JP2010132742A - Organic-inorganic composite dispersion liquid and method for producing the same, organic-inorganic composite film and method for producing the same, and component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic-inorganic composite film excellent in hydrophilicity and lipophilicity, and a method for producing the same; to provide an organic-inorganic composite dispersion liquid producing the organic-inorganic composite film, and a method for producing the same; and to provide a component using the organic-inorganic composite film. <P>SOLUTION: The organic-inorganic composite dispersion liquid includes a microparticulate dehydration condensate (A1) of metal hydroxide and a particle of water-insoluble resin (B) having an anionic group, wherein the microparticulate dehydration condensate (A1) of metal hydroxide entirely or partially adheres to the water-insoluble resin (B) having an anionic group, and liquid property is pH 1-5. The organic-inorganic composite dispersion liquid is preferable for production of an organic-inorganic composite film including a particle of water-insoluble resin (b) the surface of which is partially coated with a microparticle of metal oxide (A2), and having a water contact angle of ≤20° and an n-hexadecane contact angle of ≤20°. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic-inorganic composite dispersion and a method for producing the same, an organic-inorganic composite film, a method for producing the same, and a member.

  In order to prevent the surface of the object from becoming cloudy or to prevent dirt from adhering to it, water can be easily repelled by water-repellent processing of the object, or water and oil can be added to the object by hydrophilic hydrophilic / lipophilic processing. Attempts have been made to make it difficult to adhere to the surface. In addition, for practical convenience, it is possible to express the water repellency and hydrophilic oleophilicity of the object surface by laminating the functional film subjected to the above water repellency and hydrophilic oleophilic processes on the base material. It is common.

  As a film having a water-repellent processed surface, a metal alkoxide, a sol having a primary particle diameter of 100 nm or less, a phase separation with these in a predetermined solvent, and removed at a temperature from room temperature to 700 ° C. A high hardness and high water slidability film is disclosed by applying a coating material for forming a high hardness and high water slidability film comprising a solution or emulsion in which a substance having the following characteristics is added to a solvent (for example, Patent Documents) 1).

  On the other hand, as a film having a hydrophilic / lipophilic finish on the surface of the object, to provide a low-cost hydrophilic / lipophilic film that maintains the transparency of the film, has super hydrophilicity, and also has surface strength that can withstand practical strength. For this purpose, a plastic film, an inorganic hard film having fine irregularities formed on at least one surface of the plastic film, and a chemisorption monomolecular film formed via siloxane bonds on the minute irregularities on the inorganic hard film, A hydrophilic / lipophilic film made of is disclosed (for example, see Patent Document 2).

In addition, a method of expressing amphiphilicity (hydrophilic lipophilicity) using titanium oxide, which is a photocatalyst, in the surface of hydrophilic / lipophilic processing is also disclosed (see, for example, Patent Documents 3 and 4). For example, in Patent Document 4, it is shown that the hydrophilic portion and the lipophilic portion are dispersed and formed in a mosaic shape by irradiating the surface of the surface with light, thereby exhibiting hydrophilic lipophilicity.
JP 2001-207123 A JP 7-82397 A Japanese Patent Laid-Open No. 10-166495 JP 11-337294 A

However, when a hydrophilic / lipophilic membrane is obtained, hydrophilic / lipophilic processing is not simple in the above method.
In view of the above circumstances, an object of the present invention is to provide an organic-inorganic composite film that is excellent in hydrophilicity and excellent in lipophilicity and a method for producing the same. It is another object of the present invention to provide an organic-inorganic composite dispersion capable of producing the organic-inorganic composite film and a method for producing the same. Furthermore, it aims at providing the member using the said organic inorganic composite film.

Specific means for achieving the above object are as follows.
<1> A fine particle metal hydroxide dehydration condensate (A1) and a particle of a water-insoluble resin (B) having an anionic group, the fine particle metal hydroxide dehydration condensate (A1) ) Are attached to the water-insoluble resin (B) particles having the anionic group, and the liquidity is an organic-inorganic composite dispersion having pH 1 to pH 5.

  <2> The organic-inorganic composite dispersion according to <1>, wherein the metal hydroxide is at least one selected from the group consisting of silicon hydroxide, zirconium hydroxide, aluminum hydroxide, and titanium hydroxide.

  <3> The organic-inorganic composite dispersion according to <1> or <2>, wherein the metal hydroxide is silicon hydroxide.

  <4> The anionic group according to any one of <1> to <3>, wherein the anionic group is one or more selected from the group consisting of a carboxy group, a sulfonic acid group, and a phosphoric acid group, or a salt thereof. It is an organic-inorganic composite dispersion.

  <5> The organic-inorganic composite dispersion according to any one of <1> to <4>, wherein the water-insoluble resin having an anionic group contains a polyurethane resin.

  <6> A part of the surface contains particles of the water-insoluble resin (b) coated with fine particles of the metal oxide (A2), the contact angle with respect to water is 20 ° or less, and with respect to n-hexadecane It is an organic-inorganic composite film having a contact angle of 20 ° or less.

  <7> The organic-inorganic composite film according to <6>, wherein the composite film surface has a structure in which the uneven surface formed by particles of the water-insoluble resin (b) is covered with fine particles of the metal oxide (A2). It is.

  <8> The particle diameter of the fine particles of the metal oxide (A2) is 0.1% to 60% of the particle diameter of the water-insoluble resin (b), described in <6> or <7>. This is an organic-inorganic composite film.

  <9> Any of the above <6> to <8>, wherein the particles of the water-insoluble resin (b) are particles of the water-insoluble resin (B) having an anionic group having a particle size of 0.05 μm to 1 μm. It is an organic-inorganic composite film described in one.

<10> A dispersion containing particles of the water-insoluble resin (B) having an anionic group is mixed with an alcohol solution or an aqueous solution of the metal alkoxide (a) to prepare a first mixed solution having a pH of 7 to 10. A first mixed solution preparation step;
A second mixed solution preparing step of preparing a second mixed solution of pH 1 to pH 5 by adding an acid catalyst to the first mixed solution;
It is a manufacturing method of the organic inorganic composite dispersion which has a heating process which heats the said 2nd liquid mixture to 30 to 90 degreeC.

  <11> A method for producing an organic-inorganic composite film comprising a step of applying the organic-inorganic composite dispersion liquid according to any one of <1> to <5> onto a support and drying.

  <12> A member obtained by laminating the organic-inorganic composite film according to any one of <6> to <9> on a substrate surface.

  <13> The member according to <12>, which is an antifogging film.

  <14> The member according to <12>, which is an antistatic film.

  According to the present invention, it is possible to provide an organic-inorganic composite film excellent in hydrophilicity and oleophilic and a method for producing the same. Moreover, the organic inorganic composite dispersion liquid which can manufacture the said organic inorganic composite film, and its manufacturing method can be provided. Furthermore, a member using the organic-inorganic composite film can be provided.

<Organic-inorganic composite dispersion and production method thereof>
The organic-inorganic composite dispersion of the present invention contains finely divided metal hydroxide dehydration condensate (A1) and particles of a water-insoluble resin (B) having an anionic group. All or part of the dehydrated condensate (A1) is attached to the particles of the water-insoluble resin (B) having the anionic group, and the liquidity is pH 1 to pH 5.
The organic-inorganic composite dispersion liquid of the present invention makes it possible to produce an organic-inorganic composite film capable of simultaneously developing hydrophilicity and lipophilicity by applying to a support and drying.
First, the metal hydroxide dehydration condensate (A1) and the water-insoluble resin (B) particles having an anionic group, which are essential components of the organic-inorganic composite dispersion of the present invention, will be described. Hereinafter, the dehydration condensate (A1) of metal hydroxide may be referred to as “component (A1)” and the water-insoluble resin (B) having an anionic group may be referred to as “component (B)”.

[Dehydration condensate of metal hydroxide (A1)]
The metal constituting the metal hydroxide dehydration condensate (A1) is, for example, Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Nb, Zr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ta, Hf, W, Ir, Tl, Pb, Bi, rare earth metals, etc. . The metal which comprises the dehydration condensate (A1) of metal hydroxide may be comprised individually or in 2 types or more.
Of these, Si, Al, Zr, Ti and the like are preferably used. Among these, silicon compounds are relatively inexpensive and easy to obtain, and the reaction proceeds slowly, so that the industrial utility value is high.

  The metal hydroxide dehydration condensate (A1) is produced by, for example, hydrolyzing a metal alkoxide (a) by adding alcohol or water, and then dehydrating from the metal hydroxide and the metal hydroxide. And can be produced by a condensation reaction.

  The organic-inorganic composite dispersion of the present invention may contain an unreacted compound such as a metal alkoxide (a), a compound that forms a dehydration condensate (A1) of a metal hydroxide, or a compound that is undergoing a reaction.

  The metal hydroxide of the component (A1) that is a component constituting the organic-inorganic composite dispersion of the present invention is one or more selected from the group consisting of silicon hydroxide, zirconium hydroxide, aluminum hydroxide, and titanium hydroxide. It is preferable that it is silicon hydroxide, and silicon hydroxide is more preferable.

  The details of the fact that the organic-inorganic composite film obtained by applying the organic-inorganic composite dispersion liquid of the present invention to a support and drying can simultaneously exhibit hydrophilicity and lipophilicity will be described later. By containing a large amount of metal hydroxide dehydration condensate (A1) in the liquid, an organic-inorganic composite film capable of simultaneously developing hydrophilicity and lipophilicity can be produced.

[Particles of water-insoluble resin (B) having an anionic group]
The organic-inorganic composite dispersion of the present invention contains particles of a water-insoluble resin (B) having an anionic group.
The particles of the water-insoluble resin (B) having an anionic group in the present invention are insoluble in water and a mixed solvent of an organic solvent having an affinity for water (aqueous medium), but are dispersible in those media. Particles containing a water-insoluble resin having an anionic group, such as emulsion polymerization method, suspension polymerization method, miniemulsion polymerization method, dispersion polymerization method, etc. The method of emulsifying resin and resin solution as described above, and further, water-insoluble with an anionic group, such as those obtained by polymerizing monomers in the presence of particles called seed polymerization to modify the particles Particles of the conductive resin are included.

Here, the anionic group is one or more selected from the group consisting of a carboxy group, a sulfonic acid group, and a phosphoric acid group, or a salt thereof. Specific examples of the salt include amine salts of carboxy groups and ammonium salts of carboxy groups. One type or two or more types of the anionic group may be contained in the component (B).
If the water-insoluble resin does not have an anionic group, an organic-inorganic composite dispersion with good dispersion stability cannot be obtained.
Anionic groups are carboxy group, sulfonic acid group, amine salt of carboxy group, ammonium salt of carboxy group, amine salt of sulfonic acid group, ammonium salt of sulfonic acid group, sodium salt of sulfonic acid group, potassium of sulfonic acid group A salt is preferable, and a carboxy group, an amine salt of a carboxy group, and an ammonium salt of a carboxy group are more preferable.

  The acid value of the water-insoluble resin (B) having an anionic group in the present invention is not particularly limited, but is preferably 1 mgKOH / g to 100 mgKOH / g from the viewpoint of storage stability of the organic-inorganic composite dispersion. It is more preferably 5 mgKOH / g to 50 mgKOH / g, and further preferably 10 mgKOH / g to 40 mgKOH / g.

  A water-insoluble resin having an anionic group is a polymer that is insoluble in water and a mixed solvent of water and an organic solvent having an affinity for water (aqueous medium), that is, dispersed in the form of particles in water (emulsification). It may be a polymer, a copolymer obtained by polymerizing a hydrophobic monomer, or a copolymer with a hydrophilic monomer. Such particles can be measured for particle size by, for example, a light scattering method.

  The water-insoluble resin having an anionic group in the present invention is not limited as long as it becomes particles that can be dispersed in an aqueous medium. Polyolefin, poly (meth) acrylate, polystyrene, polyurethane, polyacrylonitrile, polyvinyl chloride , Polyvinylidene chloride, polyvinyl acetate, polybutadiene, polyester, polyamide, AS resin, ABS resin, polyvinyl butyral, epoxy resin, phenol resin, urea resin, melamine resin, diallyl phthalate resin, silicone resin, fluorine resin, polycarbonate, acetal resin , Polyphenylene oxide, polyphenylene sulfide, polyimide, polysulfone, polyethersulfone, polyarylate and the like. The water-insoluble resins having an anionic group may be used alone or as a mixture of two or more.

  Among these, a water-insoluble resin selected from polyolefin, poly (meth) acrylic ester, polystyrene, polyurethane, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, and polybutadiene is preferable. Acrylonitrile and polyvinylidene chloride are preferred because of their excellent lipophilic function among hydrophilic lipophilic functions.

  A water-insoluble resin having an anionic group can be prepared by a method of synthesizing resin particles from dispersed monomers such as an emulsion polymerization method, a suspension polymerization method, a mini-emulsion polymerization method, a dispersion polymerization method, and an emulsion dispersion method. It is obtained by emulsifying and synthesizing polymerized resin particles and resin particle solutions, and by polymerizing monomers in the presence of particles called seed polymerization, and at this time water-insoluble with an anionic group The resin is made into particles and an aqueous dispersion can be obtained.

  The emulsion polymerization method is a method of polymerizing a water-insoluble monomer using a raw material composed of a water-insoluble monomer, an emulsifier, water, and a polymerization initiator. The emulsifier forms micelles that form particles in water as a continuous phase, and has a role of stably dispersing the generated water-insoluble resin particles, and is used by ionic emulsifiers or nonionic emulsifiers or both. Is done. As the polymerization initiator, a water-soluble peroxide or a water-soluble azo compound is used, and a redox initiator system such as ascorbic acid-hydrogen peroxide is used.

  In the suspension polymerization method, a water-insoluble polymerization initiator is dissolved in a water-insoluble monomer, and this is suspended in water by mechanical stirring and heated. This is a method for obtaining a dispersion of water-soluble resin particles. Stirring with high-speed shear is indispensable for the formation of monomer droplets, and microdroplets can be stabilized by selecting a dispersion stabilizer.

  The mini-emulsion polymerization method is a method in which monomer droplets are refined to sub-micron size by applying a strong shearing force with an ultrasonic oscillator, etc., to stabilize the refined monomer oil droplets. A water-insoluble substance called hydrophobe is added. Compared with the above-described emulsion polymerization method, it is not necessary for the monomer to diffuse in the aqueous phase during polymerization, and ideally, monomer oil droplets are polymerized to change into water-insoluble resin particles.

  The dispersion polymerization method is a method used in the case of a water-insoluble resin in which the monomer is soluble in water but becomes insoluble in water after polymerization. A dispersion stabilizer for the water-insoluble resin is added to the system.

  The emulsion dispersion method is a method of preparing a dispersion of a water-insoluble resin such as polyurethane, polyethylene, polyester, polybutene, and epoxy resin that cannot be radically polymerized, such as emulsion polymerization or suspension polymerization. And transfer emulsification method.

  In the forced emulsification method, a polymer solution or a polymer melted by heat is dispersed in an aqueous dispersion medium containing a dispersion stabilizer using a high-pressure homogenizer, a high-pressure homomixer, an extrusion kneader, an autoclave, or the like. Examples thereof include a method and a method of spraying from pores.

  The self-emulsification method is a method of easily emulsifying and dispersing by mixing with water due to the emulsifying ability of the anionic group of the water-insoluble resin itself. Since the resin can be polymerized without using a dispersion stabilizer, the method is preferably used in the present invention.

  In the phase inversion emulsification method, water is gradually added by dissolving an emulsifier in a water-insoluble resin solution and gradually adding water, or by gradually adding an aqueous emulsifier solution in the resin solution and stirring and mixing. This is a method for producing a dispersion (C) which is a continuous phase. When mixing of the organic solvent into the dispersion is not preferable, the organic solvent can be removed by distillation or the like.

  In preparing the dispersion (C), a filtration step may be provided in the process for the purpose of removing foreign substances and the like. In such a case, for example, a stainless steel filter (wire diameter 0.035 mm, plain weave) of about 300 mesh may be installed and pressure filtration (air pressure 0.2 MPa) may be performed.

  Water in the case of preparing the dispersion (C) is not particularly limited, and distilled water, ion exchange water, city water, industrial water, and the like can be used, but it is preferable to use distilled water or ion exchange water. . In addition, the organic solvent having an affinity for water in the above method is not particularly limited as long as the other dispersoid is soluble. For example, isopropyl alcohol, acetone, acetonitrile, methanol, ethanol, dimethyl sulfoxide, dimethylformamide. Etc. If it is not preferable to mix the organic solvent into the dispersion, the organic solvent can be removed by distillation or the like after preparing a dispersion containing the other dispersoid.

  Hereinafter, polyurethane resin particle dispersion, polystyrene and polyacrylate resin particle dispersion, and polyvinylidene chloride resin as a dispersion of water-insoluble resin using a resin suitable as an anionic water-insoluble resin The particle dispersion is described in detail.

[Polyurethane resin particle dispersion]
[Polyurethane resin (i)]
The polyurethane-based water-insoluble resin (i) preferably used in the present invention constitutes an anionic self-emulsifying polyurethane resin, has a high total concentration of urethane groups and urea groups, and has an anionic group. The polyurethane resin can be obtained by a reaction of a polyisocyanate compound (ii) containing at least one selected from the group of aromatic, araliphatic and alicyclic polyisocyanates with a polyhydroxy acid (iii). it can. The polyurethane resin may further be a copolymer obtained by reaction with other components, for example, 30% by weight of at least one selected from the group of aromatic, araliphatic and alicyclic polyisocyanates. % Or more of the polyisocyanate compound (ii), the polyhydroxy acid (iii), and at least one component selected from the polyol component (iv) and the chain extender component (v). The (ii) polyisocyanate compound may contain at least one selected from xylylene diisocyanate and hydrogenated xylylene diisocyanate. The polyol component (iv) may be a polyol compound containing 90% by weight or more of a polyol having 2 to 8 carbon atoms, and the chain extender component (v) is selected from, for example, diamine, hydrazine and hydrazine derivatives. At least one kind.

  The total concentration of urethane groups and urea groups (urea groups) in the polyurethane resin is about 25 to 60% by weight (for example, 30 to 55% by weight), preferably about 35 to 55% by weight (particularly 35 to 50% by weight). . The urethane group concentration and the urea group concentration are the molecular weight of the urethane group [59 g / equivalent] or the molecular weight of the urea group [primary amino group (amino group): 58 g / equivalent, secondary amino group (imino group): 57 g / Equivalent value] is divided by the molecular weight of the repeating structural unit structure. In the case of using a mixture, the concentration of the urethane group and urea group can be calculated based on the charge base of the reaction components, that is, the use ratio of each component.

  Examples of the anionic group of the polyurethane resin include acid groups such as a carboxyl group and a sulfonic acid group as described above. The anionic group may be located at the terminal or side chain (particularly at least the side chain) of the polyurethane resin. This anionic group may be in a form in which the acid group is neutralized by a neutralizing agent (base), or in a form in which the acid group forms a salt with the base.

  As the neutralizing agent, conventional bases such as organic bases [eg, tertiary amines (tri-C1-4 alkylamines such as trimethylamine and triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, triisopropanolamine, etc. Alkanolamines, heterocyclic amines such as morpholine)], inorganic bases [ammonia, alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (sodium carbonate, potassium carbonate) Etc.)]. These bases can be used alone or in combination of two or more. From the lipophilic viewpoint, volatile bases, for example, tri-C1-3 alkylamines such as triethylamine, alkanolamines such as dimethylethanolamine, and ammonia are preferable.

  The degree of neutralization with the neutralizing agent may be, for example, 30 to 100%, preferably 50 to 100%, particularly about 75 to 100%.

  The number average molecular weight of the polyurethane resin (i) can be selected from the range of about 800 to 1,000,000, preferably 800 to 200,000, and more preferably about 800 to 100,000.

  Such a polyurethane resin (i) can be obtained by a reaction of at least a polyisocyanate compound (ii) (particularly a diisocyanate compound) and a polyhydroxy acid (iii) (for example, a polyhydroxyalkanoic acid, particularly a dihydroxy acid). The polyurethane resin (i) comprises, in addition to the components (ii) and (iii), a polyol component (iv) (particularly a diol component such as alkylene glycol) and a chain extender (v) (particularly a bifunctional chain extender). It can also be obtained by reaction with at least one component selected from

[Polyisocyanate compound (ii)]
The polyisocyanate compound (ii) includes aromatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, aliphatic polyisocyanates, and the like. As the polyisocyanate compound, a diisocyanate compound is usually used.

  Examples of aromatic diisocyanates include tolylene diisocyanate (TDI), phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (MDI), and 4,4′-toluidine. Examples thereof include diisocyanate (TODI) and 4,4′-diphenyl ether diisocyanate.

  Examples of the araliphatic diisocyanate include xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and ω, ω′-diisocyanate-1,4-diethylbenzene.

  Examples of alicyclic diisocyanates include 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorodiisocyanate, IPDI), methylene bis (cyclohexyl isocyanate) (hydrogenated MDI (H12MDI ), Dicyclohexylmethane diisocyanate), methylcyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane (hydrogenated XDI), and the like.

  Examples of the aliphatic diisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl capate.

  As the polyisocyanate compound (particularly diisocyanate compound) (ii), it is preferable to use a polyisocyanate compound containing a compound having a hydrocarbon ring. Examples of such compounds include aromatic, araliphatic and alicyclic polyisocyanates (particularly diisocyanates). More specifically, from the viewpoint of lipophilicity, aromatic diisocyanates (TDI, MDI, NDI, etc.), araliphatic diisocyanates (XDI, TMXDI, etc.) and alicyclic diisocyanates (IPDI, hydrogenated XDI, hydrogenated MDI). MDI, XDI, hydrogenated XDI, hydrogenated MDI and the like are particularly preferable. These polyisocyanate compounds can be used alone or in combination of two or more.

  The content of at least one polyisocyanate compound selected from aromatic, araliphatic and alicyclic polyisocyanates is 30% by weight or more (30 to 100% by weight, preferably based on the whole polyisocyanate compound (ii). Is 50 to 100% by weight, more preferably 70 to 100% by weight.

  The polyisocyanate compound (ii) preferably contains at least one selected from xylylene diisocyanate and hydrogenated xylylene diisocyanate. The proportion of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate is usually 20% by weight or more (20 to 100% by weight), preferably 25 to 100% by weight, more preferably 30 to 100%, based on the whole polyisocyanate compound. % By weight.

  These diisocyanate components can be used singly or in combination of two or more, and a tri- or higher functional polyisocyanate can be used in combination as required.

[Polyhydroxy acid (iii)]
As the polyhydroxy acid (iii), at least one organic acid selected from carboxylic acids and sulfonic acids, in particular, polyhydroxycarboxylic acids and polyhydroxysulfonic acids can be used.

  Examples of the polyhydroxycarboxylic acid (particularly dihydroxycarboxylic acid) include dihydroxy C2-10 alkane-carboxylic acid such as dimethylolpropionic acid, dimethylolbutanoic acid and 2,2-dimethylolhexanoic acid, and dihydroxyC4 such as dioxymaleic acid. Examples include -10 alkane-polycarboxylic acid, dihydroxy C4-10 alkene-polycarboxylic acid, and dihydroxy C6-10 arene-carboxylic acid such as 2,6-dihydroxybenzoic acid. These polyhydroxy acids can be used alone or in combination of two or more. Preferred polyhydroxy acids are polyhydroxyalkane carboxylic acids, especially dihydroxy alkanoic acids such as dihydroxy C2-8 alkane-carboxylic acids.

  The polyhydroxy acid may be used in the form of a salt. Examples of polyhydroxy acid salts include ammonium salts, amine salts (such as trialkylamine salts), metal salts (such as sodium salts), and the like.

  The polyurethane resin (i) can be obtained by reaction with at least the components (ii) and (iii), but is combined with at least one selected from the polyol component (iv) and / or the chain extender component (v). In many cases. In addition, the acid value of polyurethane resin (i) can be adjusted with the usage-amount of the said polyhydroxy acid (iii).

[Polyol component (iv)]
The polyol component (particularly diol component) (iv) is usually a low molecular weight glycol such as alkylene glycol (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1) from the viewpoint of lipophilicity. , 4-butanediol, pentanediol, hexanediol, neopentylglycol, heptanediol, octanediol and other linear or branched C2-10 alkylene glycol), (poly) oxy C2-4 alkylene glycol (diethylene glycol, triethylene glycol) Ethylene glycol, tetraethylene glycol, dipropylene glycol, etc.) are used. Preferred glycol components are C2-8 polyol components [eg C2-8 alkylene glycol (especially ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol)], di- or trioxy C2-3 alkylene glycol (diethylene glycol, triethylene glycol, dipropylene glycol, etc.), and particularly preferred diol components are C2-8 alkylene glycol (especially C2). -6 alkylene glycol).

  These diol components can be used alone or in combination of two or more. Furthermore, you may use together low molecular weight diol components, such as an aromatic diol and an alicyclic diol, as needed. Furthermore, if necessary, a tri- or higher functional polyol component can be used in combination.

  The polyol component preferably contains at least a C2-8 polyol component (particularly a C2-6 alkylene glycol) and / or a di- or trioxy C2-3 alkylene glycol component. The ratio of the C2-8 polyol component (especially C2-6 alkylene glycol) and the di- or trioxy C2-3 alkylene glycol to the entire polyol component is usually 90% by weight or more (90% by weight to 100% by weight).

[Chain extender (v)]
As the chain extender, at least one selected from nitrogen-containing compounds having an active hydrogen atom, particularly diamine, hydrazine and hydrazine derivatives is used. Examples of the diamine component as a chain extender include aliphatic amines (for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4 , 4-trimethylhexamethylenediamine, C2-10 alkylenediamine such as octamethylenediamine, etc.), aromatic amines (eg, m- or p-phenylenediamine, 1,3- or 1,4-xylylenediamine or mixtures thereof) ), Alicyclic amines (for example, hydrogenated xylylenediamine, bis (4-aminocyclohexyl) methane, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, etc.), hydroxyl group-containing diamine [2- [(2′-amino Amino C2-6 alkylamino C2-3 alkyl such as ethyl) amino] ethanol, 2-aminoethylaminopropanol, 2- (3′-aminopropyl) aminoethanol (3- (2′-hydroxyethyl) aminopropylamine) Alcohol, etc.].

  Examples of the hydrazine and hydrazine derivatives include hydrazine, hydroxyl group-containing hydrazine (hydrazino C2-3 alkyl alcohol such as 2-hydrazinoethanol), dicarboxylic acid hydrazide [aliphatic dicarboxylic acid hydrazide (succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid). Dihydrazide, C4-20 alkane-dicarboxylic acid dihydrazide such as dodecanedioic acid dihydrazide), aromatic dicarboxylic acid hydrazide (C6-10 arene-dicarboxylic acid hydrazide such as isophthalic acid dihydrazide) and the like. These chain extender components can be used alone or in combination of two or more.

  Among these chain extenders, from the viewpoint of lipophilicity, usually a low molecular weight chain extender having 8 or less carbon atoms (C2-8, especially C2-6), for example, diamine (for example, ethylenediamine, tetramethylenediamine, pentane). C2-6 alkylenediamine such as methylenediamine and hexamethylenediamine, 2-aminoethylaminoethanol, xylylenediamine, etc.), hydrazine, hydrazine derivatives (for example, 2-hydrazinoethanol, adipic acid dihydrazide, etc.) are used. In addition, the chain extender can use triamine or more polyamine components (polyamine, polyhydrazide, etc.) together as needed.

  If necessary, a compound having reactivity with an isocyanate group (for example, polyester diol, polyether diol, etc.) may be reacted in preparation of the polyurethane resin.

[Method for preparing polyurethane resin particle dispersion]
Although the manufacturing method of polyurethane resin (i) is not specifically limited, It can prepare using a normal self-emulsification method. In the urethanization reaction, a urethanization catalyst such as an amine catalyst, a tin catalyst, or a lead catalyst may be used as necessary. More specifically, a polyisocyanate compound (ii), a polyhydroxy acid (iii) and, if necessary, a polyol component (iv) are reacted in an inert organic solvent (in particular, a hydrophilic or water-soluble organic solvent) A prepolymer having an isocyanate group is formed, and if necessary, the acid group of the polyurethane resin is neutralized with a neutralizing agent and dispersed in an aqueous medium, and then a chain extender component (v) is added and reacted as necessary. A polyurethane resin dispersion can be prepared by removing the organic solvent. The volume average particle diameter of the polyurethane resin dispersion is preferably 0.01 μm to 1 μm from the viewpoint of film forming properties and lipophilicity.

  In addition, the total amount ratio of each component having an active hydrogen atom [polyhydroxy acid (iii), polyol component (iv) and chain extender component (v)] is 1 mol of isocyanate group of polyisocyanate compound (ii). The total amount of each component (iii), (iv) and (v) active hydrogen atom (or an organic group having an active hydrogen atom) is 0.5 mol to 1.5 mol, preferably 0.7 mol to 1. mol. It is about 3 mol, more preferably about 0.8 mol to 1.2 mol.

[Polystyrene and polyacrylate resin particle dispersion]
The polystyrene and polyacrylic ester resin particle dispersion is obtained by emulsion polymerization of styrene, acrylic ester and vinyl monomer. The volume average particle size of the polystyrene and polyacrylic ester particle dispersion is 0.01 μm to It is 1 micrometer, and 0.01 micrometer-0.5 micrometer are preferable from the surface of film forming property and lipophilicity. The volume average particle diameter is a value measured using Microtrac UPA (Honeywell).

  The vinyl monomer used in the present invention is not particularly limited, and specific examples thereof include monomers usually used for radical polymerization, such as methyl-, ethyl-, Isopropyl-, n-butyl-, isobutyl-, n-amyl-, isoamyl-, n-hexyl-, 2-ethylhexyl-, octyl-, decyl-, dodecyl-, octadecyl-, cyclohexyl-, phenyl-, benzyl-, etc. Acrylic acid esters or methacrylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; acrylonitrile, methacrylonitrile, etc .; α-methylstyrene, 2-methylstyrene, vinyltoluene, t-butylstyrene , Chlorostyrene, vinyl anisole, vinyl naphthalene, divinylbenzene Aromatic vinyls; acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, diacetone acrylamide and other amide groups; epoxy derivatives such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether; N-methyl Alkylamino esters of acrylic acid or methacrylic acid such as aminoethyl acrylate, N-methylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate and dimethylaminopropyl methacrylate; monovinylpyridines such as vinylpyridine Vinyl ethers having an alkylamino group such as dimethylaminoethyl vinyl ether; N- (2-dimethyl); Amides having an alkylamino group such as tilaminoethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide; having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid Such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, etc. Saturated sulfonates: ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol Diacrylate esters or dimethacrylates such as dimethacrylate; vinylidene chloride, vinylidene halide such as vinylidene fluoride; other ethylene, propylene, isoprene, butadiene, vinyl pyrrolidone, vinyl chloride, vinyl amides, a chloroprene. These vinyl monomers can be used alone or in combination of two or more.

  Among these vinyl monomers, acrylic acid esters, methacrylic acid esters, carboxyl group-containing compounds, amide group-containing compounds, and hydroxyl group-containing compounds are more preferable, and acrylic acid esters and carboxyl group-containing compounds are preferred. A combination of classes is most preferred.

  Production of the polystyrene and polyacrylate resin dispersion used in the present invention is carried out by a conventional emulsion polymerization method. As the surfactant used, sodium alkylbenzene sulfonate, sodium alkyl sulfate, sodium dialkyl sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium alkyl naphthalene sulfonate, sodium naphthalene sulfonate, Anionic surfactants such as potassium oleate, alkyl diphenyl ether sodium disulfonate, ammonium polyoxyethylenepropenyl alkylphenyl sulfate; fatty acid monoglyceride, sorbitan fatty acid ester, sugar fatty acid partial ester, polyglycerin fatty acid partial ester, polyoxyethylene alkyl ether, Polyoxyethylene alkyl phenyl ether, polyoxy Ethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyoxyethylene glycerin fatty acid partial ester, polyoxyethylene fatty acid amine, polyoxyethylene (cured) castor oil, polyoxyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene Nonionic surfactants such as block copolymers, hydroxyethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, and methylcellulose; amphoteric surfactants such as alkylammonium chloride, trimethylalkylammonium bromide, alkylpyridinium chloride, and casein; water-soluble polyvalent metals Examples include salts. These surfactants can be used singly or in combination of two or more.

  Any polymerization initiator may be used as long as it is used in ordinary emulsion polymerization. For example, peroxides such as potassium persulfate and sodium persulfate, organic peroxides such as benzoyl peroxide, azobisisobutyrate. Azo compounds such as ronitrile. If necessary, it can also be used as a redox initiator in combination with a reducing agent.

  In order to produce an emulsion, polymerization is usually carried out by adding vinyl monomers all at once, in a divided manner or continuously in the presence of the aforementioned surfactant and polymerization initiator.

The particle size of the emulsion is controlled by the amount of surfactant and polymerization initiator used. Increasing the amount of surfactant used decreases the particle size, and decreasing the amount of polymerization initiator decreases the particle size.
Further, the weight average molecular weight is controlled by the amount of the chain transfer agent, and the weight average molecular weight decreases as the amount of the chain transfer agent is increased.

  Examples of the basic substance used for neutralization of the emulsion obtained as described above include the neutralizing agents described above.

If necessary, a cross-linking agent may be added to the polystyrene and polyacrylic ester resin dispersion used in the present invention. Examples of the cross-linking agent include polyvalent metal ions, ammonia of polyvalent metal ions, and amine complexes (particularly NH ₃ coordinated). The polyvalent metal ion can be added to the composition in the form of an oxide, hydroxide or basic salt, acidic salt or neutral salt having a remarkable solubility of at least about 1% by weight in water. Beryllium, cadmium, copper, calcium, magnesium, zinc, zirconium, barium, strontium, aluminum, bismuth, antimony, lead, cobalt, iron, nickel, or other multivalent metal ions. Examples of amines that can form ammonia complexes and amine complexes of the polyvalent metal ions include morpholine, monoethanolamine, diethylethanolamine, and ethylenediamine. Moreover, the polyvalent metal complex salt of the organic acid which can be solubilized in alkaline pH range can also be used. In addition, anions such as acetate ion, glutamate ion, formate ion, carbonate ion, salicylate ion, glycolate ion, octoate ion, benzoate ion, gluconate ion, oxalate ion and lactate ion are also used. A polyvalent metal chelate whose ligand is a bidentate amino acid such as glycine or alanine is also used. Other crosslinking agents include urea resin-based crosslinking agents such as alkylated melamine, epoxy-based crosslinking agents, isocyanate-based crosslinking agents, carbodiimide-based crosslinking agents, hydrazide-based crosslinking agents, etc., and those obtained by making these crosslinking agents aqueous. Can be mentioned.

[Polyvinylidene chloride resin particle dispersion]
The polyvinylidene chloride resin particle dispersion used in the present invention is composed of vinylidene chloride, methacrylonitrile, 2-hydroxyethyl acrylate and one or more vinyl monomers copolymerizable therewith. Can be produced according to the method described in 1. The preferred range of vinylidene chloride is 89% to 93%, preferably 90% to 92%, methacrylonitrile is 2% to 8%, preferably 4% to 6%. 2-hydroxyethyl acrylate is 0.5 wt% to 3 wt%, preferably 1 wt% to 2 wt% and 0 wt% to 3 wt% of one or more vinyl monomers copolymerizable therewith It is obtained from the body by emulsion polymerization.

  There are no particular restrictions on the type of emulsifier, polymerization initiator, surfactant, etc. used for the polymerization of the polyvinylidene chloride resin particle dispersion, but the amount used is preferably as small as possible. It is further desirable to remove as much as possible by applying. In addition, it is known that the stability to heat and light is inferior at low molecular weights, and the discoloration resistance is recognized to have a parallel relationship with these stability, so the molecular weight is a weight average measured by gel permeation chromatography. The molecular weight is desirably 100,000 or more.

  Here, the dispersion mode of the dehydrated condensate (A1) of fine metal hydroxide in the organic-inorganic composite dispersion of the present invention and the particles of the water-insoluble resin (B) having an anionic group is shown in FIGS. This will be described with reference to FIG.

FIG. 1 is a schematic view showing an example of a dispersion mode of the organic-inorganic composite dispersion of the present invention. FIG. 1 is a cross-sectional view assuming that the organic-inorganic composite dispersion of the present invention is vertically split.
As shown in FIG. 1, the organic-inorganic composite dispersion of the present invention has an anionic group in which fine-particle metal hydroxide dehydration condensate (A1) 4 is present as emulsion particles in the organic-inorganic composite dispersion. It adheres so that the particle | grains 2 of the water-insoluble resin (B) which has may be coat | covered, and it contains in an organic inorganic composite dispersion liquid. The fine particles of the metal hydroxide dehydration condensate (A1) 4 may all be attached to the particles 2 of the water-insoluble resin (B) having an anionic group, or a part thereof may be attached. .

The dispersion mode of the organic-inorganic composite dispersion of the present invention described in FIG. 1 can be observed by a TEM photograph.
FIG. 2 is a TEM image of the diluted organic / inorganic composite dispersion of the present invention, which was developed on a TEM observation support film and used as an observation specimen. FIG. 3 shows an organic-inorganic composite dispersion prepared without going through a heating step in the method for producing an organic-inorganic composite dispersion (hereinafter also referred to as “non-heated composite dispersion”) and then developed on a support film for TEM observation. This is a TEM image of an observation specimen.

FIG. 2 showing the dispersion state of the organic-inorganic composite dispersion of the present invention shows a dehydrated condensate (A1) of small metal hydroxide around the water-insoluble resin (B) particles having a large anionic group. Particles 6 in a state where the fine particles are adhered are confirmed. In addition, fine particles 4 of the metal hydroxide dehydration condensate (A1) are scattered around the particles 6. Since the particles 6 are black and dark, the particles of the water-insoluble resin (B) having an anionic group are covered with many fine particles of the dehydration condensate (A1) of metal hydroxide. I understand.
On the other hand, in FIG. 3 showing the dispersion state of the non-heated composite dispersion, only the particles 2 of the water-insoluble resin (B) having a large anionic group are confirmed. It is confirmed that the product (A1) is hardly present. The fine particles of the metal hydroxide dehydration condensate (A1) are slightly confirmed in the TEM image of FIG. 3. The unheated composite dispersion is spread on the support film for TEM observation and irradiated with an electron beam. It is considered that the dehydration condensate (A1) of the metal hydroxide that was linear in the non-heated composite dispersion aggregates in the process of concentrating the dispersion medium.

  As described above, fine particles of the metal hydroxide dehydration condensate (A1) 4 are confirmed in the organic-inorganic composite dispersion of the present invention, but the metal hydroxide dehydration condensate ( A1) Fine particles of 4 are not confirmed.

[Liquid (pH)]
A composition containing a metal alkoxide or metal hydroxide and a water-insoluble resin generally has poor dispersion stability and tends to thicken, but the organic-inorganic composite dispersion of the present invention has a water-insoluble resin having an anionic group. By containing, the dispersion stability of the dispersion is improved, and the viscosity of the dispersion can be kept low by setting the liquid property of the dispersion to pH 1 to pH 5.

  The liquid property of the organic-inorganic composite dispersion liquid of the present invention is preferably pH 2 to pH 4 and more preferably pH 2.5 to pH 3.5 from the viewpoint of suppressing the viscosity increase of the dispersion liquid.

[Quantity ratio of component (A1) to component (B)]
Quantity ratio of dehydration condensate (A1) of metal hydroxide as component (A1) and water-insoluble resin (B) having an anionic group as component (B) in the organic-inorganic composite dispersion of the present invention (Weight basis) is preferably from 99: 1 to 1:99, more preferably from 95: 5 to 5:95, from the viewpoint of contact angle with water and n-hexadecane, More preferably, it is 90: 10-10: 90.

[Dispersion medium of organic-inorganic composite dispersion]
In the organic-inorganic composite dispersion of the present invention, the dispersion medium for dispersing the dehydration condensate (A1) of metal hydroxide and the water-insoluble resin (B) having an anionic group is mainly water. An aqueous solvent or alcohol can also be used.
As said alcohol, methanol, ethanol, 1-propyl alcohol, 2-propyl alcohol, etc. can be used. As the aqueous solvent, water or a liquid obtained by mixing water and alcohol, acid, base, etc. dissolved in water can be used.
Alcohol, acid, base and the like are preferably added so that the dispersion stability of the organic-inorganic composite dispersion does not become unstable.

〔Particle size〕
In the organic-inorganic composite dispersion of the present invention, the particle sizes of the fine particles of the metal hydroxide dehydrated condensate (A1) and the water-insoluble resin (B) having an anionic group are as shown in FIGS. The size obtained as a particle diameter (maximum diameter) measured from a TEM image of an observation specimen developed after diluting the organic-inorganic composite dispersion liquid as described above.

The fine particles of the metal hydroxide dehydration condensate (A1) are anionic to improve the hydrophilicity and lipophilicity of the organic-inorganic composite membrane obtained by applying and drying the organic-inorganic composite dispersion of the present invention on a support. It is preferably 0.1% to 60% of the particle diameter of the water-insoluble resin (B) having a functional group.
The particle diameter of the water-insoluble resin (B) having an anionic group is preferably 0.05 μm to 1 μm, and more preferably 0.06 μm to 0.5 μm.

〔viscosity〕
The viscosity of the organic-inorganic composite dispersion of the present invention is 0.1 mPa · s to 100 mPa · s from the viewpoint of production of an organic-inorganic composite film, more specifically, application of the organic-inorganic composite dispersion onto a support. It is necessary to be.
The viscosity of the organic-inorganic composite dispersion of the present invention is preferably 0.5 mPa · s to 50 mPa · s, and more preferably 1 mPa · s to 10 mPa · s.

[Method for producing organic-inorganic composite dispersion]
In the method for producing an organic-inorganic composite dispersion according to the present invention, a dispersion containing particles of a water-insoluble resin (B) having an anionic group is mixed with an alcohol solution or an aqueous solution of a metal alkoxide (a) to a pH of 7 A first mixed solution preparing step of preparing a first mixed solution of pH 10; a second mixed solution preparing step of preparing a second mixed solution of pH 1 to pH 5 by adding an acid catalyst to the first mixed solution; A heating step of heating the second mixed liquid to 30 ° C to 90 ° C. The heating temperature is preferably 35 ° C. or higher, more preferably 40 ° C. or higher.

  In the first mixed liquid preparation step, a dispersion (hereinafter referred to as “dispersion d”) containing particles of a water-insoluble resin (B) having an anionic group in an alcohol solution or an aqueous solution of the metal alkoxide (a). To prepare a first mixed solution of pH 7 to pH 9.

-Metal alkoxide (a)-
In the present invention, the metal alkoxide (a) is a compound represented by the following formula (1). Hereinafter, “metal alkoxide (a)” is also referred to as “component (a)”.

(R ¹ ) _x M (OR ² ) _y (1)

In the formula (1), R ¹ is a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), an aryl group (for example, a phenyl group, a tolyl group, etc.), or a carbon-carbon double bond. An organic group (for example, an acryloyl group, a methacryloyl group, a vinyl group, or the like) or a halogen-containing group (for example, a halogenated alkyl group such as a chloropropyl group or a fluoromethyl group) is represented.
R ² represents a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
x and y represent integers such that x + y = 4 and x ≦ 2.

M is a metal constituting the metal alkoxide (a), and examples thereof include the same metals as those constituting the metal hydroxide. The metal which comprises metal alkoxide (a) may be comprised individually or in 2 types or more.
Of these, Si, Al, Zr, Ti and the like are preferably used. Among these, silicon compounds are relatively inexpensive and easy to obtain, and the reaction proceeds slowly, so that the industrial utility value is high.

  Specifically, the metal alkoxide (a) includes tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetrapropoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxy Silane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-s Riltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane , Alkoxysilanes such as 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, and the corresponding alkoxyaluminum, alkoxyzirconium, and alkoxytitanium. Can be mentioned.

  In the present invention, the metal alkoxide (a) is an alkoxysilane in which M is silicon (Si), alkoxyzirconium in which M is zirconium (Zr), and alkoxy in which M is aluminum (Al). Aluminum and alkoxytitanium in which M is titanium (Ti) are preferable, and alkoxysilane in which M is silicon (Si) is particularly preferable.

  The metal alkoxide (a) may be replaced with another compound capable of forming a dehydration condensate (A1) of metal hydroxide, which is a constituent of the organic-inorganic composite dispersion of the present invention. It is most preferable to use the metal alkoxide (a) from the viewpoints of properties and reaction rate. Examples of other compounds capable of generating the metal hydroxide dehydration condensate (A1) include metal halides, metal diketonates, metal acetates, and metal carboxylates.

In the first mixed liquid preparation step in the method for producing an organic-inorganic composite dispersion of the present invention, the metal alkoxide is used as an alcohol solution or an aqueous solution. This is to promote the hydrolysis reaction of the metal alkoxide.
As said alcohol, methanol, ethanol, 1-propyl alcohol, 2-propyl alcohol, etc. can be used. As an aqueous solvent for preparing the aqueous solution, water or a liquid obtained by mixing water and alcohol, acid, base, etc. dissolved in water can be used.
Alcohol, acid, base and the like are preferably added so that the dispersion stability of the first mixed solution does not become unstable.

In the first mixed solution preparation step, when an alcohol solution of the metal alkoxide (a) is used, the metal alkoxide (a) is preferably added in an amount of 1 to 1000 parts by weight with respect to 100 parts by weight of the alcohol. It is more preferable to add part by weight to 500 parts by weight.
When an aqueous solution of the metal alkoxide (a) is used, the metal alkoxide (a) is preferably added in an amount of 1 to 1000 parts by weight with respect to 100 parts by weight of the aqueous solvent, and 10 to 500 parts by weight. It is more preferable to add part.

In the first mixed liquid preparation step in the method for producing an organic-inorganic composite dispersion of the present invention, a water-insoluble solution having an anionic group in an alcohol solution or an aqueous solution containing the metal alkoxide (a) obtained as described above. The dispersion liquid (d) containing particles of the functional resin (B) is mixed to prepare a first mixed liquid having a pH of 7 to 10.
Mixing the alcohol solution or aqueous solution containing the metal alkoxide (a) with the dispersion liquid (d) should be gently mixed with stirring at room temperature so that the dispersion stability of the first liquid mixture does not become unstable. Is preferred.
The dispersion liquid (d) containing the water-insoluble resin (B) particles having an anionic group can be prepared as an emulsion of resin particles as described above.

  Here, the amount ratio (weight basis) of the metal alkoxide (a) and the water-insoluble resin (B) having an anionic group is such that a: B is based on weight from the viewpoint of contact angle with water and n-hexadecane. 99.9: 0.1 to 0.1: 99.9 is preferable, 99.5: 0.5 to 0.5: 99.5 is more preferable, and 99: 1 to 1 is more preferable. : 99 is more preferable.

Moreover, in order to adjust the liquid property of the first mixed solution to pH 7 to pH 10, a known acid (for example, aqueous hydrochloric acid solution) and a known base (for example, aqueous ammonia solution, aqueous sodium hydroxide solution, etc.) are used as appropriate. Can be adjusted. When adding an acid and a base to a 1st liquid mixture for liquid property adjustment, it is preferable to carry out, stirring at room temperature.
The liquid property of the first mixed solution is preferably pH 7.5 to pH 9, and more preferably pH 7.8 to pH 8.5.

In the method for producing an organic-inorganic composite dispersion of the present invention, in the second mixed solution preparing step, an acid catalyst is added to the first mixed solution to prepare a second mixed solution having a pH of 1 to pH 5.
By adding an acid catalyst to the first mixed solution, the reaction in the hydrolysis / condensation reaction of the metal alkoxide (a) is promoted.
In the second mixed liquid preparation step, if the acid catalyst is not added to the first mixed liquid, the first mixed liquid thickens and gels, so that the target organic-inorganic composite dispersion cannot be produced. An inorganic composite film cannot be manufactured.

  What is used as an acid catalyst for metal alkoxides (a) is “the latest functional sol-gel fabrication technology by sol-gel method” (by Hirashima Satoshi, General Technology Center Co., Ltd., page 29) and “Science of sol-gel method” ”(Sakuo Sakuo, Agne Jofu Co., Ltd., page 154) and the like, and is an acid catalyst used in a general sol-gel reaction.

  Specific examples include inorganic and organic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, succinic acid, tartaric acid, and toluenesulfonic acid.

  The liquid property of the second mixed solution is preferably pH 2 to pH 4, and more preferably pH 2.5 to pH 3.5.

  From the viewpoint of reactivity, it is preferable to use hydrochloric acid, nitric acid, or the like, in which the reaction proceeds relatively gently. The amount of the acid catalyst used is preferably 0.001 mol to 0.05 mol, more preferably 0.001 mol to 0.04 mol, based on 1 mol of the metal alkoxide (a). More preferably, the content is 0.001 mol to 0.03 mol.

In the manufacturing method of the organic-inorganic composite dispersion of the present invention, in the heating step, the second mixed solution obtained in the second mixed solution preparing step is heated to 30 ° C. to 90 ° C.
By heating the second mixed liquid to 30 ° C. to 90 ° C., the hydrolysis and dehydration condensation reaction of the metal alkoxide (a) can be facilitated, and the dehydration condensate (A1) of the metal hydroxide is generated. It becomes easy.

The heating temperature of the second mixed liquid is preferably 35 ° C. to 80 ° C., more preferably 38 ° C. to 75 ° C., from the viewpoint of the reaction rate of hydrolysis of the metal alkoxide (a) and dehydration condensation reaction. .
Moreover, although the heating time of a 2nd liquid mixture is suitably adjusted from the relationship with heating temperature, it is preferable that it is 1 minute-240 minutes, and it is more preferable that it is 5 minutes-180 minutes.
A preferable combination of heating temperature and heating time is preferably heating at 35 ° C. to 80 ° C. for 1 minute to 240 minutes, more preferably heating at 38 ° C. to 75 ° C. for 5 minutes to 180 minutes.

The organic-inorganic composite dispersion of the present invention may contain other components such as inorganic particles and a water-soluble polymer as long as the effects of the present invention are not impaired.
Inorganic particles include silica, zirconium, titania, alumina, talc, and the like, and can be contained in an amount of 0.1 to 100 parts by weight with respect to the total mass of the organic-inorganic composite dispersion. Examples of the water-soluble polymer include water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acid, and can be contained in an amount of 0.1 to 100 parts by weight with respect to the total mass of the organic-inorganic composite dispersion. The inorganic particles or the water-soluble polymer is preferably added after the heating step of the present invention because of liquid stability.

<Organic inorganic composite membrane>
The organic-inorganic composite film of the present invention contains particles of a water-insoluble resin (b) whose surface is coated with fine particles of metal oxide (A2), has a contact angle with water of 20 ° or less, and n -The contact angle with respect to hexadecane is 20 degrees or less.

The organic / inorganic composite film of the present invention has a structure in which the surfaces of the water-insoluble resin (b) particles are coated with the metal oxide (A2) fine particles, so that both hydrophilicity and lipophilicity are exhibited simultaneously. The contact angle with respect to water is 20 ° or less, and the contact angle with respect to n-hexadecane is considered to be 20 ° or less. The relationship between the structure in which the surface of the water-insoluble resin (b) particles are coated with the fine particles of the metal oxide (A2) and the organic-inorganic composite film of the present invention simultaneously exhibits hydrophilicity and lipophilicity. This will be described with reference to FIGS.
Here, FIG. 4 and FIG. 5 are schematic views showing an example of the surface structure of the organic-inorganic composite film of the present invention produced using the organic-inorganic composite dispersion of the present invention, and FIG. It is a schematic diagram which shows an example of the surface structure of the organic inorganic composite film manufactured using the organic inorganic composite dispersion liquid (non-heated composite dispersion liquid) prepared without passing through the heating step in the inorganic composite dispersion manufacturing method.

The organic-inorganic composite film of the present invention is obtained by further heating and mixing a mixed solution (second mixed solution) obtained by mixing metal alkoxide (a) and water-insoluble resin (b) particles by a predetermined method. The organic-inorganic composite dispersion liquid of the present invention can be obtained by coating on a support and drying.
When the second mixed liquid is applied to a support without heating and dried to obtain an organic-inorganic composite film, that is, an unheated composite dispersion is applied to the support and dried to obtain an organic-inorganic composite film. The water-insoluble resin (b) in the organic-inorganic composite film and the metal alkoxide (a) in the case of obtaining the above (the organic-inorganic composite film at this time is also referred to as “non-heated composite film”) are shown in FIG. It is thought to exist in the manner shown.
Since the water-insoluble resin (b) in the non-heated composite dispersion has a smaller surface free energy than the metal alkoxide (a), as shown in FIG. 6, the water-insoluble resin particles 2b, the metal alkoxide 8, In general, the lipophilic water-insoluble resin particles 2b are likely to be exposed on the surface of the non-heated composite film containing. Therefore, it is considered that the non-heated composite membrane exhibits exclusively lipophilicity.

However, the hydrolysis reaction of the metal alkoxide (a) is carried out by further heating and mixing the second mixed liquid in the present invention obtained by mixing the metal alkoxide (a) and the water-insoluble resin (b) particles. As compared with the reaction at room temperature, the dehydration condensation reaction tends to proceed, and the metal hydroxide dehydration condensate (A1) is easily generated. At this time, as shown in FIG. 1 described above, the dehydration condensate (A1) 4 of the metal hydroxide is a water-insoluble resin (B) particle 2 having an anionic group which is a water-insoluble resin (b). It is considered that the particles of the water-insoluble resin (B) having an anionic group coated with the dehydration condensate (A1) of fine metal hydroxide as shown in FIG. 2 are obtained.
The mixed liquid obtained by mixing the metal alkoxide (a) and the water-insoluble resin (b) is prepared, and further mixed by heating to contain the dehydration condensate (A1) of the metal hydroxide. The organic-inorganic composite dispersion of the present invention is obtained.

  Furthermore, by applying the organic-inorganic composite dispersion of the present invention to a support and drying, the dehydration condensate (A1) of metal hydroxide is further dehydrated to produce a metal oxide (A2). Thus, it is considered that a film having a structure in which the surface of the particles of the lipophilic water-insoluble resin (b) is coated with the hydrophilic metal oxide (A2) is obtained.

As shown in FIG. 4, the film having a structure in which the surface of the water-insoluble resin (b) particles are covered with the metal oxide (A2) fine particles, the surface of the water-insoluble resin (b) particles 2b is It seems that the fine particles 10 of the metal oxide (A2) having a particle diameter smaller than that of the water-insoluble resin (b) are coated in a fractal shape. By adopting such a structural form, as shown in FIG. 5, the film has a gap between the metal oxide (A2) fine particles 10 and the metal oxide (A2) fine particles 10, thereby making the film non-water-soluble. It is considered that the particles 2b of the conductive resin (b) are covered without being completely covered. By having such a gap, it is presumed that when the oily solvent comes into contact with the surface of the organic-inorganic composite film of the present invention, the lipophilic water-insoluble resin acts through the gap.
Therefore, the organic-inorganic composite film of the present invention exhibits hydrophilicity due to the hydrophilic metal oxide (A2) present on the film surface, and also exhibits lipophilicity due to the lipophilic water-insoluble resin acting through the gap. It is considered a thing.

The structure as shown in FIG. 5 can be confirmed by observing the surface of the organic-inorganic composite film as shown in FIG. 7 with an AFM.
FIG. 7 is an AFM image showing an example of the surface of the organic-inorganic composite film of the present invention, (A) is a height image, and (B) is a phase image. Specifically, from FIG. 7A, it is confirmed that fine particles 10 of small metal oxide (A2) are scattered around the particles 2b of the water-insoluble resin (b) shown in large particles. Is done.

Due to the above structure, when water contacts the surface of the organic-inorganic composite film, the surface of the organic-inorganic composite film is easily wetted by the action of the hydrophilic metal oxide (A2) (the contact angle with water is small). When the oil such as n-hexadecane comes into contact with the surface, it is considered that the surface of the organic-inorganic composite film is easily wetted by the action of the particles of the lipophilic water-insoluble resin (b) (the contact angle with respect to n-hexadecane is small). .
Here, the contact angle for water and n-hexadecane on the surface of the organic-inorganic composite film of the present invention was measured using a contact angle meter “CA-XE type” manufactured by Kyowa Interface Chemical Co., Ltd. at 23 ° C. and RH 50%. Value.
The contact angle with water is preferably 20 ° or less and more preferably 10 ° or less at 23 ° C. and RH 50%. Further, the contact angle with respect to n-hexadecane is preferably 20 ° or less, more preferably 10 ° or less at 23 ° C. and RH 50%.

  In the organic-inorganic composite film of the present invention, the amount ratio (weight basis) between the metal oxide (A2) and the water-insoluble resin (b) is such that A2: b is from the viewpoint of contact angle with water and n-hexadecane. 99: 1 to 1:99, more preferably 95: 5 to 5:95, and still more preferably 90:10 to 10:90.

  In the organic-inorganic composite film of the present invention, the water-insoluble resin (b) particles may be water-insoluble resin (B) particles having an anionic group, but the water-insoluble resin having no anionic group There is no particular limitation as long as the polymer is insoluble in water and a mixed solvent of water and an organic solvent having an affinity for water (aqueous medium).

  However, when the organic / inorganic composite membrane of the present invention is produced by applying an organic / inorganic composite dispersion on a support, the organic / inorganic composite dispersion contains a dehydration condensate (A1) of fine metal hydroxide. It is important that the pH is 1 to 5, that is, the organic-inorganic composite dispersion of the present invention is used. If the organic-inorganic composite dispersion liquid of the present invention is used, the viscosity of the dispersion liquid is low (1 mPa · s to 10 mPa · s), so that the organic-inorganic composite dispersion liquid can be easily applied to the support, and the dispersion stability of the organic-inorganic composite dispersion liquid. Therefore, the finely divided metal hydroxide dehydration condensate (A1) can be uniformly coated on the support.

  As described above, in order to obtain an organic-inorganic composite dispersion liquid containing finely divided metal hydroxide dehydration condensate (A1) and having low viscosity and good dispersion stability, the particles of the water-insoluble resin (b) are: The particles of the water-insoluble resin (B) having an anionic group are necessary. Therefore, when the organic-inorganic composite film of the present invention is produced by applying an organic-inorganic composite dispersion on a support, it is necessary to use the organic-inorganic composite dispersion of the present invention.

  The organic-inorganic composite film of the present invention preferably has a structure in which the surface of the organic-inorganic composite film has a metal oxide (A2) coated on an uneven surface formed by particles of the water-insoluble resin (b). This is because when the surface is uneven, the adhesion amount of the fine particles of the metal hydroxide dehydration condensate can be increased, and thereby the hydrophilicity can be increased. The structure will be described with reference to FIGS.

As described above, FIG. 7 is an AFM image obtained by observing the surface structure of the surface of the organic-inorganic composite film of the present invention with an AFM (atomic force microscope). (A) is a height image, and (B) is a phase image. FIG. 8 is an AFM image obtained by observing the surface structure of an organic-inorganic composite film obtained using an unheated composite dispersion by AFM, (A) is a height image, and (B) is a phase image. .
The height image is obtained by observing the unevenness of the film surface, and a portion shown white and bright indicates a high convex shape, and a dark portion indicates a low and concave shape. The phase image is an observation of the hardness of the film surface.

(A) of FIG. 9 is the thing of this invention manufactured using the organic inorganic composite dispersion liquid obtained through the heating process (The 2nd liquid mixture is stirred at 50 degreeC) in the manufacturing method of the organic inorganic composite dispersion liquid of this invention. It is the TEM image which observed the cross section of the organic inorganic composite film by TEM, (B) is the enlarged view to which the surface of the film was expanded.
(A) of FIG. 10 is the organic manufactured using the dispersion liquid (non-heated dispersion liquid) which did not pass through a heating process (stirring the 2nd liquid mixture at 25 degreeC) in the manufacturing method of the organic inorganic composite dispersion liquid of this invention. It is the TEM image which observed the cross section of the inorganic composite film (non-heating composite film) with TEM, (B) is the enlarged view which expanded the surface of the non-heating composite film.

FIG. 7A shows that the large-sized water-insoluble resin (b) particles 2b and the metal oxide (A2) particles 10 are shown in white. That is, the surface of the organic-inorganic composite film of the present invention is composed of an uneven surface formed by the particles 2b of the water-insoluble resin (b) and an uneven surface formed by the fine particles 10 of the metal oxide (A2). I understand that.
Further, since the phase image shown in FIG. 7B has uniform color density, it can be seen that the surface of the organic-inorganic composite film of the present invention has the same hardness over the entire surface. . Thereby, it is considered that the metal oxide (A2) is coated on the uneven surface formed by the particles of the water-insoluble resin (b).

  Furthermore, the TEM image shown in FIG. 9 shows an organic-inorganic composite film formed by providing a coating layer 12 that is a layer obtained by applying an organic-inorganic composite dispersion on the support 14 and drying it. The organic-inorganic composite film shown in FIG. 9 is manufactured using the organic-inorganic composite dispersion liquid of the present invention manufactured through the heating step (50 ° C.) as the organic-inorganic composite dispersion liquid. It is.

By applying the organic-inorganic composite dispersion to the support and drying, the dehydration condensate (A1) of the metal hydroxide is further dehydrated to form the metal oxide (A2), and the water-insoluble resin (b) The process for obtaining a film having a structure in which the surface of the particle is covered with the hydrophilic metal oxide (A2) is as described above.
When the organic-inorganic composite dispersion liquid of the present invention is used as the organic-inorganic composite dispersion liquid, it is assumed that particles of the water-insoluble resin (b) whose surface is coated with the dehydration condensate (A1) of metal hydroxide are obtained. . The organic-inorganic composite having a structure in which the surface of the water-insoluble resin (b) particles is coated with the metal oxide (A2) by applying the organic-inorganic composite dispersion liquid of the present invention to the support and drying it. It is thought that a film is formed.
The surface structure of the organic-inorganic composite film is shown in FIG. That is, a group 18 of fine particles of metal oxide (A2) is present on the film surface so as to cover the particles 2b of the water-insoluble resin (b) shown as a white lump.

On the other hand, a non-heated composite film produced using a dispersion liquid (non-heated dispersion liquid) obtained by stirring at 25 ° C. without heating the second mixed liquid in the method for producing an organic-inorganic composite dispersion liquid of the present invention, The hydrolysis / dehydration condensation reaction of the metal alkoxide (a) is difficult to proceed, and as shown in the schematic diagram of FIG. 6, the particles 2b of the water-insoluble resin (b) are exposed on the surface of the non-heated composite film. It is considered a thing.
In the height image of the AFM shown in FIG. 8A, the particles 2b of the water-insoluble resin (b) are mainly confirmed, and the fine particles of the metal oxide (A2) are difficult to confirm. Further, in the phase image shown in FIG. 8 (B), large particles 2b of the water-insoluble resin (b) are mainly observed, and the particles 2b of the water-insoluble resin (b) are exposed on the surface, so that It can be seen that the hardness is not uniform.

Furthermore, from the TEM image shown in FIG. 10B, it can be seen that the water-insoluble resin (b) particles 2b are exposed on the surface of the non-heated composite film.
The TEM image shown in FIG. 10 shows a non-heated composite film formed by providing a coating layer 20 that is a layer obtained by applying a non-heated dispersion on the support 14 and drying it.

  The protective layer 16 shown in FIGS. 9 and 10 is a film that covers the organic-inorganic composite film and the non-heated composite film of the present invention so as not to damage each composite film when measured by TEM.

The fine particles of the metal oxide (A2) are smaller in size than the particles of the water-insoluble resin (b), so that they are easily arranged on the surface of the particles of the water-insoluble resin (b). It is considered that when formed, it can exert an action capable of simultaneously expressing hydrophilicity and lipophilicity.
Therefore, the fine particles of the metal oxide (A2) are preferably 0.1% to 60% and more preferably 1% to 50% of the particle size of the water-insoluble resin (b).
Here, the particle diameter of the fine particles of the metal oxide (A2) and the particles of the water-insoluble resin (b) refers to the maximum diameter obtained from the observation result of the TEM image obtained by observing the cross section of the organic-inorganic composite film with a TEM. “The fine particles of the metal oxide (A2) are 0.1% to 60% of the particle size of the water-insoluble resin (b)” means that the fine particles of the metal oxide (A2) in the figure of the TEM image This is a value obtained by actually measuring the diameter and the particle diameter of the water-insoluble resin (b) and calculating the ratio.

  From the viewpoint of producing the organic-inorganic composite film of the present invention by coating an organic-inorganic composite dispersion on a support, the particles of the water-insoluble resin (b) are formed of the water-insoluble resin (B) having an anionic group. Particles are preferred. The particle diameter of the water-insoluble resin (B) having an anionic group is preferably 0.05 μm to 1 μm, and more preferably 0.06 μm to 0.5 μm.

The method for producing an organic-inorganic composite film of the present invention includes a step of applying the above-described organic-inorganic composite dispersion of the present invention on a support and drying.
More specifically, a coating layer formed by applying the organic-inorganic composite dispersion of the present invention is provided on a support, and the coating layer is heated and dried. An intermediate layer may be formed between the coating layer and the support as long as the effect of the organic-inorganic composite film of the present invention is not impaired.

The heating temperature of the coating layer is preferably 100 ° C. to 200 ° C., more preferably 105 ° C. to 150 ° C., from the viewpoint of further dehydration of the metal hydroxide dehydration condensate.
The heating time of the coating layer is preferably 1 minute to 360 minutes, more preferably 3 minutes to 150 minutes, from the viewpoint of further dehydration of the metal hydroxide dehydration condensate.

  The thickness of this coating layer (layer thickness after heating and drying) is preferably 0.05 μm to 100 μm, and more preferably 0.1 μm to 10 μm.

[Support]
The support used for production of the organic-inorganic composite film of the present invention is not particularly limited, such as a glass plate, a metal plate, or a plastic substrate, but a plastic substrate can be preferably used from the viewpoint of convenience of processing.

Specific examples of the resin used for the plastic substrate include polyolefin resins such as polyethylene, polypropylene and cycloolefin copolymer, polyamide resins such as nylon 6 and nylon 66, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyimide Resins, polycarbonate resins, polyacrylonitrile resins, polyurethane resins, polythiourethane resins, polymethacrylate resins, polystyrene resins, AB resins, ABS resins, PEEK resins, PEK resins, PES resins, polylactic acid resins, and the like. Moreover, the mixture of these resin or the laminated body of these resin may be sufficient. When these resins are films, they may be unstretched films or stretched films.
Furthermore, the surface of the plastic substrate can be subjected to surface modification such as corona treatment, plasma treatment, UV ozone treatment, and alkali treatment to improve the adhesion of the coating layer.

  As the intermediate layer, an adhesive layer using an epoxy adhesive, a urethane adhesive, a cyanoacrylate instantaneous adhesive, a modified acrylate adhesive or the like in order to improve the adhesion between the coating layer and the support. And a pressure-sensitive adhesive layer using a known pressure-sensitive adhesive material.

[Uses of organic-inorganic composite films]
The organic-inorganic composite film of the present invention can be laminated on a substrate and used as various members.
As a base material, the board | substrate, a film, etc. equivalent to the said support body can be used. Moreover, the said plastics base material can be used as a base film, the organic-inorganic composite film | membrane of this invention can be laminated | stacked on a base film, and it can be used as an anti-fog film or an antistatic film.

  In addition, the organic-inorganic composite film of the present invention is used as a primer for applying an aqueous or oil-based paint, etc., by utilizing the function that the organic-inorganic composite film of the present invention easily wets both aqueous and oily solvents. Can also be used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “parts” are based on weight.

[Example 1]
(Preparation of organic-inorganic composite dispersion)
-First mixed solution preparation step-
As an anionic water-insoluble resin particle as component (B), an anionic polyurethane emulsion manufactured by Mitsui Chemicals Polyurethanes Co., Ltd. (product name: WPB-6601 / self-emulsifying type, carboxylic acid / amine salt containing type, solid content 25) Polyurethane emulsion aqueous dispersion P1 diluted to 5% by weight with distilled water.
Hereinafter, the organic-inorganic composite dispersion may be simply referred to as “composite dispersion”.
Next, as a metal alkoxide as component (a), 15 parts by weight of methanol was added to 10 parts by weight of tetramethoxysilane (TMOS) and stirred at room temperature to obtain a TMOS solution M1.
5 wt% polyurethane emulsion aqueous dispersion P1 (65 parts by weight) was added to the obtained TMOS solution M1, and the mixture was stirred at room temperature for 3 minutes to adjust the pH of the solution to 8, whereby a first mixed solution K1-1 was obtained.

-Second mixed solution preparation step-
Thereafter, 13.5 parts by weight of 0.1N hydrochloric acid as an acid catalyst was gradually dropped into the first mixed solution K1-1 to adjust the pH to 3 to obtain a second mixed solution K2-1.

-Heating process-
Then, 2nd liquid mixture K2-1 was stirred at 50 degreeC for 1 hour, the hydrolysis condensation reaction of TMOS was performed, and the organic inorganic composite dispersion liquid D1 was obtained.

(Production of organic-inorganic composite film)
The organic-inorganic composite dispersion D1 prepared by the above method was applied to a 12 μm thick Al ₂ O ₃ vapor-deposited PET film (manufactured by Tosero Co., Ltd., TL-PET) using a bar coater. The organic-inorganic composite dispersion D1 was applied so that the thickness after drying was about 0.3 μm to form a coating layer C1.
Thereafter, the coating layer C1 was heated at 110 ° C. for 1.5 hours to obtain the organic-inorganic composite film of Example 1.

[Example 2]
15 parts by weight of distilled water was added to 10 parts by weight of tetramethoxysilane (TMOS) as component (a) and stirred at room temperature to obtain a TMOS solution M2.
To the obtained TMOS solution M2, 5 wt% polyurethane emulsion aqueous dispersion P1 (65 parts by weight) prepared in Example 1 was added, stirred at room temperature for 3 minutes to adjust the pH of the solution to 8, and the first mixture K1 -2 was obtained.
Thereafter, 13.5 parts by weight of 0.1N hydrochloric acid is gradually added dropwise to the first mixed solution K1-2 to adjust the pH to 3, and the second mixed solution K2-2 is obtained. The mixture was stirred at 40 ° C. for 10 minutes, and TMOS hydrolysis condensation reaction was performed to obtain an organic-inorganic composite dispersion D2.
The organic-inorganic composite dispersion D2 prepared by the above method was applied to a 12 μm thick Al ₂ O ₃ vapor-deposited PET film (TL-PET, manufactured by Tosero Co., Ltd.) using a bar coater. The organic-inorganic composite dispersion D2 was applied so that the thickness after drying was about 0.3 μm to form a coating layer C2.
Thereafter, the coating layer C2 was heated at 110 ° C. for 1.5 hours to obtain an organic-inorganic composite film of Example 2.

[Example 3]
15 parts by weight of distilled water was added to 11.5 parts by weight of component (A) tetramethoxysilane (TMOS) and stirred at room temperature to obtain a TMOS solution M3.
To the obtained TMOS solution M3, the 5% by weight polyurethane emulsion aqueous dispersion P1 (32.5 parts by weight) prepared in Example 1 was added and stirred at room temperature for 3 minutes to adjust the pH of the solution to 8. First mixing A liquid K1-3 was obtained.
Thereafter, 15 parts by weight of 0.1N hydrochloric acid was gradually added dropwise to the first mixed solution K1-3 to adjust the pH to 3 to obtain the second mixed solution K2-3, and then the second mixed solution K2-3 was heated to 70 ° C. The mixture was stirred for 2 hours and subjected to hydrolysis condensation reaction of TMOS to obtain an organic-inorganic composite dispersion D3.
The organic-inorganic composite dispersion D3 prepared by the above method was applied to a 12 μm thick Al ₂ O ₃ vapor-deposited PET film (manufactured by Tosero Co., Ltd., TL-PET) using a bar coater. The organic-inorganic composite dispersion D3 was applied so that the thickness after drying was about 0.3 μm to form a coating layer C3.
Thereafter, the coating layer C3 was heated at 110 ° C. for 1.5 hours to obtain an organic-inorganic composite film of Example 3.

[Example 4]
As component (B), an anionic polyurethane emulsion manufactured by Mitsui Chemicals Polyurethane Co., Ltd. [Product name: WPB363 / self-emulsifying type, carboxylic acid / ammonium salt-containing type, solid content: 25% by weight] is used, and it is made 5% by weight with distilled water. A diluted polyurethane emulsion aqueous dispersion P2 was prepared.
To the TMOS solution M2 prepared in Example 2, 5% by weight polyurethane emulsion aqueous dispersion P2 (65 parts by weight) was added, stirred at room temperature for 3 minutes to adjust the pH of the solution to 8, and the first mixed solution K1-4 was Obtained.
Thereafter, 21 parts by weight of 0.1N hydrochloric acid was gradually added dropwise to the first mixed solution K1-4 to adjust the pH to 3 to obtain the second mixed solution K2-4, and then the second mixed solution K2-4 was cooled to 50 ° C. The mixture was stirred for 2 hours and subjected to hydrolysis condensation reaction of TMOS to obtain an organic-inorganic composite dispersion D4.
The organic-inorganic composite dispersion D4 prepared by the above method was applied to a 12 μm thick Al ₂ O ₃ vapor-deposited PET film (manufactured by Tosero Co., Ltd., TL-PET) using a bar coater. The organic-inorganic composite dispersion D2 was applied so that the thickness after drying was about 0.3 μm to form a coating layer C4.
Thereafter, the coating layer C4 was heated at 110 ° C. for 1.5 hours to obtain an organic-inorganic composite film of Example 4.

[Examples 5 to 9]
In the same manner as in Examples 1 to 3, organic-inorganic composite dispersions D5 to D9 were prepared under the conditions shown in Table 1. To a 12 μm thick Al ₂ O ₃ vapor-deposited PET film (manufactured by Tosero Co., Ltd., TL-PET), the organic-inorganic composite dispersions D5 to D9 prepared with the components and amounts shown in Table 1 were used using a bar coater. It applied so that the thickness after hardening might be set to about 0.3 micrometer. Then, it heated at 110 degreeC for 1.5 hours, and obtained the coating film.

[Comparative Example 1]
To the TMOS solution M1 prepared in Example 1, the 5% by weight polyurethane emulsion aqueous dispersion P1 (65 parts by weight) prepared in Example 1 was added and stirred at room temperature for 3 minutes to adjust the pH of the solution to 8. A mixed solution K1-1 was obtained.
Thereafter, when the mixture was allowed to stand for 10 minutes without the addition of an acid catalyst, the solution suddenly thickened and gelled, so that an organic-inorganic composite film could not be obtained.

[Comparative Example 2]
After obtaining the second mixture K2-1 in the same manner as in Example 1, immediately thickness 12μm of the _Al 2 _{O 3} deposited PET film [Tohcello Co., TL-PET], the prepared by the above method The second mixed solution K2-1 was applied using a bar coater. The second mixed solution K2-1 was applied so that the thickness after drying was about 0.3 μm to form a coating layer C102.
Thereafter, the coating layer C102 was heated at 110 ° C. for 1.5 hours to obtain an organic-inorganic composite film of Comparative Example 2.

[Comparative Example 3]
After obtaining the second mixture K2-3 in the same manner as in Example 3, immediately thickness 12μm of the _Al 2 _{O 3} deposited PET film [Tohcello Co., TL-PET], the prepared by the above method The second mixed solution K2-3 was applied using a bar coater. The second mixed solution K2-3 was applied so that the thickness after drying was about 0.3 μm to form a coating layer C103.
Thereafter, the coating layer C103 was heated at 110 ° C. for 1.5 hours to obtain an organic-inorganic composite film of Comparative Example 3.

[Comparative Example 4]
(B) polyurethane emulsion water dispersion diluted to 5 wt% with distilled water using nonionic polyurethane emulsion [product name W-635 / PEG-containing type, solid content 35 wt%] manufactured by Mitsui Chemicals Polyurethane Co., Ltd. Liquid P3 was prepared.
To the TMOS solution M1 prepared in Example 1, 5 wt% polyurethane emulsion P3 (65 parts by weight) was added as the component (B), and stirred at room temperature for 3 minutes to adjust the pH of the solution to 6.8. K1-101 was obtained.
Thereafter, 13.5 parts by weight of 0.1N hydrochloric acid is gradually added dropwise to the first mixed solution K1-101 to obtain a second mixed solution K2-101 with a pH of 2, and then 50% of the second mixed solution K2-101 is obtained. The mixture was stirred at 0 ° C. for 10 minutes, and TMOS hydrolysis condensation reaction was performed to obtain an organic-inorganic composite dispersion D101.
The organic-inorganic composite dispersion D101 prepared by the above method was applied to a 12 μm thick Al ₂ O ₃ vapor-deposited PET film (manufactured by Tosero Co., Ltd., TL-PET) using a bar coater. The organic-inorganic composite dispersion D101 was applied so that the thickness after drying was about 0.3 μm to form a coating layer C104.
Thereafter, the coating layer C104 was heated at 110 ° C. for 1.5 hours to obtain an organic-inorganic composite film of Comparative Example 4.

[Comparative Example 5]
Using a bar coater, an anionic polyurethane emulsion [product name WPB-6601] manufactured by Mitsui Chemicals Polyurethane Co., Ltd. is directly applied to a 12 μm thick Al ₂ O ₃ vapor-deposited PET film [TL-PET manufactured by Tosero Co., Ltd.]. And applied.
An anionic polyurethane emulsion [product name WPB-6601] was applied so that the thickness after drying was about 0.3 μm to form a coating layer C105.
Thereafter, the coating layer C105 was heated at 110 ° C. for 1.5 hours to obtain an organic-inorganic composite film of Comparative Example 5.

  In addition, the ratio (content rate) of the silica which occupies in the organic-inorganic composite film | membrane of Example 1- Example 9 and Comparative Example 1- Comparative Example 4 was computed with the following method, and was shown in following Table 1.

- calculation method of the silica (SiO ₂₎ content -
The silica content in the organic-inorganic composite film was calculated on the assumption that TMOS as component (A) in Examples 1 to 9 and Comparative Examples 1 to 4 reacted to 100% and became SiO ₂ . .
That is, when the molecular weight (Mw) of TMOS is 152 and the molecular weight (Mw) of SiO ₂ is 60, SiO ₂ /TMOS=60/152=0.395.
That is, the value obtained by multiplying the amount of TMOS added by 0.395 is the SiO ₂ content in the organic-inorganic composite film. From this, the silica (SiO ₂ ) content was calculated using the following formula (2).

Silica (SiO ₂ ) content = [TMOS] × 0.395 / ([B] + ([TMOS] × 0.395)) (2)

In said formula (2), [B] shows each weight part of urethane emulsion P1-P3 containing the urethane resin which is (B) component, and [TMOS] shows the weight part of TMOS.
For example, in the case of the organic-inorganic composite dispersion of Example 1, the silica (SiO ₂ ) content is
Silica (SiO ₂ ) content in the composite dispersion = (10 × 0.395) = 3.95
Emulsion particle content in composite dispersion = (65 × 0.05) = 3.25
Silica (SiO ₂ ) content (%) = 3.95 / (3.25 + 3.95) × 100 = 55
It is.

  The pH was measured using a pH meter “MP225” manufactured by Mettler, and the viscosity was measured using an E-type viscometer “TV-22” manufactured by Toki Sangyo Co., Ltd.

(Evaluation of presence or absence of A1 fine particles in organic-inorganic composite dispersion)
Obtained in organic-inorganic composite dispersions D1 to D9 obtained in Examples 1 to 9, gel-like material obtained in Comparative Example 1, and second mixed liquid K2-2 obtained in Comparative Example 2 and Comparative Example 3 The presence or absence of the dehydrated condensate (A1) of A1 fine particles, that is, fine metal hydroxide, in the second mixed liquid K2-3 and the organic-inorganic composite dispersion D101 obtained in Comparative Example 4 was determined by TEM (transmission type). It examined by visual observation using the electron microscope, the JEOL Co., Ltd. make, JEM-2200FS.
The evaluation results are shown in Table 1 below. The evaluation criteria are as follows.
-Evaluation criteria-
A: A characteristic structure in which the surface of the urethane resin particles was covered with silica particles having a particle size of about 5 to 20 nm was observed.
X: The characteristic structure coat | covered with the silica particle on the urethane resin particle surface is not observed.

2 is obtained for the organic-inorganic composite dispersion D3 obtained in Example 3, and the TEM image shown in FIG. 3 is obtained for the second mixed liquid K2-3 obtained in Comparative Example 3. Obtained.
Note that the TEM images of the organic-inorganic composite dispersion D3 and the second mixed solution K2-3 are obtained by diluting D3 and K2-3 with water, developing the sample on a support film for TEM observation, and drying the sample. (Transmission electron microscope, manufactured by JEOL Ltd., JEM-2200FS) was used for observation.

As can be seen from FIG. 2, in D3 of Example 3, the surface of the urethane resin particles derived from the emulsion particles was coated with a fine metal hydroxide dehydration condensate (A1) having a particle size of about 5 to 20 nm. A typical structure was observed.
On the other hand, in K2-3 of Comparative Example 3, as can be seen from FIG. 3, no characteristic structure was observed on the surface of the urethane resin particles derived from the emulsion particles.
In addition, as for the particle diameter of the silica particles, the particle diameter (maximum diameter) of silica in the figure of the TEM image was measured.

  In Table 1, the unit of silica content is [% by weight], and the unit of the amount of component A1, diluent solvent, component B and acid catalyst is [parts by weight].

[Evaluation of organic-inorganic composite film]
The following evaluation was performed on the organic-inorganic composite films of Examples 1 to 9 and Comparative Examples 2 to 5 obtained as described above.

(1. Contact angle)
Using a contact angle meter “CA-XE type” manufactured by Kyowa Interface Chemical Co., Ltd., the contact angle of the droplet dropped on the surface of the organic-inorganic composite film was measured by the droplet method. As the liquid, distilled water and n-hexadecane (n-C ₁₆ H ₃₄ ) were used. Table 2 shows the evaluation results of the organic-inorganic composite films of Examples 1 to 9 and Comparative Examples 2 to 5.

(2. Surface irregularities)
The surface irregularities of the organic-inorganic composite films of Example 1, Comparative Example 2, and Comparative Example 5 were evaluated using an atomic force microscope (AFM) nanoscope IIIA manufactured by Vecco. The measurement was performed in a tapping mode.
AFM images of the organic-inorganic composite films of Example 1, Comparative Example 2, and Comparative Example 5 are shown in FIGS. 11 to 13 (Example 1; FIG. 11, Comparative Example 2; FIG. 12, Comparative Example 5; FIG. 13). .

  In all of the organic-inorganic composite films of Example 1, Comparative Example 2, and Comparative Example 5, an uneven shape of about 50 to 100 nm reflecting the particle size of the urethane resin particles derived from the emulsion particles was observed. Furthermore, in Example 1 which shows amphiphilicity, the characteristic uneven | corrugated structure where the urethane resin particle surface derived from emulsion particle | grains was coat | covered with the silica particle with a particle size (maximum diameter) of about 5-20 nm was observed. On the other hand, in Comparative Example 2 and Comparative Example 5, an uneven structure due to silica particles was not observed.

(3. Observation of shape of membrane cross section)
Using the organic-inorganic composite films of Example 1 and Comparative Example 2, a sample coated on an Al ₂ O ₃ vapor-deposited PET substrate (TL-PET, manufactured by Tosero Co., Ltd.) was cut out by focused ion beam (FIB) processing. . Then, the shape of this film | membrane cross section was observed using TEM (Transmission electron microscope, JEOL Co., Ltd. product, JEM-2200FS).
TEM images of the organic-inorganic composite films of Example 1 and Comparative Example 2 are shown in FIG. 14A (Example 1) and FIG. 15A (Comparative Example 2).
In both of the organic-inorganic composite films of Example 1 and Comparative Example 2, urethane resin particles derived from emulsion particles having a particle size of about 50 nm to 100 nm were observed. In addition, the particle diameter (maximum diameter) of the urethane particle in the figure of a TEM image measured the particle size of the urethane resin particle.

Further, the details of the organic-inorganic composite film were examined by EELS (Electron Energy Loss Spectroscopy-Mapping Method).
EELS images of the organic-inorganic composite films of Example 1 and Comparative Example 2 are shown in FIGS. 14 (B) to (D) (Example 1) and FIGS. 15 (B) to (D) (Comparative Example 2). .
In the organic-inorganic composite film of Example 1 showing amphiphilic properties, a characteristic structure in which the surface of the urethane resin particles derived from the emulsion particles was coated with silica particles having a particle diameter of about 5 to 20 nm was observed. In addition, as for the particle diameter of the silica particles, the particle diameter (maximum diameter) of silica in the figure of the TEM image was measured.

(4. Composition analysis of film surface)
The elemental composition ratio of the coated sample surface was measured by ESCALAB220iXL (X-ray source AlKα) manufactured by VG. That is, a narrow spectrum was further measured for the elements detected from the wide spectrum of the sample, and the composition ratio was calculated from the peak area.
Table 3 shows the results of determining the composition ratio of the surfaces of the organic-inorganic composite films of Example 2, Example 3, and Comparative Example 2.

From observation of surface irregularities and cross-sectional shape of the film, in the coating film exhibiting amphiphilic properties, silica particles having a particle diameter of about 5 to 20 nm are formed on the surface of urethane resin particles having a particle diameter (maximum diameter) of about 50 nm to 100 nm derived from emulsion particles. The characteristic covering structure is observed, and this characteristic structure is judged as one of the factors showing amphipathic properties. Further, the ratio of Si element is higher on the surface of the coating film exhibiting amphiphilic properties than the film not exhibiting amphiphilic properties. This is presumed to be due to the silica particles covering the surface of the emulsion particles in the organic-inorganic composite dispersion.
In addition, the particle diameter of the urethane resin particle is the actual measurement of the particle diameter (maximum diameter) of the urethane particle in the TEM image, and the particle diameter of the silica particle is the particle diameter (maximum diameter) of silica in the TEM image. Was actually measured.

(5. Antifogging property)
Anti-fogging films 1 to 3 were prepared by laminating the organic-inorganic composite films of Example 1, Example 2, and Comparative Example 4 on a PET film, respectively. Water vapor was applied to the anti-fogging films 1 to 3 for 1 minute, separated from the water vapor, and then placed in an environment of 25 ° C. and RH 10%, and the fogging condition and its change were sensory evaluated in three stages according to the following criteria.
The evaluation results are shown in Table 4. In Table 4, the antifogging films 1 to 3 are abbreviated as “film 1” and the like.
-Evaluation criteria-
○: No cloudiness is observed Δ: Cloudy, but recovers within 10 seconds, no cloudiness is seen ×: Cloudy, no cloudiness recovers even after 10 seconds

(6. Antistatic property)
The organic-inorganic composite films of Example 1, Example 2, and Comparative Example 4 were respectively laminated on a PET film to prepare antistatic films 1 to 3.
The surface resistivity of the antistatic films 1 to 3 obtained above was measured using an insulation resistance measuring instrument (VE-30 type; manufactured by Kawaguchi Electric Co., Ltd.) at 25 ° C. and 10 RH%.
Table 4 shows the evaluation results. In Table 4, the antistatic films 1 to 3 are abbreviated as “film 1” and the like.

It is a schematic diagram which shows an example of the dispersion aspect of the organic inorganic composite dispersion liquid of this invention. It is a TEM image of what was developed on the support film for TEM observation after diluting the organic inorganic composite dispersion liquid of the present invention, and made it an observation specimen. It is a TEM image of what was developed on the support membrane for TEM observation after diluting a non-heating compound dispersion, and was used as an observation specimen. It is a schematic diagram which shows an example of the surface structure of the organic inorganic composite film of this invention. It is a schematic diagram which shows an example of the surface structure of the organic inorganic composite film of this invention. It is a schematic diagram which shows an example of the surface structure of the non-heated composite film manufactured using the non-heated composite dispersion. It is an AFM image which shows an example of the surface of the organic inorganic composite film of this invention, (A) is a height image, (B) is a phase image. It is an AFM image which shows an example of the surface of the non-heated composite film manufactured using the non-heated composite dispersion, (A) is a height image, and (B) is a phase image. (A) is a TEM image which shows an example of the cross section of the organic inorganic composite film of this invention, (B) is the enlarged view which expanded the film | membrane surface among the cross sections shown to (A). (A) is the TEM image which shows an example of the cross section of the non-heated composite film manufactured using the non-heated composite dispersion liquid, (B) is the enlarged view which expanded the film | membrane surface among the cross sections shown to (A). It is. 2 is an AFM image (height image) showing the surface of the organic-inorganic composite film of Example 1. FIG. 6 is an AFM image (height image) showing the surface of an organic-inorganic composite film of Comparative Example 2. 10 is an AFM image (height image) showing the surface of an organic-inorganic composite film of Comparative Example 5. (A) is a TEM image showing a cross section of the organic-inorganic composite film of Example 1, (B) is an EELS image showing the presence of carbon atoms, and (C) is an EELS image showing the presence of oxygen atoms. Yes, (D) is an EELS image showing the presence of silicon atoms. (A) is a TEM image showing a cross section of the organic-inorganic composite film of Comparative Example 2, (B) is an EELS image showing the presence of carbon atoms, and (C) is an EELS image showing the presence of oxygen atoms. Yes, (D) is an EELS image showing the presence of silicon atoms.

Explanation of symbols

2 Particles of a water-insoluble resin (B) having an anionic group 4 Fine dehydration condensation product of metal hydroxide (A1)
6 Particles of water-insoluble resin (B) having an anionic group to which dehydration condensate (A1) of fine particle metal hydroxide is attached 8 Metal alkoxide (a)
DESCRIPTION OF SYMBOLS 10 Fine particle of metal oxide (A2) 12 Coating layer 14 formed using the organic-inorganic composite dispersion of the present invention Support 16 Protective layer 18 Fine particle group 20 of metal oxide (A2) Using unheated composite dispersion Coating layer formed

Claims (14)

  All of the dehydration condensate (A1) of the fine particle metal hydroxide containing the dehydration condensate (A1) of the fine particle metal hydroxide and the particles of the water-insoluble resin (B) having an anionic group Or the organic-inorganic composite dispersion liquid which part adheres to the particle | grains of the water-insoluble resin (B) which has the said anionic group, and a liquid property is pH1-pH5.   The organic-inorganic composite dispersion according to claim 1, wherein the metal hydroxide is at least one selected from the group consisting of silicon hydroxide, zirconium hydroxide, aluminum hydroxide, and titanium hydroxide.   The organic-inorganic composite dispersion according to claim 1 or 2, wherein the metal hydroxide is silicon hydroxide.   The organic-inorganic composite dispersion according to any one of claims 1 to 3, wherein the anionic group is one or more selected from the group consisting of a carboxy group, a sulfonic acid group, and a phosphoric acid group, or a salt thereof. liquid.   The organic-inorganic composite dispersion liquid according to any one of claims 1 to 4, wherein the water-insoluble resin having an anionic group contains a polyurethane resin.   A part of the surface contains particles of the water-insoluble resin (b) coated with fine particles of the metal oxide (A2), the contact angle with water is 20 ° or less, and the contact angle with n-hexadecane is An organic-inorganic composite film that is 20 ° or less.   The organic-inorganic composite film according to claim 6, wherein the surface of the composite film has a structure in which the uneven surface formed by the particles of the water-insoluble resin (b) is coated with fine particles of the metal oxide (A2).   The organic-inorganic composite film according to claim 6 or 7, wherein a particle diameter of the fine particles of the metal oxide (A2) is 0.1% to 60% of a particle diameter of the water-insoluble resin (b). .   The particle | grains of the said water-insoluble resin (b) are particles of the water-insoluble resin (B) which has an anionic group with a particle size of 0.05 micrometer-1 micrometer, The any one of Claims 6-8. Organic-inorganic composite film. A first mixture in which a dispersion containing particles of a water-insoluble resin (B) having an anionic group is mixed with an alcohol solution or an aqueous solution of a metal alkoxide (a) to prepare a first mixed solution of pH 7 to pH 10. A liquid preparation step;
A second mixed solution preparing step of preparing a second mixed solution of pH 1 to pH 5 by adding an acid catalyst to the first mixed solution;
The manufacturing method of the organic inorganic composite dispersion which has a heating process which heats the said 2nd liquid mixture to 30 to 90 degreeC.   The manufacturing method of the organic inorganic composite film which has the process of apply | coating the organic inorganic composite dispersion liquid of any one of Claims 1-5 on a support body, and drying.   The member which laminated | stacked the organic inorganic composite film of any one of Claims 6-9 on the base-material surface.   The member according to claim 12, which is an antifogging film.   The member according to claim 12, which is an antistatic film.