JP2019181900A - Laminate, freshness-retention material and composition - Google Patents

Abstract

To provide a laminate having excellent appearance, a freshness-retention material and a composition.SOLUTION: A laminate including: a base material; and a surface layer arranged at least on one surface of the base material, in which the surface layer includes a component A having the solubility to water at 25°C of 0.1 g/100 g of water to 40 g/100 g of water, and a component B that is other than the component A and satisfies the following requirements (1) to (4). Requirement (1): a polymer containing a structural unit derived from ethylene and at least one kind of monomer selected from α-olefin of 3 to 20 carbons in the range of 90 mol% or larger and smaller than 100 mol% to a total structural unit. Requirement 2: a number average molecular weight (Mn) is 1500 to 30000. Requirement (3): the viscosity at 25°C when 10 g of the component B is dissolved in 100 g of toluene is 5 mPa s to 200 mPa s. Requirement (4): an amount of a polar group is 1.00×10mol/g to 1.00×10mol/g.SELECTED DRAWING: None

Description

  The present invention relates to a laminate, a material for maintaining freshness, and a composition.

Nanoparticles having a very small average primary particle diameter have a large surface energy, and it is difficult to uniformly disperse the nanoparticles and the like in a matrix resin, a solvent, and the like, and various studies have been made so far.
As one method for uniformly dispersing the nanoparticles in the matrix resin, for example, there is a method in which the surface of the nanoparticles is modified by chemical modification, physical modification, or the like (see, for example, Patent Documents 1 and 2).
As another method for uniformly dispersing the nanoparticles in the matrix resin, for example, there is a method using a dispersant (see, for example, Patent Documents 3 and 4).

JP 2002-338775 A JP 2003-73558 A JP 2002-177757 A JP-A-2005-8651

Since the methods described in Patent Documents 1 and 2 are effective only when the surface of the nanoparticle has a reaction activity, it is difficult to apply when the surface is inactive. A technique that can be applied without depending on the state of the surface is required. Furthermore, this method has a problem that it takes time for surface modification, and nanoparticles are likely to aggregate during the surface modification.
In the methods described in Patent Documents 3 and 4, there is a problem that it is necessary to prepare a dispersant that is compatible with the matrix resin, which is troublesome.

  This invention is made | formed in view of the above situations, and makes it a subject to provide the laminated body which is excellent in an external appearance, the material for freshness maintenance, and a composition.

Means for solving the problems include the following aspects.
<1> a base material;
A surface layer disposed on at least one surface of the substrate,
The surface layer has a solubility in water at 25 ° C. of 0.1 g / 100 g of water to 40 g / 100 g of water, and other than the component A and satisfies the following requirements (1) to (4) A laminate comprising B.
Requirement (1) A weight having a constitutional unit derived from at least one monomer selected from ethylene and an α-olefin having 3 to 20 carbon atoms in a range of 90 mol% or more and less than 100 mol% with respect to all constitutional units. Coalescence.
Requirement (2) Number average molecular weight (Mn) is 1500-30000.
Requirement (3) The viscosity at 25 ° C. when 10 g of the component B is dissolved in 100 g of toluene is 5 mPa · s to 200 mPa · s.
Requirement (4) The amount of polar groups is 1.00 × 10 ⁻⁶ mol / g to 1.00 × 10 ⁻⁴ mol / g.
<2> The laminate according to <1>, wherein the haze value is 0.5% to 10%.
<3> The component A has at least one structure selected from the group consisting of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from an amino acid, and has a weight average molecular weight of 500 to 10,000. The laminate according to <1> or <2>, wherein
<4> The laminate according to any one of <1> to <3>, wherein the polar group is at least one functional group selected from the group consisting of a carboxy group, a hydroxy group, an acetyl group, and an amino group. body.
<5> The layered product according to any one of <1> to <4>, wherein the component B does not have a critical micelle concentration measured by electrophoresis.
<6> The laminate according to any one of <1> to <5>, wherein the content of the component B is 100 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the component A.
<7> The laminate according to any one of <1> to <6>, wherein the component A is a molecule A having a structure derived from guanidine represented by the following formula (G-1).

[In Formula (G-1), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituent, and the wavy line represents a bonding site with another structure. ]

<8> In any one of <1> to <7>, the base material is a polymer film containing at least one polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, and polyethylene terephthalate. The laminated body of description.
<9> The laminate according to any one of <1> to <8>, wherein the base material is a container-shaped formed body.
<10> A freshness-keeping material comprising the laminate according to any one of <1> to <9>.
<11> The freshness-keeping material according to <10>, which is used for packing an article.
<12> The freshness-keeping material according to <11>, wherein the surface layer is a surface facing the article.
<13> Component A having a solubility in water at 25 ° C. of 0.1 g / 100 g of water to 40 g / 100 g of water;
Component B other than Component A and satisfying the following requirements (1) to (4);
A solvent,
At least one selected from the group consisting of polyolefin, methacrylic acid and methyl methacrylate;
A composition comprising:
Requirement (1) A weight having a constitutional unit derived from at least one monomer selected from ethylene and an α-olefin having 3 to 20 carbon atoms in a range of 90 mol% or more and less than 100 mol% with respect to all constitutional units. Coalescence.
Requirement (2) Number average molecular weight (Mn) is 1500-30000.
Requirement (3) The viscosity at 25 ° C. when 10 g of the component B is dissolved in 100 g of toluene is 5 mPa · s to 200 mPa · s.
Requirement (4) The amount of polar groups is 1.00 × 10 ⁻⁶ mol / g to 1.00 × 10 ⁻⁴ mol / g.
<14> The composition according to <13>, wherein the average primary particle diameter of the component A is 50 nm to 1000 nm.
<15> The content of the component A is 0.00001 parts by mass to 30 parts by mass with respect to 100 parts by mass of the solvent, and the content of the component B is 1 part by mass to 70 parts by mass. > Or <14>.
<16> The component A has at least one structure selected from the group consisting of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from an amino acid, and has a weight average molecular weight of 500 to 10,000. The composition according to any one of <13> to <15>.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body excellent in an external appearance, the material for a freshness maintenance, and a composition can be provided.

Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In addition, in this specification, “film” is not only what is generally referred to as “film” (for example, having a thickness of 100 μm or less), but is generally referred to as “sheet” ( For example, it is a concept including a thickness of 100 μm or more.
In addition, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
In the present specification, the term “excellent in appearance” includes that the laminate according to the present disclosure is excellent in transparency.

<Laminate>
The laminate according to the present disclosure includes a base material,
A surface layer disposed on at least one surface of the substrate,
The surface layer is a component A having a solubility in water at 25 ° C. of 0.1 g / 100 g to 40 g / 100 g of water (hereinafter also simply referred to as “component A”), other than the component A, and And component B (hereinafter also simply referred to as “component B”) that satisfies the following requirements (1) to (4) (hereinafter also referred to as “specific requirements”).
Since the surface layer included in the laminate according to the present disclosure contains component A and component B other than component A and satisfying the specific requirements, the laminate according to the present disclosure is excellent in appearance.
The reason for this is not clear, but is presumed as follows.

In general, in a W / O or O / W type emulsion, the critical particle size of emulsion droplets is determined by Ostwald ripening. In Ostwald ripening, when the emulsified droplets become smaller, the solubility of the components constituting the emulsified droplets in the medium increases, so the emulsified droplets eventually disappear. Moreover, the component which comprises the emulsified droplet melt | dissolved in the medium is reabsorbed by the remaining emulsified droplet, and an emulsified droplet becomes large. By repeating the above phenomenon, the critical particle size of the emulsified droplets is determined.
In addition, if a substance that is difficult to dissolve in the medium is dissolved in the components constituting the emulsified droplets, the disappearance of the emulsified droplets is suppressed, so that the limit particle diameter can be further reduced.
In the present invention, by containing the A component that is difficult to dissolve in the B component and the B component, the A component becomes a hardly soluble substance, and smaller emulsion droplets are easily formed. It is presumed that it is excellent in transparency, that is, excellent in appearance.
Hereinafter, each component which comprises the laminated body which concerns on this indication is demonstrated.

<Surface layer>
The surface layer includes component A and component B. Further, the surface layer is in contact with at least a part of the base material described later, and preferably is in contact with at least a part of the surface of the base material.

(Component A)
Component A has a solubility in water at 25 ° C. of 0.1 g / 100 g of water to 40 g / 100 g of water. According to the present disclosure, since the surface layer includes the component A having a solubility in water within the above range and the component B described later, an emulsion droplet having a smaller diameter can be formed using the component A as a core. The laminate is excellent in appearance and particularly excellent in transparency.

Here, the solubility in water refers to the amount of component A added at 25 ° C., mixed with water, stirred with a magnetic stirrer for 120 minutes, filtered using filter paper, and the precipitate on the filter paper The maximum value of the mass (g) of component A with respect to 100 g of water when the presence or absence is visually confirmed and the precipitate on the filter paper cannot be confirmed is shown.
Component A is not particularly limited as long as the solubility in water is within the above range, and examples include polylysine, antibacterial agents such as chitosan and silver, and molecule A described later.

-Molecule A-
The molecule A is preferably an antibacterial compound having at least one structure selected from the group consisting of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from an amino acid.
The molecule A may be a compound having any one of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from an amino acid, and is a compound having two or more of these structures. May be.
The molecule A is preferably at least one compound selected from the group consisting of a compound having a structure derived from guanidine, a compound having a structure derived from glucosamine, and a compound having a structure derived from lysine.
Hereinafter, a compound having a structure derived from guanidine, a compound having a structure derived from glucosamine, and a compound having a structure derived from lysine will be described.

-Compounds having a structure derived from guanidine-
The structure derived from guanidine is not particularly limited, and for example, a structure represented by the following formula (G-1) is preferable.

In formula (G-1), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituent, and the wavy line represents a bonding site with another structure.
From the viewpoint of antibacterial properties, R ^{1 to} R ⁴ included in the formula (G-1) are each independently preferably a hydrogen atom or an alkyl group, and more preferably all are hydrogen atoms. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.

The compound having a structure derived from guanidine is preferably a compound having a structure derived from guanidine and a structure derived from amino acid, more preferably a compound having an amino acid having a structure derived from guanidine, and arginine. A compound having a derived structure is more preferable, and a peptide including a structural unit derived from arginine is particularly preferable.
The arginine may be arginine having a known substituent, but is preferably unsubstituted arginine.
The structure derived from arginine and the structural unit derived from arginine include a structure derived from guanidine.
In the present disclosure, an amino acid refers to a compound having an amino group (—NH ₂ ) and a carboxy group (—COOH) in one molecule.
In the present disclosure, a peptide refers to a compound in which 2 to 100 amino acid molecules are linked by peptide bonds.

  The compound having a structure derived from guanidine preferably contains at least one of protamine and a salt of protamine (hereinafter also referred to as “protamine etc.”), and more preferably contains a salt of protamine. In addition, the compound having a structure derived from guanidine may be at least one of protamine and a salt of protamine, and preferably a salt of protamine.

Protamine and the like are not particularly limited, and a basic protein obtained by hydrolyzing a nuclear protein present in the testis of fish, birds, mammals and the like into DNA and protein; protamine obtained by further hydrolyzing the basic protein; These salts are mentioned. Examples of the salt of protamine include inorganic salts such as hydrochloride, sulfate, and phosphate; and organic salts such as acetate, propionate, and gluconate.
There is no restriction | limiting in particular as usage methods, such as these protamines, It is preferable to select according to a use. Protamine etc. may be used individually by 1 type, and may use 2 or more types together. Protamine etc. may be a commercial item.

-A compound having a structure derived from glucosamine-
Examples of the compound having a structure derived from glucosamine include chitosan and chitosan salts.
The compound having a structure derived from glucosamine is preferably at least one of chitosan and chitosan salt (hereinafter, at least one of chitosan and chitosan salt may be referred to as “chitosan etc.”). More preferred.
Examples of the chitosan salt include inorganic salts such as hydrochloride, sulfate, and phosphate; and organic salts such as acetate, propionate, and gluconate.

There is no restriction | limiting in particular as chitosan etc. For example, deacetylation is carried out by the boiling process etc. in the concentrated alkali etc. from chitin (poly-beta1-4-N-acetylglucosamine) obtained from crustacean exoskeletons, such as crab and shrimp. And those obtained by conversion to these salts.
Chitosan etc. may be used individually by 1 type, and may use 2 types together. Moreover, a commercial item may be sufficient as chitosan etc.

-Compound having a structure derived from lysine-
Examples of the compound having a structure derived from lysine include polylysine and polylysine salts, and polylysine is preferable. Hereinafter, at least one of polylysine and a salt of polylysine is also referred to as “polylysine or the like”. Examples of polylysine salts include inorganic salts such as hydrochlorides, sulfates, and phosphates; and organic salts such as acetates, propionates, and gluconates.

The polylysine and the like are not particularly limited. For example, ε-polylysine (ε-poly-L-lysine) produced by a fermentation method, α-polylysine (α-poly-L-lysine, α- produced by chemical synthesis). Poly-D-lysine) and salts thereof.
These polylysine and the like are preferably selected according to the application. Polylysine etc. may be used individually by 1 type and may use 2 types together. Polylysine etc. may be a commercial item.

  As the component A, only one type of compound having at least one structure selected from the group consisting of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from amino acids may be used, or two or more types may be used. Good.

The weight average molecular weight (Mw) of Component A is preferably 500 or more and 10,000 or less, more preferably 1000 or more and 9000 or less, further preferably 2000 or more and 8000 or less, and more preferably 3000 or more and 7000 from the viewpoint of antibacterial properties and antibacterial maintenance. The following are particularly preferred:
In addition, the measurement of the said molecular weight and molecular weight distribution is performed on condition of the following using GPC (gel permeation chromatography) method.
Apparatus: Build-up GPC system (manufactured by Tosoh Corporation) (Degasser / SD-8022, pump / DP-8020, autosampler / AS-8021, column heater / CO-8020, differential refractometer / RI-8020)
Mobile phase: 0.1 M NaNO ₃ aqueous solution Column: TSKgel G3000PWXL-CP (7.8 mm ID × 30 cm) 2 (Tosoh Corporation)
Flow rate: 1.0 mL / min Sample: A sample solution having a concentration of 4 mg / mL is prepared using a mobile phase solvent, and 100 μL is injected. Detector: RI (differential refractometer), polarity = (+)
Temperature: 40 ° C
Molecular weight calibration: Standard polyethylene oxide (PEO) (Agilent Technology Co., Ltd.)

The amount of component A per unit area of the surface layer is preferably from the viewpoint of enhancing the antimicrobial and antibacterial maintaining property ^{is 0.2mg / m 2 ~300mg / m 2} , 0.3mg / m 2 ~200mg / more preferably m ^{2, and} more preferably from ^{0.6mg / m 2 ~150mg / m 2} , particularly preferably from ^{0.9mg / m 2 ~50mg / m 2} , 1.0mg / m it is more preferably ^{2 ~30mg} / ^{m 2.}
In addition, when 2 or more types of component A is contained in the surface layer, "surface amount of component A" refers to the sum total of these surface amounts.

Moreover, as content of the component A in a surface layer, 0.01 mass% or more and 50 mass% or less are mentioned with respect to the whole surface layer, for example, 0.05 mass% or more and 30 mass% or less from a viewpoint of antimicrobial maintenance property. Is preferable, and 0.1 mass% or more and 10 mass% or less are more preferable.
As content of the component A in a surface layer, it is mentioned that it is 0.01 mass% or more and 70 mass% or less with respect to the total content of the component A and the component B, and it is 0.05 from an antimicrobial maintenance viewpoint. The mass% is preferably 50% by mass or less, and more preferably 0.1% by mass or more and 20% by mass or less.

The equivalent of the basic group in Component A is preferably 50 g / eq to 500 g / eq, more preferably 80 g / eq to 350 g / eq, and still more preferably 100 g / eq to 250 g / eq. .
Here, the “basic group” means a functional group having a pKa of a conjugate acid calculated by ACD pKa DB ver.12.0 of 11 to 14, for example, an amino group contained in the structure derived from the guanidine. It is done.
The “equivalent of the basic group in component A” refers to the mass of component A relative to 1 mol of the basic group.
The equivalent of the basic group is calculated by conducting a structural analysis of component A.

(Component B)
Component B consists of compounds other than Component A and satisfies the following requirements (1) to (4).
Requirement (1) A polymer having 90 to 100 mol% of structural units derived from at least one monomer selected from ethylene and an α-olefin having 3 to 20 carbon atoms, based on all structural units.
Requirement (2) Number average molecular weight (Mn) is 1500-30000.
Requirement (3) The viscosity at 25 ° C. when 10 g of the component B is dissolved in 100 g of toluene is 5 mPa · s to 200 mPa · s.
Requirement (4) The amount of polar groups is 1.00 × 10 ⁻⁶ mol / g to 1.00 × 10 ⁻⁴ mol / g.
When the surface layer of the laminate according to the present disclosure includes the component A and the component B described above, the laminate including the surface layer is excellent in transparency, that is, in appearance.
Hereinafter, each requirement that the component B satisfies will be described.

-Requirement (1)-
Component B is a heavy component having a structural unit derived from at least one monomer selected from ethylene and an α-olefin having 3 to 20 carbon atoms in a range of 90 mol% to less than 100 mol% with respect to all the structural units. It is a coalescence (hereinafter also referred to as “α-olefin polymer”).
The α-olefin-based polymer as Component B may be ethylene or a homopolymer of an α-olefin having 3 to 20 carbon atoms, and may be a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. May be.
The α-olefin having 3 to 20 carbon atoms is not particularly limited, and may be linear or branched.

Specific examples of the monomer constituting the α-olefin polymer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, Linear α-olefins such as 1-dodecene, 1-tricene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene, and 3 -Methyl-1-pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6-methyl-1-undecene, 6,8-dimethyl-1-decene, etc. An α-olefin having a branch may be mentioned.
The structural units constituting these α-olefin polymers may be used alone or in combination of two or more.

When the α-olefin polymer is a copolymer, specific examples include a copolymer of an α-olefin having 3 to 20 carbon atoms, and ethylene and an α-olefin having 3 to 20 carbon atoms. And a copolymer of at least one selected monomer.
Among these, from the viewpoint of excellent balance between the viscosity index and the low temperature fluidity, the α-olefin having 3 to 20 carbon atoms is preferably a linear α-olefin having 3 to 12 carbon atoms, and more preferably. There are 3-9.

  From the viewpoint of excellent balance between viscosity index and low temperature fluidity, the polymer contained in Component B is a homopolymer of an α-olefin having 3 to 20 carbon atoms or ethylene and an α-olefin having 3 to 20 carbon atoms. A copolymer is preferable, and a copolymer of ethylene and a linear α-olefin having 3 to 12 carbon atoms is more preferable.

  In the polymer included in Component B, from the viewpoint of excellent low-temperature viscosity characteristics, the content of the structural unit derived from the α-olefin having 3 to 20 carbon atoms is based on the total structural unit of the polymer included in Component B. It is preferable that it is 90 mol% or more and less than 100 mol%, Preferably it is 95 mol% or more and less than 100 mol%.

  In the polymer contained in Component B, from the viewpoint of excellent low-temperature viscosity characteristics, the content of structural units derived from ethylene is preferably 0 mol% to 10 mol%, more preferably 0 mol% to 5 mol%. It is.

-Requirement (2)-
Component B has a number average molecular weight (Mn) of 1500 to 30000, preferably in the range of 1500 to 16000, and more preferably 10,000.
When the number average molecular weight (Mn) weight average molecular weight is in the above range, it can be easily dissolved in a solvent described later.
The number average molecular weight (Mn) is a value obtained from a gel permeation chromatography (GPC) method, and is a value measured under the following conditions.
In addition, a weight average molecular weight (Mw) and a number average molecular weight (Mn) create a calibration curve using a commercially available monodisperse standard polystyrene, and obtain | require based on the following conversion method.

Apparatus: HLC8321 GPC / HT (manufactured by Tosoh Corporation)
Solvent: O-dichlorobenzene Column: 2 TSKgel GMH6-HTL, 2 TSKgel GMH6-HTL columns (manufactured by Tosoh Corporation)
Flow rate: 1.0 ml / min Sample: O-dichlorobenzene solution 0.10 mg / mL
Temperature: 140 ° C
Molecular weight conversion: Polypropylene (PP) conversion / General calibration method

-Requirement (3)-
When 10 g of Component B is dissolved in 100 g of toluene, the viscosity at 25 ° C. (hereinafter also simply referred to as “viscosity”) is 5 mPa · s to 200 mPa · s.
When the viscosity of component B in toluene is within the above range, component A and component B can be dispersed.
From the above viewpoint, the viscosity of component B in toluene is preferably 5 mPa · s to 100 mPa · s, and more preferably 5 mPa · s to 50 mPa · s.
The viscosity of B component means the viscosity in 25 degreeC and 60 rpm measured with a B-type viscometer.
More specifically, a bottle containing 10 g of the component B dissolved in 100 g of toluene was placed in a thermostatic bath at 25 ° C. for 2 hours, and the No. 1 rotor was installed under the condition that the temperature of the sample was kept constant. And can be measured and obtained under measurement conditions of 60 rpm.

-Requirement (4)-
Component B has a polar group content of 1.00 × 10 ⁻⁶ mol / g to 1.00 × 10 ⁻³ mol / g, preferably 1 × 10 ⁻⁶ mol / g to 1 × 10 ^−4. mol / g.
When the amount of the polar group is within the above range, it can be easily dissolved in a solvent described later.
The amount of the polar group can be determined by measuring Component B using ¹ H-NMR and calculating from the integration ratio of the peak derived from the polar group and the peak derived from the requirement (1).

  Examples of polar groups include hydroxyl groups, acyl groups, acetyl groups, formyl groups, benzoyl groups, carboxy groups, carboxylic acid amide groups, thioamide groups, imide groups, amidine thiol groups, sulfide groups, disulfide groups, sulfenic acid groups, isonitriles. Carbonyl group, amino group, imino group, cyano group, azo group, azide group, thiol group, sulfo group, nitro group and the like.

From the viewpoint of excellent dispersibility when mixed with Component A, the polar group is at least one functional group selected from the group consisting of a carboxy group, a hydroxy group, an acetyl group and an amino group (hereinafter referred to as “specific functional group”). Is also referred to as “.”
From the above viewpoint, the polar group is preferably at least one functional group selected from the group consisting of a carboxy group, an acetyl group, and an amino group, and more preferably a carboxy group.

There is no restriction | limiting in particular as a method to introduce | transduce a polar group into Component B, A specific functional group can be introduce | transduced into an alpha-olefin type polymer by a well-known and publicly used method.
For example, usually, in the presence of a radical initiator such as di-t-butyl peroxide, a monomer having a specific functional group is added to the α-olefin polymer and introduced by copolymerization or addition reaction. Preferably, a polar group is preferably introduced by a graft copolymerization reaction.

When the specific functional group is a carboxy group, specific examples of the monomer having a carboxy group include monobasic acids such as acrylic acid and methacrylic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, 5-norbornene- Examples thereof include dibasic acids such as 2,3 dicarboxylic acid and carboxylic acid anhydrides such as maleic acid, itaconic acid, citraconic acid and 5-norbornene-2,3 dicarboxylic acid. Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid diethyl ester And esters and half esters.
Among these, the monomer having a carboxy group is preferably maleic acid or maleic anhydride from the viewpoint of high polarity and the difficulty of forming by-products such as homopolymers in the modification reaction using peroxide. preferable.

In Component B, the α-olefin polymer may have a functional group other than the specific functional group (hereinafter, also referred to as “other functional group”) as long as the effects of the present invention are not impaired. .
Examples of other functional groups include hydroxy groups.

Component B preferably does not have a critical micelle concentration as measured by electrophoresis.
Here, the critical micelle concentration measured by the electrophoresis method indicates the concentration of the inflection point when the molar conductivity is plotted against the concentration of the component B, and does not have the critical micelle concentration. Means that it cannot be confirmed.

The content of Component B is preferably 100 parts by mass to 1000 parts by mass, and more preferably 100 parts by mass to 600 parts by mass with respect to 100 parts by mass of Component A.
When the content of component B is within the above range, the dispersibility of component A can be improved.

(Other ingredients)
The surface portion included in the laminate according to the present disclosure may include components other than Component A and Component B (hereinafter, also referred to as “other components”) within a range that does not impair the object of the present invention.
Examples of other components include water-soluble resins such as polyethylene glycol, polyethylene oxide, mono- or diglyceride, and polyvinyl alcohol (PVA); antibacterial agents other than molecule A; sorbitan monooleate (SMOL), polyethylene glycol (PEG), and the like Nonionic surfactants of
Other components may be used alone or in combination of two or more.

<Base material>
The laminate according to the present disclosure includes a base material. The base material preferably contains a polymer.

(High molecular)
The polymer is not particularly limited. For example, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate (hereinafter also referred to as “PET”), polyolefin such as ethylene propylene copolymer, polyethylene naphthalate, polybutylene terephthalate, cellophane. , Rayon, polystyrene, polycarbonate, polyimide, polyamide, polyacryl, polysulfone, polyether, polyurethane, and cellulose. These polymers may be used alone or in combination of two or more.

-Polyethylene-
As the polyethylene, for example, low density polyethylene, medium density polyethylene, high density polyethylene, and high pressure method low density polyethylene, which are produced by a conventionally known method, can be used.

-Polypropylene-
Examples of the polypropylene include isotactic polypropylene and syndiotactic polypropylene. The isotactic polypropylene may be a homopolypropylene, a propylene / α-olefin having 2 to 20 carbon atoms (excluding propylene) random copolymer, or a propylene block copolymer. .

-Polymethylpentene-
Examples of polymethylpentene include a homopolymer of 4-methyl-1-pentene; a structural unit derived from 4-methyl-1-pentene, and an α-olefin having 2 to 20 carbon atoms (provided that 4-methyl And a copolymer derived from (excluding -1-pentene).

-Polyethylene terephthalate (PET)-
Examples of polyethylene terephthalate (PET) include polyethylene terephthalate obtained from an aromatic dicarboxylic acid containing terephthalic acid or an ester derivative thereof and a diol containing ethylene glycol.
As PET, amorphous polyethylene terephthalate (A-PET) is preferable from the viewpoint of moldability into a container shape and the like.

(Other ingredients)
The base material may contain other components other than the polymer as long as the object of the present invention is not impaired.
Examples of other components include a dispersant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, a lubricant, a slip agent, a nucleating agent, an antiblocking agent, an antistatic agent, an antifogging agent, a pigment, and a dye.
Other components may be used alone or in combination of two or more.
The content of other components is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less with respect to 100% by mass of the total amount of the antibacterial material. .

The substrate provided in the laminate according to the present disclosure is preferably a polymer film containing at least one polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, and polyethylene terephthalate.
In the laminate according to the present disclosure, the base material is preferably a container-shaped molded body containing at least one polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, and polyethylene terephthalate.
When the base material is a container-shaped molded body, the base material more preferably contains polyethylene terephthalate (PET).

(Haze value)
The laminate according to the present disclosure preferably has a haze value of 0.5% to 20%. When the haze value is 0.5% to 20%, the dispersibility of Component A is good, and a laminate that is more excellent in transparency can be obtained.
From the above viewpoint, the haze value of the laminate is more preferably 0.5% to 10%, and still more preferably 5% or less.
In the present disclosure, the haze value can be determined, for example, by measuring a laminate according to the present disclosure having a thickness of 0.003 mm with a haze meter (manufactured by Tokyo Denshoku Co., Ltd.).
When the laminate according to the present disclosure has a haze value of 10% or less when the thickness of the laminate is 0.003 mm, it can be said that the laminate is particularly excellent in transparency.

  As a preferable form of the laminate according to the present disclosure, specifically, an antibacterial film using a polymer film (hereinafter also referred to as “base film”) as a base material, and an antibacterial using a molded body as a base material. An antibacterial nonwoven fabric using a nonwoven fabric as a base material and a base material.

<Antimicrobial film>
Examples of the antibacterial film include packaging films, packaging laminate films, and molding films. The antibacterial film may be a non-stretched film, a uniaxial or biaxially stretched film, and may be a single layer or a plurality of layers (multilayers).

As the antibacterial film, the substrate is preferably a substrate film.
Examples of the polymer contained in the substrate film (substrate) include the polymers exemplified above, and among them, at least one polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, and polyethylene terephthalate. Is preferred.

When the antibacterial film is a packaging film, the base film preferably contains at least one polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, and polyethylene terephthalate (PET).
When the antibacterial film is a film for molding, the base film preferably contains polyethylene terephthalate (PET) from the viewpoint of moldability into a container shape or the like.
These polymers may be used alone or in combination of two or more.

  When the antibacterial film is a packaging film, the thickness of the packaging film is preferably 15 μm to 200 μm, more preferably 20 μm to 120 μm, and still more preferably 25 μm to 100 μm.

When the antibacterial film is a packaging laminate film, examples of the packaging laminate film include a base film A, a seal layer disposed on the base film A, and a seal layer. An aspect provided with the surface part containing ingredient A is mentioned. In the case of this aspect, the base film A and the seal layer correspond to the base material (base film).
The ratio of the thickness of the base film A is preferably 10% to 80%, more preferably 20% to 50% with respect to the thickness of the entire antibacterial film.
The thickness of the sealing layer is preferably 10 μm to 100 μm, more preferably 20 μm to 80 μm, and still more preferably 25 μm to 70 μm.
In the case of the said aspect, since the surface part containing the component A is arrange | positioned on a sealing layer, it is preferable that this surface part turns into an opposing surface with articles | goods (preferably fresh food).

When the antibacterial film is a molding film, the thickness of the molding film is preferably selected according to the use of the molded body.
In particular, when the forming film is a vacuum forming film, the thickness of the vacuum forming film is preferably 50 μm to 800 μm, more preferably 100 μm to 700 μm, and still more preferably 200 μm to 600 μm. In this case, the base film of the film for vacuum forming is preferably a base film (film containing PET (preferably PET film)) of the mode (2) described later.
In the case of the said aspect, it is preferable that the surface part containing the component A becomes an inner surface of a container after container shaping | molding. That is, the surface area surface of the component A is 0.2mg ^{/ m 2} ~300mg ^/ m 2 is preferably formed with opposing surfaces of the article (preferably fresh food).

Preferred embodiments of the substrate film when the antibacterial film is a container-forming film include, for example, the following embodiments (1) to (3).
(1) A mode in which the base film contains at least one polymer selected from the group consisting of polyethylene, polypropylene, and polymethylpentene, and a film containing PET (preferably a PET film) is bonded to the base film side.
In the above aspect (1), the film containing PET (preferably a PET film) is pasted together, so that it is particularly excellent in moldability to a container shape or the like.
(2) A mode in which the base film contains PET (preferably a PET film).
The base film of the aspect (2) is particularly excellent in moldability into a container shape and the like, and in particular, excellent in moldability into a container shape by vacuum (pressure air) molding.
In addition, the film for shaping | molding provided with the base film of the aspect of said (2) is obtained by apply | coating the coating liquid containing component A directly to the film (preferably PET film) containing PET as a base film. It is done.
(3) A film containing at least one polymer selected from the group consisting of polyethylene, polypropylene and polymethylpentene, and a film containing PET (preferably, in order from the side of the surface part containing component A) The aspect which is a multilayer film by which PET film) was laminated | stacked.
The base film of the above aspect (3) is particularly excellent in moldability to a container shape or the like.

<Antimicrobial molding>
Although there is no restriction | limiting in particular as an antibacterial molded object, For example, a molded object of a container shape, a molded object of component shapes, such as a robot and a motor vehicle, etc. are mentioned.
As an antibacterial molded object, it is preferable that a base material is a molded object (a container-shaped molded object, a component-shaped molded object etc.).
Examples of the polymer contained in the molded body (base material) include the polymers exemplified above, among which at least one polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, and polyethylene terephthalate is used. Preferably, polyethylene terephthalate is more preferable.
For example, a container-shaped molded body can be obtained by molding the aforementioned molding film into a container-shaped molded body. As a forming film for forming a container-shaped formed body, a forming film provided with the base film of the above aspect (2) is preferable.
In addition, the container-shaped molded body is formed by forming a base film of a molding film into a container shape and then applying a coating liquid containing component A onto the base film (molded body) formed into a container shape. Can also be obtained. The base material of the antibacterial molded body may be a commercial product.

<Antimicrobial nonwoven fabric>
Although there is no restriction | limiting in particular as an antibacterial nonwoven fabric, For example, the antibacterial nonwoven fabric used as a drip sheet (nonwoven fabric for drip sheets), a mask, an air filter etc. is mentioned. The antibacterial nonwoven fabric may be a single layer or a plurality of layers (multilayers).

As the antibacterial nonwoven fabric, the substrate is preferably a nonwoven fabric, and the substrate (nonwoven fabric) preferably contains a polymer composed of fibers.
Examples of the polymer contained in the nonwoven fabric include the same polymers as those exemplified above.
When the antibacterial nonwoven fabric is a nonwoven fabric for drip sheets, the thickness of the nonwoven fabric for drip sheets is preferably 50 μm to 800 μm, more preferably 100 μm to 700 μm, and still more preferably 200 μm to 600 μm.
In the case of the above aspect, for example, in a package in which fresh food is packaged, since the drip from the fresh food easily moves in the package, any inner surface of the package can be a surface facing the fresh food. For this reason, the surface part containing the component A may be formed in any surface of the nonwoven fabric for drip sheets.

[Usage]
The laminated body according to the present disclosure is, for example, a tape, an adhesive tape, a masking tape, a masking film, a temporary attachment film, a plastic envelope, an easy open packaging bag, an automatic packaging film, a shopping bag, a standing bag, a transparent packaging box, a building material, Films for pasting, films for agriculture, materials for maintaining freshness (food packaging materials, vegetable packaging materials, fruit packaging materials, meat packaging materials, seafood packaging materials such as seafood, packaging materials such as processed food packaging materials; flower packaging materials Containers for food, vegetables (cut vegetables, etc.), fruits, meat, marine products, processed foods, soba, ramen, bento containers, electronic parts packaging materials, mechanical parts packaging materials, grain packaging materials, medical films, medical Widely used as a tape for medical use, a cell culture pack, and the like.
In particular, when the antibacterial material is an antibacterial nonwoven fabric, it can also be used for filters (air conditioners, automobiles, home appliances, etc.), food tray mats, masks, seat covers for seats, table cloths, carpets and the like.

  When the layered product according to the present disclosure contains the molecule A as the component A, a layered product having high antibacterial properties can be obtained. It can be suitably used as an antibacterial material such as an antibacterial film, an antibacterial molded article, and an antibacterial nonwoven fabric for maintaining the freshness of foods, flowers and processed products. Thereby, the freshness of fresh food and processed products can be maintained.

[Material for maintaining freshness]
The freshness-keeping material according to the present disclosure includes the laminate according to the present disclosure. The freshness-keeping material according to the present disclosure is a freshness-keeping material obtained using the laminate (for example, an antibacterial film, an antibacterial molded body, and an antibacterial nonwoven fabric) according to the present disclosure. Thereby, a freshness-keeping material having high antibacterial properties and good operability can be obtained.
It is preferable that the freshness-keeping material according to the embodiment is used for packing an article.
In particular, the freshness-keeping material according to the present disclosure includes an antibacterial material having high antibacterial properties, so that the freshness of, for example, fresh foods such as vegetables, fruits, meat, fresh fish, and processed foods, flowers, and processed products is maintained. Therefore, it can be suitably used as a packaging material such as a packaging bag or a container.
The packaging bag as the packaging material is formed by bending the antibacterial material such that the antibacterial surface of the antibacterial material such as an antibacterial film (surface part including the component A) is opposed to each other. After overlapping at least two or more, a predetermined part can be obtained by heat-sealing (heat sealing) by a known method.

In Freshness material according to the present disclosure, the surface portion The amount of the component A is 0.2mg ^{/ m 2} ~300mg ^/ m 2 is preferably a surface facing the article.
Thereby, the surface of the article is kept clean, and particularly when the article is a food, its freshness is maintained.

"Composition"
The composition according to the present disclosure includes component A having a solubility in water at 25 ° C. of 0.1 g / 100 g of water to 40 g / 100 g of water;
A component B other than the component A and satisfying the requirements (1) to (4);
A solvent,
at least one compound selected from the group consisting of α-polyolefin, methacrylic acid and methyl methacrylate (hereinafter also referred to as “specific compound”);
including.
The composition according to the present disclosure can improve the dispersibility of the component A in the composition by including the component A, the component B, the solvent, and the specific compound, and the composition can be used as a raw material of the laminate. In such a case, a laminate having excellent transparency can be obtained.
Hereinafter, each component constituting the composition will be described. In addition, since the component A and the component B are synonymous with the component A and the component B in the above-mentioned laminated body, description is abbreviate | omitted.

In the composition according to the present disclosure, the average primary particle size of Component A is preferably 50 nm to 1000 nm. When the average primary particle size of component A in the composition is in the above range, component A is superior to component B due to dispersibility.
From the above viewpoint, the average primary particle size of Component A is more preferably 50 nm to 300 nm.
The average primary particle size of component A can be determined with a particle size analyzer (product name; Micro Track UPA, manufactured by Micro Track Bell Co., Ltd.).

The composition according to the present disclosure includes a solvent. The wettability with respect to a base material can be improved because a composition contains a solvent.
The solvent is not particularly limited. For example, acetone, isobutyl alcohol, isopropyl alcohol (2-propanol), isopentyl alcohol (isoamyl alcohol), ethyl ether, ethylene glycol monoethyl ether (cellosolve), ethylene glycol monoethyl ether acetate (Cellosolve acetate), ethylene glycol mono-n-butyl ether (butyl cellosolve), ethylene glycol monomethyl ether (methyl cellosolve), ortho-dichlorobenzene, xylene cresol, chlorobenzene, isobutyl acetate acetate, isopentyl acetate (isoamyl acetate), acetic acid Ethyl, n-butyl acetate, n-propyl acetate, n-pentyl acetate (n-amyl acetate), methyl acetate, cyclohexanol, cyclohexane Sanone, N, N-dimethylformamide, tetrahydrofuran, toluene, 1,1,1-trichloroethanetoluene, n-hexane, 1-butanol, 2-butanol, methanol, methyl ethyl ketone, methylcyclohexanol and methylcyclohexanone methyl-n-butyl ketone Is mentioned.
Among these, from the viewpoint of the dispersibility of Component A, the solvent is preferably toluene, methylcyclohexane or ethyl acetate, and more preferably toluene or methylcyclohexane.

  As content of a solvent, it is preferable that it is 50 mass%-95 mass% with respect to the total mass of a composition, More preferably, it is 70 mass%-90 mass%.

  It is preferable that content of the above-mentioned component A is 0.00001 mass part-30 mass parts with respect to 100 mass parts of solvent, More preferably, it is 0.00001 mass part-15 mass parts.

  Moreover, it is preferable that content of the above-mentioned component B with respect to 100 mass parts of solvent is 1 mass part-70 mass parts, More preferably, it is 1 mass part-40 mass parts.

  The composition according to the present disclosure includes at least one compound (specific compound) selected from the group consisting of α-polyolefin, propylene-butene-ethylene rubber (PBER), methacrylic acid, and methyl methacrylate. When the composition contains the specific compound, it can be uniformly applied to a polypropylene (PP) film or the like.

There is no restriction | limiting in particular as (alpha) -polyolefin, Homopolymers, such as olefins, such as ethylene, propylene, butene, pentene, hexene, octene, a decene, and 4-methyl-1- pentene, or 2 or more types of alpha-olefins A copolymer is mentioned.
The α-polyolefin may contain a structural unit derived from styrene in addition to the α-olefin.
Among these, from the viewpoint of adhesion to PP, an α-polyolefin homopolymer is preferable, and polyethylene or polypropylene is more preferable.

  From the above viewpoint, the specific compound is preferably at least one compound selected from polypropylene and PBER, and more preferably a mixture of polypropylene and PBER.

The composition which concerns on this indication may further contain components (other components) other than the component A, the component B, a solvent, and a specific compound as needed.
Examples of the other components include other components in the above-described laminate.

[Manufacturing method of laminate]
The manufacturing method of the laminated body which concerns on this indication is not specifically limited, The process (henceforth "application film | membrane) which forms the above-mentioned surface layer by apply | coating the coating liquid containing the component A and the component B on a base material. It is preferable to include a “forming step”. Thereby, the antibacterial material excellent in transparency can be manufactured.
As the coating liquid containing component A and component B, it is preferable to use the composition described above.
In addition, about the detail of a surface layer, a base material, and a composition, since it is the same as that of the surface layer, base material, and composition in the above-mentioned laminated body, the description is abbreviate | omitted.

<Coating film formation process>
In the coating film forming step, the amount of component A ^is preferably ^{0.2mg / m 2 ~300mg / m 2} , more preferably ^{0.2mg / m 2 ~200mg / m 2} , 0.6mg / ^m 2 is more preferably to 150 mg / ^{m 2,} particularly preferably from 0.9 mg / m 2 to 50 mg / ^{m 2,} and still more preferably 1.0 mg / m 2 to 30 mg / ^{m 2} .
It is preferable to apply the coating solution on the base material while adjusting the content of the component A.

  The method for applying the coating solution is not particularly limited, and known methods such as a spin coating method, a bar coating method, a spray method, a roller method, a dip method, and an ink jet method can be applied.

Although there is no restriction | limiting in particular as a manufacturing method of a base material, When the form of a base material is a film (unstretched film, uniaxial or biaxially stretched film), for example, the material (material containing a polymer) which comprises a base material A method of forming an extrusion film by a film forming machine; a method of co-extrusion forming a material of a layer (a material containing a polymer) constituting a base material by a multilayer film forming machine, for example, when the base material is formed of a multilayer film; Is mentioned.
When the form of the base material is a molded body (for example, a container-shaped molded body), a molded body as the base material can be produced by molding a film as the base material (base material film) by a known method.
When the form of the substrate is a nonwoven fabric, for example, using fibers containing one or more of the above polymers, an air-through method, a spunbond method, a needle punch method, a melt blown method, a card method, a thermal fusion method, A nonwoven fabric as a substrate can be produced by a known method such as hydroentanglement method or solvent adhesion method.
Commercially available products may be used for the base materials (films, molded products, nonwoven fabrics).
The surface of the base material may be subjected to the surface treatment described above.

<Drying process>
The method for producing an antibacterial material according to the present disclosure preferably includes at least a step of drying the surface layer (coating film) at a temperature of 50 ° C. to 120 ° C. (hereinafter also referred to as “drying step”).
As drying temperature of the coating film in a drying process, 50 to 80 degreeC is more preferable, and 50 to 60 degreeC is still more preferable.
The drying time, the drying atmosphere, and the pressure at which drying is performed can be appropriately selected according to the composition of the coating solution, the coating amount, and the like.

The method for drying the coating film is not particularly limited as long as it is a method for promoting the volatilization of the solvent contained in the coating solution. For example, a method for applying heat to the coating film, a method for blowing warm air on the coating film, and the like. The method which combined these is mentioned. Among these, a method of blowing warm air on the coating film is preferable from the viewpoint of suppressing the repelling of the coating solution on the coating surface.
The method for applying heat to the coating film is not particularly limited as long as it uses a furnace, a hot plate, a vacuum heater, or the like.
The method of spraying warm air on the coating film is not particularly limited as long as it uses a device that can heat a gas.
In the method of spraying warm air on the coating film, the preferable range of the temperature of the warm air is the same as the preferable range of the drying temperature.

<Surface treatment process>
The method for producing an antibacterial material according to the present disclosure preferably further includes a step of performing a surface treatment on the base material before the application liquid is applied (hereinafter also referred to as “surface treatment step”). The surface treatment may be performed on the entire surface of the base material, or may be performed on at least a part of the base material.
The surface treatment method for the substrate is not particularly limited, and examples include surface activation treatment such as corona treatment, itro treatment, ozone treatment, ultraviolet treatment, chemical treatment, high frequency treatment, glow discharge treatment, plasma treatment, and laser treatment. . Among these, corona treatment is preferable from the viewpoint of reducing unevenness of distribution by increasing the wettability of component B on the surface and preventing component B from falling off.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1
<Manufacture of single layer stretched polypropylene film>
A propylene homopolymer (melting point (Tm): 160 ° C., MFR: 3 g / 10 minutes (manufactured by Prime Polymer Co., Ltd., trade name: F300SP)) was prepared. Using a biaxial stretching machine, a propylene homopolymer is biaxially stretched 5 times in length and 10 times in width to produce a single layer stretched polypropylene film (hereinafter also referred to as “single layer OPP film”). Manufactured. The stretching temperature of the single-layer OPP film was longitudinal stretching: 100 ° C., lateral stretching: 180 ° C., the heat setting temperature was 180 ° C., and the setting time was 10 seconds.
The thickness of the single layer OPP film was 30 μm.
Furthermore, the corona treatment was performed so that one surface of the single-layer OPP film had a wet tone (wetting index) of 38 dyn (dyne). The measurement of the wetting index was confirmed according to whether or not the wet tension test mixed liquid (NO. 38.0) of Wako Pure Chemical Industries, Ltd. could be applied according to JIS K 6768 (1999).

<Formation of surface layer>
(Preparation of component A)
As component A, the following protamine salt which is an antibacterial agent was used. The weight average molecular weight of the protamine salt was measured by the method described above.
Protamine salt: Protamine hydrochloride, Maruha Nichiro Co., Ltd., Protamine content (content of protamine salt with respect to the whole) 88.3 mass%, ignition residue 11.4%, weight average molecular weight 5800, basic group equivalent 200 g / eq, solubility in water at 25 ° C. 30 (g / 100 g of water)

(Preparation of component B)
An ethylene-propylene copolymer (trade name; Lucant HC-2000, manufactured by Mitsui Chemicals) was added to a glass 5 L reactor equipped with a stirrer equipped with a nitrogen blowing tube, a water-cooled condenser, a thermometer, and two dropping funnels. 500 mL was charged, nitrogen bubbling was started at 120 ° C. after the temperature was raised, and the system was kept at 160 ° C.
Then, 138.5 mL of maleic anhydride (previously heated to around 70 ° C. and liquidized) and 45.2 mL of di-tertiary butyl peroxide previously charged in two dropping funnels over 4 hours. The reaction was continued for 1 hour after completion of the supply. Next, the temperature was further raised to 175 ° C., and after depressurization in the system, the pressure was reduced for 8 hours while gradually ventilating nitrogen with a vacuum pump to remove impurities (unreacted maleic anhydride and di-tertiary butyl peroxide). The decomposition product) was removed to obtain a modified copolymer (B-1).

The obtained modified copolymer (B-1) has a number average molecular weight (Mn) of 8325, and a viscosity at 25 ° C. when 10 g of the modified copolymer (B-1) is dissolved in 100 g of toluene is 10 mPa · s. The amount of maleic anhydride (polar group) was 5.72 × 10 ⁻⁵ mol / g. Moreover, the critical micelle concentration by electrophoresis was not confirmed.
The number average molecular weight (Mn) and the viscosity and the amount of polar groups in 100 g of toluene were calculated by the methods described above.

(Coating solution adjustment)
A solution obtained by dissolving 0.15 g of protamine salt having the values shown in Table 1 in 0.85 g of distilled water, 0.75 g of modified copolymer (B-1), and 8: 2 ratio of methylcyclohexane and ethyl acetate as a solvent. 30 parts by weight of the solvent mixed in (hereinafter also referred to as “mixed solvent of methylcyclohexane and ethyl acetate”), polypropylene (PP) and propylene-butene-ethylene rubber (PBER) are dispersed for 2 minutes using an ultrasonic homogenizer. Then, a coating solution (composition) was prepared.
Next, the solvent and water were distilled off with an evaporator at 40 ° C., and the remaining emulsion was treated with XP10B (product name) (a compound in which maleated PP and PBER were dissolved in a mixed solvent of methylcyclohexane and ethyl acetate, Mitsui An arbitrary amount was mixed with Chemical Co., Ltd. and stirred with a magnetic stirrer for 10 minutes to prepare a coating solution (composition).

    Further, the particle size distribution of the component A in the composition obtained above was measured with a particle size analyzer (product name: Micro Track UPA, manufactured by Micro Track Bell Co., Ltd.). The average primary particle diameter was 278.3 nm, and the dispersibility of the component A in the composition was good.

(Coating solution application)
Next, the coating solution is applied to the corona-treated surface of the single-layer OPP film (base material) by hand coating (coating method) using a coating bar at a coating speed of 0.3 (mL / (m ² · sec)). Coating was performed to form a coating film. Next, the coating liquid was dried by spraying the coating film with warm air at a wind speed of 40 m / min and 120 ° C. for 20 seconds. This formed the coating film on the single layer OPP film.
In addition, the coating liquid of the quantity adjusted beforehand so that the surface amount (mg / m < ² >) of the component A might be 20 (mg / m < ² >) was mounted on the coat bar.

As described above, a laminate including a single-layer OPP film and a surface layer disposed on the single-layer OPP film was obtained. The thickness of the laminate was 0.003 mm.
Table 1 shows the results of the following evaluation using the obtained laminate.

[Evaluation]
-Transparency-
About the laminated body created above, the haze value was measured with the haze meter (made by Tokyo Denshoku Co., Ltd.).
The smaller the haze value of the laminate, the higher the transparency and the better the appearance.

(Example 2)
In Example 1, except that polylysine was used in place of the protamine salt as component A, a coating solution was prepared in the same manner as in Example 1, a laminate was prepared, and the same evaluation was performed. The results are shown in Table 1.
When the solubility of polylysine in 100 g of water was measured, it was 30 g / 100 g of water.

  As shown in Table 1, it can be seen that the laminates of the examples have low haze values and are excellent in transparency, that is, in appearance.

Claims (16)

A substrate;
A surface layer disposed on at least one surface of the substrate,
The surface layer has a solubility in water at 25 ° C. of 0.1 g / 100 g of water to 40 g / 100 g of water, and other than the component A and satisfies the following requirements (1) to (4) A laminate comprising B.

Requirement (1) A weight having a constitutional unit derived from at least one monomer selected from ethylene and an α-olefin having 3 to 20 carbon atoms in a range of 90 mol% or more and less than 100 mol% with respect to all constitutional units. Coalescence.
Requirement (2) Number average molecular weight (Mn) is 1500-30000.
Requirement (3) The viscosity at 25 ° C. when 10 g of the component B is dissolved in 100 g of toluene is 5 mPa · s to 200 mPa · s.
Requirement (4) The amount of polar groups is 1.00 × 10 ⁻⁶ mol / g to 1.00 × 10 ⁻⁴ mol / g.   The laminated body of Claim 1 whose haze value is 0.5%-10%.   The component A has at least one structure selected from the group consisting of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from an amino acid, and has a weight average molecular weight of 500 to 10,000. The laminate according to claim 1 or 2.   The laminate according to any one of claims 1 to 3, wherein the polar group is at least one functional group selected from the group consisting of a carboxy group, a hydroxy group, an acetyl group, and an amino group.   The said component B is a laminated body of any one of Claims 1-4 which does not have the critical micelle density | concentration measured by the electrophoresis method.   Content of the said component B is a laminated body of any one of Claims 1-5 which are 100 mass parts-1000 mass parts with respect to 100 mass parts of said component A. The said component A is a laminated body of any one of Claims 1-6 which is the molecule | numerator A which has a structure derived from the guanidine represented by a following formula (G-1).

[In Formula (G-1), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituent, and the wavy line represents a bonding site with another structure. ]   The laminate according to any one of claims 1 to 7, wherein the substrate is a polymer film containing at least one polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, and polyethylene terephthalate. body.   The said base material is a container-shaped molded object, The laminated body of any one of Claims 1-8.   A freshness-keeping material comprising the laminate according to any one of claims 1 to 9.   The freshness-keeping material according to claim 10, which is used for packing an article.   The freshness-keeping material according to claim 11, wherein the surface layer is a surface facing the article. Component A having a solubility in water at 25 ° C. of 0.1 g / 100 g of water to 40 g / 100 g of water;
A component B other than the component A and satisfying the following requirements (1) to (4);
A solvent,
At least one selected from the group consisting of polyolefin, methacrylic acid and methyl methacrylate;
A composition comprising:

Requirement (1) A weight having a constitutional unit derived from at least one monomer selected from ethylene and an α-olefin having 3 to 20 carbon atoms in a range of 90 mol% or more and less than 100 mol% with respect to all constitutional units. Coalescence.
Requirement (2) Number average molecular weight (Mn) is 1500-30000.
Requirement (3) The viscosity at 25 ° C. when 10 g of the component B is dissolved in 100 g of toluene is 5 mPa · s to 200 mPa · s.
Requirement (4) The amount of polar groups is 1.00 × 10 ⁻⁶ mol / g to 1.00 × 10 ⁻⁴ mol / g.   The composition of Claim 13 whose average primary particle diameter of the said component A is 50 nm-1000 nm.   The content of the component A is 0.00001 parts by mass to 30 parts by mass with respect to 100 parts by mass of the solvent, and the content of the component B is 1 part by mass to 70 parts by mass. Item 15. The composition according to Item 14.   The component A has at least one structure selected from the group consisting of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from an amino acid, and has a weight average molecular weight of 500 to 10,000. The composition according to any one of claims 13 to 15.