JP7021944B2 - Laminated body and its manufacturing method - Google Patents

Description

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

Conventionally, in the field of packaging containers for cosmetics and foods, objects that can come into contact with containers and trays (for example, objects such as cosmetics and foods themselves that are filled in containers or packaged with a film). Surface films have been developed to prevent the adhesion of fluids such as dirt and dirt. Recently, a porous polymer film having a network structure in which fibrous polymers are entangled with each other in a three-dimensional direction and having a continuous pore structure as voids thereof, and the inside of the pores of the porous polymer film. A water-sliding / lubricating film characterized by having a lubricating liquid impregnated in is known (Patent Document 1), and Patent Document 1 exemplifies a fluorine-based oil or a silicone oil as the lubricating liquid. (Claim 7).

Japanese Unexamined Patent Publication No. 2016-011375

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

Therefore, the present invention relates to a laminated body having a structure having excellent adhesiveness between the upper layer body and the lower layer body constituting the laminated body and also excellent performance (durability of the upper layer body) capable of maintaining the performance of the upper layer body. Further, the present invention relates to a method for producing such a laminate.

The present invention relates to the following [1] to [2].
[1] A laminate in which an upper layer and a lower layer are laminated, and the upper layer is hydrophobic in which a modifying group is bonded to one or more selected from the carboxy group and the hydroxyl group of the carboxy group-containing cellulose fiber. A laminate which is a film having a modified cellulose fiber and an organic medium having an SP value of 10 or less, and the lower layer is a lower layer containing a resin having a hydrogen bond group.
[2] A coating liquid containing a hydrophobically modified cellulose fiber in which a modifying group is bonded to one or more selected from the carboxy group and the hydroxyl group of the carboxy group-containing cellulose fiber and an organic medium having an SP value of 10 or less is hydrogenated. A method for producing a laminated body, which comprises a step of coating a lower layer body containing a resin having a bonding group.

According to the present invention, a laminated body having a structure excellent in adhesiveness between an upper layer body and a lower layer body and also having an excellent performance (durability of the upper layer body) capable of maintaining the performance of the upper layer body, and the laminated body. A manufacturing method is provided.

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

[Laminate]
The laminated body of the present invention is a laminated body in which an upper layer body and a lower layer body are laminated.
A preferred embodiment of the laminated body of the present invention is a laminated body in which an upper layer body is laminated on an upper surface of a lower layer body, and a cross-sectional view thereof 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 preferred embodiment of the laminate of the present invention is a laminate in which a base material is further laminated on the laminate of the above aspect, for example, an upper layer is laminated on the upper surface of the lower layer, and a base material is formed on the lower surface of the lower layer. Is a laminated body further laminated, and a cross-sectional view thereof 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 in a position where it does not come into direct contact with the base material, the lower layer is located between the upper layer and the base material, and the lower layer comes into contact with the base material. In this embodiment, the lower layer 2 serves as an adhesive between the upper layer 1 and the base material 3.

The laminated body of the present invention may include a layer or a film other than the upper layer body, the lower layer body and the base material, for example, 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 that is not in contact with the lower layer of the base material.

The thickness of the laminated body of the present invention is preferably 0.6 μm or more, more preferably 2 μm or more, still more preferably 13 μm or more, from the viewpoint of ensuring the mechanical strength of the laminated body. On the other hand, from the viewpoint of ensuring the flexibility of the laminated body, it is preferably 240 μm or less, more preferably 170 μm or less, and further preferably 125 μm or less.

The thickness of the upper layer in the laminated body is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 10 μm or more, from the viewpoint of ensuring 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 further preferably 60 μm or less.

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

The thickness of the base material in the laminated body is preferably 8 μm or more, more preferably 20 μm or more, still more preferably 50 μm or more, from the viewpoint of ensuring the mechanical strength of the laminated body. On the other hand, from the viewpoint of ensuring the flexibility of the laminated body, it is preferably 120 μm or less, more preferably 80 μm or less, and further 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 achieved by the interaction between the upper layer and the lower layer. As a result of making it difficult for the lower layer to absorb the organic medium which is a component of the upper layer, it is presumed that the performance of maintaining the performance of the upper layer (durability of the upper layer) is improved.

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

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

Here, the film means a film that retains its shape without flowing at room temperature.

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

The laminate of the present invention is shown in the literature (superhydrophobic, superoil-repellent, synovial surface technology / publisher: Hiroshi Motoki / publisher: Science & Technology Co., Ltd./issued on January 28, 2016). It is preferable to show the surface property of the synovial fluid. The synovial fluid surface property is expressed by the upper layer body which is the upper layer surface of the laminated body, and can be evaluated by the method described in Examples described later.

Synovial fluid surface properties can be measured, for example, by the method described in the paper (Nature 2011, vol477, p443-447). Specifically, for the surface property of synovial fluid, 2 μL droplets (20 ° C.) are dropped on the membrane surface at room temperature of 20 ° C., allowed to stand for 10 seconds, and then the surface is surfaced at a speed of 1 ° / s. It can be evaluated by tilting and measuring the angle at which the droplet begins to flow (hereinafter, also referred to as the 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 exhibiting the surface property of synovial fluid. 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, still more preferably 0.7 μm or more, from the viewpoint of ensuring the synovial fluid surface property of 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 further preferably 2.0 μm or less. The arithmetic mean roughness of the upper layer surface of the laminated body is obtained by the method described in Examples described later.

The upper layer in the present invention is, for example, a membrane for modifying 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 of suppressing the adhesion of fluid (adhesion suppressing effect) to the solid surface.

One of the features of the film of the present invention is that it has a high effect of suppressing adhesion of fluids in contact with the film. Specifically, the sliding speed is preferably 1.5 cm / min or more, more preferably 2.0 cm / min or more, and further preferably 2.5 cm / min or more. The sliding speed can be measured according to the method described in Examples described later.

The amount of the 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 adhesiveness and durability. It is more preferably 10% by mass or more, and from the same viewpoint, it is 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 adhesiveness and durability. It is 50% by mass or more, more preferably 55% by mass or more. 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, still more preferably 75% by mass or less. When there are two or more kinds of organic media, the amount of the organic medium is the total amount of each organic medium.

The upper layer may contain components other than the hydrophobically modified cellulose fiber and an organic medium having an SP value of 10 or less, for example, an additive such as a polymer, a small molecule active agent, a filler, or a plasticizer. Specific examples of the polymer include polyamide resin and the like. The content of these additives in the upper layer is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, from the viewpoint of exhibiting the effects of the present invention. Yes, more preferably 1% by mass or less.

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

(Cellulose fiber)
The cellulose fiber as a raw material is preferably a natural cellulose fiber from an environmental point of view, and for example, wood pulp such as coniferous pulp and broadleaf pulp; cotton pulp such as cotton linter and cotton lint; straw pulp, bagus pulp and the like. Non-wood pulp; bacterial cellulose and the like can be mentioned, and one of these can be used alone or in combination of two or more.

(Oxidized cellulose fiber)
The raw material cellulose fiber oxidized by a known method is a carboxy group-containing cellulose fiber (hereinafter, also referred to as an oxidized cellulose fiber).
As the cellulose oxide fiber, for example, 2,2,6,6, -tetramethyl-1-piperidin-N-oxyl (TEMPO) is used as a catalyst, and an oxidizing agent such as sodium hypochlorite, sodium bromide and the like are further used. The method of oxidizing in combination with the bromide of is applicable. More specifically, the method described in JP-A-2011-140632 can be referred to, and further, it can be prepared as an oxidized cellulose fiber from which aldehyde has been removed by performing a post-oxidation treatment or a reduction treatment.

By oxidizing the cellulose fiber using TEMPO as a catalyst, the group at the C6 position (-CH ₂ OH) of the cellulose constituent unit is selectively converted into 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 constituent unit is a carboxy group.

(Carboxy 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, still more preferably 0.6 mmol / g or more, from the viewpoint of introducing a modifying group. It is 0.8 mmol / g or more. Further, from the viewpoint of improving handleability, it is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, and further preferably 1.8 mmol / g or less. The "carboxy group content" means the total amount of carboxy groups in the cellulose constituting the hydrophobically modified cellulose fiber or the oxidized cellulose fiber, and is specifically measured by the method described in Examples described later.

Further, the preferable ranges of the average fiber diameter, the average fiber length and the average aspect ratio of the oxidized cellulose fiber are the same as those of the hydrophobic modified cellulose fiber described later, and are determined by the same measuring method as the hydrophobic modified cellulose fiber described later. Can be done.

(Modifying group)
In the present specification, the bond of the modifying group in the hydrophobically modified cellulose fiber is an ionic bond of one or more groups selected from the group consisting of a carboxy group and a hydroxyl group on the surface of the oxidized cellulose fiber, preferably a carboxy group. And / or means a state of being bonded via a covalent bond. Examples of the bonding mode to the carboxy group include 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, an amide bond is preferable from the viewpoint of adhesiveness and durability. Further, as a bonding mode to a hydroxyl group, a covalent bond can be mentioned, and specific examples thereof include an ester bond; an ether bond such as carboxymethylation and carboxyethylation; and a urethane bond. From the viewpoint of adhesiveness and durability, the hydrophobically modified cellulose fiber in the present invention is obtained by ionic bonding and / or amide bonding a compound for introducing a modifying group to a carboxy group already existing on the surface of the oxidized cellulose fiber. What is obtained is preferable.

(Compound for introducing a modifying group)
As the compound for introducing the modifying group, any compound can be used as long as it can introduce the modifying group described later, and for example, the following compounds can be used depending on the bonding mode. In the case of an ionic bond, any of a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium compound, and a phosphonium compound may be used. Among these, from the viewpoint of adhesiveness and durability, a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium compound are preferable. Further, as the anion component of the ammonium compound or the phosphonium compound, from the viewpoint of reactivity, halogen ions such as chlorine ion and bromine ion, hydrogen sulfate ion, perchlorate ion, tetrafluoroborate ion and hexa are preferable. Fluorophosphate ion, trifluoromethanesulfonic acid ion, hydroxy ion can be mentioned, and more preferably, hydroxy ion can be mentioned. In the case of covalent bonds, the following can be used depending on the functional group to be substituted.

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

In the case of ester bond, acid anhydride is preferable for modification to a hydroxyl group, and examples thereof include acetic anhydride, propionic anhydride, and succinic anhydride. In the case of ether bonding, epoxy compounds (eg, alkylene oxides and alkylglycidyl ethers), alkyl halides and derivatives thereof (eg, 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)
Examples of the hydrocarbon group include a chain-type saturated hydrocarbon group, a chain-type unsaturated hydrocarbon group, a ring-type saturated hydrocarbon group, and an aromatic hydrocarbon group, from the viewpoint of suppressing side reactions and stability. From the viewpoint, chain-type saturated hydrocarbon groups, cyclic-type saturated hydrocarbon groups, and aromatic hydrocarbon groups are preferable.

The chain saturated hydrocarbon group may be linear or branched. From the viewpoint of adhesiveness and durability, 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 in one modifying group. , More preferably 8 or more. From the same viewpoint, it is preferably 30 or less, more preferably 24 or less, still more preferably 18 or less, still more preferably 16 or less. In the following, the carbon number of the hydrocarbon group means the carbon number of one modifying group.

Specific examples of the chain saturated hydrocarbon group include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, and a 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 and the like can be mentioned and have adhesiveness. And from the viewpoint of durability, preferably 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. These may be introduced alone or in two or more kinds at arbitrary ratios.

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

Specific examples of the chain unsaturated hydrocarbon group include ethylene group, propylene group, butene group, isobutene group, isoprene group, penten group, hexene group, heptene group, octene group, nonen group, decene group and dodecene group. , Tridecene group, tetradecene group, octadecene group, preferably ethylene group, propylene group, butene group, isobutene group, isoprene group, pentene group, hexene group, heptene group, octene group from the viewpoint of adhesiveness and durability. , Nonen group, decene group, dodecene group. These may be introduced alone or in two or more kinds at arbitrary ratios.

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

From the viewpoint of adhesiveness and durability, the number of carbon atoms of one modifying group is 6 or more, and from the same viewpoint, the number of carbon atoms of the aromatic hydrocarbon group is preferably 30 or less, more preferably 24 or less. Yes, more preferably 18 or less, still 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 is, for example, a linear chain having 1 to 6 carbon atoms, provided that the number of carbon atoms 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; a halogen atom such as a bromine atom or an iodine atom; an acyl group having 1 to 6 carbon atoms; an aralkyl group; an aralkyloxy. Group; Alkylamino group having 1 to 6 carbon atoms; Dialkylamino group having 1 to 6 carbon atoms of the alkyl group, a hydroxyl group, an ether, an amide or the like may be used. The above-mentioned various hydrocarbon groups themselves may be bonded to another hydrocarbon group as a substituent.

As the primary amine, the secondary amine, the tertiary amine, the quaternary ammonium compound, the phosphonium compound, the acid anhydride, and the isocyanate compound for introducing the hydrocarbon group, a commercially available product may be used or a known method may be used. Can be prepared according to.

The primary to tertiary amines preferably have 2 or more carbon atoms, more preferably 6 or more carbon atoms from the viewpoint of adhesiveness and durability, and preferably 30 or less carbon atoms from the same viewpoint. , More preferably 24 or less, still more preferably 18 or less (excluding amino-modified silicone compounds). Specific examples of the primary amine to the tertiary amine include ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, dibutylamine, hexylamine, dihexylamine, octylamine, dioctylamine, and trioctylamine. , Dodecylamine, didodecylamine, stearylamine, distearylamine, monoethanolamine, diethanolamine, triethanolamine, aniline, benzylamine, amino-modified silicone compounds and the like. Examples of the quaternary ammonium compound include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetraethylammonium chloride, tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), and tetra. Examples thereof include butylammonium chloride, lauryltrimethylammonium chloride, dilauryldimethylchloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, and alkylbenzyldimethylammonium chloride. Among these, from the viewpoint of adhesiveness and durability, propylamine, dipropylamine, butylamine, dibutylamine, hexylamine, dihexylamine, octylamine, dioctylamine, trioctylamine, dodecylamine and didodecyl are preferable. Amines, distearylamines, amino-modified silicone compounds, tetraethylammonium hydroxides (TEAH), tetrabutylammonium hydroxides (TBAH), tetrapropylammonium hydroxides (TPAH), aniline, more preferably propylamines, dodecylamines, amino-modified It is a silicone compound, tetrabutylammonium hydroxide (TBAH), aniline, and more preferably an amino-modified silicone compound.

Among these compounds, the hydrophobically modified cellulose fiber obtained by using the amino-modified silicone compound is particularly useful as a raw material for the upper layer. Therefore, as one aspect of the hydrophobically modified cellulose fiber, a hydrophobically modified cellulose fiber obtained by binding a modifying group introduced by an amino-modified silicone compound to one or more groups selected from the carboxy group and the hydroxyl group of the oxidized cellulose fiber is provided. Will be done. When the hydrophobically modified cellulose fiber is used as a raw material for the upper layer, it can exhibit the effects of excellent synovial fluid surface property and ability to suppress the transfer of the organic medium to the fluid.

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

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

The amino equivalent is preferably 400 to 8,000 g / mol, more preferably 600 to 5,000 g / mol, and even more preferably 800 to 3,000 g / mol from the viewpoint of adhesiveness and durability. The amino equivalent is the 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 obtained by gel permeation chromatography using polystyrene as a standard substance, and the number of nitrogen atoms can be obtained by an elemental analysis method.

Specific examples of the amino-modified silicone compound include a compound represented by the general formula (a1).

[In the formula, 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, and is preferably a methyl group from the viewpoint of adhesiveness and durability. Or it is 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 adhesiveness 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. x and y indicate the average degree of polymerization, respectively, and are selected so that the kinematic viscosity and amino equivalent of the compound at 25 ° C. are within the above ranges. R ^1a , R ^2a , and R ^3a may be the same or different from each other, and a plurality of R ^2a may be the same or different from each other. ]

In the compound of the general formula (a1), 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, from the viewpoint of adhesiveness and durability. It is a number. y is preferably a number of 1 to 1,000, more preferably a number of 1 to 500, and even more preferably a number of 1 to 200. The mass 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, 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 numbers 1 to 30, respectively.)

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

The amino-modified silicone compound is preferably a monoamino-modified silicone having one amino group in one side chain B and an amino group in one of the side chains B from the viewpoint of adhesiveness and durability. Is one or more selected from the group consisting of two diamino-modified silicones, and more preferably, the side chain B having an amino group is represented by -C _{3H 6} -NH ₂ [hereinafter, (a1-1). ) Component] and a compound whose side chain B having an amino group is represented by -C ₃ H ₆ -NH-C ₂ H ₄ -NH ₂ [hereinafter referred to as (a1-2) component]. One or more.

The amino-modified silicone compound in the present invention includes TSF4703 (kinematic viscosity: 1000, amino equivalent: 1600), TSF4708 (kinematic viscosity: 1000, amino equivalent: 2800) manufactured by Momentive Performance Materials, Inc. from the viewpoint of performance. SS-3551 (Dynamic Viscosity: 1000, Amino Equivalent: 1600), SF8457C (Dynamic Viscosity: 1200, Amino Equivalent: 1800), SF8417 (Dynamic Viscosity: 1200, Amino Equivalent: 1700) manufactured by Toray Dow Corning Silicone Co., Ltd. ), BY16-209 (Dynamic Viscosity: 500, Amino Equivalent: 1800), BY16-892 (Dynamic Viscosity: 1500, Amino Equivalent: 2000), BY16-898 (Dynamic Viscosity: 2000, Amino Equivalent: 2900), FZ-3760 (Dynamic Viscosity: 220, Amino Equivalent: 1600), KF8002 (Dynamic Viscosity: 1100, Amino Equivalent: 1700), KF867 (Dynamic Viscosity: 1300, Amino Equivalent: 1700), KF-864 (Dynamic Viscosity: 1300, Amino Equivalent: 1700) The kinematic viscosity: 1700, amino equivalent: 3800), BY16-213 (kinematic viscosity: 55, amino equivalent: 2700), BY16-853U (kinematic viscosity: 14, amino equivalent: 450) are preferable. In (), the kinematic viscosity shows a measured value (unit: mm ² / s) at 25 ° C., 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 bond amount of one or more groups selected from the group consisting of a modifying group, preferably a hydrocarbon group and a silicone group in the hydrophobically modified cellulose fiber is determined from the viewpoint of adhesiveness and durability per hydrophobically modified cellulose fiber. It is preferably 0.01 mmol / g or more, more preferably 0.05 mmol / g or more, still more preferably 0.1 mmol / g or more, still more preferably 0.3 mmol / g or more, still more preferably 0.5 mmol / g or more. .. 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. It is less than or equal to g. Here, when a hydrocarbon group selected from a chain-type saturated hydrocarbon group, a chain-type unsaturated hydrocarbon group, and a cyclic-type saturated hydrocarbon group and an aromatic hydrocarbon group are simultaneously introduced as modifying groups. Even if there is, it is preferable that the individual average binding amount is within the above range.

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

In the present specification, the average binding amount of the modifying group shall be adjusted according to the amount of the compound added for introducing the modifying group, the type of the compound for introducing the modifying group, the reaction temperature, the reaction time, the solvent and the like. Can be done. The average bond amount (mmol / g) and introduction rate (%) of the modifying group in the hydrophobically modified cellulose fiber are the amount and the ratio of the modifying group introduced into the carboxy group or the hydroxyl group on the surface of the hydrophobically modified cellulose fiber. 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 the method described in Examples described later, and is hydrophobic. The hydroxyl group content of the modified cellulose fiber can be calculated by measuring according to a known method (for example, titration, IR measurement, etc.).

<Manufacturing method of 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 a modifying group can be introduced into the above-mentioned oxidized cellulose fiber. For example, there is a method in which the step of introducing a modifying group into the oxidized cellulose fiber and the step of refining the target cellulose fiber are carried out in any order. The cellulose oxide fiber referred to here can be used as a cellulose oxide fiber obtained by referring to a known method, for example, the description of the oxidation reaction step described in JP-A-2011-140632, or further, a post-oxidation treatment. Alternatively, it can be prepared as an oxidized cellulose fiber from which aldehyde has been removed by performing a reduction treatment.

(Step of introducing a modifying group)
Specific steps include an embodiment in which the modifying group is bound to the oxidized cellulose fiber by an ionic bond (aspect A) and an embodiment in which the modifying group is bound to the oxidized cellulose fiber by a covalent bond (aspect B). The case of an amide bond as a covalent bond is shown below.
(Aspect A)
The step of mixing the oxidized cellulose fiber and the compound having a modifying group.
(Aspect B)
A step of amidating a cellulose oxide fiber and a compound having a modifying group.
As a specific method, the aspect A refers to the method described in the step (B) of JP-A-2015-143336, and the embodiment B refers to the method described in the step (B) of JP-A-2015-143337. Can be carried out. The "amine having an EO / PO copolymerization section" in the step (B) of both publications corresponds to the "compound for introducing a modifying group" in the present invention.

(Miniaturization process)
This step is a step of refining the cellulose oxide fiber (or the cellulose oxide fiber into which a modifying group is introduced), and a fine cellulose oxide fiber can be obtained. In the miniaturization step, it is preferable to disperse the oxidized cellulose fibers that have undergone the purification step in a solvent and perform the miniaturization treatment. Specifically, it can be carried out with reference to the description of the miniaturization step of Japanese Patent Application Laid-Open 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, and more, from the viewpoint of adhesiveness and durability. More preferably, it is 3 nm or more. From the same viewpoint, 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, still more 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 adhesiveness and durability. From the same viewpoint, it is preferably 1000 nm or less, more preferably 750 nm or less, still more preferably 500 nm or less, still more 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, still more preferably, from the viewpoint of adhesiveness 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, still more preferably 90. It is as follows. 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, still more preferably 45 or less, and the lower limit, from the viewpoint of adhesiveness and durability. Is not particularly set, but is preferably 4 or more from the viewpoint of economic efficiency. Since the hydrophobically modified cellulose fiber having a low aspect ratio has excellent dispersibility in the dispersion, 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 obtained by the methods described in Examples described later.

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

The SP value in the present specification indicates a solubility parameter (unit: (cal / cm ³ ) ^1/2 ) calculated by the Fedors method, and for example, the reference "SP value basics / applications and calculation methods" (Information Mechanism). , 2005), Polymer handbook Calculation (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, preferably 100,000 or less, more preferably 50,000 or less, and further preferably 20,000. It is as follows.

Examples of the organic medium having an SP value of 10 or less used in the present invention include oleic acid (SP value: 9.2), D-lymonen (SP value: 9.4), and PEG400 (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), Johova oil (SP value: 8.6), Squalane (SP value: 7.9), Liquid paraffin (SP value: 7.9), Florinate FC-40 (3M company, SP value: 6) .1), Florinate FC-43 (3M company, SP value: 6.1) Florinate FC-72 (3M company, SP value: 6.1), Florinate FC-770 (3M company, SP value: 6) .1), KF96-1cs (manufactured by Shin-Etsu Chemical Co., SP value: 7.3), KF-96-10cs (manufactured by Shin-Etsu Chemical Co., SP value: 7.3), KF-96-50cs (manufactured by Shin-Etsu Chemical Co., Ltd.) , SP value: 7.3), KF-96-100cs (manufactured by Shin-Etsu Chemical Co., SP value: 7.3), KF-96-1000cs (manufactured by Shin-Etsu Chemical Co., SP value: 7.3) and the like. .. Among these, the SP value of the organic medium is preferably 9.5 or less, more preferably 9.0 or less, still more preferably 8.5 or less, from the viewpoint of adhesiveness and durability.

<Method of forming the upper layer>
As an example of the method for forming the upper layer body, a coating solution containing at least the hydrophobically modified cellulose fiber and the organic medium, which are constituents of the upper layer body, is prepared, and then this coating solution is applied to the lower layer body. There is a method of construction.

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

The amount of the 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 further preferably 1 from the viewpoint of adhesiveness and durability. It is 5.5% 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, and further 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 adhesiveness and durability. It is more preferably 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. be.

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, still more preferably 90% by mass or more, from the viewpoint of adhesiveness and durability. From the same viewpoint, it is preferably 99% by mass or less, more preferably 98% by mass or less, and further preferably 97% by mass or less.

The coating liquid may contain components other than these.

As the mixing condition of these components, for example, 15 to 35 ° C. is preferable. Further, the mixing time is preferably 10 minutes to 36 hours.

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

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, still more preferably 30 μm, from the viewpoint of synovial fluid speed and durability. From the viewpoint of properties, it is preferably 2000 μm or less, more preferably 1500 μm or less, still more preferably 1200 μm or less.

Then, the applied coating liquid is dried. The drying conditions may be under reduced pressure or normal pressure, and the temperature range is preferably 15 to 75 ° C. The time for drying is preferably 1 to 24 hours.

In this way, a film-like upper layer is formed.

[Lower body]
The lower layer body in the present invention is a lower layer body containing a resin having a hydrogen bond group. The lower layer is a layer that comes into contact with the upper layer. If there is a base material, the lower layer is a layer that comes into contact with the base material.

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 amide group, an amino group, a hydroxyl group and the like, and among these, adhesiveness From the viewpoint of durability, a carboxyl group, an amide group and an amino group are preferable.

The mass average molecular weight of the resin having a hydrogen bond group is preferably 1000 or more from the viewpoint of adhesiveness and durability, and preferably 500,000 or less from the same viewpoint.

A preferable specific example of the resin having a hydrogen bonding group is 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. Examples include more than seed resins. Among these, from the viewpoint of adhesiveness and durability, polyamide resin, acrylic resin, epoxy resin, phenoxy resin and polyurethane resin are preferable, and polyamide resin, acrylic resin and polyurethane resin are more preferable.

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

The lower layer may contain components other than the resin having a hydrogen bond group, for example, a polymer such as a leveling agent, a strengthening agent, an antistatic agent, an ultraviolet absorber, 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, still more preferably 10% by mass or less in the lower layer body.

<Method of forming the lower layer>
Resins having hydrogen bonding groups are commercially available as solutions or dispersions. A lower layer can be easily formed by applying such a solution or a dispersion liquid onto, for example, a substrate and drying it. Alternatively, the lower layer can be formed by applying such a solution or a dispersion on the previously formed upper layer and drying the solution. In this case, the coating method for obtaining the lower layer can be the same as the coating method for forming the upper layer described above.
The resin having a hydrogen bond group is also commercially available as pellets. In such a case, a lower layer having a film shape or a molded body shape can be formed by various molding methods such as film molding, injection molding, blow molding, pressure molding, and extrusion molding.

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

The shape of the base material is not particularly limited, such as a film shape, a desired container shape, a sheet shape, a plate shape, a tubular shape, and a molded body shape.

[Manufacturing method of laminated body]
The method for producing a laminate of the present invention comprises a hydrophobically modified cellulose fiber in which a modifying group is bonded 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. The step of applying the coating liquid containing the coating liquid to the lower layer containing the resin having a hydrogen bonding group is included. The laminate of the present invention can be produced, for example, by the method for producing a laminate of the present invention.

The method for preparing the coating liquid and the method for applying the coating to the lower layer can be carried out in the same manner as the method described above.

A film-like upper layer is formed by the production method of the present invention, and a laminated body in which the upper layer and the lower layer are laminated can be obtained.

Further, 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 may be prepared in advance. A base material may be laminated or formed on the obtained laminate. Specifically, a manufacturing method 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 is exemplified.

Hereinafter, the present invention will be specifically described with reference to examples. It should be noted that this embodiment is merely an example of the present invention and does not mean any limitation. The part in the example is a mass part unless otherwise specified. The "normal pressure" indicates 101.3 kPa, and the "room temperature" indicates 25 ° C.

[Average fiber diameter, average fiber length, average aspect ratio of oxidized cellulose fiber and hydrophobic modified cellulose fiber]
Water is added to the oxidized cellulose fiber or the hydrophobic 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 as an observation sample. Atomic force microscope (AFM, Nanoscopy III Tapping mode AFM, Digital instrument, probe used Point Probe (NCH) from Nanosensors), oxidized cellulose fiber or hydrophobic 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 cellulose fibers are extracted, and the average fiber diameter is calculated from the fiber heights thereof. 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.

[Carboxy group content of oxidized cellulose fiber and hydrophobic modified cellulose fiber]
Take 0.5 g of dry mass of oxidized cellulose fiber or hydrophobic modified cellulose fiber in a 100 mL beaker and add ion-exchanged water or a mixed solvent of methanol / water = 2/1 to make a total of 55 mL, and then add 5 mL of 0.01 M sodium chloride aqueous solution. Is added to prepare a dispersion, and the dispersion is stirred until the oxidized cellulose fibers or the hydrophobically modified cellulose fibers are sufficiently dispersed. Add 0.1 M hydrochloric acid to this dispersion to adjust the pH to 2.5 to 3, and use an automatic titrator (manufactured by Toa DKK, trade name "AUT-710") to add a 0.05 M aqueous sodium hydroxide solution. It is added dropwise to the dispersion under the condition of a waiting time of 60 seconds, the electric conductivity and pH values are measured every minute, and the measurement is continued until the pH reaches about 11 to obtain an electric conductivity curve. From this conductivity curve, the quantification of sodium hydroxide titration is obtained, and the carboxy group content of the oxidized cellulose fiber or the hydrophobically modified cellulose fiber is calculated by the following formula.
Carboxy group content (mmol / g) = sodium hydroxide droplet quantification x sodium hydroxide aqueous solution concentration (0.05M) / mass of oxidized cellulose fiber or hydrophobically modified cellulose fiber (0.5 g)

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

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

[Solid content in dispersion]
This is performed using a halogen moisture meter (manufactured by Shimadzu Corporation; trade name "MOC-120H"). Measurement is performed every 30 seconds at a constant temperature of 150 ° C. for 1 g of a sample, and the value at which the mass loss is 0.1% or less is defined as the solid content.

[Average bond amount and introduction rate (ionic bond) of modifying groups of hydrophobically modified cellulose fiber]
The binding amount of the modifying group is obtained by the following IR measurement method, and the average binding amount and introduction rate are calculated by the following formula. Specifically, the IR measurement is performed by measuring the dried hydrophobically modified cellulose fiber by the ATR method using an infrared absorption spectroscope (IR) (manufactured by Thermo Fisher Scientific Co., Ltd .; trade name "Nicolet 6700"). The average binding amount and introduction rate of the modifying group are calculated by the following equations.
Average bond amount of modifying group (mmol / g) = [Carboxy group content of cellulose oxide fiber (mmol / g)] × [(Peak strength of 1720 cm ^-1 of cellulose oxide fiber-1702 cm ^-1 of hydrophobically modified cellulose fiber Peak strength) ÷ Peak strength of 1720 cm ^-1 of cellulose oxide fiber]
Peak intensity of 1720 cm ^-1 : Peak intensity derived from carbonyl group of carboxylic acid Introduction rate of modifying group (%) = {Bond amount of modifying group (mmol / g) / Carboxy group content in oxidized cellulose fiber before introduction (Mmol / g)} × 100

[Average bond amount and introduction rate of modifying groups of hydrophobically modified cellulose fibers (amide bond)]
The average binding amount of the modifying group is calculated by the following formula.
Average bond amount of modifying group (mmol / g) = carboxy group content in oxidized cellulose fiber before introduction of modifying group (mmol / g) -carboxy group content in hydrophobically modified cellulose fiber after introduction of modifying group (mmol / g) g)
Modification group introduction rate (%) = {average binding amount of modifying group (mmol / g) / carboxy group content in cellulose oxide fiber before introduction (mmol / g)} × 100

[Measurement of arithmetic mean roughness of the upper layer surface of the laminated body]
The arithmetic mean roughness of the upper layer surface of the laminated body is measured under the following measurement conditions using a laser microscope (manufactured by KEYENCE CORPORATION; trade name “VK-9710”). The measurement conditions are objective lens: 10 times, light intensity: 3%, brightness: 1548, Z pitch: 0.5 μm. The surface arithmetic mean roughness is measured at 5 points using the built-in image processing software, and the average value is used.

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

[Sliding angle measurement test]
At room temperature of 20 ° C, 2 μL of dodecane droplets (20 ° C) are dropped onto the membrane, allowed to stand for 10 seconds, and then the membrane surface is tilted at a speed of 1 ° / s to determine the angle at which the droplets begin to flow. Measure. As a typical example, the sliding angle of the film of Example 1 was 2 °.

[Preparation of Oxidized Cellulose Fiber Dispersion]
Preparation Example 1 (Dispersion solution of oxidized cellulose fiber obtained by reacting a natural cellulose fiber with an N-oxyl compound)
Bleached kraft pulp of coniferous tree (Fletcher Challenge Canada, trade name "Mackenzie", CSF 650 ml) was used as a natural cellulose fiber. As the TEMPO, a commercially available product (manufactured by ALDRICH, Free radical, 98% by mass) was used. As the sodium hypochlorite, a commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used. As sodium bromide, a commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used.

First, 100 g of coniferous bleached kraft pulp fiber is sufficiently stirred with 9900 g of ion-exchanged water, and then 1.25 g of TEMPO, 12.5 g of sodium bromide, and 28.4 g of sodium hypochlorite are added to the pulp mass of 100 g. It was added in order. Using a pH stud, 0.5 M sodium hydroxide was added dropwise to keep the pH at 10.5. After the reaction was carried out for 120 minutes (20 ° C.), the dropping of sodium hydroxide was stopped to obtain oxidized pulp. The obtained oxidized pulp was thoroughly washed with ion-exchanged water and then dehydrated. Then, 3.9 g of oxidized pulp and 296.1 g of ion-exchanged water were refined twice at 245 MPa using a high-pressure homogenizer (Sugino Machine Limited, Starburst Lab HJP-2 5005) to obtain an oxidized cellulose fiber dispersion liquid (Sugino Machine Limited, Starburst Lab HJP-2 5005). Solid content content 1.3% by mass) was obtained. The average fiber diameter of the oxidized cellulose fibers was 3.3 nm, the carboxy group content was 1.62 mmol / g, and the aldehyde group content was 0.27 mmol / g.

Preparation Example 2 (Dispersion of Oxidized Cellulose Fiber with Reduced Aldehyde Group)
3846.15 g (solid content content: 1.3% by mass) of the cellulose oxide fiber dispersion obtained in Preparation Example 1 was put into a beaker, and a 1M sodium hydroxide aqueous solution was added thereto to adjust the pH to about 10, and then boron borohydride was added. 2.63 g of sodium (manufactured by Wako Pure Chemical Industries, Ltd., purity 95% by mass) was charged and reacted at room temperature for 3 hours for aldehyde reduction treatment. After completion of the reaction, 405 g of a 1 M hydrochloric acid aqueous solution and 4286 g of ion-exchanged water were added to make a 0.7 mass% aqueous solution, which was reacted at room temperature for 1 hour for protonation. After completion of the reaction, the cake was filtered, and the obtained cake was washed with ion-exchanged water to remove hydrochloric acid and salt. Finally, the solvent was replaced with isopropanol to obtain an oxidized cellulose fiber dispersion liquid in which the aldehyde group was reduced. The average fiber diameter of the obtained oxidized cellulose fiber dispersion (solid content content 2.0% by mass) obtained by reducing the aldehyde group is 3.3 nm, the carboxy group content is 1.62 mmol / g, and the aldehyde group content is 0. It was 0.02 mmol / g.

[Preparation of hydrophobic modified cellulose fiber]
Production Example 1
A beaker equipped with a magnetic stirrer and a stirrer was charged with 300 g (solid content content: 2.0% by mass) of the oxidized cellulose fiber dispersion obtained in Preparation Example 2. Subsequently, an amino-modified silicone (BY16-209, manufactured by Toray Dow Corning Co., Ltd., abbreviated as "silicone 1") was added in an amount corresponding to 0.5 mol of amino groups with respect to 1 mol of carboxy groups of the cellulose oxide fiber. It was charged, 100 g of isopropanol was added, and the mixture thereof was reacted at room temperature (25 ° C.) for 14 hours. After completion of the reaction, the cake is filtered, and the obtained cake is washed with isopropanol, then stirred with an ultrasonic homogenizer (US-300E, manufactured by Nissei Tokyo Office) for 2 minutes, and then stirred with a high-pressure homogenizer (manufactured by Sugino Machine Limited, Starburst Lab HJP). -By finely treating the oxidized cellulose fiber with 1 pass at 100 MPa and 9 passes at 150 MPa in 5005), a hydrophobically modified cellulose fiber in which amino-modified cellulose was linked via an ionic bond was obtained. 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 the lower layer]
Example 1
First, in a corona processing device (manufactured by Kasuga), a linear low-density polyethylene (LLDPE) film (MCS, manufactured by Mitsui Chemicals Tohcello) with a film thickness of 50 μm was used as a base material, with an output of 6 and a moving speed of 30 cm / s. Was treated with corona. Next, a bar coater (OSP-13, manufactured by OSG System Products Co., Ltd.) was used on the corona-treated surface of the LLDPE film, and an aqueous urethane emulsion (NeoRez R-9603, manufactured by DSM) was used as a coating liquid to form a lower layer. (Abbreviated as "urethane 1") was applied. It was dried at room temperature (25 ° C.) for 24 hours and the solvent was volatilized to obtain a laminated structure of a base material (LLDPE film) and a lower layer. The thickness of the lower layer formed of urethane 1 was 3 μm.

[Preparation of upper layer on lower layer]
Using the hydrophobically modified cellulose fiber obtained in Production Example 1, an upper layer was produced on the surface of the laminated structure on the lower layer side as follows. Hydrophobic modified cellulose fiber Cellulosic fiber: Squalane (lubricating oil): Polyamide (manufactured by Kao, SP-40N) has a mass ratio of 1: 3: 1 and the solvent is 97% of the total dispersion liquid. As described above, hydrophobically modified cellulose fiber, squalane, polyamide and a solvent (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 liquid for forming an upper layer as a sample for a coating film, an applicator (manufactured by Tester Sangyo Co., Ltd.) is used on the lower layer side of the laminated structure so that the thickness of the sample liquid for a coating film becomes 1800 μm. Painted. The solvent was volatilized by drying at room temperature (25 ° C.) for 12 hours to obtain a laminated body of the upper layer body, the lower layer body and the base material, in which an upper layer body having a film thickness of about 50 μm was prepared. The Martens hardness of the film of the obtained laminate was measured as described above and found to be 2.6 (N / mm ² ).

Example 2
The 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 acrylic emulsion (NeoCryl A-1127 manufactured by DSM), and the upper layer, the lower layer and the base material are used. Was obtained. The thickness of the lower layer formed of acrylic was 3 μm.

Example 3
Polyamide (manufactured by Kao Corporation, SP-40N) was stirred in a solvent (isopropyl alcohol: toluene = 1: 1 mixed solvent) in a screw tube at room temperature for 1 hour so as to be 10 wt%. Then, the lower layer was formed by the same method as in Example 1 except that the obtained liquid was changed as the coating liquid for forming the lower layer, and a laminated body of the upper layer, the lower layer and the base material was obtained. .. The thickness of the lower layer made of polyamide was 3 μm.

[Preparation of upper layer to single lower layer]
Example 4
Using the hydrophobically modified cellulose fiber obtained in Production Example 1, an upper layer was prepared on the lower layer as follows. The coating film sample for forming the upper layer used in Example 1 was placed on a nylon film (Bonil RX, manufactured by Kojin Co., Ltd.) having a thickness of 15 μm as the lower layer, and the thickness of the coating film sample was 1800 μm. I painted it so that it would be. The solvent was volatilized by drying at room temperature (25 ° C.) for 12 hours to obtain a laminated body of the upper layer body and the lower layer body in which an upper layer body having a film thickness of about 50 μm was prepared.

Examples 5-7
Urethane 2 (DSM, NeoRez R-9637), Urethane 3 (DSM, NeoRez R-966) or Urethane 4 (DSM, NeoRez R-960), which is an aqueous urethane emulsion, is used as a coating liquid to form the lower layer. ) Was applied, and the coating liquid was applied in the same manner as in Example 1 to obtain a laminated body of the upper layer body, the lower layer body, and the base material.

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

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

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

Test Example 2 (Evaluation of adhesion between upper layer and lower layer)
The adhesiveness between the upper layer and the lower layer was evaluated as follows. Wipe off the lubricating oil on the upper layer of the laminate manufactured in the examples or comparative examples with a paper wipe, and use a cutter (manufactured by Olfa, 142BY) so that each square has 25 squares of 2 mm x 2 mm. I made a notch in the film. A tape (PET50 (A) MF 8LK2 manufactured by Lintec Corporation) was attached on the squares, and the tape was rubbed firmly with a finger so that the coating film could be seen through. Within 5 minutes after the adhesion, the number of remaining coating film pieces of the upper layer remaining on the laminated body was measured when the coating film was peeled off at an angle of 60 ° within 1 second. It can be said that the larger the number of remaining coating film pieces, the stronger the adhesiveness between the upper layer body and the lower layer body.

From the above table, we found the following.
Regarding the adhesiveness, the lower layer and the upper layer containing the resin having a hydrogen bond group shown in the examples are said to have better adhesiveness than the lower layer and the upper layer containing the resin having no hydrogen bond group. Results were obtained.

Test Example 3 (Durability Evaluation)
The durability of the laminated body was evaluated as follows. The adhesion suppressing effect immediately after the production of the laminate produced in Example or Comparative Example was evaluated as in Test Example 1. Further, the effect of suppressing adhesion of the laminate after storage at room temperature (25 ° C.) for 2 weeks was evaluated again in the same manner.

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

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

1 Upper layer 2 Lower layer 3 Base material

Claims (6)

A laminate in which an upper layer and a lower layer are laminated, and the upper layer is a hydrophobically modified cellulose fiber in which a modifying group is bonded to one or more selected from the carboxy group and the hydroxyl group of the carboxy group-containing cellulose fiber. A laminated body, which is a film having an organic medium having an SP value of 10 or less, and the lower layer is a lower layer containing a resin having a hydrogen bonding group. The resin comprises one or more resins selected from the group consisting of polyamide resins, acrylic resins, polycarbonate resins, phenolic resins, melamine resins, furan resins, epoxy resins, phenoxy resins, polyester resins and polyurethane resins. The laminate according to 1. The laminate according to claim 1 or 2, 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, wherein the base material is further laminated. A coating liquid containing a hydrophobically modified cellulose fiber in which a modifying group is bonded to one or more selected from the carboxy group and the hydroxyl group of the carboxy group-containing cellulose fiber and an organic medium having an SP value of 10 or less is used as a hydrogen bonding group. A method for producing a laminated body, which comprises a step of coating a lower layer body containing a resin to have. The production method according to claim 5, wherein the coating liquid further contains an organic solvent.

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