JP2005239780A - Finely particulate alumina-dispersed hydrophilic polyurethane resin composition and production method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a finely particulate alumina-dispersed hydrophilic polyurethane resin composition in which a large amount of a finely particulate filler is well dispersed to hold transparency, and which has excellent adhesiveness to various raw materials and can form coating films having good water absorbability, fog resistance, transparency, flexibility, water-based ink writability, water resistance, blocking resistance and lubricity, and to provide a method for producing the same. <P>SOLUTION: The composition comprising a hydrophilic polyurethane resin obtained by reacting an organic polyisocyanate with a high mol. wt. hydrophilic polyol and/or a polyamine, a polysiloxane, a compound having an active hydrogen-containing group and a tertiary amino group in the identical molecule and a compound having a reactive group and a hydrolysable silyl group in the identical molecule, and finely particulate alumina. The method for producing the same is also provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a fine particle alumina-dispersed hydrophilic polyurethane resin composition comprising a hydrophilic polyurethane resin and fine particle alumina and a method for producing the same, more specifically, excellent adhesion to various materials, and excellent water absorption, antifogging, Fine particle alumina-dispersed hydrophilicity that is transparent and flexible, and suitable for the formation of water-based inks with excellent writability, water resistance, blocking resistance, and slipperiness (ink receiving layer of ink jet recording sheet, etc.) The present invention relates to a polyurethane resin composition and a method for producing the same.

  Polyurethane resin is excellent in abrasion resistance, adhesion, flexibility, chemical resistance, etc., and is also excellent in applicability to various processing methods, so it can be used as a binder for various coating agents, paints, inks, etc. It is widely used as a resin for producing sheets and other molded articles, and a polyurethane resin suitable for each application is provided. Here, the polyurethane resin is a generic term for a polyurethane resin, a polyurea resin, and a polyurethane-polyurea resin. These polyurethane resins are basically obtained by reacting a high molecular weight polyol and an organic polyisocyanate in the presence of a chain extender, if necessary. By using in combination, polyurethane resins having various physical properties can be produced.

However, for polyurethane resins, for example, surface treatment agents such as antifogging paints for agricultural resin sheets and resin wallpaper for interiors, fiber coating agents, and coating agents for forming ink-receiving layers for inkjet recording sheets, etc. In general, hydrophilicity and blocking resistance are usually required simultaneously with the above characteristics.
However, a polyurethane resin obtained by using polyethylene glycol obtained from ring-opening polymerization of ethylene oxide as a high molecular weight hydrophilic polyol has high strength, high elasticity, and excellent hydrophilicity, but has poor water resistance, A film formed using a resin swells or whitens due to moisture, resulting in a decrease in strength, and has a problem that it is not suitable for uses such as binders, molded articles, films, and sheets of various paints and printing inks.

In order to solve these problems, the above polyurethane resin was synthesized by adding a fine particle filler such as calcium carbonate, alumina, titanium oxide, or by dispersing the fine particle filler in the raw material high molecular weight polyol component in advance. It is common practice to use a polyurethane resin.
However, in any of the above cases, the fine particle filler can be satisfactorily dispersed in the polyurethane resin only at most about 5% by mass, and it has been difficult to favorably disperse a large amount of the fine particle filler in the polyurethane resin.

  The reason is that the powdered fine particle filler is widely known as a thickener or thixotropic agent for various resin solutions, and when it is dispersed in a large amount in a polyurethane resin or a high molecular weight polyol, This is because the viscosity of the dispersion becomes extremely high. In addition, the fine particle filler is generally used as a matting agent of a polyurethane resin, and when dispersed in a polyurethane resin, the transparency of the polyurethane resin is lowered, and a small dispersion amount of 5% by mass or less. Even so, the transparency is significantly reduced. However, a technique for dispersing a fine particle filler in a polyurethane resin in an amount of 5% by mass or more without reducing the transparency of the polyurethane resin has not been known yet.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to adhere to various materials without causing the above-described dispersion problem even when a fine particle filler is dispersed in a large amount in a polyurethane resin. Fine particle alumina-dispersed hydrophilic polyurethane resin with excellent water absorption, antifogging properties, transparency, flexibility, water-based ink writing properties, water resistance, blocking resistance and slipperiness It is to provide a composition and a method for its production.

  As a result of repeated studies to achieve the above-mentioned object, the inventors of the present invention have prepared a high-molecular-weight polyol in which fine-particle alumina is added in advance as a high-molecular-weight polyol and / or polyamine as a raw material when producing a hydrophilic polyurethane resin. Alternatively, by using a polyamine, the resulting hydrophilic polyurethane resin composition has a dispersion in which fine particle alumina is stably dispersed in the solution of the hydrophilic polyurethane resin in the solution even when the content of fine particle alumina is large. And the film formed using the same was found to be transparent, thereby completing the present invention.

  That is, according to the present invention, organic polyisocyanate, high molecular weight hydrophilic polyol and / or polyamine (hereinafter referred to as “hydrophilic component”), polysiloxane having at least one active hydrogen-containing group in the molecule, A compound having at least one active hydrogen-containing group and at least one tertiary amino group in the same molecule; at least one reactive group and at least one hydrolyzable silyl group in the same molecule; A composition comprising a hydrophilic polyurethane resin obtained by reacting a compound having a fine particle alumina with fine particle alumina, wherein the fine particle alumina is stably dispersed in the hydrophilic polyurethane resin solution in the solution. Provided is a fine particle alumina-dispersed hydrophilic polyurethane resin composition (hereinafter referred to as “the composition of the present invention”).

  According to the present invention, the organic polyisocyanate, the hydrophilic component, the polysiloxane having at least one active hydrogen-containing group in the molecule, at least one active hydrogen-containing group and at least one third A hydrophilic polyurethane resin obtained by reacting a compound having a secondary amino group in the same molecule with a compound having at least one reactive group and at least one hydrolyzable silyl group in the same molecule; In the method of producing a composition comprising fine particle alumina, a hydrophilic polyurethane resin to which fine particle alumina is added as the hydrophilic component is used to synthesize a hydrophilic polyurethane resin. It is a manufacturing method.

  According to the present invention as described above, the film is excellent in adhesiveness to various materials and excellent in water absorption, antifogging property, transparency, flexibility, water-based ink writing property, water resistance, blocking resistance and lubricity. As a coating agent for forming an ink receiving layer of an ink jet recording sheet, as an antifogging paint for various films, a surface treatment agent for preventing condensation on an interior resin wallpaper, or a water-absorbing clothing coating agent, Provides a composition comprising a hydrophilic polyurethane resin and fine particle alumina, which are useful as a synthetic artificial leather material.

Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention.
The composition of the present invention is composed of a hydrophilic polyurethane resin and fine particle alumina. The hydrophilic polyurethane resin used in the present invention comprises an organic polyisocyanate, a hydrophilic component, a polysiloxane having at least one active hydrogen-containing group in the molecule, at least one active hydrogen-containing group and at least one A chain extender, if necessary, with a compound having a tertiary amino group in the same molecule and a compound having at least one reactive group and at least one hydrolyzable silyl group in the same molecule It is a hydrophilic polyurethane resin obtained by making it react in presence of this.

  In the present invention, the fine particle alumina is contained in the hydrophilic polyurethane resin to be produced by synthesizing the polyurethane resin by adding fine particle alumina in advance to the hydrophilic component when the hydrophilic polyurethane resin is synthesized ( Distributed). The fine particle alumina is stably dispersed in the obtained solution of the hydrophilic polyurethane resin without being separated or settled although a dispersant is not used. The film formed from this solution is also characterized by being transparent even when the amount of fine particle alumina dispersed is large. In the present invention, the polyurethane resin is a general term for a polyurethane resin, a polyurea resin, and a polyurethane-polyurea resin.

  In the present invention, as the mixture of the hydrophilic component and the fine particle alumina, a mixture obtained by mechanically mixing and dispersing the fine particle alumina in the hydrophilic component can be used. From the mixture of the hydrophilic component and the alumina sol, the alumina sol It is preferable to use one obtained by removing the dispersion medium. When the hydrophilic component is used as a solution of the soluble organic solvent, the organic solvent is also removed from the mixture together with the alumina sol dispersion medium. The alumina sol in the present invention is a dispersion in which fine particle alumina is usually stably dispersed in water and / or alcohol as a dispersion medium. As the dispersion medium, ketones, esters and other organic solvents are also used. The average particle diameter of the fine particle alumina in the alumina sol is usually 1 μm or less, particularly preferably 1 to 300 mμm (nm).

  Usually, even if alumina sol is added and dispersed in a hydrophilic polyurethane resin solution, the dispersion stability of the particulate alumina in the resin solution is low, and the particulate alumina easily separates and settles from the resin solution with time. This is because, for example, the compatibility (affinity) between the hydrophilic polyurethane resin and the alumina sol, the stability of both of them against changes in pH, and the properties of the hydrophilic polyurethane resin and the surface of the particulate alumina particles are different. Moreover, when synthesizing a hydrophilic polyurethane resin with an alumina sol, a method of adding it to the synthesis reaction system is also conceivable, but water or alcohol, which is a dispersion medium of the alumina sol, reacts with polyisocyanate which is a raw material of the polyurethane resin. Of course, even if other solvent-based alumina sols are used, a hydrophilic polyurethane resin solution having excellent dispersion stability of fine particle alumina cannot be obtained.

  However, the hydrophilic component described later used in the present invention has extremely high compatibility (affinity) with the alumina sol due to its hydrophilicity, and can be stably mixed with the alumina sol at an arbitrary ratio. Then, by removing the dispersion medium of the alumina sol from this mixture by an arbitrary method, a hydrophilic component in which the particulate alumina is dispersed extremely stably is obtained, and the dispersion amount of the particulate alumina in the hydrophilic component is increased. However, the increase in the viscosity of the hydrophilic component is small, and the fine particle alumina uses a dispersant in the hydrophilic polyurethane resin solution by reacting the fine particle alumina dispersed hydrophilic component with another polyurethane raw material in a solvent. Even if not, a stably dispersed dispersion can be obtained. When the hydrophilic polyurethane resin is synthesized without a solvent, the same stable dispersion as above can be obtained by dissolving the obtained hydrophilic polyurethane resin in the soluble organic solvent. All of these dispersions are extremely transparent, and the film (film) formed from them is also transparent.

  The removal of the dispersion medium of the alumina sol from the mixture of the hydrophilic component and the alumina sol can generally be easily performed under reduced pressure. In this case, the dispersion medium is preferably distilled off under reduced pressure and at a low temperature, and the dispersion medium is particularly preferably distilled off at a temperature of 70 ° C. or lower. When the dispersion medium is distilled off at a higher temperature than this, aggregation of fine particle alumina in the alumina sol may occur, and the dispersion stability of the fine particle alumina is lowered and a finely divided fine particle alumina dispersed hydrophilic component is generated. Sometimes. When the hydrophilic component is used as a solution of the organic solvent, the organic solvent is removed together with the dispersion medium of the alumina sol. The mixing ratio of the hydrophilic component and the fine particle alumina is preferably an amount occupying 5 to 95% by mass in the composition of the present invention consisting of the hydrophilic polyurethane resin and the fine particle alumina in which the fine particle alumina is finally obtained. Is an amount occupying 10 to 90% by mass.

  In the present invention, the hydrophilic polyurethane resin constituting the composition of the present invention comprises a hydrophilic segment having a hydrophilic component as a structural unit, a polysiloxane segment having a structural unit of polysiloxane, and a tertiary amino group in the molecule. And a tertiary amino group-containing segment having a constituent unit as a constituent unit and a hydrolyzable silyl group-containing segment having a constituent unit having a hydrolyzable silyl group in the molecule as a constituent unit. When a chain extender is not used during the synthesis of the hydrophilic polyurethane resin, these segments are bonded at random by urethane bonds, urea bonds, or urethane-urea bonds, respectively. When a chain extender is used during the synthesis of the hydrophilic polyurethane resin, a short chain that is a residue of the chain extender exists between these bonds, in addition to the above bonds.

  By introducing a polysiloxane segment, a tertiary amino group, and a hydrolyzable silyl group into the hydrophilic polyurethane resin, the composition of the present invention is provided with excellent adhesion to various materials, and the above The film formed using the composition is imparted with excellent water absorption, antifogging properties, transparency, flexibility, water-based ink writing properties, water resistance, blocking resistance and lubricity.

In the case of printing using a printing ink on a recording sheet having an ink receiving layer formed by using the composition of the present invention, a polysiloxane segment introduced into the above hydrophilic polyurethane resin, a tertiary amino acid The action of the group and hydrolyzable silyl group will be described.
Introducing a polysiloxane segment that is inherently hydrophobic (water repellent) into a polyurethane resin structure should not be expected to have good water absorption and hydrophilicity for the polyurethane resin. However, the coating surface formed from a polyurethane resin having a low polysiloxane segment content is completely covered with the polysiloxane segment in a dry state, but when the coating is immersed in water, the polysiloxane segment is not contained in the resin coating. It is known that there is a phenomenon of being buried in the surface, that is, environmental responsiveness (Polymer Journal, Vol. 48 [No. 4], p. 227 (1991), etc.).

  The hydrophilic polyurethane resin in the present invention utilizes the above phenomenon, and by appropriately controlling the content of the polysiloxane segment in the resin, the film formed using the resin is placed in a high humidity atmosphere. When exposed or printed with aqueous ink on the film, the surface of the film exhibits hydrophilicity due to the environmental responsiveness, while the surface of the film after drying or after drying is covered with a polysiloxane segment, As a result, it is considered that excellent water resistance, blocking resistance, slipperiness, etc. are exhibited in the above-mentioned film or printed image. The present inventors have already clarified these effects in patent applications such as Japanese Patent Application No. 10-235545, Japanese Patent Application No. 10-240811, and Japanese Patent Application No. 10-170296.

  By introducing a tertiary amino group into the hydrophilic polyurethane resin molecule, the composition of the present invention is imparted with excellent adhesiveness to various materials, and ink formed using the composition The receiving layer (coating) is provided with excellent water absorption, antifogging properties, transparency, flexibility, water-based ink writing properties, water resistance, blocking resistance and lubricity.

  For example, when printing on a recording sheet using an inkjet ink, the dye in the ink generally has an anionic carboxyl group or sulfonic acid group in the molecule, and forms an ink receiving layer. When the hydrophilic polyurethane resin comes into contact with the ink, an ionic bond is formed between the anionic group in the dye and the tertiary amino group in the resin. As a result, it is considered that the fixing property of the dye in the ink receiving layer and the water resistance of the recorded image are improved.

  However, in the presence of moisture, the ionic bonds as described above are easily dissociated, and it should not be expected to improve the water resistance of the ink receiving layer and the image formed thereon. The water resistance of the printed image is remarkably improved. The reason for this improvement in water resistance is not clear, but the polyurethane resin used in the present invention is hydrophilic, but also has a hydrophobic portion in the molecule, and the tertiary amino group and dye in the resin are present. After the ionic bond is formed between the polyurethane resin, the hydrophobic part of the polyurethane resin surrounds the hydrophilic part (hydrophilic segment) and the ionic bond part. It is.

  The hydrophilic polyurethane resin can be crosslinked by moisture by the hydrolyzable silyl group introduced therein, and the composition of the present invention is imparted with excellent adhesiveness to various materials by the crosslinking, and the composition The film formed by using the above-mentioned film is imparted with excellent water absorption, antifogging properties, transparency, flexibility, water-based ink writing properties, water resistance, blocking resistance and lubricity. The site for introducing the hydrolyzable silyl group in the hydrophilic polyurethane resin is not particularly limited, but is usually a molecular chain terminal and / or a side chain of the resin.

  The hydrolyzable silyl group introduced into the molecular chain terminal and / or side chain of the hydrophilic polyurethane resin crosslinks the resin with moisture by, for example, the reaction shown in the following formula (I) and / or (II). be able to. By the crosslinking, the resin has improved water resistance, the surface strength of the resin film is improved, and the blocking resistance is also improved.

  The crosslinking of the hydrophilic polyurethane resin used in the present invention is caused by moisture. However, since the resin is hydrophilic, it can be crosslinked using moisture in the air. Crosslinking is performed by converting a hydrolyzable silyl group into a silanol group by moisture as described above, and condensing this silanol group. Therefore, a catalyst is added to the composition of the present invention to promote silanol condensation. It is preferable to keep it. Such a catalyst is generally preferably a tin carboxylate, an acidic catalyst or a basic catalyst, and the amount used is preferably in the range of 0.0001 to 10% by mass relative to the hydrophilic polyurethane resin.

Next, the raw material of the hydrophilic polyurethane resin used in the present invention will be described.
In the present invention, the polysiloxane used for introducing the polysiloxane segment into the hydrophilic polyurethane resin is an active hydrogen-containing group containing one or more active hydrogens in the molecule, for example, an amino group, an epoxy A polysiloxane having a reactive group such as a group, a hydroxyl group, a mercapto group, or a carboxyl group. Preferable examples of the polysiloxane having an active hydrogen-containing group include the following compounds.

(1) Amino-modified polysiloxane

(2) Epoxy-modified polysiloxane (used by opening these epoxy groups)

(3) Alcohol-modified polysiloxane

(4) Mercapto-modified polysiloxane

(5) Carboxyl-modified polysiloxane

  The polysiloxanes having active hydrogen-containing groups listed above are examples of preferred compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only these exemplified compounds but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.

  In the present invention, the compound used for introducing the tertiary amino group into the hydrophilic polyurethane resin is, for example, an amino group, an epoxy group, a hydroxyl group, a mercapto group, as at least one active hydrogen-containing group in the molecule. It is a compound having a carboxyl group or a reactive group such as an alkoxy group, an acid halide group, a carboxyester group, an acid anhydride group, etc. that can be converted into a hydroxyl group or a carboxyl group, and a tertiary amino group in the molecular chain.

（式中の、Ｒ₁は炭素数２０以下のアルキル基、脂環族基、又は芳香族基（ハロゲン、アルキル基で置換されていてもよい）であり、Ｒ₂及びＲ₃は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＮＨＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−等で連結されていてもよい低級アルキレン基であり、Ｘ及びＹは−ＯＨ、−ＣＯＯＨ、−ＮＨ₂、−ＮＨＲ₁、−ＳＨ等の反応性基であり、Ｘ及びＹは同一でも異なってもよい。又、Ｘ及びＹは上記の反応性基に誘導できるエポキシ基、アルコキシ基、酸ハライド基、酸無水物基、又はカルボキシルエステル基でもよい。） Preferable examples of the tertiary amino group-containing compound having a reactive group as described above include compounds represented by the following general formulas (1) to (3).

(In the formula, R ₁ is an alkyl group having 20 or less carbon atoms, an alicyclic group, or an aromatic group (which may be substituted with a halogen or an alkyl group), and R ₂ and R ₃ are —O—. , —CO—, —COO—, —NHCO—, —S—, —SO—, —SO ₂ — and the like, and X and Y are —OH, —COOH, — Reactive groups such as NH ₂ , —NHR ₁ , —SH, etc. X and Y may be the same or different, and X and Y are epoxy groups, alkoxy groups, acid halides that can be derived from the above reactive groups. It may be a group, an acid anhydride group, or a carboxyl ester group.)

（式中の、Ｒ₁、Ｒ₂、Ｒ₃、Ｘ及びＹは前記と同じ定義であるが、但し二つのＲ₁同士は環状構造を形成するものであってもよい。Ｒ₄は−(ＣＨ₂)_n−（ｎは０〜２０の整数）である。）

(In the formula, R ₁ , R ₂ , R ₃ , X and Y have the same definitions as above, but two R _{1 s} may form a cyclic structure. R ₄ is-( CH _{2) n} - (n is an integer of 0 to 20)).

（式中の、Ｘ及びＹは前記の定義と同じであり、Ｗは窒素含有複素環、窒素と酸素含有複素環、又は窒素と硫黄含有複素環を表す。）

(In the formula, X and Y are as defined above, and W represents a nitrogen-containing heterocycle, nitrogen and oxygen-containing heterocycle, or nitrogen and sulfur-containing heterocycle.)

  Specific examples of the compounds represented by the above general formulas (1), (2) and (3) include the following. N, N-dihydroxyethyl-methylamine, N, N-dihydroxyethyl-ethylamine, N, N-dihydroxyethyl-isopropylamine, N, N-dihydroxyethyl-n-butylamine, N, N-dihydroxyethyl-t-butylamine Methyliminobispropylamine, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-m-toluidine, N, N-dihydroxyethyl-p-toluidine, N, N-dihydroxyethyl-m-chloroaniline, N , N-dihydroxyethylbenzylamine, N, N-dimethyl-N ′, N′-dihydroxyethyl-1,3-diaminopropane, N, N-diethyl-N ′, N′-dihydroxyethyl-1,3-diamino Propane, N-hydroxyethyl-piperazine, N, N-di Droxyethyl-piperazine, N-hydroxyethoxyethyl-piperazine, 1,4-bisaminopropyl-piperazine, N-aminopropyl-piperazine, dipicolinic acid, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,6- Diaminopyridine, 2,6-diamino-4-methylpyridine, 2,6-dihydroxypyridine, 2,6-pyridine-dimethanol, 2- (4-pyridyl) -4,6-dihydroxypyrimidine, 2,6-diamino Triazine, 2,5-diaminotriazole, 2,5-diaminooxazole and the like.

（上記式中のｎは１〜６０の整数を、ｍは１〜６の整数を表す。） Also, ethylene oxide adducts and propylene oxide adducts of these tertiary amino compounds can be used in the present invention. Examples of the adduct include compounds represented by the following structural formula.

(In the above formula, n represents an integer of 1 to 60, and m represents an integer of 1 to 6.)

  In the present invention, the compound used for introducing the hydrolyzable silyl group into the hydrophilic polyurethane resin includes at least one reactive group such as an amino group, an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, Examples thereof include a silane coupling agent having a reactive group such as an isocyanate group and a hydrolyzable silyl group, or a reaction product of the silane coupling agent and an organic polyisocyanate. Typical examples of the hydrolyzable silyl group in the silane coupling agent are alkoxylated silyl groups such as a methoxylated silyl group, an ethoxylated silyl group, and a methoxyethoxylated silyl group. Of course, it can be used.

（式中のＲ₁は低級アルキル基、Ｒ₂は低級アルキル基、低級アルコキシ基又はイソシアネート基を、Ｘは、何もないか、又は２価の有機基、好ましいものはＣ₀〜Ｃ₅₀のアルキレン鎖、芳香族環又は脂肪族環であり、これらの基はその中に連結基として、−Ｎ−、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＮＨＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−等を含んでいてもよい。又、ｍ＝０〜３の整数、ｎ＝３−ｍである。） Examples of the silane coupling agent having a reactive group used in the present invention include the following compounds.
[1] A silane coupling agent represented by the general formula (1) having at least one free isocyanate group.

Wherein R ₁ is a lower alkyl group, R ₂ is a lower alkyl group, a lower alkoxy group or an isocyanate group, X is nothing or a divalent organic group, preferably a C _{0 to} C ₅₀ An alkylene chain, an aromatic ring or an aliphatic ring, and these groups include —N—, —O—, —CO—, —COO—, —NHCO—, —S—, —SO as a linking group therein. -, - SO ₂ - and the like may also contain the addition, m = 0 to 3 integers and n = 3-m)..

Preferred specific examples of the compound represented by the general formula (1) are as follows.

（式中のＹは、−ＮＨ−、−ＮＲ₃−、−Ｏ−、−Ｓ−であり、Ｒ₁、Ｒ₂、Ｘ、ｍ、ｎは前記定義の通りである。Ｒ₃は低級アルキル基である。） [2] A reaction product of a silane coupling agent having an active hydrogen-containing group and an organic polyisocyanate, wherein the product has at least one free isocyanate group in the molecule.
As said silane coupling agent, what is represented by following General formula (2) is mentioned, for example.

(In the formula, Y is —NH—, —NR ₃ —, —O—, —S—, and R ₁ , R ₂ , X, m, and n are as defined above. R ₃ is lower alkyl. Group.)

Preferred specific examples of the silane coupling agent represented by the general formula (2) are as follows. In addition, the epoxy group in the following compound is used by opening the ring.

以上のシランカップリング剤は、本発明において使用する好ましいシランカップリング剤の例示であって、本発明はこれらに限定されるものではない。従って、上記の例示の化合物のみならず、その他公知の現在市販されており、市場から容易に入手し得る化合物は、いずれも本発明において使用することができる。

The above silane coupling agents are examples of preferred silane coupling agents used in the present invention, and the present invention is not limited thereto. Therefore, not only the above-exemplified compounds, but also other known compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.

In addition, a hydrolyzable silyl group can be introduced into the hydrophilic polyurethane resin at the time of synthesis. However, after synthesizing a hydrophilic polyurethane resin into which no hydrolyzable silyl group has been introduced, the molecular chain terminal and / or Alternatively, it is preferable to introduce a hydrolyzable silyl group at these sites by reacting the reactive group in the side chain with the silane coupling agent as described below, for example.
[1] Introduction to molecular chain end

（上記式中のＲ₁、Ｒ₂、Ｘ及びＹは前記と同じであり、Ｚは−Ｏ−、−Ｓ−、−ＮＲ₃−、−ＮＨ−であり、〔Ｐ〕は重合体１分子当たり少なくとも２つのウレタン結合及び／又はウレア結合を含有する親水性ポリウレタン樹脂の分子鎖を表す。又、Ｒ₃は低級アルキル基であり、ｍ及びｎは前記定義の通りである。） [2] Introduction to molecular chain side chain

(R ₁ , R ₂ , X and Y in the above formula are the same as above, Z is —O—, —S—, —NR ₃ —, —NH—, and [P] is one molecule of polymer. This represents a molecular chain of a hydrophilic polyurethane resin containing at least two urethane bonds and / or urea bonds per unit, R ₃ is a lower alkyl group, and m and n are as defined above.

  As the organic polyisocyanate used in the present invention, any conventionally known ones in the synthesis of polyurethane resins can be used and are not particularly limited. Preferred examples include 4,4′-diphenylmethane diisocyanate (MDI), hydrogenated MDI, isophorone diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2, Polyurethane obtained by reacting 6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, etc., or these organic polyisocyanates with low molecular weight polyols or polyamines to be terminal isocyanates A prepolymer or the like can also be used.

As the hydrophilic component used in the present invention, those having a hydroxyl group, an amino group, a carboxyl group and the like and having a weight average molecular weight in the range of 400 to 8,000 are preferable.
Examples of the polyol having a terminal hydroxyl group and hydrophilicity include polyethylene glycol, polyethylene glycol / polytetramethylene glycol copolymer polyol, polyethylene glycol / polypropylene glycol copolymer polyol, polyethylene glycol adipate polyol, polyethylene glycol succinate polyol, polyethylene Examples include glycol / polyε-lactone copolymer polyol, polyethylene glycol / polyvalerolactone copolymer polyol, and the like. Particularly preferred is polyethylene glycol.

  Examples of the polyamine having a terminal amino group and hydrophilicity include polyethylene oxide diamine, polyethylene oxide propylene oxide diamine, polyethylene oxide triamine, and polyethylene oxide propylene oxide triamine. Other examples include ethylene oxide adducts having a carboxyl group or a vinyl group.

  In the present invention, in order to impart water resistance to the hydrophilic polyurethane resin, it is also possible to use other polyols, polyamines, polycarboxylic acids and the like not having a hydrophilic chain together with the above hydrophilic component.

  As the chain extender used as necessary in the present invention, for example, any conventionally known chain extender such as a low molecular weight diol or diamine can be used, and it is not particularly limited. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, ethylenediamine, hexamethylenediamine and the like can be mentioned.

  The composition of the present invention is obtained by removing the dispersion medium of alumina sol from the mixture of the hydrophilic component and alumina sol, that is, the fine particle alumina-dispersed hydrophilic component, the organic polyisocyanate, and the intramolecular molecule. A polysiloxane having at least one active hydrogen-containing group, a compound having at least one active hydrogen-containing group and at least one tertiary amino group in the same molecule, and at least one reactive group And a compound having at least one hydrolyzable silyl group in the same molecule, if necessary, in the presence of a chain extender according to a conventionally known method for producing a polyurethane resin. it can. The reaction may be carried out in an organic solvent or without a solvent. When performed in an organic solvent, the resulting composition of the present invention is in a state in which fine-particle alumina is stably dispersed in an organic solvent solution of a hydrophilic polyurethane resin. When the reaction is performed in the absence of a solvent, the obtained composition of the present invention is in the form of a solid, and the solid composition is used as a soluble organic solvent for the hydrophilic polyurethane resin constituting the composition. Dissolve and use. The soluble organic solvent is not particularly limited, and examples thereof include dimethylformamide and methyl ethyl ketone. As the soluble organic solvent, a solvent used for the synthesis of a hydrophilic polyurethane resin can also be used.

  The molecular weight of the hydrophilic polyurethane resin constituting the composition of the present invention is not particularly limited, and the weight average molecular weight measured by GPC is preferably in the range of 3,000 to 800,000, more preferably. Is in the range of 5,000 to 500,000.

  In the composition of the present invention, the content of the particulate alumina is preferably an amount occupying 5 to 95% by mass, more preferably 10 to 90% by mass in the composition (solid content). When the content of the fine particle alumina is less than 5% by mass, the surface properties such as blocking resistance and lubricity in the coating formed using the hydrophilic polyurethane resin which is the object of the present invention are insufficient, while 95% by mass. If it exceeds%, the strength of the coating film, the adhesiveness to the substrate sheet and the like are inferior. Surprisingly, when the content of the fine particle alumina occupies 75 to 95% by mass, when the coating liquid using the composition of the present invention is coated on the base sheet, a microporous size of several m μm (nm) is obtained. A film having quality and excellent transparency is formed.

  The polysiloxane segment in the hydrophilic polyurethane resin in the present invention may be contained in the main chain or side chain of the hydrophilic polyurethane resin, or in both. The content of the polysiloxane segment in the hydrophilic polyurethane resin is preferably 0.1 to 10% by mass, and more preferably 2 to 10% by mass. If the content of the polysiloxane segment is less than 0.1% by mass, the surface properties such as water resistance, blocking resistance and slipperiness of the film formed using the resin, which is the object of the present invention, are insufficient. If it exceeds 10% by mass, the water repellency due to the polysiloxane segment becomes strong and the environmental responsiveness utilized by the present invention becomes poor, and the coating film is poor in water absorption, antifogging properties and transparency. It is not preferable.

  The content of the hydrolyzable silyl group in the hydrophilic polyurethane resin in the present invention is preferably in the range of 0.001 to 10 meq (milli equivalent) / g, more preferably 0.01 to 1.0 meq / g. When the content of the hydrolyzable silyl group is less than 0.001 meq / g, that is, less than 0.01 per 10,000 molecular weight, the ratio of the hydrophilic segment in the resin becomes relatively large, When the film formed using the resin, which is the purpose of the period, has insufficient expression of properties such as water resistance and blocking resistance, while the hydrolyzable silyl group content exceeds 10 meq / g, When the molecular weight exceeds 10,000 per 10,000, the ratio of hydrophilic segments in the resin is relatively reduced, and the water resistance of the coating is increased due to the cross-linked structure of the resin. It is not preferable because it becomes inferior to.

  The content of the tertiary amino group in the hydrophilic polyurethane resin in the present invention is preferably in the range of 0.1 to 50 meq (milli equivalent) / g, more preferably 0.5 to 20 meq / g. When the content of the tertiary amino group is less than 0.1 meq / g, that is, less than 1 per 10,000 molecular weight, the proportion of hydrophilic segments in the resin is relatively large, When the coating film formed using the resin, which is the object, exhibits insufficient properties such as water resistance and blocking resistance, on the other hand, when the content of the tertiary amino group exceeds 50 meq / g, that is, a molecular weight of 10 When the number exceeds 500 per 1,000, the ratio of the hydrophilic segment in the resin is relatively reduced, and as a result, the water repellency of the coating becomes strong, and the water absorption performance and antifogging property become inferior. Absent.

  The content of the hydrophilic segment in the hydrophilic polyurethane resin in the present invention is preferably in the range of 30 to 80% by mass, more preferably in the range of 50 to 75% by mass. When the content of the hydrophilic segment is less than 30% by mass, a film formed using the resin is inferior in water absorption and anti-fogging properties. On the other hand, when the content exceeds 80% by mass, the film is water resistant. It becomes inferior to blocking resistance and is not preferable.

  The film formed using the composition of the present invention as described above has adhesiveness to various materials, water absorption, antifogging property, transparency, flexibility, water-based ink writing property, water resistance, blocking resistance and Excellent lubricity. Therefore, the composition of the present invention is used as a coating agent for forming an ink receiving layer of an ink jet recording sheet, as an antifogging paint for imparting antifogging properties to various films, and as a surface treatment agent for preventing dew condensation on interior resin wallpaper. It is very useful as a coating agent for clothing that gives water absorption to clothing, as a material for synthetic leather, or as a water-based ink writing treatment for synthetic paper. Moreover, the composition of this invention can be used also for manufacture of a various molded object in a solid state.

  Next, the present invention will be described in more detail with reference examples, examples and comparative examples. In the text, “part” or “%” is based on mass unless otherwise specified.

Reference example 1
700 parts of polyethylene glycol (molecular weight: 1,000) and 750 parts of alumina water sol (average particle diameter of alumina: 150 to 160 nm, solid content: 40%) are mixed thoroughly, and the resulting mixture is decompressed at 70 ° C. while stirring. Dehydration was performed. After the theoretical amount of water was distilled off, the temperature was raised to 120 ° C. and water was further removed under reduced pressure of 133.3 Pa or less to obtain a white solid polyol (A) having an alumina content of 30%. This polyol (A) was a transparent liquid at a hydroxyl value of 76 mgKOH / g, a water content of 0.15% and at 80 ° C., and the viscosity of the liquid at that time was 380 dPa · s.

Reference example 2
100 parts of polyethylene glycol (molecular weight 590) and 500 parts of alumina water sol (average particle size of alumina 10-20 nm, solid content 20%) are thoroughly mixed, and the resulting mixture is stirred under reduced pressure at 70 ° C. under reduced pressure. went. After the theoretical amount of water was distilled off, the temperature was raised to 120 ° C. and water was further removed under reduced pressure of 133.3 Pa or less to obtain a white solid polyol (B) having an alumina content of 50%. This polyol (B) was softened at 90 ° C. with a hydroxyl value of 95 mgKOH / g, a moisture content of 0.12%.

Reference example 3
Obtained by sufficiently mixing 100 parts of polyethylene oxide diamine (Jefamine ED manufactured by Texaco Chemical Co., Ltd .; molecular weight 600) and 2,250 parts of alumina water sol (alumina average particle size 150 to 160 nm, solid content 40%). The mixture was dehydrated under reduced pressure at 70 ° C. while stirring. After the theoretical amount of water was distilled off, the temperature was raised to 120 ° C. and water was further removed under reduced pressure of 133.3 Pa or less to obtain a white solid polyamine (C) having an alumina content of 90%. This polyamine (C) was softened at an amine equivalent of 30 g / mol, a water content of 0.20%, and 110 ° C.

上記構造のポリジメチルシロキサンポリオール（分子量３，２００）５部と、ポリエチレングリコール（分子量２，０４０）３０部と、参考例１のポリオール（Ａ）１２０部と、１，３−ブチレングリコール７部と、Ｎ−メチルジエタノールアミン９部とを、２００部のメチルエチルケトンと２００部のジメチルホルムアミドとの混合溶剤中に溶解し、６０℃でよく攪拌しながら、６６部の水添ＭＤＩを１００部のメチルエチルケトンに溶解した溶液を徐々に滴下した。滴下終了後、８０℃で８時間反応させた。得られた樹脂を赤外分光光度計で分析した結果、赤外吸収スペクトルには水酸基の吸収は認められず、又、ピリジン法（ＪＩＳ Ｋ００７０ ２．５）による定量分析によっても水酸基は確認されなかった。 Example 1
(Production of the composition of the present invention)

5 parts of polydimethylsiloxane polyol (molecular weight 3,200) having the above structure, 30 parts of polyethylene glycol (molecular weight 2,040), 120 parts of polyol (A) of Reference Example 1, 7 parts of 1,3-butylene glycol, , 9 parts of N-methyldiethanolamine are dissolved in a mixed solvent of 200 parts of methyl ethyl ketone and 200 parts of dimethylformamide, and 66 parts of hydrogenated MDI are dissolved in 100 parts of methyl ethyl ketone while stirring well at 60 ° C. The solution was slowly added dropwise. After completion of the dropping, the reaction was carried out at 80 ° C. for 8 hours. As a result of analyzing the obtained resin with an infrared spectrophotometer, no absorption of hydroxyl groups was observed in the infrared absorption spectrum, and no hydroxyl groups were confirmed by quantitative analysis by the pyridine method (JIS K0070 2.5). It was.

Add 8 parts of a silane coupling agent [(C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NCO] having an isocyanate group to the above resin solution and react for 8 hours at 80 ° C., and the isocyanate group disappears from the resin solution. After confirming this, dimethylformamide was added to adjust the solid content to 20% to obtain a solution of the composition of the present invention. The solution of the above composition has a viscosity of 21 dPa · s (25 ° C.) and is measured by GPC of the hydrophilic polyurethane resin constituting the composition, and the weight average molecular weight in terms of standard polystyrene (in the following examples) The content of polysiloxane segments in the resin is 2.7%, the content of tertiary amino groups is 4.75 meq / g, and the content of hydrolyzable silyl groups is 58,000. The content of the hydrophilic segment was 0.88 meq / g, and the content of alumina in the composition (solid content) was 14.7%.

Example 2
(Production of the composition of the present invention)
(1) Production of isocyanate-terminated silane coupling agent 270 parts of an adduct of hexamethylene diisocyanate and water (Duranate 24A-100: manufactured by Asahi Kasei Co., Ltd., NCO% = 23.5) was thoroughly stirred at 25 ° C. 111 parts of γ-aminopropyltriethoxysilane were gradually added dropwise and reacted to give a colorless and transparent liquid product (D). The obtained product has 10.5% of free isocyanate groups (theoretical value (the amount of the groups in the reaction product which is stoichiometrically generated when 100% of the reaction is performed) is 11.2%). Theoretically, it has the following structure.

（２）上記の液状生成物（Ｄ）８部と、トルエンジイソシアネート５１部と、参考例２のポリオール（Ｂ）１５０部と、上記構造のポリジメチルシロキサンジアミン（分子量３，８８０）４部と、Ｎ，Ｎ−ジメチル−Ｎ′，Ｎ′−ジヒドロキシエチル−１，３−ジアミノプロパン９部とを、２００部のジメチルホルムアミドとメチルエチルケトン（１／１質量比）との混合溶剤中で、８０℃、５時間反応させ、イソシアネート末端ポリウレタン樹脂を得た。該樹脂溶液の温度を２０℃に調整し、９部の１，４−ジアミノブタンを５０部のメチルエチルケトンに溶解した溶液を徐々に滴下し、滴下終了後、同温度で１時間反応させた。更に、１４部のγ−アミノプロピルトリメトキシシランを５０部のメチルエチルケトンに溶解した溶液を徐々に滴下し、３０℃で１時間反応させた。生成した樹脂からイソシアネート基が消失していることを確認した後、ジメチルホルムアミドを加え、固形分２０％の本発明の組成物の溶液を得た。

(2) 8 parts of the above liquid product (D), 51 parts of toluene diisocyanate, 150 parts of polyol (B) of Reference Example 2, 4 parts of polydimethylsiloxane diamine (molecular weight 3,880) having the above structure, N, N-dimethyl-N ′, N′-dihydroxyethyl-1,3-diaminopropane (9 parts) in a mixed solvent of 200 parts of dimethylformamide and methyl ethyl ketone (1/1 mass ratio) at 80 ° C., It was made to react for 5 hours and the isocyanate terminal polyurethane resin was obtained. The temperature of the resin solution was adjusted to 20 ° C., and a solution of 9 parts of 1,4-diaminobutane dissolved in 50 parts of methyl ethyl ketone was gradually added dropwise. After completion of the addition, the mixture was reacted at the same temperature for 1 hour. Further, a solution of 14 parts of γ-aminopropyltrimethoxysilane dissolved in 50 parts of methyl ethyl ketone was gradually added dropwise and reacted at 30 ° C. for 1 hour. After confirming that the isocyanate group had disappeared from the produced resin, dimethylformamide was added to obtain a solution of the composition of the present invention having a solid content of 20%.

  The solution of the composition had a viscosity of 33 dPa · s (25 ° C.). The weight-average molecular weight of the hydrophilic polyurethane-polyurea resin constituting the composition is 61,000, the content of the polysiloxane segment in the resin is 2.0%, and the content of the tertiary amino group is 0.58 meq / g, hydrolyzable silyl group content is 0.29 meq / g, hydrophilic segment content is 44.1%, and alumina content in the composition (solid content) is 30 6%.

Example 3
(Production of the composition of the present invention)
18 parts of hydrogenated MDI, 3 parts of polydimethylsiloxane diamine (molecular weight 3,880) used in Example 2, 4 parts of polyethylene oxide diamine (Jeffamine ED; molecular weight 2,000), and polyamine of Reference Example 3 (C) 146 parts and 2 parts of methyliminobispropylamine were reacted in 200 parts of dimethylformamide at 30 ° C. for 4 hours to obtain an isocyanate-terminated polyurea resin. The temperature of the resin solution was adjusted to 20 ° C., and a solution of 1 part of 1,4-diaminobutane dissolved in 50 parts of methyl ethyl ketone was gradually added dropwise. Further, a solution obtained by dissolving 3 parts of γ-aminopropyltrimethoxysilane in 50 parts of methyl ethyl ketone was gradually added dropwise and reacted at 30 ° C. for 1 hour. After confirming that the isocyanate group had disappeared from the produced resin Dimethylformamide was added to adjust the solid content to 20% to obtain a solution of the composition of the present invention.

  The solution of the composition has a viscosity of 16 dPa · s (25 ° C.), the weight average molecular weight of the hydrophilic polyurea resin constituting the composition is 37,000, and the polysiloxane segment in the resin Content of 3.9%, tertiary amino group content of 0.46 meq / g, hydrolyzable silyl group content of 0.20 meq / g, hydrophilic segment content of 42.0% The alumina content in the composition (solid content) was 74.6%.

Comparative Example 1
The same materials as in Example 1 except that the polydimethylsiloxane polyol, N-methyldiethanolamine and the isocyanate group-containing silane coupling agent were not used, and the polyol of the polyol (A) of Reference Example 1 was used except for the alumina. A polyurethane resin solution was obtained according to the formulation. This resin solution had a solid content of 20%, a viscosity of 47 dPa · s (25 ° C.), and the polyurethane resin had a weight average molecular weight of 86,000.

Comparative Example 2
Polydimethylsiloxane diamine, N, N-dimethyl-N ′, N′-dihydroxyethyl-1,3-diaminopropane, isocyanate-terminated silane coupling agent and γ-aminopropyltrimethoxysilane are not used. A polyurethane-polyurea resin solution was obtained using the same materials and formulation as in Example 2 except that the polyol (B) except for the polyol (B) was used. This resin solution had a solid content of 20%, a viscosity of 55 dPa · s (25 ° C.), and the weight-average molecular weight of the resin was 91,000.

Comparative Example 3
The same material as in Example 3 except that polydimethylsiloxane diamine, methyliminobispropylamine and γ-aminopropyltrimethoxysilane are not used, and the polyamine (C) of Reference Example 3 except for the polyamine is used. A polyurea resin solution was obtained according to the formulation. This resin solution had a solid content of 20%, a viscosity of 25 dPa · s (25 ° C.), and the weight-average molecular weight of the resin was 68,000.

Comparative Examples 4-6
The alumina water sol used in Reference Examples 1 to 3 was added to the resin solutions of Comparative Examples 1 to 3 with stirring, but fine-particle alumina precipitated, and these solutions became opaque.

Comparative Example 7
A 5% aqueous solution of polyvinyl alcohol (polymerization degree 550) having a saponification degree of 98.5% was prepared.

  Inkjet recording sheets were prepared using the compositions of the present invention obtained in Examples 1 to 3 and the resin solutions obtained in Comparative Examples 1 to 7, and the following characteristics were evaluated by the following methods.

[1] Evaluation of Inkjet Recording Sheet Each of the compositions and resin solutions obtained in Examples 1 to 3 and Comparative Examples 1 to 7 was dried on a 100 μm thick PET film so that the thickness after drying would be 25 μm. The ink receiving layer was formed by coating and drying, and printing was recorded on the obtained recording sheet with a color ink jet printer (PM-800C manufactured by Seiko Epson Corporation), and the following items were evaluated.

(1) Blocking resistance An untreated PET film was layered on the surface of the ink receiving layer, and the blocking resistance after standing at a load of 0.29 MPa and a temperature of 40 ° C. for one day was evaluated. The results are displayed as follows:
○: No blocking property Δ: Some blocking property ×: Blocking property

(2) Transparency The haze on the surface of the ink receiving layer was visually determined. The results are displayed as follows:
○: Completely transparent △: Slightly cloudy ×: Completely opaque

(3) Colored vividness After color printing was performed on the ink receiving layer with an inkjet printer, the colored vividness of the obtained color image was visually observed. The results are displayed as follows:
○: Clear with no blurring △: Slightly blurring and slightly blurry

(4) Ink drying property After color printing on the ink receiving layer with an inkjet printer, the filter paper was pressed for 5 seconds with a load of 50 g / m ² , and the time until the ink was not transferred to the filter paper was measured.

(5) Water resistance of printed image After color printing on the ink receiving layer with an ink jet printer, the recording sheet is immersed in water (20 ° C., 1 hour) and then dried at room temperature. The change was observed visually. The results are displayed as follows:
○: No blurring or color change in the recorded image Δ: Change is observed in the recorded image and the ink receiving layer ×: The recorded image can be considerably taken or can be taken together with the ink receiving layer.

Comparative Example 8
The resin solution obtained in Comparative Example 1 and a nonionic surfactant (polyoxyethylene nonylphenyl ether: manufactured by Nippon Oil & Fats Co., Ltd.) were mixed and dissolved in a mass ratio of 95: 5.

Comparative Example 9
100 parts of polyvinyl butyral (degree of polymerization 700: manufactured by Sekisui Chemical Co., Ltd.), 50 parts of trioctyl phosphate, and 3 parts of polyoxyethylene lauryl ether ester (phosphate ester surfactant: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) It was mixed and dissolved in 400 parts.

[2] Application to anti-fogging / antistatic coatings The compositions and resin solutions obtained in Examples 1 to 3, Comparative Example 1, Comparative Example 8, and Comparative Example 9 were each dried on a transparent acrylic resin plate. The following methods are used to evaluate the surface hardness, antifogging property, water resistance, and antistatic property of the coating film of each sample by applying a brush and drying so that the thickness afterwards becomes 25 μm to form a coating film. I went there.

(1) Surface hardness It evaluated by the surface damage of the coating film by a pencil hardness test (JISK5400.88.4).

(2) Anti-fogging property The fogging of the coating film was evaluated when a sample plate was set at 5 cm on an 80 ° C. warm bath and exposed to water vapor for 10 minutes. The results are displayed as follows:
○: No cloudiness △: Partially cloudy ×: Cloudy

(3) Water resistance The state of the coating film was visually evaluated when a sample plate was set at 5 cm on an 80 ° C. warm bath and exposed to water vapor for 10 minutes. The results are displayed as follows:
○: No change △: Some change in coating film ×: Peeling or dissolution of coating film

(4) Antistatic property The adhesion of the charged carbon to the coating film was evaluated by a dust chamber test. The results are displayed as follows:
○: No carbon adhesion Δ: Partial carbon adhesion ×: Carbon adhesion Table 2 shows the above evaluation results.

The composition of the present invention has various moldings, films, sheets and the like due to its excellent adhesion to various materials, water absorption, water resistance, anti-fogging properties, transparency, flexibility, blocking resistance, slipperiness, etc. As a raw material for coatings, as a binder for paints, printing inks, and inkjet inks, coating agents for forming ink-receiving layers for inkjet recording sheets, fiber coating agents, antifogging coatings for agricultural resin sheets, and resin wallpaper for interiors, etc. It can be used as a surface treatment agent.

Claims (11)

  Organic polyisocyanates, high molecular weight hydrophilic polyols and / or polyamines, polysiloxanes having at least one active hydrogen-containing group in the molecule, at least one active hydrogen-containing group and at least one tertiary amino A hydrophilic polyurethane resin obtained by reacting a compound having a group in the same molecule with a compound having at least one reactive group and at least one hydrolyzable silyl group in the same molecule, and fine particles A fine particle alumina-dispersed hydrophilic polyurethane resin composition comprising a composition comprising alumina, wherein the fine particle alumina is stably dispersed in the hydrophilic polyurethane resin solution.   The fine particle alumina-dispersed hydrophilic polyurethane resin composition according to claim 1, wherein the content of the fine particle alumina is an amount occupying 5 to 95% by mass in the composition.   The fine particle alumina-dispersed hydrophilic polyurethane resin composition according to claim 1, wherein the fine particle alumina is added to the high molecular weight hydrophilic polyol and / or polyamine when the hydrophilic polyurethane resin is synthesized.   The fine particle alumina-dispersed hydrophilic polyurethane resin composition according to claim 1, wherein the fine particle alumina is fine particle alumina having an average particle diameter of 1 to 300 nm.   The content of hydrophilic segment, polysiloxane segment, tertiary amino group and hydrolyzable silyl group in the hydrophilic polyurethane resin is 30 to 80% by mass, 0.1 to 10% by mass, and 0.1 to 50 meq, respectively. The fine particle alumina-dispersed hydrophilic polyurethane resin composition according to claim 1, which is / g and 0.001 to 10 meq / g.   The fine particle alumina-dispersed hydrophilic polyurethane resin composition according to claim 1, wherein the hydrophilic segment is a polyethylene oxide segment.   Organic polyisocyanates, high molecular weight hydrophilic polyols and / or polyamines, polysiloxanes having at least one active hydrogen-containing group in the molecule, at least one active hydrogen-containing group and at least one tertiary amino A hydrophilic polyurethane resin obtained by reacting a compound having a group in the same molecule with a compound having at least one reactive group and at least one hydrolyzable silyl group in the same molecule, and fine particles In the method for producing a composition comprising alumina, a hydrophilic polyurethane resin is synthesized using the high molecular weight hydrophilic polyol and / or polyamine to which fine particle alumina is added as the above high molecular weight hydrophilic polyol and / or polyamine. A method for producing a fine particle alumina-dispersed hydrophilic polyurethane resin composition.   The fine particle alumina according to claim 7, wherein the high molecular weight hydrophilic polyol and / or polyamine added with the fine particle alumina is obtained by removing the dispersion medium of the alumina sol from the mixture of the high molecular weight hydrophilic polyol and / or the polyamine and the alumina sol. A method for producing a dispersed hydrophilic polyurethane resin composition.   The method for producing a fine particle alumina-dispersed hydrophilic polyurethane resin composition according to claim 7, wherein the content of the fine particle alumina is an amount occupying 5 to 95% by mass in the composition.   The method for producing a fine particle alumina-dispersed hydrophilic polyurethane resin composition according to claim 7, wherein the fine particle alumina is fine particle alumina having an average particle diameter of 1 to 300 nm.   The content of hydrophilic segment, polysiloxane segment, tertiary amino group and hydrolyzable silyl group in the hydrophilic polyurethane resin is 30 to 80% by mass, 0.1 to 10% by mass, and 0.1 to 50 meq, respectively. The fine particle alumina-dispersed hydrophilic polyurethane resin composition according to claim 7, which is / g and 0.001 to 10 meq / g.