μm from the viewpoint of synovial velocity and durability. From the viewpoint of the properties, it is preferably 2000 μm or less, more preferably 1500 μm or less, and still more preferably 1200 μm or less.

  Then, the applied coating liquid is dried. Drying conditions may be under reduced pressure or normal pressure, and a temperature range of 15 to 75 ° C. is preferable. Moreover, as time for drying, 1 to 24 hours are preferable.

  Thus, a film-like upper layer is formed.

[Lower body]
The lower layer in the present invention is a lower layer containing a resin having a hydrogen bonding group. The lower layer is a layer in contact with the upper layer. Moreover, when there is a substrate, the lower layer body is a layer in contact with the substrate.

  The hydrogen bonding group in the resin having a hydrogen bonding group means a group having a proton donor or an acceptor, and examples thereof include a carboxy group, a carbonyl group, an amido group, an amino group, a hydroxyl group and the like. And from the viewpoint of durability, preferably a carboxyl group, an amido group and an amino group.

  The mass average molecular weight of the resin having a hydrogen bonding group is preferably 1,000 or more from the viewpoint of adhesion and durability, and preferably 500,000 or less from the same viewpoint.

  Preferred specific examples of the resin having a hydrogen bonding group are selected from the group consisting of polyamide resin, acrylic resin, polycarbonate resin, phenol resin, melamine resin, furan resin, epoxy resin, phenoxy resin, polyester resin, and polyurethane resin 1 There may be mentioned species or more of resins. Among these, from the viewpoint of adhesiveness and durability, preferred are polyamide resins, acrylic resins, epoxy resins, phenoxy resins, and polyurethane resins, and more preferred are polyamide resins, acrylic resins, and polyurethane resins.

  The amount of the resin having a hydrogen bonding group in the lower layer is preferably as large as possible from the viewpoint of adhesion, specifically, preferably 30% by mass or more, and more preferably 50% by mass or more. Preferably it is 70 mass% or more. On the other hand, a preferable upper limit is 100 mass% or less.

  The lower layer may contain components other than the resin having a hydrogen bonding group, for example, leveling agents, reinforcing agents, polymers such as antistatic agents, ultraviolet absorbers, and additives such as various activators. When these additives are contained, the content of these additives is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 10% by mass or less in the lower layer body.

<Method of forming lower layer body>
Resins having hydrogen bonding groups are commercially available as solutions or dispersions. The lower layer can be easily formed by, for example, applying such a solution or dispersion on a substrate and drying it. Alternatively, the lower layer can also be formed by applying such a solution or dispersion on a preformed upper layer and drying it. The coating method for obtaining the lower layer in this case can be performed by the same method as the coating method for forming the upper layer described above.
Also, resins having hydrogen bonding groups are commercially available as pellets. In such a case, the lower layer body in the form of a film or in the form of a molded article can be formed by various molding methods such as film molding, injection molding, blow molding, pressure forming, and extrusion molding.

[Base material]
Resin, glass, metal, ceramics, paper etc. are mentioned as a raw material of a base material. Examples of the resin include polyethylene (PE) resin such as linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP) resin, ABS resin, polyamide resin, Acrylic resin, polycarbonate resin, phenol resin, melamine resin, furan resin, epoxy resin, phenoxy resin, polyester resin, polyurethane resin and the like can be mentioned. Among these, from the viewpoint of versatility, polyethylene resins, polypropylene resins and polyester resins are preferable.

  The shape of the substrate is not particularly limited, and may be film-like, desired container-like, sheet-like, plate-like, tubular, molded-like or the like.

[Method of manufacturing laminate]
The method for producing a laminate of the present invention comprises: a hydrophobically modified cellulose fiber in which a modifying group is bonded to at least one selected from the carboxy group and the hydroxyl group of a carboxy group-containing cellulose fiber, and an organic medium having an SP value of 10 or less. The process of applying the coating liquid containing to the lower layer body containing resin which has a hydrogen bond group is included. The laminate of the present invention can be produced, for example, by the method of producing a laminate of the present invention.

  The preparation method of a coating liquid and the method of coating to a lower layer body can be performed similarly to the method as described above.

  According to the manufacturing method of the present invention, a film-like upper layer is formed, and a laminate in which the upper layer and the lower layer are laminated is obtained.

  Furthermore, in the embodiment in which the base is laminated, the base material and the lower layer may be prepared in advance, and the upper layer may be formed on the obtained laminated structure, or the upper layer and the lower layer are prepared in advance. The base material may be laminated or formed on the resulting laminate. Specifically, the manufacturing method is exemplified in which the coating liquid is applied to the upper surface of the lower layer body, and the base material is further laminated on the lower surface of the lower layer body.

  Hereinafter, the present invention will be specifically described by way of examples. Note that this example is merely an example of the present invention and does not mean any limitation. Parts in the examples are parts by weight unless otherwise stated. In addition, "atmospheric pressure" shows 101.3 kPa and "room temperature" shows 25 degreeC.

[Average fiber diameter, average fiber length, average aspect ratio of oxidized cellulose fiber and hydrophobic modified cellulose fiber]
Water is added to oxidized cellulose fiber or hydrophobically modified cellulose fiber to prepare a dispersion having a concentration of 0.0001% by mass, and the dispersion is dropped onto mica (mica) and dried to obtain an observation sample. Atomic force microscope (AFM, Nanoscope III Tapping mode AFM, manufactured by Digital instrument, using a point probe (NCH) manufactured by Nano Sensors Co., Ltd.), oxidized cellulose fiber or hydrophobically modified cellulose fiber in the observation sample Measure the fiber height of At that time, in a microscope image in which the cellulose fibers can be confirmed, 100 or more of the cellulose fibers are extracted, and the average fiber diameter is calculated from the heights of the fibers. The average fiber length is calculated from the distance in the fiber direction. The average aspect ratio is calculated from the average fiber length / average fiber diameter, and the standard deviation is also calculated.

[Carboxyl group content of oxidized cellulose fiber and hydrophobically modified cellulose fiber]
A dry mass of 0.5 g of oxidized cellulose fiber or hydrophobically modified cellulose fiber is placed in a 100 mL beaker, and ion-exchanged water or a mixed solvent of methanol / water = 2/1 is added to make a total of 55 mL, to which 5 mL of 0.01 M aqueous sodium chloride solution Is added to prepare a dispersion, and the dispersion is stirred until the oxidized cellulose fiber or the hydrophobic modified cellulose fiber is sufficiently dispersed. The pH is adjusted to 2.5 to 3 by adding 0.1 M hydrochloric acid to this dispersion, and a 0.05 M aqueous solution of sodium hydroxide is added using an automatic titrator (trade name "AUT-710" manufactured by Toa DK Co., Ltd.). The solution is dropped on the dispersion under the condition of a waiting time of 60 seconds, the value of the conductivity and pH is measured every minute, and the measurement is continued until the pH becomes around 11, to obtain a conductivity curve. From this conductivity curve, the sodium hydroxide titer is determined, and the carboxy group content of the oxidized cellulose fiber or the hydrophobic modified cellulose fiber is calculated by the following equation.
Carboxy group content (mmol / g) = sodium hydroxide titer × sodium hydroxide aqueous solution concentration (0.05 M) / mass of oxidized cellulose fiber or hydrophobically modified cellulose fiber (0.5 g)

[Aldehyde group content of oxidized cellulose fiber and hydrophobically modified cellulose fiber]
In a beaker, 100.0 g of oxidized cellulose fiber or hydrophobically-modified cellulose fiber (solid content: 1.0% by mass), acetate buffer (pH 4.8), 0.33 g of 2-methyl-2-butene, sodium chlorite Add 0.45 g and stir at room temperature for 16 hours to oxidize the aldehyde group. After completion of the reaction, the reaction product is washed with ion exchange water to obtain oxidized cellulose fiber or hydrophobically modified cellulose fiber obtained by oxidizing aldehyde. The reaction solution is subjected to lyophilization treatment, and the obtained dried product is subjected to the measurement of the carboxy group content of the oxidized cellulose fiber or the hydrophobic modified cellulose fiber by the method described above, and the carboxy of the oxidized cellulose fiber or the hydrophobic modified cellulose fiber Calculate the group content. Subsequently, the aldehyde group content of the oxidized cellulose fiber or the hydrophobic modified cellulose fiber is calculated by the formula 1.

  Aldehyde group content (mmol / g) = (carboxy group content of oxidized oxidized cellulose fiber or hydrophobic modified cellulose fiber)-(carboxy group content of oxidized cellulose fiber or hydrophobic modified cellulose fiber) Formula 1

[Solid content in dispersion]
It carries out using a halogen moisture meter (made by Shimadzu Corporation; brand name "MOC-120H"). Measurement is carried out every 30 seconds at a constant temperature of 150 ° C. with respect to 1 g of the sample, and a value at which the mass loss is 0.1% or less is taken as a solid content.

[Average binding amount and introduction ratio of modifying groups of hydrophobic modified cellulose fiber (ion binding)]
The binding amount of the modifying group is determined by the following IR measurement method, and the average binding amount and the introduction ratio are calculated by the following formula. Specifically, the IR measurement is performed by ATR method using a dried hydrophobic modified cellulose fiber by using an infrared absorption spectrometer (IR) (manufactured by Thermo Fisher Scientific Co., Ltd .; trade name “Nicolet 6700”), The average bonding amount and the introduction rate of the modifying group are calculated by the following formula.
The average amount of binding of the modifying group (mmol / g) = [a carboxyl group content of the oxidized cellulose fibers (mmol / g)] × [ ( peak intensity of 1720 cm ^-1 of the oxidized cellulose fibers - the hydrophobically modified cellulose fibers 1720 cm ^-1 Peak strength) 1720 cm ^-1 peak strength of oxidized cellulose fiber]
Peak intensity at 1720 cm ^-1 : Peak intensity derived from carbonyl group of carboxylic acid Introduction rate of modification group (%) = {Modified amount of modification group (mmol / g) / Carboxy group content in oxidized cellulose fiber before introduction (Mmol / g)} × 100

[Average binding amount and introduction ratio of modifying groups of hydrophobic modified cellulose fiber (amide bond)]
The average bonding amount of the modifying group is calculated by the following formula.
Average binding amount of modifying group (mmol / g) = carboxyl group content in oxidized cellulose fiber before introducing modifying group (mmol / g) -carboxyl group content in hydrophobic modified cellulose fiber after introducing modifying group (mmol / g) g)
Introduction ratio of modification group (%) = {average binding amount of modification group (mmol / g) / carboxy group content in oxidized cellulose fiber before introduction (mmol / g)} × 100

[Measurement of Arithmetic Average Roughness of Upper Body Surface of Laminate]
The arithmetic mean roughness of the upper layer surface of the laminate is measured under the following measurement conditions using a laser microscope (manufactured by Keyence Corporation; trade name "VK-9710"). Measurement conditions are: objective lens: 10 ×, light quantity: 3%, brightness: 1548, Z pitch: 0.5 μm. The surface arithmetic average roughness is measured at 5 points using built-in image processing software, and the average value is used.

[Measurement of film hardness]
The surface hardness (Martens hardness) of the surface of the obtained laminate, that is, the film of the upper layer is measured using the hardness tester DUH-211 (manufactured by Shimadzu Science Co., Ltd.) under the following conditions.
Test force: 0.1 mN
Load holding time: 5 (s)
Unloading holding time: 1 (s)

[Slip angle measurement test]
Drop 2 μl of dodecane (20 ° C) onto the membrane at room temperature 20 ° C, and let it stand for 10 seconds, then tilt the surface of the membrane at a rate of 1 ° / s to make the angle at which the drop begins to flow taking measurement. As a representative example, the sliding angle of the membrane of Example 1 was 2 °.

[Preparation of oxidized cellulose fiber dispersion]
Preparation Example 1 (Dispersion of oxidized cellulose fiber obtained by reacting N-oxyl compound with natural cellulose fiber)
Softwood bleached kraft pulp (Fletcher Challenge Canada, trade name "Machenzie", CSF 650 ml) was used as a natural cellulose fiber. As TEMPO, a commercial item (manufactured by ALDRICH, Free radical, 98% by mass) was used. A commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used as sodium hypochlorite. A commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used as sodium bromide.

  First, 100 g of softwood bleached kraft pulp fiber is sufficiently stirred with 9900 g of ion-exchanged water, and 1.25 g of TEMPO, 12.5 g of sodium bromide and 28.4 g of sodium hypochlorite with respect to 100 g of the pulp mass. It added in order. The pH was kept at 10.5 by dropwise addition of 0.5 M sodium hydroxide using a pH stud. The reaction was carried out for 120 minutes (20 ° C.), after which the dropping of sodium hydroxide was stopped to obtain an oxidized pulp. The resulting oxidized pulp was thoroughly washed with ion exchanged water and then subjected to a dehydration treatment. After that, 3.9 g of oxidized pulp and 296.1 g of ion-exchanged water were finely pulverized twice at 245 MPa using a high-pressure homogenizer (Starburst Lab HJP-2505 manufactured by Sugino Machine Co., Ltd.) to obtain an oxidized cellulose fiber dispersion ( A solid content of 1.3% by mass was obtained. The average fiber diameter of this oxidized cellulose fiber was 3.3 nm, the carboxy group content was 1.62 mmol / g, and the aldehyde group weight was 0.27 mmol / g.

Preparation Example 2 (Dispersion of Oxidized Cellulose Fiber in which Aldehyde Group is Reduced)
Into a beaker, 3846.15 g (solid content: 1.3% by mass) of the oxidized cellulose fiber dispersion obtained in Preparation Example 1 is added, and a 1 M aqueous solution of sodium hydroxide is added thereto to adjust the pH to about 10, and then borohydride 2.63 g of sodium (manufactured by Wako Pure Chemical Industries, Ltd., purity: 95% by mass) was charged, reacted at room temperature for 3 hours, and subjected to aldehyde reduction treatment. After completion of the reaction, 405 g of a 1 M aqueous hydrochloric acid solution and 4286 g of ion-exchanged water were added to make a 0.7 mass% aqueous solution, and reaction was performed at room temperature for 1 hour to perform protonation. After completion of the reaction, the resulting cake was filtered and washed with deionized water to remove hydrochloric acid and salts. Finally, solvent substitution was performed with isopropanol to obtain an oxidized cellulose fiber dispersion in which the aldehyde group was reduced. The average fiber diameter of the oxidized cellulose fiber dispersion (solid content: 2.0% by mass) obtained by reduction treatment of the obtained aldehyde group is 3.3 nm, the carboxyl group content is 1.62 mmol / g, and the amount of aldehyde group is 0 It was .02 mmol / g.

[Preparation of hydrophobic modified cellulose fiber]
Production Example 1
In a beaker equipped with a magnetic stirrer and a stirrer, 300 g (solid content: 2.0% by mass) of the oxidized cellulose fiber dispersion obtained in Preparation Example 2 was charged. Subsequently, an amino-modified silicone (BY16-209, manufactured by Toray Dow Corning Co., Ltd., abbreviated as “silicone 1”) is added in an amount corresponding to 0.5 mol of amino group to 1 mol of carboxy group of oxidized cellulose fiber. Charged, 100 g of isopropanol was added, and the mixture was reacted at room temperature (25 ° C.) for 14 hours. After completion of the reaction, the resulting cake is washed with isopropanol and stirred for 2 minutes with an ultrasonic homogenizer (US-300E, manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then a high pressure homogenizer (Sugino Machine, Starburst Lab HJP) The hydrophobic modified cellulose fiber in which the amino-modified silicone is linked to the oxidized cellulose fiber via an ionic bond is obtained by minute processing of 1 pass at 100 MPa and 9 passes at 150 MPa at -2 5005). The introduction rate of the modifying group in the obtained hydrophobically modified cellulose fiber was 40% of the carboxy group of the oxidized cellulose fiber.

[Coating of lower layer body]
Example 1
First, using a corona treatment apparatus (made by Kasuga), a linear low density polyethylene (LLDPE) film (Mitsui Chemical Higashi Cello Co., Ltd., MCS) with a film thickness of 50 μm as a base material, output 6, moving speed 30 cm / s Treated with corona. Next, using a bar coater (OSP-13 manufactured by OSG Systems Products Co., Ltd.) on the corona-treated surface of the LLDPE film, an aqueous urethane emulsion (manufactured by DSM, NeoRez R-9603, as a coating liquid for forming a lower layer body It coated (it abbreviated as "urethane 1"). It dried under room temperature (25 degreeC) for 24 hours, the solvent was volatilized, and the laminated structure of a base material (LLDPE film) and a lower layer body was obtained. The thickness of the lower layer body formed of urethane 1 was 3 μm.

[Preparation of upper layer on lower layer]
Using the hydrophobic modified cellulose fiber obtained in Production Example 1, an upper layer was produced on the surface of the lower layer side of the laminated structure as follows. Cellulose fiber of hydrophobically modified cellulose fiber: squalane (lubricating oil): polyamide (Kao Corp., SP-40N) in a mass ratio of 1: 3: 1, and the solvent becomes 97% of the whole dispersion liquid Thus, hydrophobically modified cellulose fiber, squalane, polyamide and a solvent (a mixed solvent of isopropyl alcohol: toluene = 100: 5) were blended, and stirred in a screw tube at room temperature for 24 hours. Using the obtained dispersion for forming the upper layer as a coating film sample, using an applicator (manufactured by Tester Sangyo Co., Ltd.) on the lower layer side of the laminated structure, the thickness of the coating solution sample liquid would be 1800 μm. It was coated. The solvent was evaporated by drying at room temperature (25 ° C.) for 12 hours to obtain a laminate of an upper layer, a lower layer and a substrate, in which an upper layer having a thickness of about 50 μm was produced. In addition, it was 2.6 (N / mm < ² >) when the Martens hardness of the film | membrane of the obtained laminated body was measured as mentioned above.

Example 2
A lower layer is formed by the same method as in Example 1 except that the coating liquid for forming the lower layer is changed to an acrylic emulsion (manufactured by DSM, NeoCryl A-1127), and the upper layer, the lower layer, and the substrate Was obtained. The thickness of the lower layer formed of acrylic was 3 μm.

Example 3
The polyamide (manufactured by Kao Corporation, SP-40N) was stirred in a screw tube at room temperature for 1 hour in a solvent (isopropyl alcohol: toluene = 1: 1 mixed solvent) to 10 wt%. And the lower layer was formed by the method similar to Example 1 except that the obtained liquid was changed as a coating liquid which forms a lower layer, and the layered product of an upper layer, a lower layer, and a substrate was obtained. . The thickness of the lower layer formed of polyamide was 3 μm.

[Preparation of upper layer body to lower layer body alone]
Example 4
Using the hydrophobically modified cellulose fiber obtained in Production Example 1, an upper layer was produced on the lower layer as follows. The coating film sample for forming the upper layer used in Example 1 was coated on a 15 μm thick nylon film (Bonille RX, manufactured by Kojin Co., Ltd.), which is the lower layer, using an applicator to obtain a coating film sample having a thickness of 1800 μm. It coated so that it might become. The solvent was evaporated by drying at room temperature (25 ° C.) for 12 hours to obtain a laminate of an upper layer and a lower layer, in which an upper layer having a thickness of about 50 μm was produced.

Examples 5 to 7
As a coating liquid for forming the lower layer body, urethane 2 of aqueous urethane emulsion (manufactured by DSM, NeoRez R-9637), urethane 3 (manufactured by DSM, NeoRez R-966) or urethane 4 (manufactured by DSM, NeoRez R-960) The coating liquid was applied in the same manner as in Example 1 except that it was changed to) to obtain a laminate of an upper layer, a lower layer and a substrate.

Comparative Example 1
A laminate of an upper layer and a lower layer was obtained in the same manner as in Example 4 except that the lower layer was changed to a 50 μm thick LLDPE film (manufactured by Mitsui Chemicals Tosoh Co., Ltd., MCS). Here, LLDPE is a resin having no hydrogen bonding group.

[Performance test of laminate]
The following tests were performed at room temperature. The details of Fluid A used in the test are as follows.
Cortamine E-80K (manufactured by Kao Corporation): 3% by mass
Propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.): 1% by mass
Ion exchange water: balance

Test Example 1 (Evaluation of adhesion suppression effect)
50 mg of fluid A was placed on the surface of the upper layer of the laminate produced in the example or comparative example, and the substrate was tilted at 90 ° and slid down. The distance over which the fluid A slipped per minute was measured.

Test example 2 (adhesion evaluation between upper layer and lower layer)
The adhesion evaluation between the upper layer and the lower layer was performed as follows. Using a paper wipe, wipe the lubricating oil on the upper layer of the laminate produced in the example or comparative example firmly, and use a cutter (OLFA company, 142 BY) to obtain 25 squares at 2 mm x 2 mm per square. Cut the membrane at. A tape (Lintech Co., Ltd., PET 50 (A) MF 8LK2) was attached onto the square, and the tape was rubbed firmly with a finger so that the coating film could be seen through. Within 5 minutes of adhesion, the number of remaining coated film pieces of the upper layer remaining on the laminate was measured when it was peeled off within 1 second at an angle of 60 °. It can be said that the adhesion between the upper layer and the lower layer is stronger as the number of remaining coating pieces is larger.

The following was found from the above table.
With regard to adhesion, the lower layer and the upper layer containing a resin having a hydrogen bonding group shown in the examples have good adhesion compared to the lower layer and the upper layer containing a resin not having a hydrogen bonding group. The results were obtained.

Test Example 3 (durability evaluation)
The durability of the laminate was evaluated as follows. The adhesion suppression effect immediately after the production of the laminate produced in the example or the comparative example was evaluated as in Test Example 1. Furthermore, the adhesion suppression effect of the laminated body after storing for 2 weeks at room temperature (25 degreeC) was evaluated again similarly.

The following was found from the above table.
In all of the examples and comparative examples, a film having an adhesion suppressing effect could be produced immediately after the production of the laminate. On the other hand, after storage for 2 weeks, Comparative Example 1 lost the adhesion suppressing effect, but Examples 1 and 5 to 7 retained the adhesion suppressing effect for a certain degree or more, so the laminate of Example 1 is a laminate. It was confirmed that the durability of the

  The laminate of the present invention can be used in the field of interior materials for packaging of cosmetics and food.

1 upper layer 2 lower layer 3 base material

Claims (6)

  It is a laminate in which an upper layer body and a lower layer body are laminated, and the upper layer body is a hydrophobically modified cellulose fiber in which a modifying group is bonded to at least one selected from carboxy group and hydroxy group of carboxy group containing cellulose fiber. A laminate having an organic medium having an SP value of 10 or less, and wherein the lower layer is a lower layer including a resin having a hydrogen bonding group.   The resin according to claim 1, wherein the resin comprises one or more resins selected from the group consisting of polyamide resin, acrylic resin, polycarbonate resin, phenol resin, melamine resin, furan resin, epoxy resin, phenoxy resin, polyester resin and polyurethane resin. The laminated body as described in 1.   The laminate according to claim 1, wherein the organic medium is an organic medium having an SP value of 8.5 or less.   The laminate according to any one of claims 1 to 3, further comprising a substrate laminated.   A hydrogen bonding group comprising a coating liquid comprising a hydrophobic modified cellulose fiber in which a modifying group is bonded to one or more selected from carboxy group and hydroxyl group of carboxy group-containing cellulose fiber, and an organic medium having an SP value of 10 or less The manufacturing method of a laminated body including the process of applying to the lower layer body containing resin to have.   The method according to claim 5, wherein the coating liquid further contains an organic solvent.

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