JP4414211B2 - Method for producing silica-dispersed hydrophilic polyurethane resin composition - Google Patents

Description

The present invention relates to a method for producing a silica-dispersed hydrophilic polyurethane resin composition, and more specifically, has excellent adhesion to various materials, and has water absorption, antifogging properties, transparency, flexibility, water-based ink writing properties and water resistance. The present invention relates to a method for producing a silica-dispersed hydrophilic polyurethane resin composition having excellent properties, blocking resistance, and lubricity.

Polyurethane resin is excellent in abrasion resistance, adhesiveness, flexibility, chemical resistance, etc., and is also excellent in applicability to various processing methods, so as a binder for various coating agents, paints, inks, or films, It is widely used as a sheet and other molded articles, and a polyurethane resin suitable for each application has been proposed.
This polyurethane resin is a generic term for polyurethane resin, polyurea resin, and polyurethane-polyurea resin. These polyurethane-based resins are basically obtained by reacting a high-molecular-weight polyol component, an organic polyisocyanate component, and, if necessary, a chain extender component. A polyurethane resin having physical properties is provided.

However, polyurethane-based resins are hydrophilic in applications such as antifogging paints for agricultural resin sheets, surface treatment agents for interior resin wallpaper, fiber coating agents, and coating agents for inkjet image-receiving sheets. Usually, blocking resistance is also required at the same time.
Among the polyurethane resins, when polyethylene glycol obtained from ring-opening polymerization of ethylene oxide is used as the high molecular weight hydrophilic polyol component, a polyurethane resin having high strength, high elasticity, and excellent hydrophilicity can be obtained. However, there is a problem that the water resistance is poor and swelling, whitening, and strength reduction occur due to moisture, and it is not suitable for various paints, binders for printing inks, molded products, films, sheets and the like.

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

  The reason for this is that powdered fine particles, as widely known as thickeners and thixotropic agents, are obtained by dispersing a large amount of them in a polyurethane resin solution or a high molecular weight polyol. This is because it becomes extremely high. In addition, the fine particle filler generally reduces the transparency of the resin as is generally used as a matting agent (matting agent) for polyurethane resins, and even if the dispersion amount is as small as 5% by mass or less. Its transparency is significantly reduced.

The present invention has been made in view of the above circumstances, and the object of the present invention is that the above-mentioned problems do not occur even when a large amount of fine particles are used, the adhesiveness to various materials is excellent, and water absorption Another object of the present invention is to provide a method for producing a fine particle-dispersed hydrophilic polyurethane resin composition having excellent antifogging properties, transparency, flexibility, writing properties of water-based inks, water resistance, blocking resistance, and lubricity.

  As a result of repeated studies to achieve the above object, the present inventors have made a high molecular weight hydrophilic polyol in a raw material component when producing a hydrophilic polyurethane resin having a hydrophilic segment and a tertiary amino group. A composition in which fine particle silica is dispersed in a hydrophilic polyurethane-based resin obtained by using a high molecular weight hydrophilic polyol and / or polyamine in which fine particle silica is dispersed in advance as a polyamine is a fine particle in the solution. The present invention was completed by finding that a dispersion liquid in which silica was stably dispersed in the above-mentioned hydrophilic polyurethane resin solution was formed, and that the film was transparent, and that the above object was achieved.

The above object is achieved by the present invention described below. That is, the present invention, organic polyisocyanates, any of the following, a high molecular weight hydrophilic polyol and / or polyamine having a weight average molecular weight of 400～8,000, at least one and at least one active hydrogen-containing group tertiary compounds having in the same molecule an amino group, an average particle diameter of the hydrophilic polyurethane resin having obtained a hydrophilic segment tertiary amino group is reacted with a chain extender as needed for In the method for producing a hydrophilic polyurethane resin composition comprising fine particle silica of 1 μm or less , a silica sol comprising the hydrophilic polyurethane resin as at least part of the high molecular weight hydrophilic polyol and / or polyamine in the raw material component what the removal of the dispersing solvent silica sol from a mixture of the high molecular weight hydrophilic polyol and / or polyamine A method for producing a silica dispersion hydrophilic polyurethane resin composition characterized by producing in use.

Polyethylene glycol,
Polyethylene glycol / polytetramethylene glycol copolymer polyol,
Polyethylene glycol / polypropylene glycol copolymer polyol,
Polyethylene glycol adipate,
Polyethylene glycol succinate,
Polyethylene glycol / polyε-lactone copolymer polyol,
Polyethylene glycol / polyvalerolactone copolymer polyol,
Polyethylene oxide diamine,
Polyethylene oxide, propylene oxide diamine,
Polyethylene oxide triamine,
Polyethylene oxide propylene oxide triamine

  According to the present invention, it has excellent adhesion to various materials, and is excellent in water absorption, anti-fogging properties, transparency, water-based ink writing properties, water resistance, blocking resistance, and slipperiness. Silica-dispersed polyurethane resin useful as an anti-fogging paint for various films, as a surface treatment agent for preventing condensation on interior resin wallpaper, as a water-absorbing clothing coating material, or as a synthetic artificial leather material A composition is provided.

The present invention will now be described in more detail.
The silica-dispersed hydrophilic polyurethane resin composition of the present invention is a composition comprising a hydrophilic polyurethane resin having a hydrophilic segment and a tertiary amino group and fine particle silica. In the solution, the fine-particle silica is stably dispersed in the hydrophilic polyurethane-based resin solution without being separated or settled without using a dispersant regardless of the amount of the silica. The film formed from this solution is characterized by being transparent even when the amount of fine-particle silica dispersed is large. In the present invention, the polyurethane-based resin is a general term for a polyurethane resin, a polyurea resin, and a polyurethane-polyurea resin.

The silica-dispersed hydrophilic polyurethane resin composition of the present invention comprising a hydrophilic polyurethane resin having a hydrophilic segment and a tertiary amino group as described above and fine particle silica comprises an organic polyisocyanate , a high molecular weight hydrophilic polyol, and / or polyamine, at least one active hydrogen-containing group and at least one compound which contains a tertiary amino group in the same molecule, is reacted with a chain extender as needed hydrophilic in the molecule When producing a polyurethane-based resin, it can be obtained by using a mixture of the polyol and / or polyamine and silica sol as a part or all of the high molecular weight hydrophilic polyol and / or polyamine.

The mixture of high molecular weight hydrophilic polyol and / or polyamine and particulate silica, using a high molecular weight and a hydrophilic polyol and / or polyamine and silica sol were mixed, the mixture obtained by removing the dispersion solvent silica sol from the mixture you. The high molecular weight polyol and / or polyamine can also be used as a solution in which they are dissolved in an organic solvent. In that case, all the solvent is removed before use.

  The silica sol in the present invention is obtained by stably dispersing fine particle silica or a fine particle silica compound in a dispersion solvent. The average particle diameter of the fine particle silica in the silica sol is usually 1 μm or less, and particularly preferably 1 to 300 mμm (nm). The dispersion medium in silica sol is usually water and / or alcohol, but ketones, esters and other organic solvents are also used.

  Usually, even if silica sol (stable dispersion solution) is added to and dispersed in a polyurethane resin solution, the dispersion stability of the fine particle silica is low, and both are easily separated with time. This is because, for example, the compatibility (affinity) between the polyurethane resin and silica, the stability of both of them against changes in pH, and the properties of the polyurethane resin and the silica sol surface are different. In addition, it is possible to add silica sol when synthesizing polyurethane-based resins. However, silica sol water and alcohol-based dispersion media cannot be used because they react with isocyanate, and other solvent-based silica sols are used. In addition, the dispersion stability of the silica fine particles cannot be obtained.

  However, the high molecular weight hydrophilic polyol and / or polyamine described later used in the present invention has extremely high compatibility (affinity) with the silica sol due to its hydrophilicity, and can be stably mixed with the silica sol at an arbitrary ratio. . Then, by removing the dispersion medium from the mixture by an arbitrary method, a high molecular weight hydrophilic polyol and / or polyamine in which fine-particle silica is dispersed very stably can be obtained, and the high molecular weight hydrophilic polyol and / or polyamine in the mixture can be obtained. Even if the dispersion amount of the fine-particle silica is increased, the viscosity increase of the polyol and / or polyamine is small, and a very transparent mixture can be obtained.

  And when this mixture is used to synthesize polyurethane-based resin, this mixture is used as at least part of the high molecular weight hydrophilic polyol and / or polyamine in the raw material components, so that during the synthesis (polymerization) reaction and after the synthesis reaction. However, the fine particle silica does not separate and does not settle and can be stably present in the reaction system, and a hydrophilic polyurethane resin composition in which the fine particle silica is stably dispersed in the polyurethane resin solution can be obtained.

  A mixture of a high molecular weight hydrophilic polyol and / or polyamine and fine-particle silica is generally easy to remove water or water and an organic solvent as a dispersion solvent in the mixture from the above-mentioned polyol and / or polyamine and silica sol mixture under reduced pressure. Can be obtained. In this case, the distillation is preferably carried out under reduced pressure at a low temperature, particularly preferably at 70 ° C. or lower. When the temperature is higher than this, the fine particle silica may aggregate, the dispersion stability of the fine particle silica may decrease, and a silica-dispersed high molecular weight hydrophilic polyol and / or polyamine having low transparency may be generated. The mixing ratio of the high molecular weight hydrophilic polyol and / or polyamine and the fine particle silica is preferably such that the fine particle silica content in the resulting silica-dispersed hydrophilic polyurethane-based resin composition (solid content) is 5 to 95% by mass. More preferably, the amount is 10 to 90% by mass.

Silica Dispersion hydrophilic polyurethane resin composition of the present invention, as a part or the whole of the high molecular weight hydrophilic polyol and / or polyamine is more obtained the child removing the dispersion solvent silica sol from mixtures thereof with silica sol A compound having a high molecular weight polyol and / or polyamine in which fine particle silica is dispersed, an organic polyisocyanate, and at least one active hydrogen-containing group and at least one tertiary amino group in the molecule. If necessary, it can be obtained by reacting with a chain extender according to a conventionally known method for producing a polyurethane resin. The reaction may be solventless or a reaction in an aqueous solution or an organic solvent. In the case of no solvent, the obtained silica-dispersed hydrophilic polyurethane resin composition can be used by dissolving in a soluble solvent of the hydrophilic polyurethane resin. Also in this case, the dispersion stability of the fine particle silica in the hydrophilic polyurethane resin solution is maintained. The polymerization solvent and the resin-soluble solvent are not particularly limited, and preferred examples include dimethylformamide and methyl ethyl ketone. The silica-dispersed hydrophilic polyurethane resin composition of the present invention is used in a solution state or in a solid state depending on the application.

  The hydrophilic polyurethane resin in the silica-dispersed hydrophilic polyurethane resin composition of the present invention comprises a hydrophilic segment having a high molecular weight hydrophilic polyol and / or polyamine in the molecule and at least one tertiary amino acid. And a tertiary amino group-containing segment having a group-containing compound as a structural unit. When the chain extender is not used, the hydrophilic segment and the segment having a tertiary amino group are randomly bonded by a urethane bond, a urea bond or a urethane-urea bond, respectively. When a chain extender is used, there is a bond in which a short chain that is a residue of the chain extender exists between the bonds.

  By introducing a tertiary amino group into the molecule, the hydrophilic polyurethane resin in the present invention has excellent adhesiveness to various materials, and excellent water absorption, antifogging properties, transparency, and flexibility. In addition, the writing property of water-based ink and excellent water resistance, blocking resistance, and lubricity are imparted.

  For example, let us consider why water resistance is imparted by taking the case of printing on a recording paper having an ink receiving layer formed of the silica-dispersed hydrophilic polyurethane resin composition of the present invention. The dye / pigment molecules of printing inks and inkjet inks generally have anionic carboxyl groups and sulfonic acid groups in the molecules, and hydrophilic polyurethane resins having tertiary amino groups introduced thereinto and the above-mentioned When the dye / pigment is mixed or contacted, an ionic bond is formed between the dye / pigment and the tertiary amino group in the resin, thereby improving the fixing property of the dye / pigment and the water resistance of the recorded image. it is conceivable that.

  However, in the presence of moisture, the ionic bonds as described above are easily dissociated and the improvement in water resistance should not be expected, but the water resistance is improved. The reason for improving the water resistance is not clear, but the polyurethane resin in the present invention is hydrophilic, but there is also a hydrophobic part in the molecule, and the hydrophilic part and tertiary amino in the resin are present. After the ionic bond is formed between the group and the dye / pigment, the hydrophobic portion is surrounded by the ionic bond portion, so that the water resistance is considered to be improved.

  In the present invention, the compound used to introduce a tertiary amino group into the molecular chain constituting the hydrophilic polyurethane-based resin is at least one active hydrogen-containing group (reactive group) in the molecule, for example, amino It is a compound having a group, an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, an alkoxy group, an acid halide group, a carboxyester group, an acid anhydride group and the like 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、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、これらの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 the following compounds.
Compound represented by general formula (1)

(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—, A lower alkylene group which may be linked by —CO—, —COO—, —NHCO—, —S—, —SO—, —SO ₂ —, etc., and X and Y are —OH, —COOH, —NH ₂ , a reactive group such as —NHR ₁ —, —SH, etc. X and Y may be the same or different, and an epoxy group, an alkoxy group, an acid halide group, an acid anhydride group that can be derived from these groups. 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。） Compound represented by general formula (2)

(In the formula, R ₁ , R ₂ , R ₃ , X and Y are as defined 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。） Compound represented by general formula (3)

(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 compound represented by the general formula (1), (2) or (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-diaminopropane,

N-hydroxyethyl-piperazine,
N, N-dihydroxyethyl-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-diaminotriazine,
2,5-diaminotriazole,
There are 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. As the adduct, for example,

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

  As the organic polyisocyanate used in the present invention, any conventionally known polyisocyanate can be used and is 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 high molecular weight hydrophilic polyol and / or polyamine used in the present invention, the weight average molecular weight having a hydroxyl group or an amino group is in the range of 400 to 8,000 , and the terminal is a hydroxyl group and has a hydrophilic property. Specifically ,
Polyethylene glycol,
Polyethylene glycol / polytetramethylene glycol copolymer polyol,
Polyethylene glycol / polypropylene glycol copolymer polyol,
Polyethylene glycol adipate,
Polyethylene glycol succinate,
Polyethylene glycol / polyε-lactone copolymer polyol,
Polyethylene glycol / poly-valerolactone copolymer a polyol Le and the like.

As a polyamine having a terminal amino group and hydrophilicity, specifically ,
Polyethylene oxide diamine,
Polyethylene oxide, propylene oxide diamine,
Polyethylene oxide triamine,
Polyethylene oxide-propylene oxide tri Amin.

In the production of hydrophilic polyurethane resins, other polyols, polyamines, polycarboxylic acids, etc. that do not have a hydrophilic chain as described above may be appropriately copolymerized in order to impart other performance to the resulting resin. Is possible.
Moreover, as a chain extender used as needed in this invention, all conventionally well-known chain extenders, such as low molecular weight diol and diamine, can be used, and it is not specifically limited. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, ethylenediamine, hexamethylenediamine and the like can be mentioned.

  The hydrophilic polyurethane resin having a hydrophilic segment and a tertiary amino group in the molecular chain in the silica-dispersed hydrophilic polyurethane resin composition of the present invention obtained by using the above raw material components has a weight average molecular weight (GPC The measured standard polystyrene conversion) is preferably in the range of 3,000 to 800,000, and more preferably in the range of 5,000 to 500,000.

  In the silica-dispersed hydrophilic polyurethane resin composition of the present invention, the content of fine-particle silica is preferably 5 to 95% by mass, more preferably 10 to 90% by mass in the composition. If the content of the fine-particle silica is less than 5% by mass, the surface properties such as blocking resistance and lubricity, which are the objects of the present invention, will be insufficiently expressed. It is not preferable because it is inferior. Surprisingly, when the content of fine-particle silica is 75 to 95% by mass, when the base material is coated with the silica-dispersed hydrophilic polyurethane resin composition of the present invention, a microporous material with a size of several mμm (nm) is obtained. And a film with excellent transparency is formed.

  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 eq (equivalent) / kg, more preferably 0.5 to 20 eq / kg. When the content of the tertiary amino group is less than 0.1 eq / kg, that is, 1 or less per 10,000 molecular weight, the properties such as water resistance and blocking resistance, which are the intended purposes of the present invention, are insufficient. On the other hand, when the content of the tertiary amino group is 50 eq / kg or more, that is, 500 or more per 10,000 molecular weight, the water repellency increases due to the decrease of the hydrophilic portion in the resin, and the water absorption performance and antifogging property are inferior. This is not preferable.

  The content of the hydrophilic segment in the 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. If the content of the hydrophilic segment is less than 30% by mass, the water absorption and antifogging properties are inferior. On the other hand, if it exceeds 80% by mass, the water resistance and blocking resistance are inferior.

  The silica-dispersed hydrophilic polyurethane-based resin composition obtained in the present invention as described above is excellent in adhesion to various materials, and has water absorption, antifogging properties, transparency, flexibility, water-based ink writing properties and water resistance. Excellent in blocking resistance and slipperiness, as a coating agent for image-receiving layers of inkjet image-receiving sheets, as an anti-fogging paint for various films, and as a surface treatment agent for preventing condensation on resin wallpaper for interiors, for water-absorbing clothing As a coating agent, it is very useful as a material for synthetic leather, a water-based ink writing treatment for synthetic paper, and the like. In addition, the silica-dispersed hydrophilic polyurethane resin composition of the present invention can be used in the production of various molded articles in a solid state.

  Next, the present invention will be described in more detail with reference examples, examples and comparative examples. In addition, the part or% in a sentence is a mass reference | standard.

Reference example 1
700 parts of polyethylene glycol (molecular weight 1,000) and 1500 parts of silica water sol (silica average particle size 10-20 nm, solid content 20%) are thoroughly mixed, and the resulting mixture is stirred under reduced pressure at 70 ° C. with stirring. went.
After the theoretical amount of water was distilled off, the temperature was raised to 120 ° C. and water was removed under reduced pressure of 133.3 Pa or less to obtain a white solid polyol (A) having a silica content of 30%. This polyol had a hydroxyl value of 76 mgKOH / g, a moisture content of 0.15%, was transparent at 80 ° C., and had a viscosity of 450 dPa · s.

Reference example 2
100 parts of polyethylene glycol (molecular weight 590) and silica water sol (silica average particle size 200-230 nm, solid content 30%) 333 parts were sufficiently mixed, and the resulting 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 removed under reduced pressure of 133.3 Pa or less to obtain a white solid polyol (B) having a silica content of 50%. This polyol had a hydroxyl value of 95 mgKOH / g, a moisture content of 0.12%, and softened at 110 ° C.

Reference example 3
100 parts of polyethylene oxide diamine (Jefamine ED manufactured by Texaco Chemical Co., Ltd .; molecular weight 600) and 2250 parts of silica methanol sol (silica average particle size 20 to 30 nm, solid content 40%) are sufficiently mixed, and the resulting mixture is stirred. Under reduced pressure dehydration at 70 ° C.
After the theoretical amount of water was distilled off, the temperature was raised to 120 ° C. and water was removed under reduced pressure of 133.3 Pa or less to obtain a white solid polyamine (C) having a silica content of 90%. This polyamine was softened at an amine equivalent of 30 g / mol, a moisture content of 0.20%, and 130 ° C.

Example 1
(Production of silica-dispersed polyurethane resin composition)
50 parts of polyethylene glycol (molecular weight 2,040), 100 parts of polyol (A) of Reference Example 1, 20 parts of N-methyldiethanolamine and 5 parts of diethylene glycol are mixed in a mixed solvent of 200 parts of methyl ethyl ketone and 200 parts of dimethylformamide. The solution which melt | dissolved and melt | dissolved 80 parts hydrogenated MDI in 200 parts methyl ethyl ketone was dripped gradually, stirring well at 60 degreeC. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 8 hours, and then 420 parts of dimethylformamide was added to obtain a solution of the silica-dispersed polyurethane resin composition of the present invention.

This solution has a solid content of 20%, a viscosity of 33 dPa · s (25 ° C.), and is measured by GPC of a polyurethane resin. The weight average molecular weight in terms of standard polystyrene (the same applies to the following examples) is 53,000. The tertiary amino group content in the resin was 0.52 eq / kg, and the silica content was 11.7%.
The film formed from this resin composition solution was transparent, the breaking strength was 25.7 Mpa, the breaking elongation was 50%, and the softening point was 165 ° C.

Example 2
(Production of silica-dispersed polyurethane-polyurea resin composition)
30 parts of polyethylene oxide diamine (Jefamine ED; molecular weight 2,000), 120 parts of polyol (B) of Reference Example 2, and N, N-dimethyl-N ′, N′-dihydroxyethyl-1,3-diaminopropane 25 A solution of 65 parts of hydrogenated MDI dissolved in 100 parts of methyl ethyl ketone was gradually added dropwise to 100 parts of methyl ethyl ketone and 200 parts of dimethylformamide mixed solvent. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 8 hours, and then 560 parts of dimethylformamide was added to obtain a solution of the silica-dispersed polyurethane-polyurea resin composition of the present invention.

This solution had a solid content of 20% and a viscosity of 35 dPa · s (25 ° C.). The weight average molecular weight of the polyurethane-polyurea resin was 48,000, the tertiary amino group content in the resin was 1.08 eq / kg, and the silica content was 24%.
The film formed from this resin composition solution was transparent, the breaking strength was 21.5 Mpa, the breaking elongation was 20%, and the softening point was 185 ° C.

Example 3
(Production of silica-dispersed polyurea resin composition)
Polyethylene oxide diamine (Jephamine ED; molecular weight 2,000) 5 parts, polyamine (C) 145 parts of Reference Example 3 and 3 parts of methyliminobispropylamine are dissolved in 250 parts of dimethylformamide, and the internal temperature is adjusted to 0- A solution prepared by dissolving 7 parts of hydrogenated MDI in 100 parts of dimethylformamide was gradually added dropwise and reacted while stirring at 5 ° C. After completion of the dropwise addition, the internal temperature was gradually raised, and the reaction was further continued for 5 hours when the temperature reached 50 ° C. Then, 310 parts of dimethylformamide was added to obtain a solution of the silica-dispersed polyurea resin composition of the present invention.

This solution has a solid content of 20%, a viscosity of 60 dPa · s (25 ° C.), the polyurea resin has a weight average molecular weight of 35,000, and the content of tertiary amino groups in the resin is 0.45 eq. / Kg, the content of silica was 79%.
The film formed from this resin composition solution was slightly translucent and porous, had a breaking strength of 3.2 Mpa, a breaking elongation of 3%, and a softening point of 220 ° C.

Comparative Example 1
A polyurethane resin solution was obtained by the same material and formulation as in Example 1 except that N-methyldiethanolamine was not used and the polyol of the polyol (A) of Reference Example 1 except for the silica was used.
This solution had a solid content of 20%, a viscosity of 50 dPa · s (25 ° C.), and the weight-average molecular weight of the polyurethane resin was 68,000.
The film formed from this resin solution had a breaking strength of 35.0 Mpa, a breaking elongation of 450%, and a softening point of 103 ° C.

Comparative Example 2
Example 2 except that N, N-dimethyl-N ′, N′-dihydroxyethyl-1,3-diaminopropane was not used and the polyol (B) of Reference Example 2 except for the silica was used. A polyurethane-polyurea resin solution was obtained using the same materials and formulation.
This solution had a solid content of 20%, a viscosity of 40 dPa · s (25 ° C.), and the weight-average molecular weight of the polyurethane-polyurea resin was 55,000.
The film formed from this resin solution had a breaking strength of 25.3 MPa, a breaking elongation of 400%, and a softening point of 95 ° C.

Comparative Example 3
A solution of a polyurea resin was obtained by the same material and formulation as in Example 3 except that methyliminobispropylamine was not used and the polyamine of Reference Example 3 except for the polyamine (C) silica was used.
This solution had a solid content of 20%, a viscosity of 25 dPa · s (25 ° C.), and the polyurea resin had a weight average molecular weight of 32,000.
The film formed from this resin solution had a breaking strength of 22.7 MPa, a breaking elongation of 350%, and a softening point of 115 ° C.

Comparative Examples 4-6
The silica water sol or silica methanol sol of Reference Examples 1 to 3 was added to each resin solution of Comparative Examples 1 to 3 with stirring, but the particles precipitated and the solution became opaque.

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

The silica-dispersed polyurethane resin composition obtained above was evaluated by the following method.
[1] Application to Inkjet Image Receiving Layer Each of the resin composition solutions obtained in Examples 1 to 3 and Comparative Examples 1 to 7 is dried to a thickness of 25 μm on a 100 μm thick PET film. A transparent sheet was prepared by coating, and printing was recorded with a color ink jet printer (PM-800C manufactured by Seiko Epson Corporation), and the following items were evaluated.

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

(2) Transparency The haze on the resin coating surface was judged visually. The results are displayed as follows:
○: Completely transparent △: Slightly cloudy ×: Completely opaque

(3) Colored sharpness After color printing with an inkjet printer, the color sharpness of the obtained color image was visually observed. The results are displayed as follows:
○: Clear without blur △: Slightly blurred and slightly blurred ×: Blurred

(4) Dryability of ink After color printing 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 with an ink jet printer, the recording sheet was immersed in water (20 ° C, 1 hour) and then dried at room temperature. . The results are displayed as follows:
○: No change Δ: Change is observed in ink and film ×: Ink can be removed considerably or the entire film can be taken Table 1 shows the above evaluation results.

Comparative Example 8
To the resin solution obtained in Comparative Example 1, a nonionic surfactant (polyoxyethylene nonylphenyl ether: manufactured by Nippon Oil & Fats) was mixed so as to have a mass ratio of 95: 5.

Comparative Example 9
Polyvinyl butyral (degree of polymerization 700: manufactured by Sekisui Chemical Co., Ltd.), trioctyl phosphate 50 parts and polyoxyethylene lauryl ether acid ester (phosphate ester surfactant: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in 400 parts of ethanol Mixed and dissolved.

[2] Application to anti-fogging / anti-static coatings Each of the resin compositions obtained in Examples 1 to 3 and Comparative Examples 1, 8, and 9 is dried on a transparent acrylic resin plate. The sample was brush-coated to a thickness of 25 μm, and the surface hardness, antifogging property and antistatic property were evaluated.
(1) Surface hardness It evaluated by the surface damage | wound 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 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 Adhesiveness of charged carbon 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.

Claims (4)

An organic polyisocyanate, any of the following high molecular weight hydrophilic polyols and / or polyamines having a weight average molecular weight of 400 to 8,000 , at least one active hydrogen-containing group and at least one tertiary amino group: From a hydrophilic segment obtained by reacting a compound having the same in the same molecule with a chain extender as necessary, a hydrophilic polyurethane resin having a tertiary amino group, and fine particle silica having an average particle size of 1 μm or less. In the method for producing a hydrophilic polyurethane-based resin composition, silica sol and the above-mentioned high-molecular weight hydrophilic polyol are obtained by using the hydrophilic polyurethane-based resin as at least part of the high-molecular weight hydrophilic polyol and / or polyamine in the raw material component. prepared using and / or a material obtained by removing the dispersion solvent silica sol from a mixture of polyamines Method for producing a silica dispersion hydrophilic polyurethane resin composition characterized and.
Polyethylene glycol,
Polyethylene glycol / polytetramethylene glycol copolymer polyol,
Polyethylene glycol / polypropylene glycol copolymer polyol,
Polyethylene glycol adipate,
Polyethylene glycol succinate,
Polyethylene glycol / polyε-lactone copolymer polyol,
Polyethylene glycol / polyvalerolactone copolymer polyol,
Polyethylene oxide diamine,
Polyethylene oxide, propylene oxide diamine,
Polyethylene oxide triamine,
Polyethylene oxide propylene oxide triamine 2. The silica-dispersed hydrophilic polyurethane resin composition according to claim 1 , wherein the content of the fine-particle silica in the mixture is 5 to 95% by mass in the silica-dispersed hydrophilic polyurethane resin composition to be formed. Manufacturing method. The method for producing a silica-dispersed hydrophilic polyurethane resin composition according to claim 1, wherein the fine particle silica has an average particle diameter of 1 to 300 nm. The content of the tertiary amino groups of the hydrophilic polyurethane resin is, 0.1~50eq / kg, silica dispersion hydrophilic polyurethane according to claim 1, wherein the content of the hydrophilic segment is 30 to 80 wt% Of the resin-based resin composition.