JP2019112552A - Dispersion liquid, resin composite material, and electronic device - Google Patents

Abstract

To provide a dispersion liquid which prevents flocculation of zeolite and has good dispersibility, and a resin composite material excellent in moisture absorbing property by the dispersion liquid.SOLUTION: A dispersion liquid contains zeolite, a resin, a dispersion medium, and an amine phosphate compound.SELECTED DRAWING: Figure 1

Description

  The present invention relates to dispersions, resin composites, and electronic devices.

  BACKGROUND ART A resin composite material in which a resin contains a hygroscopic filler is widely used as a constituent material for lowering the water vapor transmission rate (WVTR) from the viewpoint of prolonging the life of an electronic device. For example, as shown in Patent Documents 1 to 4, if a resin composite material containing a hygroscopic filler is made into a film and used in the construction of an electronic device, it is possible to prevent the deterioration of the electronic device susceptible to moisture.

JP, 2013-108057, A JP, 2006-272190, A International Publication No. 2015/133152 brochure

  Patent Document 1 describes an example in which organic aluminum is used as a hygroscopic filler. However, since organic aluminum generally has high reactivity, there is a problem that it is difficult to control the stability of the resin composite film. Moreover, although the example which used barium oxide as a hygroscopic filler is described in patent document 2, since it heats | generates violently at the time of water absorption, and the barium hydroxide after water absorption is strongly basic, it is a resin composite material It may deteriorate the properties of the film. Moreover, although the example which used nanoporous silica as a hygroscopic filler is also described in patent document 2, in order for a resin composite material film to express hygroscopicity, since much nanoporous silica content is required, There is a problem that the film is easily embrittled.

  On the other hand, Patent Document 3 describes that a resin composite film containing zeolite and a resin acts as a hygroscopic film. Here, since the zeolite has high hygroscopicity and does not have a problem such as intense heat generation with respect to the hygroscopic fillers described in Patent Documents 1 to 3, it is considered preferable to use the zeolite as the hygroscopic filler .

  However, according to the study of the present inventors, it has been found that when zeolite is used as a hygroscopic filler, a highly hygroscopic resin composite film can not be obtained unless the zeolite is uniformly present in the resin composite film. . That is, although a resin composite material film containing zeolite can be produced from a dispersion containing zeolite and a resin, a resin excellent in hygroscopicity if the dispersibility of the zeolite in the dispersion is poor. It turned out that the production of the composite film is difficult. Then, an object of this invention is to provide the dispersion liquid containing highly dispersible zeolite and resin.

  The present inventors have found that the above problems can be solved by using a dispersion comprising zeolite, a resin, a dispersion medium, and an amine phosphate compound as a dispersing agent. The present invention has been reached.

  That is, the gist of the present invention is as follows.

[1] A dispersion containing zeolite, a resin, a dispersion medium, and a phosphoric acid amine compound.
[2] The dispersion according to claim 1, wherein the average primary particle diameter of the zeolite is 15 to 200 nm.
[3] The dispersion according to claim 1 or 2, wherein the ratio of the phosphoric acid amine compound to the zeolite in the dispersion is 5% by weight or more and 50% by weight or less.
[4] A resin composite film containing zeolite, a resin, and a phosphoric acid amine compound.
[5] An electronic device having the resin composite film according to [4].

  It is possible to provide a dispersion having good dispersibility, in which zeolite is less likely to aggregate. Moreover, the resin composite material film excellent in hygroscopicity can be provided by the said dispersion liquid.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure showing typically the dispersion liquid containing the zeolite which is one Embodiment of this invention, resin, a dispersion medium, and a dispersing agent (phosphoric acid amine compound). It is a figure which represents typically the dispersion liquid containing the zeolite which is other embodiment of this invention, resin, a dispersion medium, a dispersing agent (phosphoric acid amine compound), and another compound. BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which represents typically the resin composite material containing the zeolite which is one Embodiment of this invention, resin, and a phosphoric acid amine compound. It is a figure showing typically the resin compound material containing the zeolite which is other embodiment of the present invention, resin, a phosphoric acid amine compound, and other compounds. It is sectional drawing which represents the structure of a field effect transistor element typically. FIG. 2 is a cross-sectional view schematically showing a configuration of an electroluminescent element. It is sectional drawing which represents the structure of a photoelectric conversion element typically. It is sectional drawing which represents the structure of a solar cell typically. It is sectional drawing which represents the structure of a solar cell module typically. It is a figure which shows the transmittance | permeability of the film measured in Example 1, 2 and the comparative example 1. FIG. FIG. 2 is a graph showing the amount of moisture absorption of the film measured in Example 1 under high humidity conditions.

  The embodiments of the present invention will be described in detail below, but these descriptions are merely examples (representative examples) of the embodiments of the present invention, and the present invention is not limited to these contents as long as the gist thereof is not exceeded.

<1. Dispersion>
As shown in FIG. 1, the dispersion liquid contains at least a zeolite, a resin, a dispersant, and a dispersion medium. In addition, as described later, the resin composite material can be formed using the dispersion liquid. Below, the various materials contained in a dispersion liquid are demonstrated.

<1-1. Zeolite>
In the present invention, zeolite is a generic term for crystalline porous aluminosilicate, aluminophosphate or silicoaluminophosphate, and more specifically, TO ₄ unit (T element constitutes a framework the elements other than oxygen) to is obtained by the basic unit, a plurality of TiO ₄ units led, are those composed of structural units called Composite Building unit (CBU). To that end, it has regular channels (tubular pores) and cavities (cavities).

  When the zeolite is an aluminosilicate, the silica / alumina molar ratio (SAR) of the zeolite is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, particularly preferably 20 or less, most preferably 10 or less is there. The smaller the value, the more hydrophilic it becomes and the more moisture is absorbed.

  When the zeolite is an aluminophosphate, the molar ratio of phosphorus / alumina is usually 1.

  When the zeolite is a silicoaluminophosphate, the Si / (Si + Al + P) molar ratio is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.15 or more, particularly preferably 0.2 or more, Most preferably, it is 0.3 or more. The larger the value, the more hydrophilic it becomes and the more it absorbs moisture.

  The molar ratio can be specified by elemental analysis. For example, it can be measured using a fluorescent X-ray analyzer Rayny EDX-700 manufactured by Shimadzu Corporation.

  Further, as the above-mentioned zeolite, elements such as gallium, iron, boron, titanium, zirconium, tin and zinc may be used instead of aluminum as long as the performance of the resin composite is not significantly impaired. It may contain elements such as titanium, zirconium, tin and zinc.

  Hereinafter, the case of the preferred aluminosilicate as the zeolite will be described.

  The structure of the zeolite can generally be shown by a code that defines the structure of the zeolite defined by the International Zeolite Association (IZA). In addition, the structure of the zeolite can be determined by an X-ray structural analysis device (for example, bench type X-ray diffraction device D2PHASER manufactured by BRUKER), and the IZA is a zeolite structure database 2017 version (http: //www.iza At -structure.org/databases/), the X-ray diffraction patterns of each zeolite structure are introduced.

The type of zeolite is not particularly limited, but the framework density is 17.0 T / 1000 Å ³ or less from the viewpoint of improving the hygroscopicity of the resin composite produced using the dispersion according to the present embodiment. Is preferred. Framework density means the number of T atoms present per unit volume of zeolite, which is a value determined by the structure of zeolite. That is, in the case of zeolite having the same composition, as the value of the framework density is smaller, the porosity is higher, and the hygroscopicity can be enhanced. As the framework density in the present invention, the numerical values described in the IZA zeolite structure database 2017 version (http://www.iza-structure.org/databases/) can be used.

Among the above, the framework density of the zeolite is preferably 16.0 T / 1000 Å ³ or less, more preferably 15.0 T / 1000 Å ³ or less, and still more preferably 14.0 T / 1000 Å ³ or less.

Examples of zeolites having a framework density of more than 16.0 T / 1000 Å ³ and 17.0 T / 1000 Å ³ or less include ACO, AFG, AFI, ATS, AWW, BOG, CAN, CFI, CGS, CSV, DOH, EDI , EON, ERI, GIS, ITG, IWW, JOZ, LOS, LOV, LTF, LTL, LTN, MAZ, MER, MOR, MOZ, MSE, MEF, NAB, NAT, NES, OFF, PHI, RSN, RTH, SAT , SBN, SEW, SFH, SFN, SFS, SIV, SOD, SOD, SOF, SOS, ^* -SSO, SSY, STF, STI, STT, STW, TER, UOV, UWY, VSV, WEI, -WEN types. be able to.

Framework density greater than 15.0T / 1000Å ^3, examples of 16.0T / 1000Å3 following zeolites, AEI, AFR, AFT, AFV , AFX, AST, AVL, * BEA, BEC, CHA, CON, EAB ETR, GME, IFW, IRN, ITE, ^* -ITN, IWR, LEV, MWW, NPO, PAU, POS, SFO, SFW, THO, UFI, USI, UTL types can be mentioned.

Examples of zeolites having a framework density of more than 14.0 T / 1000 Å ³ and 15.0 T / 1000 Å ³ or less include AFS, AFY, BPH, DFO, ^* -EWT, ISV, IWS, IWV, JST, KFI, LTA , MEI, PUN, RHO, SAO, SAS, SAV, and VFI types can be mentioned.

Examples of zeolite having a framework density of 14.0 T / 1000 Å ³ or less include BOZ, -CLO, EMT, FAU, -IFU, IRR, -IRY, ITT, -ITV, JSR, NPT, OBW, OSO, RWY, SBE, SBS, SBT, and TSC types can be mentioned.

  The particle size of the zeolite is not particularly limited as long as the effects of the present invention are not impaired, but the average primary particle size of the zeolite is preferably 15 nm or more, more preferably 20 nm or more, and still more preferably 25 nm Or more, particularly preferably 30 nm or more, while preferably 200 nm or less, more preferably 175 nm or less, still more preferably 150 nm or less, particularly preferably 125 nm or less, most preferably 100 nm or less .

  Generally, when the particle size of zeolite is reduced, it is considered that high transparency can be easily obtained from the resin composite film obtained, but when the particle size of zeolite is reduced, the surface energy of zeolite is increased and zeolite is dispersed in the dispersion. It tends to aggregate and secondary particles tend to be formed, and as a result, it is difficult to obtain a resin composite film with high transparency. However, in the present invention, by using a specific dispersant as described later, aggregation of the zeolite is suppressed and uniform dispersion becomes possible. If the resin composite material film can be provided, and if it is not less than the above lower limit value, the zeolite skeleton is maintained and the crystallinity can be easily maintained, so that the durability of the obtained resin composite material film can be improved.

  The average primary particle size of zeolite is determined by measuring the particle size of 30 or more primary particles arbitrarily selected in observation of particles by a scanning electron microscope (SEM), and averaging the particle sizes of the primary particles. . In addition, a particle diameter shall mean the diameter of the circle | round | yen used as the largest diameter which has an area equal to the projection area of particle | grains.

  The counter cation of the zeolite is not particularly limited as long as the effect of the present invention is not impaired, but is usually a structure directing agent, a proton, an alkali metal ion or an alkaline earth metal ion, preferably a proton, an alkali It is a metal ion or an alkaline earth metal ion, more preferably an alkali metal ion or an alkaline earth metal ion, still more preferably an alkali metal ion. If it is an alkali metal ion, improvement of the hygroscopicity of the zeolite can be expected by its hydration ability. As an alkali metal ion, lithium ion, sodium ion or potassium ion is mentioned. Among them, preferred is sodium ion or potassium ion, and most preferred is sodium ion.

  There is no particular limitation on the method for producing zeolite, and it can be produced by a known hydrothermal synthesis method. For example, when manufacturing a CHA type zeolite, it can be manufactured with reference to the method described in Japanese Patent No. 4896110.

  In addition, in the case of producing a zeolite having a small average particle diameter, the hydrothermal synthesis may be performed by controlling the synthesis time or temperature more than usual, or the zeolite obtained by the hydrothermal synthesis may be used as a bead mill, ball mill, etc. It may be crushed and / or ground by wet grinding.

  As a pulverizing apparatus used for the above-mentioned crushing and / or pulverization, for example, "OB mill" manufactured by Freund-Terbo, "Nano getter" manufactured by Ashizawa Finetech, "Nano-getter mini", " Examples include Star Mill, Labostar, and Starburst manufactured by Sugino Machine Co., Ltd. Also, in general, although the crystallinity of the crushed zeolite is lowered, it can be recrystallized in a solution containing alumina, silica and the like as in the method described in JP-A-2014-189476. .

  From the viewpoint of suppressing the reaggregation of the zeolite after crushing and / or crushing, it is preferable to perform wet grinding in a solvent to disperse the zeolite having a small average particle size in the solvent. Among these, bead milling is particularly preferable in that the average particle size can be reduced. In addition, in order to suppress reaggregation after dispersion, a dispersing agent may be used during wet grinding. As the above-mentioned solvent and dispersant, solvents and dispersants described later can be used.

  In addition, in order to further reduce the average particle size of the zeolite in the dispersion in which the crushed and / or crushed zeolite is dispersed, centrifugation may be performed to remove particles having a large average particle size. It is preferable because the resin composite material can be uniformly dispersed more easily, and furthermore, the transparency of the obtained resin composite material can be increased. In addition, a commercially available apparatus can be used for the centrifuge used for centrifugation.

  The content of zeolite in the dispersion is not particularly limited, but is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, and further preferably 3% by weight or more. Particularly preferably, it is 5% by weight or more, most preferably 10% by weight or more, while usually 80% by weight or less, preferably 70% by weight or less, more preferably 65% by weight or less, still more preferably 60% by weight or less Particularly preferably, it is 55% by weight or less, and most preferably 50% by weight or less.

  If it is more than the said lower limit and below the upper limit, it is preferable from the ability to adjust a dispersion liquid appropriately, suppressing aggregation of a zeolite.

  The zeolite used in the present invention may be used alone in the dispersion, or two or more may be used in any combination and ratio.

<1-2. Resin>
The resin is not particularly limited, but it is preferable that the resin also has a high transmittance, since it is preferable that the transmittance of the resin composite is high. Specifically, the transmittance at a wavelength of 450 nm is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, and particularly preferably 90% or more.

  The type of resin is not particularly limited, and any of the curable resin, the thermoplastic resin and the rubber component can be used without limitation. An active energy ray curable resin and a crosslinkable curable resin such as a thermosetting resin are preferable to a thermoplastic resin in that uniform distribution of the resin and the zeolite in the resin composite is high. The active energy ray-curable resin composite material is, for example, a resin which is cured by ultraviolet light, visible light, infrared light, electron beam or the like. Among them, a thermosetting resin is preferable in that the manufacturing cost is low because the exposure machine is not used.

  Examples of the curable resin include polyimide resins, polybenzoxazole resins, urea resins, benzocyclobutene resins, silicone resins, epoxy resins, and the like. Among them, epoxy resins and polyimide resins are particularly preferable in terms of good compatibility with zeolite.

  The epoxy resin is, for example, alcohol type epoxy resin, bisphenol A type epoxy resin, phenoxy type epoxy resin such as bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl Epoxy resins such as epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, polyfunctional phenol type epoxy resin Be

  The epoxy resin is preferably a phenoxy type epoxy resin having at least one skeleton selected from the group consisting of naphthalene skeleton, fluorene skeleton, biphenyl skeleton, anthracene skeleton, pyrene skeleton, xanthene skeleton, adamantane skeleton and dicyclopentadiene skeleton. . Among them, a phenoxy type epoxy resin having a fluorene skeleton and / or a biphenyl skeleton is particularly preferable because heat resistance is further enhanced, and a skeleton of at least one or more of biphenol A skeleton, bisphenol F skeleton and biphenyl skeleton is particularly preferable. It is preferable that it is a phenoxy type | mold epoxy resin which has these.

  Specific examples of polyimide resins include polyimide resins, polyamino bismaleimide (polybismaleimide) resins, bismaleimide triazine resins, polyamide imide resins, and polyimide resins such as polyether imide resins.

  Examples of thermoplastic resins include polyolefin resins such as polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, etc .; polyethylene terephthalate resin, polybutylene terephthalate resin, liquid crystal polyester resin, etc. Polyester resins; polyether resins such as polyphenylene ether resin, polyether sulfone resin, polyether ketone resin, polyether ether resin etc; polyvinyl chloride resin; polyvinyl alcohol resin; polystyrene resin; polynorbornene resin Acrylic resin; acetal resin; polycarbonate resin; polyphenylene sulfide resin; polyamide resin such as aramid and nylon; acetyl cellulose, nitrocellulose Cellulose resins such as chill cellulose; polyvinylidene fluoride resin, fluorocarbon resin such as polytetrafluoroethylene resin; polyvinylidene chloride-based resin; ABS (acrylonitrile-butadiene - styrene) resin and the like. In addition, copolymers such as block copolymers and graft copolymers thereof are also included.

  Also, as the rubber component, for example, natural rubber, styrene-butadiene copolymer rubber, silicone rubber, fluororubber, polyurethane rubber, hydrogenated styrene-isobutylene copolymer rubber having a nucleus-hydrogenated aromatic compound, etc. It can be mentioned. Examples of the hydrogenated styrene-isobutylene copolymer rubber having a nucleus-hydrogenated aromatic compound include a resin described in JP-A-2016-135860 and a resin described in JP-A-2013-216902.

  In addition, a resin precursor such as a monomer may be contained in the dispersion liquid, and the resin precursor may be polymerized to be converted into a desired resin when the resin composite is molded and processed. Therefore, in the present invention, the resin in the dispersion liquid contains a resin precursor.

  Among the above, the amine value of the resin is preferably 20 or less, preferably 10 or less, and particularly preferably 5 or less. On the other hand, the acid value of the resin is preferably 20 or less, preferably 10 or less, and particularly preferably 5 or less. In the present specification, the amine value is a value indicating the amount of amine in the resin, and the number of mg of potassium hydroxide (molecular weight 56.11) equivalent to the acid required to neutralize 1 g of the sample. Say Moreover, an acid value is a value which shows the quantity of the acidic group in a dispersing agent, and says the mg number of potassium hydroxide required in order to neutralize the sample 1g quantity. By being in the said range, the dispersing agent in a dispersion liquid can be taken in by the resin side, and the phenomenon called a shock which a zeolite condenses can be suppressed, and it leads to the improvement of the dispersibility with respect to resin of a zeolite.

  Among them, a hydrogenated styrene-isobutylene copolymer rubber having a nuclear-hydrogenated aromatic compound is preferable because both the acid value and the amine value are almost zero. Examples of the hydrogenated styrene-isobutylene copolymer rubber having a nucleus-hydrogenated aromatic compound include a resin described in JP-A-2016-135860 and a resin described in JP-A-2013-216902.

  Further, from the viewpoint of the barrier property to suppress the penetration of water of the obtained resin composite, the resin is preferably hydrophobic, and has a highly hydrophobic olefin resin or a nuclear-hydrogenated aromatic compound. Further preferred is a hydrogenated styrene-isobutylene copolymer rubber, and particularly preferred is a hydrogenated styrene-isobutylene copolymer rubber having a nucleus-hydrogenated aromatic compound.

  The molecular weight of the resin is not particularly limited, but is usually 1000 or more, preferably 3000 or more, more preferably 5000 or more as a polystyrene equivalent weight average molecular weight (Mw) value measured by gel permeation chromatography (GPC). is there. Also, it is usually at most 200,000, preferably at most 180000, and more preferably at most 150,000. By being in the said range, since the solubility with respect to a solvent, a viscosity, etc. become a tendency which is easy to handle with a normal manufacturing installation, it is preferable.

  The number average molecular weight (Mn) of the resin is usually 500 or more, preferably 1000 or more, more preferably 2500 or more. Also, it is usually 100,000 or less, preferably 90000 or less, more preferably 80000 or less. By being in the said range, since the solubility with respect to a solvent, a viscosity, etc. will tend to be easy to handle with a normal manufacturing installation, it is preferable. The polystyrene equivalent number average molecular weight can be determined by the same method as the weight average molecular weight.

  Moreover, the value (Mw / Mn) which remove | divided Mw of resin by Mn is 1.5 or more normally, Preferably it is 2 or more, More preferably, it is 2.5 or more. On the other hand, the upper limit thereof is usually 5 or less, preferably 4.5 or less, more preferably 4 or less. It is preferable in the point which the uniformity of the zeolite in a resin composite material becomes high, and the molded object of the resin composite material excellent in smoothness is obtained by being in said range.

  There is no particular limitation on the method of producing the resin, and the resin can be produced by a known method. For example, it can be produced by a known method such as the method described in 5th edition Experimental Chemistry Lecture 26 Polymer Chemistry Chapter 2, Polymer Synthesis (edited by The Chemical Society of Japan).

  The content of the resin contained in the dispersion is not particularly limited as long as the effects of the present invention are not impaired, and usually 0.5% by weight or more, preferably 1% by weight or more, more preferably 3% by weight or more , More preferably 5% by weight or more, particularly preferably 7% by weight or more, most preferably 10% by weight or more, while usually 90% by weight or less, preferably 85% by weight or less, more preferably 80% by weight The following content is more preferably 75 wt% or less, particularly preferably 73 wt% or less, and most preferably 70 wt% or less. By being within the above range, even in the dispersion liquid, the dispersed state can be maintained without causing the resin to precipitate or the like.

  The resins contained in the dispersion may be used alone or in any combination of two or more in any proportion.

<1-3. Dispersion medium>
The dispersion medium is not particularly limited, but, for example, water; aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane or decane; aromatic hydrocarbons such as toluene, xylene, chlorobenzene or orthodichlorobenzene Alcohols such as methanol, ethanol, isopropanol, 2-butoxyethanol, 1-methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, cyclopentanone or cyclohexanone; esters such as ethyl acetate, butyl acetate or methyl lactate Halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane or trichloroethylene; propylene glycol monomethyl ether acetate (PGMEA), ethyl ether, tetrahydrofuran or dioxane Ethers such as emissions; N- methylpyrrolidone, amides such as dimethylformamide or dimethylacetamide; and the like.

  Among them, water; aromatic hydrocarbons such as toluene, xylene, chlorobenzene or orthodichlorobenzene; and halogens such as chloroform, methylene chloride, dichloroethane, trichloroethane or trichloroethylene because of the high solubility of the amine phosphate dispersant. Hydrocarbons; Alcohols such as methanol, ethanol, isopropanol, 2-butoxyethanol, 1-methoxy-2-propanol and the like; Propylene glycol monomethyl ether acetate (PGMEA), ethers such as ethyl ether, tetrahydrofuran or dioxane; N- Amides such as methyl pyrrolidone, dimethylformamide or dimethylacetamide are preferred.

  Furthermore, aromatic hydrocarbons such as toluene, xylene, chlorobenzene or ortho dichlorobenzene; halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane or trichloroethylene; propylene glycol monomethyl ether acetate in that the solubility of the resin is high; (PGMEA), ethers such as ethyl ether, tetrahydrofuran or dioxane; and amides such as N-methylpyrrolidone, dimethylformamide or dimethylacetamide are preferred.

  In particular, aromatic hydrocarbons such as toluene, xylene, chlorobenzene or ortho-dichlorobenzene are preferable because the solubility of hydrogenated styrene-isobutylene copolymer rubber is high.

  The dispersion medium used for the dispersion liquid is usually 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more in the ink, while usually 99% by weight or less, preferably 95% by weight or less More preferably, it is 90% by weight or less. Being within the above range is preferable in that the dispersion has an appropriate viscosity and a resin composite material having an appropriate thickness after drying can be obtained.

  The dispersion medium may be used alone or in any combination of two or more kinds in any proportion. In addition, since the dispersion liquid may remain in the resin composite, the boiling point of the dispersion medium is not specified.

<1-4. Dispersant>

<1.4. Dispersant>
The dispersion according to the present embodiment contains a dispersant. The dispersant means a compound for uniformly dispersing the zeolite in the dispersion liquid, and the dispersion liquid according to the present embodiment contains a dispersant containing a phosphoric acid amine compound. In the present invention, the phosphoric acid amine compound means a compound having both a phosphoric acid group and an amino group functional group.

  The dispersion of the zeolite in the dispersion can be improved by using a dispersant containing a phosphoric acid amine compound. Although this reason is not clear, the following reason can be considered. Zeolites have a higher isoelectric point than fillers such as silica particles, and are considered to be more compatible with acidic functional groups than basic functional groups such as amine dispersants. Among the acidic functional groups, dispersants having a phosphoric acid group, in particular, have high adsorptivity to oxides, so the phosphoric acid group forms a hydrogen bond with the hydroxyl group on the zeolite surface to strongly bond to the surface of the zeolite. It is considered that the dispersibility can be improved. Furthermore, the amine group of the phosphoric acid amine compound is highly compatible with any dispersion medium except for the ketone having reactivity with the amine, and the amine group is positioned on the dispersion medium side, so that it is in phase with the dispersion medium. Solubility can be enhanced. It is considered that the dispersibility of the zeolite is improved by using the phosphoric acid amine compound as a dispersant by these actions.

  100 or more are preferable, as for the molecular weight of a phosphoric acid amine compound, 300 or more are more preferable, and 500 or more are especially preferable. On the other hand, 40000 or less is preferable, 30000 or less is preferable, and 20000 or less is particularly preferable. The molecular weight as referred to herein is a polystyrene-equivalent weight average molecular weight (Mw). If it is above the above lower limit, the phosphoric acid amine compound will easily cover the surface of the zeolite, and if it is below the above upper limit, the viscosity of the dispersion will be appropriate and it will be easy to handle.

  The dispersant may contain a compound other than the above-mentioned phosphoric acid amine compound. For example, a solvent etc. are mentioned. Examples of the solvent include toluene, xylene and the like. Moreover, you may contain the stabilizer etc. so that a dispersing agent may not deteriorate.

  The amine value of the dispersant is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 20 or more, more preferably 25 or more, still more preferably 30 or more, particularly preferably 35 or more, and most preferably 40 or more. preferable. On the other hand, 100 or less is preferable, 95 or less is more preferable, 90 or less is more preferable, 85 or less is especially preferable, and 80 or less is the most preferable. The amine value referred to herein is a value indicating the amount of amine in the dispersant, and refers to the number of mg of potassium hydroxide (molecular weight 56.11) equivalent to the acid required to neutralize the amount of 1 g of sample. Within the above range, the amine group tends to form a hydrogen bond which is a weak bond with the dispersion medium or the resin, and the dispersibility of the zeolite tends to be improved.

  The acid value of the dispersant is not particularly limited as long as the effect of the present invention is not impaired, but 20 or more is preferable, 25 or more is more preferable, 30 or more is more preferable, 35 or more is particularly preferable, 40 or more is most preferable. On the other hand, 100 or less is preferable, 95 or less is more preferable, 90 or less is more preferable, 85 or less is especially preferable, and 80 or less is the most preferable. The acid value as used herein is a value indicating the amount of phosphoric acid group in the dispersant, and refers to the number of mg of potassium hydroxide (molecular weight 56.11) required to neutralize the amount of 1 g of sample. If it is in the said range, many bonds with a zeolite and a dispersing agent will be formed moderately, As a result, favorable dispersibility can be obtained.

  In addition, the absolute value of the difference between the acid value of the dispersant and the amine value of the dispersant is preferably 20 or less, more preferably 15 or less, and particularly preferably 10 or less. By being in the above-mentioned range, the acidity by the phosphate group becomes milder, and damage to the zeolite can be suppressed, leading to long-term stabilization of the dispersed state of the zeolite.

  The structure of the phosphoric acid amine compound is not particularly limited, but it is preferable to use one having at least one of a primary amine structure, a secondary amine structure, and a tertiary amine structure, and a primary aromatic It is more preferable to use one having at least one of an amine structure, a secondary aromatic amine structure, and a tertiary aromatic amine structure, and at least one of a secondary aromatic amine structure and a tertiary aromatic amine structure. It is particularly preferred to use one having one. In particular, the secondary aromatic amine structure and the tertiary aromatic amine structure have particularly high affinity with the organic solvent, and the zeolite particles have excellent dispersion stability over a long period of time.

  A commercial item may be used for a dispersing agent. For example, the compounds described in “Additives for BYK coating ink (the 43rd edition) such as DISPERBYK (R) -142, DISPERBYK (R) -145, DISPERBYK (R) -180, etc. (Bick Chemie Japan 2015), And compounds listed in Borcher's catalog such as Borchi (R) Gen ND plus.

  As the dispersing agent, one type of phosphoric acid amine compound may be used alone, or two or more types may be used in combination in an optional combination and ratio. In addition to the amine phosphate compound, other compounds may be contained as long as the effects of the present invention are not impaired.

  Other dispersants include, for example, polysiloxane compounds such as methylhydrogenpolysiloxane, polymethoxysilane, dimethylpolysiloxane or dimethicone PEG-7 succinate and salts thereof; silane compounds etc. (methyldimethoxysilane, dimethyldimethoxysilane Organosilicon compounds such as methyltrimethoxysilane, phenyltrimethoxysilane, 3-aminopropyltriethoxysilane or 3-carboxypropyltrimethyltrimethoxysilane); formic acid, acetic acid, lauric acid, stearic acid, oleic acid, 6-hydroxy Carboxylic acid compounds such as hexanoic acid; organophosphorus compounds such as lauryl ether phosphoric acid or trioctyl phosphine; dimethylamine, tributylamine, trimethylamine, cyclohexylamine, ethylenediamine or Amine compounds such as Li ethyleneimine, may be selected from carboxylic acid amine compound. In addition, a surface treatment agent or surfactant described later may function as a dispersant.

  The content of the phosphoric acid amine compound in the dispersion is not particularly limited, but is usually 0.01% by weight or more, preferably 0.03% by weight or more, more preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, particularly preferably 0.5% by weight or more, while usually 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, still more preferably 3% by weight or less, Particularly preferably, it is 1% by weight or less. By being in the above-mentioned range, even in the dispersion liquid, the zeolite or the resin can maintain a good dispersion state without causing precipitation or the like.

  The ratio of the dispersant to the zeolite in the dispersion is preferably 5% by weight or more, more preferably 7% by weight or more, and 10% by weight or more in order for the dispersant to exert its effect. More preferably, it is particularly preferably 12% by weight or more, and most preferably 15% by weight or more. On the other hand, it is preferable that the content of the dispersant is 50% by weight or less, more preferably 45% by weight or less, since the content such as hygroscopicity or negative expansion of the zeolite may be impaired. It is further preferable that the content be at most 50% by weight, particularly preferably at most 35% by weight, and most preferably at most 30% by weight.

<1-5. Other compounds>
As shown in FIG. 2, the dispersion may contain other compounds in addition to the zeolite, the resin, the dispersion medium, and the dispersant. For example, a surface treatment agent, surfactant, polymerization initiator, etc. may be included.

<1-5-1. Surface treatment agent>
A surface treatment agent may be contained to prevent further aggregation of the zeolite and to uniformly disperse it in the dispersion or the resin composite described later.

  There is no particular limitation on the surface treatment agent, and known ones may be used, and those used as the above-mentioned dispersant may be used as the surface treatment agent. Specifically, polysiloxane compounds such as methylhydrogenpolysiloxane, polymethoxysilane, dimethylpolysiloxane or dimethicone PEG-7 succinate and salts thereof; silane compounds etc. (methyldimethoxysilane, dimethyldimethoxysilane, methyltrimethoxy) Organosilicon compounds such as silane, phenyltrimethoxysilane, 3-aminopropyltriethoxysilane or 3-carboxypropyltrimethyltrimethoxysilane); formic acid, acetic acid, lauric acid, stearic acid, stearic acid, oleic acid, 6-hydroxyhexanoic acid, etc. Carboxylic acid compounds; organophosphorus compounds such as lauryl ether phosphoric acid or trioctyl phosphine; dimethylamine, tributylamine, trimethylamine, cyclohexylamine, ethylenediamine or polyethyleneimine Amine compounds such as mentioned carboxylic acid amine compounds.

  When a surface treatment agent is used, the content of the surface treatment agent in the dispersion is usually 0.001% by weight or more, preferably 0.003% by weight or more, more preferably 0.005% by weight or more, and still more preferably 0.01% by weight or more, particularly preferably 0.05% by weight or more, while usually 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, still more preferably 3% by weight or less, Particularly preferably, it is 1% by weight or less. By being in the said range, in a dispersion liquid, a zeolite and resin become difficult to raise precipitation etc., and can maintain a favorable dispersed state.

  The surface treatment agent may be used alone or in any combination of two or more in any proportion.

<1-5-2. Surfactant>
At the time of production of the resin composite, dents may occur due to the adhesion of fine bubbles or foreign matter, or the like, and drying unevenness may occur. Therefore, the dispersion liquid contains a surfactant for the purpose of preventing these. It is also good.

  The surfactant is not particularly limited, and known surfactants (cationic surfactants, anionic surfactants, nonionic surfactants) can be used. Specific examples of the surfactant include Triton X100 (manufactured by Dow Chemical Co.) as a nonionic surfactant, Zonyl FS 300 (manufactured by DuPont) as a fluorine surfactant, and BYK-310 as a silicon surfactant. BYK-320, BYK-345 (manufactured by Bick Chemie), as an acetylene glycol surfactant, Surfynol 104, Surfynol 465 (manufactured by Air Products), Olfin EXP 4036, or Olfin EXP 4200 (manufactured by Nisshin Chemical Industry) Can be mentioned.

  When a surfactant is used, the content of the surfactant in the dispersion is usually 0.001% by weight or more, preferably 0.003% by weight or more, more preferably 0.005% by weight or more, and still more preferably 0.01% by weight or more, particularly preferably 0.05% by weight or more, while usually 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, still more preferably 3% by weight or less, Particularly preferably, it is 1% by weight or less.

  One surfactant may be used alone, or two or more surfactants may be used in any combination and ratio.

  Further, the wettability of the dispersion can be improved by the surfactant. The wettability can be evaluated by the contact angle other than the actual application to the substrate. The contact angle is usually 45 ° or less, preferably 30 ° or less, and more preferably 15 ° or less, with respect to the PET substrate MRF 50 (manufactured by Mitsubishi Chemical Corporation). In addition, since spreading on the entire surface of the substrate means that the contact angle is not detected, it is particularly preferably not detected. By being 45 degrees or less, the ink can be applied on any substrate. The contact angle can be measured by a contact angle meter. For example, it can be measured by DM-501 manufactured by Kyowa Interface Science Co., Ltd.

1-5-3. Polymerization initiator>
As described above, since the resin precursor can be used as a resin in the dispersion liquid to polymerize the resin precursor during the production of the resin composite to synthesize the resin, the dispersion liquid contains a polymerization initiator. May be.

  The polymerization initiator is not particularly limited, but may be selected according to the method of producing the resin composite. For example, in the case of a photocuring method, a photopolymerization initiator may be selected, and in the case of a heat curing method, a thermal polymerization initiator may be selected. The photo-curing method is a curing method using ultraviolet light, visible light and infrared light among active energy ray curing methods.

  Examples of the photopolymerization initiator include acetophenones, benzophenones, benzoin ethers, hydroxyketones, acyl phosphine oxides, diazonium cation onium salts, iodonium cation onium salts, sulfonium cation onium salts and the like. Further, as a thermal polymerization initiator, for example, amine curing agents such as phenol curing agents, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, acid anhydride curing agents, amide curing agents Tertiary amines, imidazoles and derivatives thereof, organic phosphines, phosphonium salts, tetraphenyl boron salts, organic acid dihydrazides, halogenated boroamine complexes, polymercaptan curing agents, isocyanate curing agents, blocked isocyanate curing agents, etc. Can be mentioned.

  When a polymerization initiator is used, the content of the polymerization initiator in the dispersion is usually 0.001% by weight or more, preferably 0.003% by weight or more, more preferably 0.005% by weight or more, and still more preferably 0.01% by weight or more, particularly preferably 0.05% by weight or more, while usually 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, still more preferably 3% by weight or less, Particularly preferably, it is 1% by weight or less.

  The polymerization initiators used in the present invention may be used alone or in any combination of two or more in any proportion. The polymerization initiator may be present alone in the composition, or may form a complex with a solvent or the like. Moreover, you may form the multimer.

<1-6. Method of Producing Dispersion>
The method for producing the dispersion is not particularly limited, and can be produced by a known method. Usually, the zeolite, the resin, the dispersion medium, and the dispersing agent are mixed and manufactured. At that time, for the purpose of improving the uniformity of the dispersion, defoaming, etc., paint shaker, bead mill, planetary mixer, stirring type dispersing machine, homogenizer, revolution / revolution stirring mixer, three rolls, kneader, single shaft or It is preferable to mix using a general kneader such as a twin-screw kneader and a stirrer.

  The order of mixing of each component is also arbitrary, and any two components or three or more components among the components of the dispersion may be mixed in advance, and then the remaining components may be mixed, or all of them may be mixed at one time. It may be mixed.

  The dispersion is preferably stable for 24 hours or more, and more preferably for 1 week or more. The more stable, the more the synthesis and long-term storage of the dispersion become possible, and the manufacturing cost can be reduced. The stability of the dispersion can be evaluated by formation of a precipitate, change in viscosity, and the like.

  The formation of precipitates can be judged visually or with a dynamic light scattering particle size measuring device. In addition, the viscosity can be determined by a rotational viscometer method (described in “Physico-chemical experiments”) (described in Adachi Takuya, Ishii Yasutaka, Yoshida Kouhiro ed., Chemical Doujin (1993)).

<2. Resin composites>
The resin composite is a resin composite containing a zeolite, a resin, and a phosphoric acid amine compound, and can be produced from the dispersion liquid according to the present embodiment. FIG. 3 is a view schematically showing a resin composite containing zeolite, a resin, and a phosphoric acid amine compound.

  The zeolite in the resin composite is described in <1-2. Zeolites> The zeolites described in the section above can be used. The content of zeolite in the resin composite is usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, and particularly preferably 15% by weight or more. On the other hand, the content is 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 55% by weight or less, and particularly preferably 50% by weight or less. By being in the said range, the effect of the added zeolite is preferable from appearing as a characteristic of a resin composite material. Moreover, it is preferable that it is 80 weight% or less from suppressing the embrittlement of resin by excess addition.

  The resin in the resin composite is described in <1-3. Resin The resin described in the item of> can be used. The content of the resin in the resin composite is usually 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 45% by weight or more, and particularly preferably 50% by weight or more. On the other hand, the content is usually 90% by weight or less, preferably 85% by weight or less, more preferably 80% by weight or less, still more preferably 75% by weight or less, particularly preferably 70% by weight or less. It is preferable at the point by which the hygroscopic effect is exhibited, maintaining the characteristic of resin also in a resin compound material by being in the said range.

  The phosphoric acid amine compound in the resin composite is described in the above <1-4. The phosphoric acid amine compound described in the item of the dispersant can be used. The content of the phosphoric acid amine compound in the resin composite is usually 0.05% by weight or more, preferably 0.1% by weight or more, and particularly preferably 0.5% by weight or more. On the other hand, it is usually 10% by weight or less, preferably 5% by weight or less, and particularly preferably 2% by weight or less. Being within the above range is preferable in that the resin properties are not deteriorated while imparting the dispersibility of the zeolite.

  The content of phosphorus element in the resin composite is usually 0.01% by weight or more, preferably 0.05% by weight or more, and particularly preferably 0.1% by weight or more. On the other hand, it is usually 2% by weight or less, preferably 1% by weight or less, and particularly preferably 0.5% by weight or less. Being within the above range is preferable in that the resin properties are not deteriorated while imparting the dispersibility of the zeolite.

  As shown in FIG. 4, in addition to the above, in the resin composite, for example, other compounds in the dispersion liquid, and decomposition products of the compound may remain. For example, the above-mentioned dispersion medium, surface treatment agent, surfactant, polymerization initiator, etc. may be included.

  The surface treatment agent is described in the above <1-5-1. Surface treating agent> The surface treating agent described in the item can be used, but may be partially decomposed after the production of the resin composite. The content ratio of the total of the surface treatment agent and the decomposition product thereof to the resin composite is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more in the resin composite. On the other hand, it is usually 10% by weight or less, preferably 5% by weight or less, more preferably 2% by weight or less. Being within the above range is preferable in that the resin properties are not deteriorated while imparting the dispersibility of the zeolite.

  The surfactant is described in <1-5-2. The surfactant described in the item of surfactant> can be used, but after production of the resin composite, part of the surfactant may be decomposed. The content of the total of the surfactant and the decomposition product thereof with respect to the resin composite is usually 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably 1% by weight or more in the resin composite. On the other hand, it is usually 10% by weight or less, preferably 5% by weight or less, more preferably 2% by weight or less. Being within the above range is preferable in that the resin properties are not deteriorated while imparting the dispersibility of the zeolite.

  The polymerization initiator is described in <1-5-3. Polymerization initiator> The polymerization initiator described in the item can be used, but after production of the resin composite, it may be partially decomposed. The content ratio of the total of the polymerization initiator and the decomposition product thereof with respect to the resin composite is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more in the resin composite. On the other hand, it is usually 10% by weight or less, preferably 5% by weight or less, more preferably 2% by weight or less. It is preferable that the content rate of a polymerization initiator is 0.5 weight% or more from the point which can suppress that an unreacted component elutes from the resin composite obtained. Moreover, it is preferable that the content rate of a polymerization initiator is 10 weight% or less in the point which the cloudiness of a resin composite material, embrittlement, etc. are suppressed.

  As described later, the resin composite is preferably used as a resin composite molded body, but the thickness of the resin composite molded body is usually larger than 0.5 μm, preferably 1 μm or more, and more preferably It is 2 μm or more, more preferably 3 μm or more, and particularly preferably 5 μm or more. On the other hand, it is usually 5 mm or less, preferably 1 mm or less, more preferably 0.5 mm or less, still more preferably 0.3 mm or less, and particularly preferably 0.1 mm or less. When the film thickness is 0.5 μm or more, the effects such as hygroscopicity and negative expansion are easily exhibited after the zeolite is uniformly dispersed. The film thickness is preferably 5 mm or less because it can be used for transparent applications.

  The film thickness of the resin composite material molded body can be measured by a normal film thickness meter such as a non-contact film thickness meter or a contact film thickness meter. As a non-contact type, a confocal microscope (for example, a shape measurement laser microscope VK-X200 manufactured by Keyence Corporation) and the like can be mentioned.

  The transparency of the resin composite can be quantified by the transmittance at a specific wavelength, the visible light transmittance, and the haze value.

  The transmittance of light with a wavelength of 450 nm of the resin composite is preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, and particularly preferably 85% or more. And 90% or more. If it is more than the said lower limit, it is preferable from the ability to use this resin composite material for the use which needs transparency. As a use which needs transparency, it is applicable with a catalyst module, a molecular sieve membrane module, an optical member, a moisture absorption member, a foodstuff, a construction member, a component member of an electronic device, a packaging member, etc. In addition, the transmittance | permeability can be measured with a spectrophotometer (For example, spectrophotometer UV-2500PC by Shimadzu Corp. make).

  The haze value of auxiliary illuminant C (C light) for color measurement is preferably 10% or less, more preferably 5% or less, and still more preferably 3% or less. It is particularly preferably 2% or less, and most preferably 1% or less. The lower the haze value, the more suitable for transparent applications. The transparent application is applicable to a catalyst module, a molecular sieve membrane module, an optical member, a hygroscopic member, a food, a building member, a component member or packaging member of an electronic device, and the like. The haze value can be measured with a haze meter (for example, haze computer HZ-2 manufactured by Suga Test Instruments Co., Ltd.).

  The water adsorption amount with respect to the weight of the resin composite at 40 ° C. and 90% RH is preferably 0.5% by weight or more, more preferably 1% by weight or more, and still more preferably 2% by weight or more It is particularly preferably 3% by weight or more, and most preferably 5% by weight or more. The higher the water adsorption amount, the more suitable for the moisture absorption film application. As a hygroscopic film use, it can be applied to a catalyst module, a molecular sieve membrane module, an optical member, a hygroscopic member, a food, a building member, a component member or packaging member of an electronic device, and the like. The water adsorption amount is measured by a method (cup method) in accordance with JIS Z0208 (1976).

The water vapor transmission rate (WVTR) as defined in JIS K 7129 (2008) of the resin composite is preferably 1 × 10 ⁻¹ g / (m ² · day) or less, and 1 × 10 ⁻² g / (m ²⁾ Day) or less is more preferable, 1 × 10 ⁻³ g / (m ² · day) or less is more preferable, and 1 × 10 ⁻⁴ g / (m ² · day) or less Particularly preferred is 1 × 10 ^-5 g / (m ² · day) or less. The lower the WVTR, the more suitable for barrier film applications. As a barrier film application, it can be applied to a catalyst module, a molecular sieve membrane module, an optical member, a hygroscopic member, a food, a building member, a component of an electronic device, a packaging member, and the like. The water vapor transmission rate (WVTR) can be measured using AQUATRAN manufactured by MOCON.

  The resin composite is preferably used as a resin composite molded body. The shape of the molded body is not particularly limited, and examples thereof include a film, a plate, a particle, a block, a fiber, a rod, a porous body, a foam, and a packing. Among them, film-like and plate-like ones are preferable because they are easy to use for applications such as catalyst modules, molecular sieve membrane modules, optical members, hygroscopic members, foods, construction members, components of electronic devices, packaging members, etc. . In the present specification, film-like means a film-like form having a thickness of 5 mm or less. Moreover, the method of manufacturing a resin compound material molded object can use a well-known method.

<3. Method of Manufacturing Resin Composite>
The resin composite can be manufactured using a dispersion containing the above-described zeolite, a resin, and a dispersant. The specific method is not particularly limited, and can be produced by a known method. However, after applying the dispersion to a substrate, it can be produced by heating and drying.

  As a method of further forming after producing a resin composite, a method generally used for forming a resin can be used. At that time, the heating necessary for the production of the resin composite and the heating for molding may be performed simultaneously.

  Moreover, when resin which comprises a resin compound material is a thermosetting resin compound material, shaping | molding of a resin compound material can be performed on the curing temperature conditions according to each composition.

  The curing temperature is preferably less than 400 ° C., more preferably 370 ° C. or less, and particularly preferably 340 ° C. or less. On the other hand, the temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and particularly preferably 100 ° C. or higher. Being less than 400 ° C. is preferable in that it is a temperature that can be handled even in a manufacturing process using a flexible substrate such as a roll-to-roll method. Further, it is preferable that the temperature is 80 ° C. or higher in that curing progresses to a certain extent and elution of unreacted components from the resin composite is suppressed.

  Moreover, when resin which comprises a resin composite material is a thermoplastic resin composite material, shaping | molding of a molded object can be performed on the conditions more than the melting temperature of a thermoplastic resin, and the predetermined shaping | molding speed and pressure.

  The melting temperature is preferably less than 400 ° C., more preferably 370 ° C. or less, and particularly preferably 340 ° C. or less. On the other hand, the temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and particularly preferably 100 ° C. or higher. Being less than 400 ° C. is preferable in that it is a temperature that can be handled even in a manufacturing process using a flexible substrate such as a roll-to-roll method. Moreover, being 80 degreeC or more is preferable at the point which resin can fuse | melt uniformly.

  Further, as the heat treatment method, a known method may be used. For example, hot air drying and drying with an infrared heater can be mentioned.

<4. Applications of Resin Composites>
The application of the resin composite obtained by the dispersion according to the present invention is not particularly limited, and can be used for applications where water absorption is required. Among them, the resin composite obtained by using the dispersion according to the present invention is effective for application in applications where transparency is required because the transparency is high. Specifically, it can be used as a catalyst module, a molecular sieve membrane module, an optical member, a hygroscopic member, a food, a building member, a component of an electronic device, a packaging member, and the like. Among them, it is preferable to use the component of the electronic device, for example, a base material, a getter material film, a sealing material, etc. in order to take advantage of the high properties of the resin composite material obtained by the present invention. Hereinafter, an electronic device which is a preferable application of the resin composite obtained by the present invention will be described.

<4-1. Electronic device>
An electronic device has two or more electrodes, and a device that controls the current flowing between the electrodes or the generated voltage by electricity, light, magnetism, a chemical substance or the like, or light or an electric field by an applied voltage or current. , It is an apparatus which generates a magnetic field. Specifically, a resistor, a rectifier (diode), a switching element (transistor, thyristor), an amplification element (transistor), a memory element, a chemical sensor or the like, or a device in which these elements are combined or integrated can be mentioned. In addition, a photodiode or a phototransistor that generates a photocurrent, an electroluminescent element that emits light by applying an electric field, and an optical element such as a photoelectric conversion element or a solar cell that generates an electromotive force by light can be given. A more specific example of the electronic device is S.I. M. Mention may be made of those described in Sze, Physics of Semiconductor Devices, 2nd Edition (Wiley Interscience 1981).

  Among them, preferable examples of the electronic device include a field effect transistor (FET) element, an electroluminescent element (LED), a photoelectric conversion element or a solar cell. With these devices, the high characteristics of the resin composite according to the present invention can be effectively utilized.

  Hereinafter, a field effect transistor element, an electroluminescent element, a photoelectric conversion element, and a solar cell will be described in detail as an example of an electronic device having the resin composite according to the present invention as a component.

<4-2. Field effect transistor (FET) element>
A field effect transistor (FET) element has the resin composite according to the present invention as a component. A field effect transistor (FET) device according to one embodiment includes a semiconductor layer, an insulator layer, a source electrode, a gate electrode, and a drain electrode on a substrate.

  Hereinafter, the FET device according to an embodiment will be described in detail. FIG. 5 is a view schematically showing a structural example of the FET element. In FIG. 5, 11 indicates a semiconductor layer, 12 indicates an insulator layer, 13 and 14 indicate source and drain electrodes, 15 indicates a gate electrode, 16 indicates a base material, and 17 indicates an FET element. Although FET elements having different structures are described in FIG. 5A to FIG. 5D respectively, each shows a structural example of the FET element. There is no particular limitation on the components forming the FET element and the method of manufacturing the same, and known techniques can be used. For example, the techniques described in known documents such as WO 2013/180230 or JP-A-2015-134703 can be used.

In the present specification, “semiconductor” is defined by the magnitude of carrier mobility in the solid state. Carrier mobility is an index indicating how fast (or many) the charge (electron or hole) can be moved, as is well known. Specifically, the “semiconductor” in the present specification usually has a carrier mobility at room temperature of 1.0 × 10 ⁻⁶ cm ² / V · s or more, preferably 1.0 × 10 ⁻⁵ cm ² / V · s or more, Preferably, it is 5.0 × 10 ⁻⁵ cm ² / V · s or more, more preferably 1.0 × 10 ⁻⁴ cm ² / V · s or more. The carrier mobility can be measured, for example, by measuring the IV characteristics of a field effect transistor.

<4-2-1. Base material>
The FET device is usually fabricated on the substrate 16. The material of the substrate 16 is not particularly limited. Preferred examples of the material of the substrate 16 may include inorganic materials such as quartz, glass, sapphire or titania; metal foils; or resins or resin composites obtained by the present invention. Among them, from the viewpoint of productivity, it is preferable to use a flexible base material.

  In the present invention, the flexible substrate is a substrate having a radius of curvature of usually 0.1 mm or more and 10000 mm or less. In the case of producing a flexible electronic device, the curvature radius is preferably 0.3 mm or more, more preferably 1 mm or more, in order to achieve both the flexibility and the characteristics as a support. And 3000 mm or less is preferable, and 1000 mm or less is more preferable. The radius of curvature can be determined by using a confocal microscope (for example, a shape measuring laser microscope VK-X200 manufactured by Keyence Corporation) that is bent to a point where breakage such as strain or crack does not appear.

  Specific examples of the flexible substrate include, but are not limited to, resins; paper materials such as paper or synthetic paper; and metal films such as silver, copper, stainless steel, titanium, or aluminum to provide insulation. Composite materials such as those coated or laminated on the surface; and resin composites obtained by the present invention.

  Furthermore, the characteristics of the FET can be improved by processing the substrate 16. This is by improving the film quality of the semiconductor layer 11 to be formed by adjusting the hydrophilicity / hydrophobicity of the substrate 16, and in particular by improving the characteristics of the interface portion between the substrate 13 and the semiconductor layer 11. It is presumed that. As such substrate treatment, hydrophobization treatment using hexamethyldisilazane, cyclohexene, octadecyltrichlorosilane or the like; acid treatment using an acid such as hydrochloric acid, sulfuric acid, or acetic acid; sodium hydroxide, potassium hydroxide, Alkaline treatment with calcium hydroxide and ammonia, etc .; ozone treatment; fluorination treatment; plasma treatment with oxygen and argon etc .; formation treatment of Langmuir Blojet film; formation treatment of other insulator or semiconductor thin film etc. Can be mentioned.

4-2-2. Insulator layer>
As a material used for insulator layer 12 of FET element, for example, epoxy resin, acrylic resin such as polymethyl methacrylate, polystyrene resin, polyvinyl phenol resin, polyimide resin, polycarbonate resin, polyester resin, Resins such as polyvinyl alcohol resin, polyvinyl acetate resin, polyurethane resin, polysulfone resin, phenol resin, and copolymers thereof; metal oxides such as silicon dioxide, aluminum oxide, titanium oxide; silicon nitride, etc. Metal nitrides; ferroelectric metal oxides such as strontium titanate and barium titanate; and resins in which particles of these metal oxides, metal nitrides and ferroelectric metal oxides are dispersed, according to the present invention The resin composite material etc. which are obtained are mentioned.

  In general, the larger the capacitance of the insulator layer 12 is, the more advantageous it is that the gate voltage can be driven at a low voltage. This can be realized by reducing the thickness of the insulator layer.

  The method for forming the insulator layer 12 is not particularly limited, and examples thereof include wet coating methods such as spin coating, blade coating and spin coating, vapor deposition, sputtering, printing such as screen printing and inkjet, aluminum The oxide film can be formed by a known method according to the material characteristics, such as a method of forming an oxide film on metal so as to form alumite.

<4-3. Electroluminescent Device (LED)>
An electroluminescent element (LED) has a component containing the resin composite according to the present invention. The electroluminescent element is a self-luminous element utilizing the principle that a fluorescent substance emits light by the recombination energy of holes injected from the anode and electrons injected from the cathode by applying an electric field.

  The electroluminescent element will be described below with reference to the drawings. FIG. 6 is a cross-sectional view schematically showing an embodiment of the electroluminescent device according to the present invention. In FIG. 6, reference numeral 31 denotes a substrate, 32 denotes an anode, 33 denotes a hole injection layer, 34 denotes a hole transport layer, 35 denotes a light emitting layer, 36 denotes an electron transport layer, 37 denotes an electron injection layer, 38 denotes a cathode, 39 Indicates an electroluminescent device. It is not necessary for the electroluminescent element to have all of these components, and the necessary components can be selected arbitrarily. For example, the hole injection layer 33, the hole transport layer 34, the electron transport layer 36, and the electron injection layer 37 need not necessarily be provided. There is no particular limitation on the components forming the electroluminescent element and the method of manufacturing the same, and known techniques can be used. For example, the techniques described in known documents such as WO 2013/180230 or JP-A-2015-134703 can be used.

  In one embodiment, the substrate 31 comprises the resin composite according to the present invention.

<4-3-1. Base material (31)>
The substrate 31 is a support of the electroluminescent element 39, and the material is not particularly limited. As a specific example, the above-mentioned <4-2-1. The base material (16)> described above can be used.

  6 shows only one embodiment of the electroluminescent device, and the electroluminescent device according to the present invention is not limited to the illustrated configuration. For example, the reverse laminated structure to that in FIG. 6 is used, that is, the cathode 38, the electron injection layer 37, the electron transport layer 36, the light emitting layer 35, the hole transport layer 34, the hole injection layer 33 and It is also possible to laminate the anode 32 in this order.

  The configuration of the electroluminescent device according to the present invention is not particularly limited, and even if it is a single device or a device having a structure arranged in an array, the anode and the cathode are formed in an XY matrix It may be an element of a disposed structure.

<4-4. Photoelectric conversion device>

  FIG. 7 is a cross-sectional view schematically showing an embodiment of the photoelectric conversion element. The photoelectric conversion element shown in FIG. 7 is a photoelectric conversion element used for a general thin film solar cell, but the photoelectric conversion element according to the present invention is not limited to that shown in FIG. In the photoelectric conversion element 57, a base 56, a cathode (electrode) 51, an electron extraction layer (buffer layer) 52, an active layer 53, a hole extraction layer (buffer layer) 54, and an anode (electrode) 55 are formed in this order. It has a layered structure. The electron extraction layer 52 and the hole extraction layer 54 are not necessarily required. There is no particular limitation on the components forming the photoelectric conversion element and the method of manufacturing the same, and known techniques can be used. For example, the techniques described in known documents such as WO 2013/180230 or JP-A-2015-134703 can be used.

<4-4-1. Base material (31)>
The base material 31 becomes a support of the photoelectric conversion element 57, and the material is not particularly limited. As a specific example, the above-mentioned <4-2-1. The base material (16)> described above can be used.
<4-5-1. Solar cell>
The photoelectric conversion element 57 is preferably used as a solar cell, particularly as a solar cell element of a thin film solar cell. FIG. 8 is a cross-sectional view schematically showing the structure of a solar cell, and FIG. 8 shows a thin film solar cell which is a solar cell. As shown in FIG. 8, the thin film solar cell 111 according to this embodiment includes the weather resistant protective film 101, the ultraviolet ray cut film 102, the gas barrier film 103, the getter material film 104, the sealing material 105, and the solar cell. The element 106, the sealing material 107, the getter material film 108, the gas barrier film 109, and the back sheet 110 are provided in this order. The thin film solar cell 111 according to the present embodiment has the photoelectric conversion element according to the present invention as the solar cell element 106. Then, light is irradiated from the side on which the weather resistant protective film 101 is formed (the lower side in FIG. 8), and the solar cell element 106 generates power. In addition, the thin film solar cell 111 does not need to have all these structural members, and a necessary structural member can be selected arbitrarily.

  There is no particular limitation on these components constituting the thin film solar cell and the method of manufacturing the same, and known techniques can be used. For example, the techniques described in known documents such as WO 2013/180230 or JP-A-2015-134703 can be used.

  The resin composite obtained by the present invention is preferably used as a molded article in any of a weather resistant protective film, a back sheet, an ultraviolet ray cut film, a gas barrier film, a getter material film, and a sealing material. Among them, a molded article using a resin composite obtained by the present invention is suitable as a material of a getter material film because it has high hygroscopicity.

  In addition, the weather-resistant protective film, back sheet, ultraviolet ray cut film, gas barrier film, getter material film, and sealing material described here are the above-mentioned field effect transistor element (FET), electroluminescent element (LED), etc. Can also be used.

  The solar cell, particularly the thin film solar cell 111 described above may be used as it is or may be used as a component of a solar cell module. For example, as shown in FIG. 9, a solar cell module 113 including the solar cell according to the present invention, in particular, the thin film solar cell 111 described above on a substrate 112 is manufactured, and the solar cell module 113 is installed at a use location. Can be used.

  As the substrate 112, known materials can be used. For example, as the material of the substrate 112, materials described in WO 2013/180230, JP-A-2015-134703, etc. can be used. . Moreover, you may use for the base material 112 the molded object using the resin composite material obtained by this invention. For example, when using the board | plate material for building materials as the base material 112, the solar cell panel for the outer wall of a building can be produced as the solar cell module 113 by providing the thin film solar cell 111 in the surface of this board | plate material.

  EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited by the following examples as long as the gist thereof is not exceeded.

<Example of resin synthesis>
Synthesis Example 1: Synthesis of Hydrogenated Styrene-Isobutylene-Styrene Copolymer
Hydrogenated styrene-isobutylene-styrene copolymer was synthesized by the same method as in JP-A-2013-216902. The hydrogenated block copolymer thus obtained was (hydrogenated styrene: isobutylene = 15: 70), and had a weight average molecular weight (Mw) of 103,000 and a number average molecular weight (Mn) of 78,200. Mw / Mn = 1.3). Moreover, the hydrogenation rate was 97%.

<Preparation of Zeolite Dispersion>
(Preparation of Zeolite Dispersion 1)
The weight ratio of LTA nano zeolite (Zeoal Z4A-005, manufactured by Nakamura Carbide Co., Ltd.), amine phosphate based dispersant (BYK 145, manufactured by BIC-Chemie Japan), and toluene is 1: 0.2: 10. The mixture was mixed in the same manner, and Dispersion 1 was prepared using a bead mill for fine pulverization and dispersion (Ashizawa Finetech Co., Ltd .: Labstar). The condition of the bead mill was 0.05 mm zirconia beads, the circumferential speed was 11 m / s, and the filling rate was 70%.

(Preparation of Zeolite Dispersion 2)
A zeolite dispersion 2 was obtained in the same manner as the dispersion 1, except that an amine compound dispersant (BYK 2155 manufactured by Bick Chemie Japan) was used instead of the phosphoric acid amine compound dispersant. In the obtained zeolite dispersion 2, aggregation of zeolite was confirmed.

(Preparation of Zeolite Dispersion 3)
Dispersion 3 was produced in the same manner as dispersion 1 except that a carboxylic acid amine compound dispersant (ANTITERRA-U100 manufactured by Bick Chemie Japan) was used instead of the phosphoric acid amine compound dispersant. In the obtained zeolite dispersion 3, aggregation of zeolite was confirmed.

(Preparation of Zeolite Dispersion 4)
An attempt was made to prepare dispersion 4 by the same method as dispersion 1 except that the phosphoric amine compound based dispersant was not used, but the compatibility between the zeolite and toluene was poor, and the powder reaggregated, leading to the inside of the apparatus The resulting powder had problems such as accumulation of powder, increase in power of the mill, and increase in temperature of the slurry, and the resulting dispersion showed remarkable aggregation of zeolite.

(Dispersion liquid 1 for forming resin composites)
The hydrogenated styrene-isobutylene-styrene copolymer obtained in Synthesis Example 1 is mixed with zeolite dispersion liquid 1 so that the weight ratio of zeolite: hydrogenated styrene-isobutylene-styrene copolymer is 1:10. The dispersion for resin composite material formation 1 was prepared by dispersing for 10 minutes using an IKA homogenizer (T18 Digital Ultratax).

(Dispersion fluid for resin composite formation 2)
A dispersion 2 for forming a resin composite was produced in the same manner as the dispersion 1 for forming a resin composite except that the zeolite dispersion 2 was used instead of the zeolite dispersion 1.

(Dispersion fluid for forming resin composites 3)
A dispersion 3 for forming a resin composite was produced in the same manner as the dispersion 1 for forming a resin composite except that the zeolite dispersion 3 was used instead of the zeolite dispersion 1.

  The prepared dispersions 1 to 3 for forming a resin composite were allowed to stand at room temperature for 1 week and visually confirmed. In the dispersions 2 and 3 for forming a resin composite, precipitates were confirmed. On the other hand, in the resin composite dispersion 1, no precipitate could be confirmed.

  From the above results, it is understood that a dispersion liquid in which zeolite aggregation is suppressed can be prepared by using a phosphoric acid amine compound based dispersant.

Example 1 Preparation of Resin Composite Film 1
Dispersion liquid 1 for resin compound material formation is dropped on the side which is not the exfoliation side of MRF 50 (made by Mitsubishi Chemical Co., Ltd.) which is exfoliation PET film of 50 μm thickness, so that the film thickness after curing becomes 40 to 45 micrometers. The resin composite film 1 was produced by stretching with a coater and then drying at 110 ° C. for 20 minutes. In addition, the film thickness of the resin composite material film 1 was 40 micrometers as a result of measuring by Toyo Seiki Co., Ltd. product THICKNESS METER B-1.

Comparative Example 1: Preparation of Resin Composite Material Film 2
A resin composite film 2 was produced in the same manner as in Example 1 except that the dispersion 2 for forming a resin composite was used. In addition, the film thickness of the resin composite material film 2 was 40 micrometers as a result of measuring by Toyo Seiki Co., Ltd. product THICKNESS METER B-1.

Comparative Example 2: Preparation of Resin Composite Film 3
A resin composite film 3 was produced in the same manner as in Example 1 except that the dispersion 3 for forming a resin composite was used. In addition, as a result of measuring by THICKNESS METER B-1 manufactured by Toyo Seiki Seisaku-sho, the film thickness of the resin composite material film 3 was 40 μm.

<Evaluation of transparency of resin composite films 1 to 3>
The haze value of each of the resin composite films 1 to 3 was measured using Haze Computer HZ-2 manufactured by Suga Test Instruments Co., Ltd. and auxiliary illuminant C (C light) for color measurement. The internal haze value was measured by using a matching oil (Imaging oil type B manufactured by Cargill Japan) at the time of measurement. The obtained results are shown in Table 1. Moreover, the transmittance | permeability in the visible light area | region of the resin composite material films 1-3 was measured using Shimadzu Corp. make make spectrophotometer UV-2500PC. The results are shown in Table 1 and FIG. In addition, the reference shown in FIG. 10 is a film made only of the hydrogenated styrene-isobutylene-styrene copolymer obtained in Synthesis Example 1.

Referring to the results in Table 1 and FIG. 10, the resin composite material films according to Comparative Examples 1 and 2 prepared from the resin composite material dispersion containing an amine compound based dispersant and a carboxylic acid amine compound based dispersant have a haze. It can be seen that the value is over 10% and high transparency is not obtained. The reason for this seems to be that in Comparative Examples 1 and 2, the zeolite has aggregated in the dispersion.
On the other hand, in the resin composite material film according to Example 1 prepared from the dispersion liquid 1 for forming a resin composite material containing a phosphoric acid amine compound based dispersant, the haze value is less than 10% and visible light of wavelength 450 nm It can be seen that the transmittance is over 70% and that it has high transparency. The reason for this seems to be that the dispersibility of the zeolite in the dispersion was good. Although the reason why the dispersibility of the zeolite in the dispersion is good is not clear, the phosphate group in the phosphoric acid amine compound bonds well with the zeolite to form a micelle structure in which the amine group faces outward. It is believed that the aggregation of the zeolite was suppressed by

<Measurement of hygroscopicity under high humidity conditions>
The film 1 of the resin composite material obtained in Example 1 was exposed to an atmosphere of 40 ° C. and 90% RH using a constant temperature and humidity machine (ETAC FX 213C) manufactured by Kushimoto Chemical Co., Ltd., and the weight change of the film with time Was measured. The results are shown in FIG. It can be seen that the resin composite film absorbs water with high performance even under high humidity conditions.

  From the above results, it can be said that the resin composite material prepared from the dispersion according to the present invention is suitable for use as a moisture absorbing film or the like for all applications because it has high hygroscopicity. In addition, the resin composite film produced from the dispersion according to the present invention can be effectively used in applications where transparency is required because zeolite has less aggregation and transparency is high.

1 dispersion 2 zeolite 3 resin 4 dispersion medium 5 dispersant (phosphorus amine compound)
6 resin composite 7 other compound 11 semiconductor layer 12 insulator layer 13, 14 source electrode and drain electrode 15 gate electrode 16 base 17 FET element 31 base 32 anode 33 hole injection layer 34 hole transport layer 35 light emitting layer 36 Electron transport layer 37 electron injection layer 38 cathode 39 electroluminescent element 51 cathode 52 electron extraction layer 53 active layer 54 hole extraction layer 55 anode 56 base material 57 photoelectric conversion element 101 weathering protective film 102 ultraviolet cut film 103, 109 gas barrier film 104, 108 getter material film 105, 107 sealing material 106 solar cell element 110 back sheet 111 thin film solar cell 112 substrate 113 solar cell module

Claims (5)

  A dispersion liquid comprising zeolite, resin, dispersion medium, and phosphoric acid amine compound.   The dispersion according to claim 1, wherein the average primary particle size of the zeolite is 15 to 200 nm.   The dispersion liquid according to claim 1 or 2, wherein a ratio of the phosphoric acid amine compound to the zeolite in the dispersion liquid is 5% by weight or more and 50% by weight or less.   A resin composite film comprising a zeolite, a resin, and a phosphoric acid amine compound.   An electronic device comprising the resin composite film according to claim 4.

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