JP2000063479A - Hydrophilic polyurethane-based resin and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydrophilic polyurethane-based resin excellent in adhesion to various kinds of materials as well as excellent in water absorption, anti- fogging property, transparency, flexibility, writability and water resistance of an aqueous ink, blocking resistance and lubricity, and to provide a process for preparing the same. SOLUTION: The objective hydrophilic polyurethane-based resin is obtained by reacting an organic polyisocyanate with a high mol.wt. hydrophilic polyol or polyamine, a polysiloxane compound containing at least one active hydrogen group, a compound containing at least one reactive group and at least one hydrolyzable silyl group in the same molecule and, if required, a chain extender, comprises a hydrophilic segment, a polysiloxane segment and a hydrolyzable silyl group-containing segment, the content of the hydrolyzable silyl group being 0.001-10 eq/g, and has a wt. average mol.wt. of 3,000-800,000.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic polyurethane resin and a method for producing the same, and more specifically, it has excellent adhesiveness to various materials, and also has water absorbency, antifogging property, transparency, flexibility and water-based ink. The present invention relates to a hydrophilic polyurethane resin excellent in writability, water resistance and blocking resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Polyurethane resins have excellent wear resistance, adhesiveness, flexibility, chemical resistance, and suitability for various processing methods. It is widely used as a binder, a film, a sheet, and other molded products, and a polyurethane resin suitable for each application has been proposed. The polyurethane resin is a general term for polyurethane resin, polyurea resin, and polyurethane-polyurea resin, and the same applies to the following inventions. Polyurethane resin is
Basically, it is obtained by reacting a high molecular weight polyol component, an organic polyisocyanate component, and optionally a chain extender component, and a polyurethane resin having various physical properties depending on the type and combination of these components. Can be manufactured.

[0003]

However, depending on the application, polyurethane resins are used, for example, in antifogging paints for agricultural resin sheets, surface treatment agents for interior resin wallpaper, fiber coating agents, and ink jet image-receiving agents. In the case of a coating agent for a sheet or the like, it is usual that hydrophilicity and blocking resistance are required together with the above-mentioned properties. When polyethylene glycol obtained from ring-opening polymerization of ethylene oxide is used as a high molecular weight hydrophilic polyol component to obtain a hydrophilic polyurethane resin, a polyurethane resin having high strength, high elasticity and excellent hydrophilicity is obtained. Although it can be obtained, it has a problem that it is not suitable for various paints, binders for printing inks, molded products, films, sheets, etc. due to poor water resistance, resulting in swelling, whitening, and reduction in strength.

Accordingly, the object of the present invention is to provide a hydrophilic material which is excellent in adhesiveness to various materials and is excellent in water absorption, antifogging property, transparency, flexibility, water-based ink writing property, water resistance and blocking resistance. PROBLEM TO BE SOLVED: To provide a polyurethane resin and a method for producing the same.

[0005]

The above object can be achieved by the present invention described below. That is, the present invention is an organic polyisocyanate, high molecular weight hydrophilic polyol or polyamine,
Obtained by reacting a polysiloxane compound having at least one active hydrogen group, a compound having at least one reactive group and at least one hydrolyzable silyl group in the same molecule, and a chain extender if necessary. A hydrophilic segment, a polysiloxane segment and a segment containing a hydrolyzable silyl group, the content of the hydrolyzable silyl group is 0.001 to 10 eq / g, and the weight average molecular weight is 3,000 to 800. And a hydrophilic polyurethane-based resin characterized by reacting the above-mentioned components.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. The hydrophilic polyurethane resin of the present invention comprises an organic polyisocyanate, a high molecular weight hydrophilic polyol or polyamine, and optionally a chain extender, a polysiloxane compound having at least one active hydrogen group and at least one reactive compound. Group and at least one
It can be obtained by copolymerizing a compound having one hydrolyzable silyl group in the same molecule.

The polyurethane resin of the present invention is composed of a hydrophilic segment, a polysiloxane segment and a segment containing a hydrolyzable silyl group, and the hydrolyzable silyl group in the resin is crosslinked with water to give a hydrophilic polyurethane. Excellent adhesion to various materials, excellent water absorption, antifogging property, transparency, flexibility, writability of water-based ink, water resistance and blocking resistance are imparted to the resin.

In the present invention, the method of synthesizing the hydrophilic polyurethane resin may be any conventionally known method of synthesizing urethane resin and is not particularly limited. The raw material components used in the synthesis of the hydrophilic polyurethane resin (hereinafter sometimes simply referred to as "resin") will be described.

(1) Introduction of hydrolyzable silyl group (hydrolyzable silyl group-containing segment) When a hydrolyzable silyl group is introduced into a resin, the water resistance of the resin is improved by crosslinking the group with water. Further, the blocking resistance is also improved by improving the surface strength of the resin film by crosslinking. The site of introduction of the hydrolyzable silyl group is not particularly limited, but is usually the molecular chain terminal and / or molecular side chain of the resin. The crosslinking of the hydrolyzable silyl group introduced at the molecular chain terminal and / or the molecular side chain of the resin with water is represented by the formula (I) and / or the formula (II).

[0010] Water may be added to crosslink the resin, but since the resin of the present invention is hydrophilic, water in the air can also be used.
It is preferable to add a catalyst to the resin in order to accelerate the silanol condensation of the crosslink formation in the above formula. As such a catalyst, a tin-based carboxylate, an acidic catalyst and a basic catalyst are generally preferable, and 0.0001 relative to the resin.
It is used in the range of 10% by weight to 10% by weight.

In the present invention, the compound used for introducing the hydrolyzable silyl group into the hydrophilic polyurethane resin is a silane coupling agent having a reactive organic functional group, the silane coupling agent and an organic polyisocyanate. And a compound having at least one free isocyanate group obtained by the reaction of.

Examples of the silane coupling agent having a reactive organic functional group used in the present invention include the following compounds. [1] A silane coupling agent represented by the general formula (1) and having at least one free isocyanate group. (In the formula, R ₁ represents a lower alkyl group, R ₂ represents a lower alkyl group or a lower alkoxy group. X represents a divalent organic group, preferably C _{0 to} C ₅₀ alkylene chain, aromatic or It is an aliphatic ring, and these groups are -N-, -O-,-
CO-, -COO-, -NHCO-, -S-, -SO-
Alternatively, they may be linked by a linking group such as —SO ₂ . or,
It is an integer of m = 0 to 3, and n = 3-m. )

Specific preferred examples of the silane coupling agent having a free isocyanate group are as follows.

[2] A reaction product of a silane coupling agent having a reactive organic functional group and an organic polyisocyanate, the product having at least one free isocyanate group in the molecule. Examples of the silane coupling agent having a reactive organic functional group used in this case include those represented by the following general formula (2). (In the formula, Y is —NH—, —NR ₃ —, —O—, or —S.
Represents —, R ₁ , R ₂ , X, m and n are as defined above, and R ₃ represents a lower alkyl group. )

Preferred specific examples of the above-mentioned silane coupling agent having a reactive organic functional group are as follows.

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

The above-mentioned silane coupling agent is reacted to introduce a hydrolyzable silyl group into the hydrophilic polyurethane resin. The introduction site of the group is not particularly limited, but usually the molecular chain end of the resin and / or It is a molecular side chain. An example of the method of introducing a hydrolyzable silyl group into the molecular chain terminal and / or the molecular side chain of the resin is shown below. 1) Introduction to the end of the molecular chain

2) Introduction into side chain of molecular chain (R ₁ , R _2, X and Y in the above formula are the same as above,
[P] represents hydrophilic polyurethane, hydrophilic polyurea or hydrophilic polyurethane-polyurea containing at least two urethane bonds and / or urea bonds per polymer molecule, and Z represents -O-, -S-,-. NR ₃ — or —NH—, R ₃ is a lower alkylene group, m = 0 to 3
, N = 3-m. ) A hydrolyzable silyl group can be introduced into the molecular chain terminal and / or the molecular side chain of the hydrophilic resin by a method other than the above, but the hydrophilic resin having the group introduced by a method other than the above examples Needless to say, also corresponds to the hydrophilic resin of the present invention.

(2) Introduction of polysiloxane segment Introducing a polysiloxane segment which is originally hydrophobic (water repellent) into the resin structure is expected to give good results with respect to water absorption and hydrophilicity. Although not possible, the film surface made of a resin having a low polysiloxane segment content is completely covered with the polysiloxane component in the dry state, but when immersed in water, the polysiloxane component is buried in the resin, In other words, it is known to have environmental responsiveness (Polymer Thesis Collection, Volume 48, [Part 4
No.], p. 227 (1991), etc.). The present invention utilizes this phenomenon, and by appropriately controlling the polysiloxane content in the resin, when printing with high humidity or water-based ink, the surface shows hydrophilicity due to environmental response, The surface during or after drying is covered with a polysiloxane component, and excellent water resistance, blocking resistance, lubricity and the like are exhibited.

In the present invention, the polysiloxane compound used for introducing the polysiloxane segment into the molecular chain constituting the hydrophilic polyurethane resin is one or more reactive groups such as amino group in the molecule. It is a polysiloxane compound having a group, an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group and the like. Preferred examples of the polysiloxane compound having a reactive group include the following compounds.

(1) Amino-modified polysiloxane compound

[0022]

(2) Epoxy-modified polysiloxane compound

(3) Alcohol-modified polysiloxane compound

[0025]

[0026]

(4) Mercapto-modified polysiloxane compound

(5) Carboxyl-modified polysiloxane compound

[0029]

(3) Introduction of hydrophilic segment As the high molecular weight hydrophilic polyol or polyamine used for introducing the hydrophilic segment into the hydrophilic polyurethane resin in the present invention, a hydroxyl group, an amino group, a carboxyl group, etc. may be used. Having a weight average molecular weight of 400 to 8.0
The range of 00 is preferable. Examples of the one having a hydroxyl group at the end and having hydrophilicity include, for example, polyethylene glycol polyethylene glycol / polytetramethylene glycol copolymer polyol polyethylene glycol / polypropylene glycol copolymer polyol polyethylene glycol adipate polyethylene glycol succinate polyethylene glycol / poly-ε-lactone copolymer. Polymerized Polyol Polyethylene glycol / poly-valerolactone copolymer Polyol Polyethylene oxide diamine polyethylene oxide propylene oxide diamine polyethylene oxide triamine polyethylene oxide propylene oxide triamine Others having a carboxyl group or vinyl group as an amino group having hydrophilicity Examples include ethylene oxide adducts It is. Further, in the present invention, in order to impart other properties, it is also possible to copolymerize another polyol, polyamine, polycarboxylic acid or the like having no hydrophilic chain.

As the organic polyisocyanate used in the present invention, any conventionally known one can be used. For example, preferred are 4,4'-diphenylmethane diisocyanate (MDI), water-added MDI, isophorone diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisotoanate, 1,5-naphthalene diisocyanate, m
-Phenylene diisocyanate, p-phenylene diisocyanate, etc., or a polyurethane prepolymer obtained by reacting such an organic polyisocyanate with a low molecular weight polyol or polyamine so as to become a terminal isocyanate can naturally be used.

In the present invention, a hydrophilic polyurethane resin having a hydrolyzable silyl group at the end of the molecular chain and / or a side chain of the molecule and having a polysiloxane segment and a hydrophilic segment in the molecular chain, that is, a hydrophilic polyurethane resin The polyurethane resin, hydrophilic polyurea resin and hydrophilic polyurea-polyurethane resin can be synthesized without solvent or in an aqueous solution or solvent according to a conventionally known method. The amount of each component used is such that the amount of hydrolyzable silyl group-containing segment, the amount of polysiloxane segment, and the amount of hydrophilic segment in the resin shown below are used. Thus obtained,
Preferred weight average molecular weight of the hydrophilic polyurethane resin of the present invention comprising a polysiloxane segment, a segment having a hydrolyzable silyl group and a hydrophilic segment in the molecular chain (in terms of standard polystyrene measured by GPC)
Is 3,000 to 800,000, and a more preferable weight average molecular weight is 5,000 to 500,000.

The hydrolyzable silyl group in the hydrophilic polyurethane resin of the present invention may be contained in either one or both of the side chain (pendant) and the main chain, and the content in the resin is As a compound having a hydrolyzable silyl group as a raw material, that is, as a group-containing segment amount of 1 to 4
A range of 0% by weight is preferred. More preferably, it is 1 to 10% by weight.

The number of hydrolyzable silyl groups in the resin is
0.001 to 10 equivalents (eq) / g is preferable, more preferably 0.01 to 1.0 eq / g, that is, about 0.001 to 10 per 1,000 molecular weight of the resin is preferable, and more preferably The ratio is 0.01 to 1.0.
If the content of the hydrolyzable silyl group is less than the above range, properties such as blocking resistance, water resistance, and moisture resistance, which are the intended purposes of the present invention, will be insufficiently expressed, while if it exceeds the above range, It is not preferable because the hydrophilic portion is reduced and the cross-linked structure of the resin increases the water resistance, resulting in poor water absorption performance and antifogging property.

The polysiloxane segment in the resin may be contained in the main chain or side chain of the resin, or in both, and the content is 0.1 to 10% by weight in the hydrophilic polyurethane resin. Preferably, more preferably 0.5
10 to 10% by weight. When the content of the polysiloxane segment is less than 0.1% by weight, the surface properties such as water resistance, blocking resistance and lubricity which are the objects of the present invention are insufficiently expressed, while when it exceeds 10% by weight, the polysiloxane segment is not contained. The water repellency by the method becomes strong, the environmental responsiveness used in the present invention becomes poor, and the water absorption, the antifogging property and the transparency become poor, which is not preferable.

The hydrophilic segment in the resin is contained in the main chain of the resin, and the content in the resin is preferably 30 to 80% by weight, more preferably 50 to 75% by weight. If the content with the hydrophilic segment is less than the above range, the water absorption and antifogging properties will be inferior, and if it exceeds the above range, the water resistance and blocking resistance will be inferior.

In the hydrophilic polyurethane resin obtained in the present invention, each of the above segments is randomly urethane-bonded,
It is linked by at least one bond of a urea bond and a urethane-urea bond (when a chain extender is not used). When chain extenders are used, there are also bonds with these bonds, with a short chain being the residue of the chain extender between these bonds. The above bond is also a constituent component of the resin of the present invention, and is collectively referred to as a bond part. The balance of the content of all the above segments is the content of the bonding portion in the resin.

The hydrophilic polyurethane-based resin of the present invention as described above has excellent adhesiveness to various materials, water absorption,
It has excellent antifogging properties, transparency, flexibility, water-based ink writing properties, water resistance, and blocking resistance. It is used as a coating agent for the image receiving layer of inkjet image receiving sheets, as an antifogging paint for various films, and as an interior resin. It is extremely useful as a surface treatment agent for preventing dew condensation on wallpaper, as a water-absorbent coating agent for clothing, as a material for synthetic leather, as a treatment agent for writing aqueous ink on synthetic paper, and the like.

[0039]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. Parts and% below are based on weight unless otherwise specified.

Example 1 (Production of molecular side chain type hydrolyzable silyl group-silicone polyurethane resin) 5 parts of polydimethylsiloxane polyol (molecular weight 3,200) having the above structure, 145 parts of polyethylene glycol (molecular weight 2,040), 15 parts of 1,3-butylene glycol, 125 parts of toluene and 100 parts of methyl ethyl ketone. 58 parts of diphenylmethane diisocyanate is added to the mixed solvent of 1) while stirring well at 70 ° C. After completion of addition, 10 more methyl ethyl ketones
0 part was added, and the mixture was reacted at 80 ° C. for 6 hours.

In the infrared absorption spectrum of the obtained resin, absorption of hydroxyl group was not recognized, and the pyridine method (JISK-0
No hydroxyl group was confirmed by quantification according to 070 2.5). Next, a silane coupling agent having an isocyanate group ((C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NCO) 8
Parts and react at 80 ° C. for 8 hours, and after confirming that the isocyanate groups have disappeared, the solid content concentration is 35%.
To obtain a solution of the hydrophilic polyurethane resin of the present invention. This solution had a viscosity of 390 dPa · s (25 ° C.).

Example 2 (Production of Molecular Terminal Hydrolyzable Silyl Group-Silicone Polyurea Resin) Dissolve 37 parts of water-added MDI in 100 parts of dimethylformamide, keep the internal temperature at 20 ° C., and stir well.
145 parts of polyethylene oxide diamine (Jeffamine ED: Texaco Chemical Co., molecular weight 2,000) dissolved in 50 parts of dimethylformamide and 5 parts of polydimethylsiloxane diamine (molecular weight: 3,880) having the above structure. Is gradually dropped, and after the dropping is completed, 50
The reaction was carried out at 0 ° C for 1 hour to obtain an isocyanate-terminated polyurea resin. The internal temperature was again set to 20 ° C., 2.8 parts of 1,4-diaminobutane dissolved in 50 parts of methyl ethyl ketone was gradually added dropwise, and after completion of the addition, reaction was carried out at the same temperature for 1 hour. Further dissolved in 100 parts of methyl ethyl ketone 1
After gradually adding 5.5 parts of γ-aminopropyltriethoxysilane and reacting at 30 ° C. for 1 hour to confirm that the isocyanate group has disappeared, the solid content concentration was adjusted to 3
It was adjusted to 5% to obtain a solution of the hydrophilic polyurea resin of the present invention. This solution had a viscosity of 250 dPa · s (25 ° C.).

Example 3 (Production of molecular terminal / side chain type hydrolyzable silyl group-silicone polyurethane-polyurea resin) (1) Production of isocyanate-terminated silane coupling agent Addition product of hexamethylene diisocyanate and water (Duranate 24A) -100; Asahi Kasei Corporation, NCO% = 2
3.5) 270 parts of 270 parts was stirred well at 25 ° C., 111 parts of γ-aminopropyltriethoxysilane was slowly added dropwise to the reaction, and a colorless transparent liquid product (I) was obtained. The product obtained had a free isocyanate group of 10.5% [theoretical value (the amount of said group in the reaction product which is stoichiometrically produced when 100% reacted): 11.2%]. Theoretically, the structure is as follows.

(2) Production of molecular terminal / side chain type hydrolyzable silyl group-silicone polyurethane-polyurea resin 8 parts of the liquid product (I) and 46 parts of toluene diisocyanate were dissolved in 200 parts of dimethylformamide to prepare 1
145 parts of polyethylene glycol (molecular weight 2,040) dissolved in 00 parts of methyl ethyl ketone, 5 parts of ethylene oxide addition type polydimethylsiloxane (molecular weight 4,500) having the above structure, and 6 parts of 1,3-butylene glycol were added. And reacted at 80 ° C. for 6 hours to obtain an isocyanate-terminated polyurethane-polyurea resin.
The internal temperature was set to 20 ° C., and 7 parts of 1,4-diaminobutane dissolved in 50 parts of methyl ethyl ketone was gradually added dropwise.
After the dropping was completed, the reaction was carried out at the same temperature for 1 hour. Further, 16 parts of γ-aminopropyltrimethoxysilane dissolved in 100 parts of methyl ethyl ketone was slowly added dropwise, and the mixture was stirred at 30 ° C. for 1 hour.
After confirming that the isocyanate group has disappeared by reacting for a time, the solid content concentration was adjusted to 35% to obtain a solution of the polyurethane-polyurea resin of the present invention. This solution is 32
It had a viscosity of 0 dPa · s (25 ° C.).

Comparative Example 1 A polyurethane resin solution was obtained by using the same materials and formulation as in Example 1 except that the polydimethylsiloxane polyol and the silane coupling agent having an isocyanate group were not used. This solution has a solid content of 35% and is 540 dPa · s.
It had a viscosity of (25 ° C.).

Comparative Example 2 A polyurea resin solution was obtained by using the same material and formulation as in Example 2 except that polydimethylsiloxane diamine and γ-aminopropyltriethoxysilane were not used. This solution had a viscosity of 260 dPa · s (25 ° C.) at a solid content of 35%.

Comparative Example 3 A polyurethane-polyurea resin solution was obtained with the same materials and formulation as in Example 3, except that polydimethylsiloxane polyol, an isocyanate-terminated silane coupling agent and γ-aminopropyltrimethoxysilane were not used. This solution has a solid content of 35%, 220 dPa · s (25 ° C)
It had a viscosity of.

Reference Example 1 Polyvinyl alcohol having a saponification degree of 98.5% (polymerization degree: 55
A 5% aqueous solution of 0) was prepared.

The weight average molecular weights (in terms of standard polystyrene measured by GPC) of the resins of Examples 1 to 3 and Comparative Examples 1 to 3 obtained above, the equivalent of the hydrolyzable silyl group, the hydrophilic segment, and the water Degradable silyl group-containing segment,
Table 1 shows the content (%) of the siloxane segment.

Table 1

Evaluation results of the resins obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the resin of Reference Example 1 are shown below. (1) Application to inkjet image-receiving layer The resin solutions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the resin solution of Reference Example 1 were applied to a PET film having a thickness of 100 μm so that the thickness after drying was 20 μm. Was applied to prepare a transparent sheet, and a color ink jet printer (Seiko Epson Co .; PM-750C) was used for printing and recording, and the following items were evaluated. (1) Blocking resistance The untreated PET film was placed on the resin coating surface, a load of 0.29 Mpa was applied, and the blocking property was evaluated after standing for 1 day at a temperature of 40 ° C. The results are displayed below. ◯: No blocking property Δ: Slight blocking property X: Blocking property (2) Printer transportability The printer transportability during printing and recording with an inkjet printer was evaluated. ○: Good transportability △: Slight noise
X: Poor transportability (3) Color vividness After printing a color image with an inkjet printer, the color vividness of the obtained color image was visually observed. ◯: Good Δ: Normal, ×: Poor (4) Water resistance of printed image After color printing with an inkjet printer, the recording sheet was immersed in water (20 ° C., 24 hours) and then dried at room temperature to obtain a recorded image. Visually observe bleeding and color change. ◯: No change Δ: Discoloration is observed X: Completely dissolved and disappeared The above results are shown in Table 2.

Table 2

Comparative Example 4 The resin obtained in Comparative Example 1 was mixed with a nonionic surfactant (polyoxyethylene nonylphenyl ether; manufactured by NOF CORPORATION) at a solid content weight ratio of 95: 5.

Reference Example 2 Polyvinyl butyral (Polymerization degree 700, Sekisui Chemical Co., Ltd.)
100 parts, 50 parts of trioctyl phosphate and 3 parts of polyoxyethylene lauryl ether phosphate (phosphate ester type surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were mixed and dissolved in 400 parts of ethanol.

(2) Application to antifogging / antistatic coatings The resin solutions obtained in Examples 1 to 3, Comparative Examples 1 and 4 and Reference Example 2 were brush coated on a transparent acrylic resin plate to prepare a sample, The antifogging property and the antistatic property were evaluated. (1) Set the sample plate at 5 cm on the antifogging boiling water bath and
The haze of the paint when exposed to water vapor at 0 ° C for 10 minutes was evaluated. ○: No cloudiness △: Partly cloudy
×: Cloudy (2) Water resistant boiling water bath, set the sample plate at 5 cm and set 50
The state of the paint when exposed to water vapor at ℃ for 10 minutes was evaluated. ◯: No change Δ: Slight change in state X:
Peeling or dissolution of coating film (3) Antistatic property Adhesion of charged carbon was evaluated by a dust chamber test. ◯: No carbon attached Δ: Partially carbon attached X: Carbon attached The above results are shown in Table 3.

Table 3

[0057]

As described above, the hydrophilic polyurethane resin obtained by the present invention has excellent adhesiveness to various materials, and also has water absorbability, antifogging property, transparency, flexibility, and writability of water-based ink. In addition, it has excellent water resistance, blocking resistance, and lubricity, as a coating agent for the image-receiving layer of inkjet image-receiving sheets, as an antifogging paint for various films, as a surface treatment agent for preventing condensation on interior resin wallpaper, and as a water-absorbing agent. It is very useful as a coating agent for clothing, as a material for synthetic artificial leather.

Continued front page    F-term (reference) 4J034 BA07 BA08 CA13 CA15 CA17                       CA32 CA34 CB01 CB03 CB07                       CC08 CC12 CC23 CC26 CC37                       CC42 CC45 CC54 CC65 CD04                       CD15 DA01 DA03 DA05 DA07                       DA08 DB01 DB03 DB04 DB05                       DB07 DG03 DG04 DG06 DG08                       DG09 DG23 DH02 DH05 DH06                       DM01 DM06 GA62 HA01 HA02                       HA04 HA07 HA08 HB03 HB05                       HB11 HB16 HC12 HC17 HC22                       HC46 HC52 HC61 HC64 HC67                       HC71 HC73 QA05 QB04 QB19                       RA03 RA07

Claims (9)

[Claims] 1. An organic polyisocyanate, a high molecular weight hydrophilic polyol or polyamine, a polysiloxane compound having at least one active hydrogen group, at least one reactive group and at least one hydrolyzable silyl group in the same molecule. It is composed of a hydrophilic segment, a polysiloxane segment and a segment containing a hydrolyzable silyl group, which is obtained by reacting a compound contained in the compound and a chain extender if necessary, and the content of the hydrolyzable silyl group is 0. 001-
10 eq / g and weight average molecular weight of 3,000 to 8
A hydrophilic polyurethane resin characterized in that it is 0,000. 2. The hydrophilic segment content is 30 to 80.
% By weight, content of polysiloxane segment is 0.1
The hydrophilic polyurethane resin according to claim 1, wherein the content of the segment having 10% by weight and the hydrolyzable silyl group is 1 to 40% by weight. 3. The hydrophilic polyurethane resin according to claim 1, wherein the hydrophilic segment is a segment composed of polyethylene oxide. 4. The hydrophilic polyurethane resin according to claim 1, wherein the segment having a hydrolyzable silyl group is located at the terminal and / or side chain of the molecular chain of the hydrophilic polyurethane resin. 5. An organic polyisocyanate, a high molecular weight hydrophilic polyol or polyamine, a polysiloxane compound having at least one active hydrogen group, at least one reactive group and at least one hydrolyzable silyl group in the same molecule. A method for producing a hydrophilic polyurethane resin, which comprises reacting a compound contained therein and, if necessary, a chain extender. 6. The content of hydrolyzable silyl groups is 0.00.
1 to 10 eq / g, and the weight average molecular weight is 3,000.
The method for producing the hydrophilic polyurethane-based resin according to claim 5, wherein the hydrophilic polyurethane-based resin is from about 800,000. 7. The amount of the high molecular weight hydrophilic polyol or polyamine used is such that the content of the segment composed of these substances in the hydrophilic polyurethane resin is 30 to 8.
The method for producing a hydrophilic polyurethane resin according to claim 5 or 6, wherein the amount is 0% by weight. 8. The amount of the polysiloxane compound used is such that the content of the segment composed of the compound in the hydrophilic polyurethane resin is 0.1 to 10% by weight. 5. The method for producing the hydrophilic polyurethane resin according to any one of 1. 9. The use amount of the compound having the hydrolyzable silyl group in the same molecule is such that the content of the segment composed of the compound in the hydrophilic polyurethane resin is 1 to 1.
The method for producing a hydrophilic polyurethane resin according to any one of claims 5 to 8, wherein the amount is 40% by weight.