JPH11240935A - Hydrophilic polyurethane resin and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide excellent adhesiveness to various materials and excellent water absorbency, antifogging property, transparency, flexibility, writing property of water-based ink, water resistance, blocking resistance, and lubricity. To provide a hydrophilic polyurethane resin. SOLUTION: An organic polyisocyanate, a high molecular weight hydrophilic polyol or a polyamine, a compound having at least one or more active hydrogen groups and one or more tertiary amino groups in the same molecule, and having at least one polysiloxane segment in the molecule It is obtained by reacting a polysiloxane compound having one or more active hydrogen groups and, if necessary, a chain extender, contains 0.1 to 50 eq / g of a tertiary amino group, and has a weight average molecular weight of 5, A hydrophilic polyurethane-based resin having a molecular weight of 000 to 500,000 and a method for producing the same.

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 particularly, to a water-based ink which is excellent in adhesiveness to various materials, and is water-absorbing, anti-fog, transparent, flexible, and water-based. The present invention relates to a hydrophilic polyurethane resin excellent in writability, water resistance, blocking resistance and lubricity.

[0002]

2. Description of the Related Art Polyurethane resins are excellent in abrasion resistance, adhesiveness, flexibility, chemical resistance and the like, and are also suitable for various processing methods. Polyurethane resins which are widely used as binders, films, sheets and other molded articles and are suitable for each application have been proposed. The polyurethane resin is a generic term for polyurethane resin, polyurea resin, and polyurethane-polyurea resin. These polyurethane resins are basically obtained by reacting a high molecular weight polyol component, an organic polyisocyanate component, and further, if necessary, a chain extender component. Polyurethane resins having physical properties are provided.

[0003]

However, polyurethane resins are used, for example, in antifogging paints for agricultural resin sheets, surface treatment agents for interior resin wallpaper, and the like.
Usually, hydrophilicity and anti-blocking property are also required at the same time as in a fiber coating agent, a coating agent for an image receiving sheet for ink jet, and the like. Among these, 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 is obtained, but water resistance is high. There is a problem that swelling, whitening, and a decrease in strength are caused by moisture, and are not suitable for various paints, binders for printing inks, molded articles, films, sheets, and the like.

[0004] Accordingly, an object of the present invention is to provide excellent adhesion to various materials, as well as water absorption, anti-fogging properties, transparency, flexibility, and the like.
Writability and water resistance of the aqueous ink, blocking resistance,
An object of the present invention is to provide a hydrophilic polyurethane resin excellent in lubricity.

[0005]

The above object is achieved by the present invention described below. That is, the present invention provides an organic polyisocyanate, a high molecular weight hydrophilic polyol or a polyamine, at least one active hydrogen group and at least one
A tertiary tertiary compound obtained by reacting a compound having a tertiary amino group in the same molecule, a polysiloxane compound having at least one or more active hydrogen groups in the molecule and a chain extender as necessary. It contains 0.1 to 50 eq / g of amino group and has a weight average molecular weight of 5.0
A hydrophilic polyurethane resin having a molecular weight of 100 to 500,000 and a method for producing the same.

[0006] By introducing a tertiary amino group and a polysiloxane segment into a polyurethane resin, the adhesiveness to various materials is excellent, and water absorption, antifogging, transparency, flexibility, and water-based ink writing are performed. A hydrophilic polyurethane-based resin having excellent water resistance, blocking resistance, and lubricity is provided.

First, dye / pigment molecules of printing inks and ink jet inks have anionic carboxyl groups or sulfonic acid groups in their molecules, and tertiary amino groups are present in the chains of the hydrophilic polyurethane resin. When the resin obtained by introducing the dye and the dye / pigment are mixed or contacted, an ionic bond is formed between the dye / pigment and the tertiary amino group in the resin, and the fixing property of the dye / pigment It is considered that the water resistance is improved.

[0008] However, considering the above-mentioned ionic bonding property, which is easily dissociated in the presence of moisture, the reason for the improvement in water resistance is not clear, but the resin of the present invention is hydrophilic, Also has a hydrophobic part, so that after the ionic bond is formed between the hydrophilic part and the tertiary amino group in the resin and the dye / pigment, the hydrophobic part surrounds the ionic bond part. Therefore, it is considered that the water resistance is improved.

Next, the introduction of a hydrophobic (water-repellent) polysiloxane segment into the resin structure is essentially as follows:
Although good results cannot be expected with respect to water absorption and hydrophilicity, the film surface made of a resin having a low polysiloxane segment content is completely covered with a polysiloxane component in a dry state, but is immersed in water. In this case, it is known that the polysiloxane component is buried in the resin, that is, it has an environmental response.
[4] 227 (1991) et al.).

The present invention utilizes this phenomenon,
By appropriately controlling the polysiloxane content in the resin, when printing in a high-humidity atmosphere or with an aqueous ink, the surface shows hydrophilicity due to environmental response, and the surface during drying or after drying becomes polysiloxane. Provided is a hydrophilic polyurethane-based resin which is covered with components and has excellent water resistance, blocking resistance, lubricity and the like.

[0011]

Next, the present invention will be described in more detail with reference to preferred embodiments. The hydrophilic polyurethane-based resin of the present invention comprises an organic polyisocyanate, a high molecular weight hydrophilic polyol or a polyamine, and a chain extender as required. Group and one or more third
It can be obtained by copolymerizing a compound having a primary amino group in the same molecule and a polysiloxane compound having at least one active hydrogen.

First, in the present invention, the compound used for introducing a tertiary amino group into the molecular chain constituting the hydrophilic polyurethane-based resin is one or more reactive groups such as one or more reactive groups in the molecule. , An amino group, an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, an alkoxy group, an acid halide group, a carboxy ester group, an acid anhydride group, and a tertiary amino group in a molecular chain. .

Preferred examples of the tertiary amino group-containing compound having a reactive group include the following compounds.

Embedded image A compound represented by the general formula (1).

(Where 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 each —O −, −
CO-, -COO-, -NHCO-, -S-, -SO
-, -SO _2- or a lower alkylene group which may be linked by X or Y, wherein X and Y are -OH, -COOH, -N
A reactive group such as H ₂ , —NHR ₁ , or —SH;
May be the same or different. Further, an epoxy group, an alkoxy group, an acid halide group, an acid anhydride group, or a carboxyl ester group which can be derived from these groups may be used. )

[0015]

Embedded image A compound represented by the general formula (2). (Here, R ₁ , R ₂ and R ₃ have the same meaning as described above, provided that two R ₁ 's may form a cyclic structure. R ₄ is-(CH ₂ ) _n- (N = 0 to 20, R ₂ or R ₃ has the same meaning as described above, and Z represents a carbon atom or a nitrogen atom.)

[0016]

Embedded image A compound represented by the general formula (3). (Here, X and Y have the same meanings as described above, and W represents a nitrogen-containing heterocycle, a nitrogen- and oxygen-containing heterocycle, or a 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, 2,5-diaminooxazole and the like .

Further, ethylene oxide adducts and propylene oxide adducts of these tertiary amino compounds can also be used in the present invention. As the addition, for example,

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[0019]

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[0020]

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[0021]

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Embedded image (In the above formula, n represents an integer of 1 to 60, and m represents an integer of 1 to 6.) The polyurethane resin containing the above tertiary amino compound as a component is prepared according to a conventionally known method. Obtainable.

As the organic polyisocyanate, any known organic polyisocyanate can be used. For example, preferred are 4,4-diphenylmethane diisocyanate (MDI), hydrogenated MDI, isophorone diisocyanate, 1,3-xylylene diisocyanate. , 1,4-
Xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisotonate, 1,
There are 5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate and the like, and polyurethane prepolymers obtained by reacting these organic polyisocyanates with low molecular weight polyols and polyamines to form terminal isocyanates are also used. can do.

The high molecular weight hydrophilic polyol or polyamine used in the present invention has a molecular weight in the range of 400 to 8,000. Examples of the polyol having a terminal hydroxyl group and having hydrophilicity include polyethylene glycol, polyethylene glycol / polytetramethylene glycol copolymer polyol, polyethylene glycol / polypropylene glycol copolymer polyol, polyethylene glycol adipate, polyethylene glycol succinate, and polyethylene glycol / poly. -Ε-lactone copolymerized polyol and polyethylene glycol / poly-valerolactone copolymerized polyol.

Examples of the polyethylene oxide derivative having an amino group at the end and having hydrophilicity include polyethylene oxide diamine, polyethylene oxide propylene oxide diamine, polyethylene oxide triamine, and polyethylene oxide propylene oxide triamine. Other examples include an ethylene oxide adduct having a carboxyl group or a vinyl group. However, when producing a polyurethane resin, it is also possible to copolymerize other polyols, polyamines, polycarboxylic acids, etc. having no hydrophilic chains as described above in order to impart other properties to the obtained resin. .

Next, 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 one or more reactive groups in the molecule. , Amino group,
It is a polysiloxane compound having 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.

[0026]

Embedded image (1) Amino-modified polysiloxane compound

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[0027]

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[0028]

Embedded image (2) Epoxy-modified polysiloxane compound

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[0029]

(3) Alcohol-modified polysiloxane compound

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[0030]

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[0031]

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[0032]

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[0033]

(4) Mercapto-modified polysiloxane compound

[0034]

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[0035]

(5) Carboxyl-modified polysiloxane compound

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The preferred molecular weight of the hydrophilic polyurethane-based resin having a tertiary amino group and a polysiloxane segment in the molecular chain obtained from the above materials is several thousand to eight.
Of those having a weight average molecular weight of 5,000 to 500,000. The resin of the present invention may be prepared without solvent, or may be prepared in an aqueous solution or solvent.

The tertiary amino group in the hydrophilic polyurethane resin of the present invention may be contained in the main chain or the side chain or both, and the content in the resin is 0.1 to 50 eq / g, preferably. Is 0.5 to 20 eq / g. When the content of the tertiary amino group is 0.1 eq / g or less, that is, the molecular weight is 1
If the number is less than 1 per 000, the desired objects of the present invention, such as water resistance and anti-blocking property, will be insufficiently developed, while the content of the tertiary amino group will be 50 eq.
/ G or more, that is, 1 or more per 20 molecular weight, is not preferable because the water repellency due to the decrease of the hydrophilic portion in the resin becomes strong, and the water absorption performance and the antifogging property become poor.

The polysiloxane segment may be contained in the main chain or the side chain or in both, and the content is 0.1 to 10 parts by weight based on 100 parts by weight of the hydrophilic polyurethane resin. . If the amount of the polysiloxane segment is less than 0.1 part by weight, the surface properties such as water resistance, blocking resistance and lubricity, which are the objects of the present invention, become insufficient. And the environmental responsiveness used by the present invention becomes poor, and the water absorption, anti-fogging property and transparency become poor.

The hydrophilic polyurethane resin obtained by the present invention as described above is excellent in adhesiveness to various materials, and has water absorbency, antifogging property, transparency, flexibility, writing property of water-based ink, and water resistance. Excellent blocking resistance, excellent lubricity, as a coating agent for the image receiving layer of the inkjet image receiving sheet,
As an anti-fog coating for various films, as a surface treatment agent for preventing condensation on resin-made wallpaper for interiors, as a coating agent for water-absorbent clothing, and also as a material for synthetic leather and a water-based ink for synthetic paper Very useful as.

[0040]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following, "parts" and "%" are based on weight unless otherwise specified. Example 1

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8 parts of polydimethylsiloxane polyol (molecular weight 3,200) having the above structure, 142 parts of polyethylene glycol (molecular weight 2,040), 20 parts of N-methyldiethanolamine, diethylene glycol 5
Was dissolved in a mixed solvent of 100 parts of methyl ethyl ketone and 200 parts of dimethylformamide, and while stirring well at 60 ° C., a solution obtained by dissolving 73 parts of hydrogenated MDI in 100 parts of methyl ethyl ketone was gradually added dropwise. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 6 hours, and then 60 parts of methyl ethyl ketone was added to obtain a polyurethane resin solution of the present invention.

This solution was 330 dPa. s (25 ° C.), and the weight average molecular weight was 75,000. or,
The content of the tertiary amino group in the obtained resin is 0.66e
q / g, and the content of the polysiloxane segment was 3.2%.

Embodiment 2

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5 parts of polydimethylsiloxanediamine (molecular weight: 3,880) having the above structure, 145 parts of polyethylene oxide diamine (Jeffamine ED; molecular weight: 2,000), 25 parts of methyliminobispropylamine and 1, Dissolve 5 parts of 4-diaminobutane in 250 parts of dimethylformamide, and adjust the internal temperature to 20 to 30 ° C.
While stirring well, add 75 parts of hydrogenated MDI to 100 parts.
What was dissolved in a part of dimethylformamide was gradually dropped to react. After dropping, gradually raise the internal temperature,
When the temperature reached 50 ° C., the reaction was continued for another 6 hours.
Five parts of dimethylformamide were added to obtain a polyurea resin solution of the present invention. This solution was 315 dPa. s (25
C) and the weight average molecular weight was 71,000. The content of the tertiary amino group in the obtained resin was 0.75 eq / g, and the content of the polysiloxane segment was 2.0%.

Embodiment 3

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Ethylene oxide addition type polydimethylsiloxane having the above structure (molecular weight: 4,500) 5
Parts, polyethylene oxide diamine (Jeffamine ED; molecular weight 2,000) 145 parts, N, N-dimethyl-N ', N'-dihydroxyethyl-1,3-diaminopropane 30 parts, 1,4-diaminobutane 5 parts Was dissolved in a mixed solvent of 150 parts of methyl ethyl ketone and 150 parts of dimethylformamide, and stirred well at 60 ° C.
A solution prepared by dissolving 72 parts of hydrogenated MDI in 75 parts of 100 parts of methyl ethyl ketone was gradually added dropwise.
After the reaction was completed at 0 ° C. for 6 hours, 75 parts of methyl ethyl ketone was added to obtain a polyurethane-polyurea resin solution of the present invention. This solution has 390 dPa. s (25 ° C.), and the weight average molecular weight was 77,000. or,
The content of the tertiary amino group in the obtained resin is 1.22e
q / g, and the content of the polysiloxane segment was 1.2%.

Comparative Example 1 A polyurethane resin solution was obtained in the same manner as in Example 1 except that polydimethylsiloxane polyol and N-methyldiethanolamine were not used in the formulation of Example 1. This solution is 500 dPa. s (25 ° C.), and the weight average molecular weight was 84,000.

Comparative Example 2 A polyurea resin solution was obtained in the same manner as in Example 2 except that polydimethylsiloxanediamine and methyliminobispropylamine were not used in the formulation of Example 2. This solution is 300 dPa. It had a viscosity of s (25 ° C) and a weight average molecular weight of 70,000.

Comparative Example 3 Polydimethylsiloxane and N, N-
Dimethyl-N ', N'-dihydroxyethyl-1,3-
A polyurethane-polyurea resin solution was obtained using the same materials and formulation as in Example 3 except that diaminopropane was not used. This solution was 220 dPa. It had a viscosity of s (25 ° C) and a weight average molecular weight of 65,000.

Comparative Example 4 Polyvinyl alcohol having a saponification degree of 98.5% (polymerization degree of 55
A 5% aqueous solution of 0) was prepared.

Application to Inkjet Image Receiving Layer The resin solutions obtained in Examples 1 to 3 and Comparative Examples 1 to 4
A 00 μm PET film is coated so that the thickness after drying becomes 20 μm to prepare a transparent sheet, and a color inkjet printer (Seiko Epson Corporation; PM-75)
0C), and the following items were evaluated to obtain the results shown in Table 1 below.

"Blocking resistance" The untreated PET film was evaluated for its blocking property after leaving it untreated at a load of 0.29 Mpa and at a temperature of 40 ° C. for one day.・ ・ ・: No blocking property. Δ: Somewhat blocking property. X: Blocking property.

"Printer transportability" Printer transportability at the time of printing and recording with an ink jet printer was evaluated.・ ・ ・: Good transportability. Δ: Slight noise is generated. ×: Poor transportability.

"Color clarity" After printing a color image with an ink jet printer, the color clarity of the obtained color image was visually observed. ○ ... Good. △: Normal. ×: Bad.

"Water resistance of printed image" After color printing with an ink jet printer, the recording sheet was immersed in water (20
(° C., 24 hours), and then bleeding of the recorded image when dried at room temperature and changes in color development were visually observed.・ ・ ・: No change. Δ: Discoloration is observed. X: Completely dissolved and disappeared.

[0056]

[Table 1] Table 1

Application to Antifogging / Antistatic Paint Comparative Example 5 A nonionic surfactant (polyoxyethylene nonylphenyl ether; manufactured by NOF Corporation) was added to the resin obtained in Comparative Example 1 in terms of solid content weight. The mixture was mixed at a ratio of 95: 5. Comparative Example 6 Polyvinyl butyral (polymerization degree 700, Sekisui Chemical Co., Ltd.)
100 parts, trioctyl phosphate 50 parts and polyoxyethylene lauryl ether phosphate (phosphate ester surfactant, Daiichi Kogyo Seiyaku Co., Ltd.)
Was mixed and dissolved in 400 parts of ethanol.

The resin solutions obtained in Examples 1 to 3 and Comparative Examples 1, 5 and 6 were brush-coated on a transparent acrylic resin plate to prepare a sample plate, and the antifogging property and the antistatic property were evaluated. The results shown in Table 2 below were obtained. "Anti-fogging property" A sample plate was set at a position of 5 cm on a boiling water bath and exposed to steam at 50 ° C for 10 minutes to evaluate the fogging of the sample plate.・ ・ ・: No fogging. Δ: Partly cloudy. ×: cloudy.

"Water resistance" A sample plate was set at a position of 5 cm on a boiling water bath and exposed to steam at 50 ° C for 10 minutes to evaluate the state of the sample plate.・ ・ ・: No change. Δ: slight change in state. X: Peeling or dissolution of the coating film occurred.

"Antistatic property" The adhesion of charged carbon was evaluated by a dust chamber test. ○ ・ ・ ・ No carbon adhesion. Δ: Some carbon adhered. ×: Carbon attached.

[0061]

[Table 2] Table 2

[0062]

As described above, the hydrophilic polyurethane resin obtained by the present invention has excellent adhesion to various materials,
It has excellent water absorbency, antifogging property, transparency, flexibility, writing properties of water-based inks, and excellent water resistance, blocking resistance, and lubricity. As a coating agent for an image receiving layer of an inkjet image receiving sheet, the antifogging property of various films is improved. It is very useful as a coating material, as a surface treatment agent for preventing dew condensation on resin-made wallpaper for interiors, as a coating agent for water-absorbing clothing, and as a synthetic artificial leather material.

Claims (6)

[Claims] 1. An organic polyisocyanate, high molecular weight hydrophilic polyol or polyamine, a compound having at least one active hydrogen group and at least one tertiary amino group in the same molecule, and a polysiloxane segment in the molecule. It is obtained by reacting a polysiloxane compound having at least one or more active hydrogen groups and, if necessary, a chain extender, contains a tertiary amino group in an amount of 0.1 to 50 eq / g, and has a weight average molecular weight of 5 2,000 to 500,000, characterized by being a hydrophilic polyurethane-based resin. 2. The ratio of the polysiloxane segment in the hydrophilic polyurethane-based resin is from 0.1 to 0.1.
The hydrophilic polyurethane resin according to claim 1, wherein the amount is 10% by weight. 3. The high molecular weight hydrophilic polyol or polyamine according to claim 1, wherein the high molecular weight hydrophilic polyol or polyamine comprises ethylene oxide segments, and the proportion of the segments in the hydrophilic polyurethane resin is 30 to 80% by weight. Hydrophilic polyurethane resin. 4. An organic polyisocyanate, high molecular weight hydrophilic polyol or polyamine, a compound having at least one active hydrogen group and at least one tertiary amino group in the same molecule, and a polysiloxane segment in the molecule. A polysiloxane compound having at least one or more active hydrogen groups and, if necessary, a chain extender, wherein the tertiary amino groups in the obtained polyurethane resin are 0.1 to 50 eq / g and the weight average molecular weight Is 5,000-500,00
A method for producing a hydrophilic polyurethane resin, wherein the reaction is carried out at a ratio of 0. 5. The proportion of the polysiloxane segment in the hydrophilic polyurethane resin is 0.1 to 5%.
The method for producing a hydrophilic polyurethane-based resin according to claim 4, which is used in an amount of 10% by weight. 6. The reaction according to claim 4, wherein the high molecular weight hydrophilic polyol or polyamine comprises an ethylene oxide segment, and is reacted in such an amount that the proportion of the segment in the hydrophilic polyurethane resin is 30 to 80% by weight. A method for producing a hydrophilic polyurethane resin.