JP5034782B2 - Manufacturing method of resin mixture - Google Patents

Description

  The present invention relates to a method for producing a resin mixed solution.

A coating solution containing a neutralized polycarboxylic acid is widely used for applications such as water-based paints. Moreover, it is known that the laminated film obtained by apply | coating the coating liquid containing polycarboxylic acid neutralized material and polyvinyl alcohol to the film which is a base material is excellent in gas-barrier property (refer patent document 1). .

Japanese Patent Application Laid-Open No. 7-102083

However, the coating liquid containing the neutralized polycarboxylic acid and polyvinyl alcohol has a problem that aggregates are easily generated.

The present invention solves such problems and provides a method for producing a resin mixed solution with less aggregates.
That is, this invention is a manufacturing method of the resin liquid mixture which contains the following processes (1)-(3) in order.
Step (1): Step (2) for preparing a first mixed solution containing a hydroxyl group-containing resin (A), an ion exchange resin, and a solvent Step (2): A neutralized polycarboxylic acid ( Step (3) of mixing B) to prepare a second mixed solution: Step of removing the ion-exchange resin residue from the second mixed solution

According to the method for producing a resin mixed solution of the present invention, a resin mixed solution with few aggregates can be obtained.

Step (1) of the present invention is a step of preparing a first mixed liquid containing a hydroxyl group-containing resin (A), an ion exchange resin, and a solvent.
The “hydroxyl group” in the resin (A) containing a hydroxyl group used in the present invention is a so-called “alcoholic hydroxyl group” and does not include a hydroxyl group in a carboxyl group. Although it does not specifically limit as resin (A) containing a hydroxyl group, Since it can be dissolved in a water-based solvent and handling is easy, it is 1 or more types chosen from a vinyl alcohol polymer and a polysaccharide. It is preferable.

  Polysaccharides are biopolymers synthesized in biological systems by polycondensation of various monosaccharides, and here include those chemically modified based on them. For example, cellulose and cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan, and the like can be given.

The vinyl alcohol polymer is a polymer having a vinyl alcohol monomer unit as a main component. Examples of such “polyvinyl alcohol” include polymers obtained by hydrolyzing the acetate portion of vinyl acetate polymers, vinyl trifluoroacetate polymers, vinyl formate polymers, vinyl pivalate polymers, t- Examples include polymers obtained by hydrolyzing butyl vinyl ether polymers, trimethylsilyl vinyl ether polymers, etc. (For details on “polyvinyl alcohol”, see, for example, “Poval World”, “PVA World”, 1992, Kokai Co., Ltd. Molecular publication society; Nagano et al., “Poval”, 1981, see Kobunshi Shuppankai). The degree of “saponification” of the ester portion of the polymer is preferably 70 mol% or more, more preferably 85 mol% or more, and more preferably 98% mol or more of a so-called completely saponified product. The degree of polymerization of the vinyl alcohol polymer used is more preferably 100 or more and 5000 or less, and 200 or more and 3000 or less.

In addition, so-called polyvinyl alcohol derivatives having a functional group other than a hydroxyl group can be used as the vinyl alcohol polymer. Examples of the functional group other than a hydroxyl group include an amino group, a thiol group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a carboxy group, and the like. Examples include a rate group, a sulfonate ion group, a phosphate ion group, an ammonium group, a phosphonium group, a silyl group, a siloxane group, an alkyl group, an allyl group, a fluoroalkyl group, an alkoxy group, a carbonyl group, and a halogen group. A part of hydroxyl groups in PVA may be replaced with one or more of these functional groups.
The vinyl alcohol polymer may be a copolymer having a vinyl alcohol monomer unit and an α-olefin monomer unit such as ethylene or propylene. When the vinyl alcohol polymer is a copolymer, the content of the monomer unit of the α-olefin contained in the copolymer is preferably 40 mol% or less from the viewpoint of solubility in an aqueous solvent. More preferably, it is 15 mol% or less.

In the present invention, commercially available ion exchange resins can be used. In general, an ion exchange resin is a polymer substrate having a fine three-dimensional network structure in which an ion exchange group is bonded, and a fixed ion fixed to the polymer substrate and a charge having a sign opposite to that of the fixed ion. And ions that can be eluted in the solvent. Ion exchange resins are classified into cation exchange resins and anion exchange resins depending on the type of ion exchange group, but the ion exchange resins used in the present invention are usually cation exchange resins and exchange with hydrogen ions. It is preferable that it is an ion exchange resin. In particular, those having a styrene-divinylbenzene copolymer as a base and having ion exchange groups such as sulfonic acid group, carboxyl group, phosphoric acid group, amino group, and quaternary ammonium group fixed thereto are preferably used. As a form of the ion exchange resin, beads are preferable. Specific examples of the ion exchange resin can be referred to the literature: “12695 Chemical Products” published by Kagaku Kogyo Nipposha, pages 909 to 914, 1995.
The average particle diameter of the beads is preferably 100 μm or more and 3 mm or less in view of the efficiency of ion exchange and the ease of removing the ion exchange resin residue in the step (3) described later.
Although it does not specifically limit about ion exchange capacity, Usually, it is 1.2 eq / l-R or more, More preferably, it is 2.0 eq / l-R or more.

The solvent used in the step (1) of the present invention may be any solvent that can dissolve the hydroxyl group-containing resin (A) and the neutralized polycarboxylic acid (B). In addition, the steps (1) to (3) In the case of producing a laminate composed of a base material layer and a coating film by coating the resin mixture obtained through the process on the base material layer to form a coating film, and then removing the solvent from the coating film, the coating film It is necessary to keep almost no solvent remaining. Therefore, it is preferable that the solvent is easy to remove.
As will be described later, in the step (1), in addition to the above-described resin (A) containing a hydroxyl group, an ion exchange resin, and a solvent, when the first mixed liquid containing an inorganic layered compound is prepared, It is preferable to use a solvent in which the layered compound swells and easily cleaves.

Examples of the solvent used in the present invention include water, alcohols (methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, etc.), dimethylformamide, dimethyl sulfoxide, acetone, etc., among which water, alcohol, water-alcohol Mixtures are preferably used.

In the present invention, in the step (1), in addition to the above-mentioned resin (A) containing a hydroxyl group, an ion exchange resin, and a solvent, a first mixed liquid containing an inorganic layered compound is prepared, and the step (2) ). As the inorganic layered compound, a clay mineral having a swelling property to a solvent and a cleavage property is preferably used.
The inorganic layered compound used in the present invention refers to a material in which unit crystal layers are stacked to form a layered structure in a raw material state. A layered structure is a structure in which atoms that are strongly bonded by a covalent bond or the like and densely arranged are stacked almost in parallel by a weak binding force such as van der Waals.
Among inorganic layered compounds, clay minerals having swelling property to a solvent are particularly preferably used.

  Clay minerals generally include (i) a type having a two-layer structure having an octahedral layer with aluminum, magnesium, etc. as a central metal above the silica tetrahedral layer, and (ii) the silica tetrahedral layer is made of aluminum. It is classified into a type having a three-layer structure in which an octahedral layer having a central metal such as magnesium is narrowed from both sides. Examples of the two-layer structure type viscosity mineral (i) include clay minerals such as kaolinite group and antigolite group. Examples of the clay mineral of the three-layer structure type (ii) include clay minerals such as smectite group, vermiculite group, and mica group depending on the number of interlayer cations.

  These clay minerals include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, tetrasilic mica, sodium tenio. Light, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite and the like. In addition, these clay minerals treated with organic substances such as ion exchange and improved dispersibility (see Asakura Shoten, “Encyclopedia of Clay”; hereinafter may be referred to as organically modified clay minerals) are also used as inorganic layered compounds. Can be used. As said organic substance which processes a clay mineral, quaternary ammonium salts, such as a dimethyl distearyl ammonium salt and a trimethyl stearyl ammonium salt, a phosphonium salt, an imidazolium salt, etc. can be used.

  Among the clay minerals, smectite group, vermiculite group and mica group clay minerals are preferable, and smectite group is particularly preferable. Examples of the smectite group include montmorillonite, beidellite, nontronite, saponite, soconite, stevensite, and hectorite. In particular, montmorillonite is preferably used.

From the viewpoint of dispersibility in the resin mixed solution, it is particularly preferable to use a clay mineral having a property of swelling and cleaving in a solvent. An example of such a clay mineral is montmorillonite having sodium ions between layers.

The degree of the property that the clay mineral swells and cleaves in the solvent can be evaluated by the following test. The swelling property of the clay mineral is preferably 5 or more, more preferably 20 or more in the following swellability test. On the other hand, the cleaving property of the clay mineral is preferably 5 or more, more preferably 20 or more in the following cleaving test.

(Swellability test)
100 ml of solvent is put into a 100 ml graduated cylinder, and 2 g of clay mineral is gradually added thereto. After standing at 23 ° C. for 24 hours, the volume (ml) of the clay mineral dispersion layer is read from the scale of the interface between the clay mineral dispersion layer and the supernatant in the graduated cylinder. It shows that swelling property is so high that this numerical value (swelling value) is large.

[Cleavage test]
Gradually add 30 g of clay mineral into 1,500 ml of solvent, and disperser (Asada Tekko Co., Ltd., Despa MH-L, blade diameter 52 mm, rotation speed 3,100 rpm, container volume 3 L, bottom-blade distance 28 mm) Then, after dispersing for 90 minutes at 23 ° C. at a peripheral speed of 8.5 m / min, 100 ml of this dispersion is collected in a graduated cylinder. After standing for 60 minutes, the volume (ml) of the clay mineral dispersion layer is read from the scale of the interface between the clay mineral dispersion layer and the supernatant in the graduated cylinder. The larger this numerical value (cleavage value), the higher the cleavage property.

The inorganic layered compound preferably has an aspect ratio of 30 to 3,000, more preferably 30 to 1,500, from the viewpoint of dispersibility in the resin mixture.
The aspect ratio (Z) of the inorganic layered compound is defined by the formula: Z = L / a. In the formula, L is the average particle diameter of the inorganic layered compound, a is the unit thickness of the inorganic layered compound, that is, the thickness of the unit crystal layer of the inorganic layered compound, and is determined by the powder X-ray diffraction method (“instrumental analysis”). No. (a) "(1985, published by Kagaku Dojinsha, supervised by Jiro Shiokawa, p. 69).
The average particle diameter of the inorganic layered compound is a particle diameter (volume-based median diameter) obtained by a diffraction / scattering method in a solvent. That is, it can be obtained by calculating the particle size distribution most consistent with the above diffraction / scattering pattern from the diffraction / scattering pattern obtained when light is passed through the dispersion of the inorganic layered compound by Mie scattering theory or the like. it can. Specifically, for example, the measurement range of the particle size distribution is divided into appropriate sections, the representative particle diameter is determined for each section, and the particle size distribution, which is originally a continuous quantity, is converted into a discrete quantity and calculated. A method is mentioned.

  Examples of the liquid medium for swelling and cleaving the inorganic layered compound include water, alcohols (methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, etc.), dimethylformamide, dimethyl sulfoxide, acetone, and the like. A water-alcohol mixture is preferred.

  As the inorganic layered compound, one type of inorganic layered compound may be used, or two or more types of inorganic layered compounds may be used.

The order in which the hydroxyl group-containing resin (A), the ion exchange resin, and the solvent are mixed in preparing the first mixed liquid is not particularly limited. For example, the method of mixing in the following order is mentioned.
(I) A method of further mixing an ion exchange resin after mixing and dissolving a resin (A) containing a hydroxyl group in a solvent.
(Ii) A method of previously mixing a hydroxyl group-containing resin (A) and an ion exchange resin, mixing the mixture and a solvent, and dissolving the hydroxyl group-containing resin (A).
(Iii) A method in which an ion exchange resin is mixed with a solvent, and then a resin (A) containing a hydroxyl group is mixed and dissolved.
(Iv) A method of mixing a liquid in which a resin (A) containing a hydroxyl group is dissolved in a solvent and a liquid in which an ion exchange resin is mixed in the solvent.
The method (i) or (iii) is preferred.

Moreover, when the 1st liquid mixture contains an inorganic layered compound in addition to resin (A) containing a hydroxyl group, an ion exchange resin, and a solvent, the order which mixes these is not specifically limited. For example, the method of mixing in the following order is mentioned.
(V) A method in which a resin (A) containing a hydroxyl group is mixed and dissolved in a solvent, and then an ion exchange resin and an inorganic layered compound are further mixed.
(Vi) A method of previously mixing a hydroxyl group-containing resin (A), an ion exchange resin, and an inorganic layered compound, mixing the mixture and a solvent, and dissolving the hydroxyl group-containing resin (A).
(Vii) A method in which an inorganic layered compound is mixed and dispersed in a solvent, and then an ion exchange resin and a resin (A) containing a hydroxyl group are further mixed.
(Viii) A method in which an ion-exchange resin is mixed with a solvent, and then a hydroxyl-containing resin (A) and an inorganic layered compound are mixed.
(Ix) A method of mixing a solution in which a resin (A) containing a hydroxyl group is dissolved in a solvent, a solution in which an ion exchange resin is mixed in a solvent, and a solution in which an inorganic layered compound is dispersed in a solvent.
The method (v) or (viii) is preferred.

Step (2) in the present invention is a step of preparing a second mixed solution by mixing the neutralized polycarboxylic acid (B) with the first mixed solution obtained in the step (1).

Although the polycarboxylic acid neutralized product (B) used in the present invention is not particularly limited, it can be dissolved in an aqueous solvent and can be easily handled in the same manner as the resin (A) containing a hydroxyl group. Acid neutralized products and / or polymethacrylic acid neutralized products are preferred. A copolymer of a neutralized acrylic acid and a neutralized methacrylic acid can also be used.
The polycarboxylic acid neutralized product (B) may be a completely neutralized product or a partially neutralized product. In the neutralized polycarboxylic acid (B), the polycarboxylic acid is preferably neutralized with alkali metal ions and / or alkaline earth metal ions. Examples of the alkali metal ion include sodium ion, lithium ion, and potassium ion, and examples of the alkaline earth metal ion include calcium ion and magnesium ion.

The weight average molecular weight of the neutralized polycarboxylic acid (B) used is preferably 2,000 or more and 5,000,000 or less, and preferably 10,000 or more and 5,000,000 or less. More preferably, it is 5,000 or more and 5,000,000 or less.

By adding the polycarboxylic acid neutralized product (B) to the first mixed solution containing the ion exchange resin, the second mixed solution can be produced without generating an aggregate. Moreover, the neutralization degree of this polycarboxylic acid neutralized material (B) is easy by adjusting the addition amount of the ion exchange resin in the said 1st liquid mixture, and the additional amount of polycarboxylic acid neutralized material (B). To a partially neutralized polycarboxylic acid (B ′) having a desired degree of neutralization.

When the total of the resin (A) containing a hydroxyl group and the neutralized polycarboxylic acid (B) contained in the resulting resin mixture is 100% by weight, the ratio of the resin (A) containing a hydroxyl group is 95-5. It is preferable that the hydroxyl group-containing resin (A) and the polycarboxylic acid neutralized product (B) are mixed so that the weight percentage of the polycarboxylic acid neutralized product (B) is 5 to 95 wt%. . The proportion of the resin (A) containing a hydroxyl group is preferably 95 to 50% by weight, more preferably 95 to 80% by weight, and the proportion of the neutralized polycarboxylic acid (B) is preferably 5 to 50% by weight. %, More preferably 5 to 20% by weight.

When the liquid containing the inorganic layered compound is used as the first mixed liquid, the amount of the inorganic layered compound contained in the resin mixed liquid obtained in the present invention is not particularly limited, but the resin containing a hydroxyl group (A) And the total volume of the neutralized polycarboxylic acid (B) and the volume ratio of the inorganic stratiform compound are preferably 50/50 to 99/1, and more preferably 70/30 to 99/1.

Step (3) in the present invention is a step of removing the ion exchange resin residue from the second mixed solution. The removal of the ion-exchange resin residue can be performed by a method of filtering the second mixed solution with a filter or the like, a method of allowing it to stand and settling, and a centrifugal separation method.

By applying the resin mixture obtained in the present invention on the base material layer to form a coating film, and then removing the solvent from the coating film, a laminate composed of the base material layer and the coating film can be obtained. .
The material which comprises the said base material layer is not specifically limited, A metal, resin, wood, ceramic, glass, etc. are mentioned. The form of the base material layer is not particularly limited, and examples thereof include paper, cloth, nonwoven fabric, and film. As the resin, a thermoplastic resin or a thermosetting resin can be used. When the multilayer structure of the present invention is used as a packaging material, the base material layer is preferably composed of a thermoplastic resin. The thermoplastic resin used is low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer. Polypropylene (PP), ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, polyolefin resin such as ionomer resin, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, nylon-6 ( Ny-6), nylon-6,6, polyxylenediamine-adipic acid condensation polymer, amide resins such as polymethylmethacrylamide, acrylic resins such as polymethylmethacrylate, polystyrene, styrene-acrylonitrile Copolymers, styrene-acrylonitrile-butadiene copolymers, styrene-acrylonitrile resins such as polyacrylonitrile, hydrophobic cellulose resins such as cellulose triacetate and cellulose diacetate, halogens such as polyvinyl chloride, polyvinylidene chloride, and polyvinylidene fluoride Containing resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, hydrogen bonding resin such as cellulose derivative, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyphenylene oxide resin, polymethylene oxide resin, etc. Can be given. Examples of the thermosetting resin include known phenol resins, melamine resins, urea resins and the like. When the laminate is a film, the base material layer may be any of a non-stretched film, a uniaxially stretched film, and a biaxially stretched film. However, the base layer is composed of any one of polypropylene, polyester resin, and amide resin. An axially stretched film is preferred. The base material layer may be a multilayer film such as Ny-6 / MXD6-Ny / Ny-6 or PP / EVOH / PP, or a film on which aluminum, alumina, or silica is deposited.

  The base material layer and the coating film may be laminated adjacent to each other, or may be laminated via another layer such as an adhesive layer. The coating film may be provided on one surface or both surfaces of the base material layer, or may be provided on a part or the entire surface of the base material layer.

  In laminating the substrate layer with other layers, corona treatment, ozone treatment, ion treatment, flame treatment using gas such as silane, atmospheric pressure or reduced pressure plasma treatment, electron beam radiation treatment, acid treatment, Surface treatment such as primer treatment or itro treatment may be performed in advance. An anchor coat layer may be provided on the surface of the base material layer. The anchor coat layer can be formed using a known ethyleneimine-based, two-component curable urethane-based anchor coat agent or the like. These treatments may be performed alone or in combination of two or more.

  Roll coating methods such as direct gravure method, gravure method such as reverse gravure method, two roll beat coat method, bottom feed three reverse coat method, etc. Method, doctor knife method, die coating method, bar coating method, dipping method, spray coating method. When the laminate is a film, a gravure method is preferably employed because a layer having a uniform thickness can be provided.

  The thickness of the coating film which comprises the laminated body in this invention is not specifically limited. The thickness of the coating film varies depending on the required performance of the laminate, but is usually 1 nm to 10 μm, preferably 100 nm to 10 μm, and more preferably 200 nm to 10 μm. When the anchor coat layer is provided on the base material layer, the thickness of the anchor coat layer is usually 0.01 to 5 μm.

In the laminate obtained by the present invention, the concentration of alkali metal ions and / or alkaline earth metal ions contained in the coating film is not particularly limited, but is a resin containing a hydroxyl group that forms the coating film ( When the total of A) and the polycarboxylic acid neutralized product (B) is 100% by weight, the weight of alkali metal ions and / or alkaline earth metal ions contained in the coating film is 0.2 to 5%. It is preferable that it is 0.2 to 2% from the viewpoint of the water resistance of the coating film in the laminate obtained in the present invention.

When the resin mixed solution is applied to the base material layer, it is preferable to add a surfactant to the resin mixed solution. A coating film formed by applying a coating liquid containing a surfactant has excellent adhesion to the base material layer. The content of the surfactant is usually 0.001 to 5% by weight in 100% by weight of the resin mixed solution.

As the surfactant, a known surfactant such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used. In particular, an alkali metal salt of a carboxylic acid having an alkyl chain having 6 to 24 carbon atoms, an ether type nonionic surfactant such as a polydimethylsiloxane-polyoxyethylene copolymer (silicone nonionic surfactant) ) Or a fluorine-type nonionic surfactant (fluorine-based nonionic surfactant) such as a perfluoroalkylethylene oxide compound is preferable from the viewpoint of improving adhesion.

It is preferable from the point of the water resistance of the coating film in the laminated body obtained by this invention that pH of the resin liquid mixture applied to a base material layer is 3-8. The pH of the resin mixture can be adjusted by the amount of ion exchange resin added. Moreover, you may adjust by adding an acid or an alkali to the resin liquid mixture obtained through process (1)-(3). The pH of the resin mixture can be measured with a commercially available pH meter or pH test paper.

For each layer constituting the laminate, a known additive, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a colorant, an anti-blocking agent, etc. may be used depending on the purpose and application. Can do. These additives may be used alone or in combination of two or more.

Moreover, it is preferable to use the resin mixed solution obtained by this invention by carrying out a high pressure dispersion process, before apply | coating to a base material layer, regardless of whether the inorganic layered compound is included. By performing the high-pressure dispersion treatment, the handling during application to the base material layer and the appearance of the resulting laminate are improved.

The high-pressure dispersion treatment means that the resin mixture is passed through a plurality of thin tubes at a high speed and then merged, and the mixed solution collides with the mixed solution or the inner wall of the thin tube, thereby causing the mixture to have high shear and / or Or it is the processing method which adds a high voltage | pressure. In the high-pressure dispersion treatment, it is preferable that the mixed solution is passed through a narrow tube having a tube diameter of about 1 μm to 1000 μm, and at this time, treatment is performed so that a maximum pressure of 100 kgf / cm ² or more is applied. Maximum pressure is more preferably at 500 kgf / cm ² or more, and particularly preferably 1000 kgf / cm ² or more. Further, when the mixed solution passes through the narrow tube, the maximum arrival speed of the dispersion is preferably 100 m / s or more, and the heat transfer rate due to pressure loss is preferably 100 kcal / hr or more. For the high-pressure dispersion treatment, a high-pressure dispersion device such as an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation, a nanomizer manufactured by Nanomizer, a Manton Gorin type high-pressure dispersion device, or a homogenizer manufactured by Izumi Food Machinery Co., Ltd. can be used. .

  It is preferable from the viewpoint of improving various performances that the laminate is heat-treated in advance at 100 ° C. or more and 300 ° C. or less before use. When heat-treated, for example, the laminate can be used for applications that require gas barrier properties such as packaging materials for foods and electronic components, the gas barrier properties can be improved, and the surface hardness of decorative sheets and the like is required. The surface hardness can be improved when used in a certain application. The heat source used for the heat treatment is not particularly limited, and various methods such as hot roll contact, heat medium contact (air, etc.), infrared heating, microwave heating and the like can be applied. The heat treatment time is usually 1 second or more and 48 hours or less. Further, when the laminate is used after being thermoformed such as vacuum forming, pressure forming, vacuum pressure forming, etc., the heat treatment can be performed by a heating process at the time of these thermoforming.

Hereinafter, the present invention will be described based on examples. First, a method for measuring physical property values in the following examples will be described.
(Thickness measurement)
The measurement was performed using a commercially available digital thickness gauge (contact thickness gauge, trade name: ultra-high precision deci micro head MH-15M, manufactured by Nippon Optical Co., Ltd.).
(Viscosity measurement)
About the produced resin mixed liquid, it measured by the Zarn cup (NO.3).
[Undissolved substance evaluation]
The mixture was filtered using a filter (fluid aperture of 297 μm) to remove the ion exchange resin. After completion of filtration, the filter was visually confirmed and evaluated for the presence of aggregates.
[PH measurement]
The resin mixture (1) and the resin mixture (2) described later were measured using a pH meter (B-211, manufactured by Horiba, Ltd.).

[Measurement of alkali metal ion concentration]
Using an inductively coupled plasma optical emission spectrometer (Optima 3000, manufactured by PerkinElmer), the sodium ion concentration of the entire laminate is measured, and the sodium contained in the layers other than the coating film formed by applying the resin mixture from there. The sodium ion concentration in the coating film was determined by subtracting the ion concentration. The sample preparation method is as follows. 1 g of each of the base material layer and the laminate was sampled, 1 ml of 96% sulfuric acid was added, and then ashed in an electric furnace, and the remaining residue was dissolved in 5% hydrochloric acid to make a constant volume. The constant volume of the solution was used in an inductively coupled plasma emission spectrometer, the sodium ion concentration was measured, and the difference was determined.

[Example 1]
Dispersion kettle (trade name: Despa MH-L, manufactured by Asada Tekko Co., Ltd.), ion-exchanged water (specific electrical conductivity 0.7 μs / cm or less) 600 g, polyvinyl alcohol (AQ2117; manufactured by Kuraray Co., Ltd., Ken) Degree of conversion: 99.6%, degree of polymerization 1,700) was mixed and heated to 95 ° C. under low speed stirring (1500 rpm, peripheral speed 4.1 m / min). The mixed system was stirred at the same temperature for 30 minutes to dissolve polyvinyl alcohol, and 340 g of ion-exchanged water was further added and cooled to 60 ° C. to obtain an aqueous polyvinyl alcohol solution. While stirring the polyvinyl alcohol aqueous solution (60 ° C.) under the same conditions as described above, 218 g of ion exchange resin (C-202F; manufactured by Nihonsuiken Co., Ltd.) was added to obtain a mixed solution (1). Thereafter, 15.0 g of sodium polyacrylate (AQUALIC FH; Nippon Shokubai Co., Ltd., completely neutralized product weight average molecular weight 4,000,000) was gradually added to the mixed solution (1). The mixture was switched to stirring (3,000 rpm, peripheral speed = 8.2 m / min) and stirred for 30 minutes to obtain a mixed liquid (2). Thereafter, 334 g of isopropanol and 145 g of 1-butanol were further added to the mixture (2) over 5 minutes, and then the mixture was cooled to room temperature to obtain a mixture (3). Thereafter, the mixture (3) was filtered using a filter (fluid aperture of 297 μm) to remove the residue of the ion exchange resin to obtain a resin mixture (1). The pH of the resin mixture (1) was 5.0.
The viscosity of the resin mixture (1) was 47 seconds, and no aggregates were observed on the filter.

[Example 2]
In a dispersion kettle, 600 g of ion-exchanged water and 60 g of the polyvinyl alcohol were mixed, and the temperature was raised to 95 ° C. with low speed stirring. The mixed system was stirred at the same temperature for 30 minutes to dissolve polyvinyl alcohol, and 340 g of ion-exchanged water was further added and cooled to 60 ° C. to obtain an aqueous polyvinyl alcohol solution. While stirring the polyvinyl alcohol aqueous solution (60 ° C.) under the same conditions as above, 226 g of the ion exchange resin was added, and 13 g of high-purity montmorillonite (trade name: Kunipia G; manufactured by Kunimine Industries Co., Ltd.) was gradually added. A liquid mixture (4) was obtained. Thereafter, 15.0 g of sodium polyacrylate was gradually added to the mixed solution (4). After the addition was completed, the mixture was further switched to high-speed stirring and stirred for 30 minutes to obtain a mixed solution (5). Thereafter, 334 g of isopropanol and 145 g of 1-butanol were further added to the mixture (5) over 5 minutes, and then the mixture was cooled to room temperature to obtain a mixture (6). Thereafter, the mixed solution (6) was filtered using a filter (fluid aperture of 297 μm) to remove the residue of the ion exchange resin, to obtain a resin mixed solution (2). The total volume of polyvinyl alcohol and sodium polyacrylate in the resin mixture and the volume ratio of the inorganic layered compound were 92/8, and the pH of the resin mixture (2) was 5.2.
The viscosity of the resin mixture (2) was 53 seconds, and no aggregate was observed on the filter.

[Comparative Example 1]
A resin mixture (3) was obtained in the same manner as in Example 1 except that no ion exchange resin was used. The resin mixture (3) had a viscosity of 180 seconds or more, and many aggregates were observed in the filter.

[Comparative Example 2]
In a dispersion kettle, 600 g of ion-exchanged water and 60 g of the polyvinyl alcohol were mixed, and the temperature was raised to 95 ° C. with low speed stirring. The mixed system was stirred at the same temperature for 30 minutes to dissolve polyvinyl alcohol, and 340 g of ion-exchanged water was further added and cooled to 60 ° C. to obtain an aqueous polyvinyl alcohol solution. While stirring the polyvinyl alcohol aqueous solution (60 ° C.) under the same conditions as described above, 15.0 g of the sodium polyacrylate was gradually added. After the addition was completed, the mixture was further stirred at a high speed (3,000 rpm, peripheral speed = 8.2 m / second). Minutes) and stirred for 30 minutes to obtain a mixed solution (7). Thereafter, 218 g of the ion exchange resin was added to the mixed solution (7) under low-speed stirring to obtain a mixed solution (8). Further, 334 g of isopropanol and 145 g of 1-butanol were added over 5 minutes, and then the mixed system was cooled to room temperature to obtain a mixed liquid (9). Thereafter, the mixture (9) was filtered using a filter (fluid aperture of 297 μm) to remove the residue of the ion exchange resin, to obtain a resin mixture (4).
The resin mixture (4) had a viscosity of 180 seconds or more, and many aggregates were observed in the filter.

Example 3
The resin mixture (1) produced in Example 1 was treated under a pressure condition of 1100 kgf / cm ² using a high-pressure dispersion device (trade name: Super High Pressure Homogenizer M110-E / H, manufactured by Microfluidics Corporation), and mixed with the resin. A liquid (5) was obtained. The resin mixture (5) had a viscosity of 12 seconds. Using the resin mixed solution (5), a laminate was produced by the following method.
A non-stretched polypropylene sheet having a thickness of 300 μm and subjected to corona treatment on one side was used as a base material layer. An anchor coating agent (EL510-1 / CAT-RT87 = 5/1 (weight ratio): manufactured by Toyo Morton Co., Ltd.) was used on the corona-treated surface of the base material layer, and a test coater (manufactured by Yasui Seiki Co., Ltd.) was used. Then, by the microgravure coating method, gravure coating was performed at a coating speed of 3 m / min and a drying temperature of 80 ° C. to form an anchor coat layer. The dry thickness of the anchor coat layer was 0.05 μm.
Next, the above-mentioned resin mixed solution (5) was gravure coated at a coating speed of 3 m / min by a micro gravure coating method (gravure roll line number 150, #: GM) using a test coater at 100 ° C. It dried and the laminated body (1) by which a coating film was laminated | stacked on a base material layer was obtained. The thickness of the coating film was 0.5 μm, and the appearance of the obtained laminate (1) was good. The Na concentration in the coating film was 0.7%.

Claims (8)

The manufacturing method of the resin liquid mixture which contains the following processes (1)-(3) in order.
Step (1): Step (2) for preparing a first mixed solution containing a hydroxyl group-containing resin (A), an ion exchange resin, and a solvent Step (2): A neutralized polycarboxylic acid ( Step (3) of mixing B) to prepare a second mixed solution: Step of removing the ion-exchange resin residue from the second mixed solution   The production of the resin mixed solution according to claim 1, wherein in the step (1), in addition to the hydroxyl group-containing resin (A), the ion exchange resin, and the solvent, a first mixed solution further containing an inorganic layered compound is prepared. Method.   When the total of the hydroxyl group-containing resin (A) and the polycarboxylic acid neutralized product (B) contained in the resin mixture is 100% by weight, the ratio of the hydroxyl group-containing resin (A) is 95 to 5% by weight. %, The ratio of the polycarboxylic acid neutralized product (B) is 5 to 95% by weight.   The method for producing a resin mixed liquid according to any one of claims 1 to 3, wherein the polycarboxylic acid neutralized product (B) is neutralized with an alkali metal ion and / or an alkaline earth metal ion.   The method for producing a resin mixed liquid according to any one of claims 1 to 4, wherein the neutralized polycarboxylic acid (B) is a neutralized poly (meth) acrylic acid.   The method for producing a resin mixed solution according to any one of claims 1 to 5, wherein the hydroxyl group-containing resin (A) is at least one selected from vinyl alcohol polymers and polysaccharides.   The resin mixture obtained by the method according to any one of claims 1 to 6 is coated on a base material layer to form a coating film, and then the solvent is removed from the coating film, and the base material layer and the coating film are formed. A method for producing a laminate.   When the total of the resin (A) containing a hydroxyl group forming the coating film and the neutralized polycarboxylic acid (B) is 100% by weight, alkali metal ions and / or alkaline earth metal ions contained in the coating film The method for producing a laminate according to claim 7, wherein the weight of the laminate is 0.2 to 5%.