JP2004244641A - Preparation process of hydrophilic polyurethane resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a preparation process of a hydrophilic polyurethane resin which is excellent in adhesiveness to various materials, water absorption properties, fog resistance, transparency, flexibility, aqueous ink wrightability, water resistance, blocking resistance, and lubricity. <P>SOLUTION: When a hydrophilic polyurethane resin is prepared by reacting an organic polyisocyanate and a hydrophilic polyol of a high molecular weight in this preparation process, a compound having at least one active hydrogen group and at least one tertiary amino group in its molecule, a polysiloxane compound having at least one active hydrogen group, and a compound having at least one reactive group and at least one hydrolyzable silyl group in its molecule are copolymerized with the components mentioned above. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a method for producing a hydrophilic polyurethane-based resin, and more particularly, has excellent adhesiveness to various materials, and has water absorbency, anti-fogging property, transparency, flexibility, writing properties of a water-based ink, and water resistance and water resistance. The present invention relates to a method for producing a hydrophilic polyurethane resin having excellent blocking properties.

  Polyurethane resins are excellent in abrasion resistance, adhesiveness, flexibility, chemical resistance, etc., and also excellent in suitability for various processing methods, so that various coating agents, paints, binders such as inks, films, Polyurethane resins which are widely used as sheets and other molded articles and are suitable for each use have been proposed. The polyurethane resin is a generic term for polyurethane resin, polyurea resin, and polyurethane-polyurea resin, and the same applies to the present invention described below. The polyurethane resin is basically obtained by reacting a high molecular weight polyol component, an organic polyisocyanate component, and further, if necessary, a chain extender component, and has various physical properties depending on the type, combination, etc. of these components. Can be produced.

  However, polyurethane-based resins, depending on the application, for example, in the antifogging paint for agricultural resin sheet or surface treatment agent for interior resin wallpaper, fiber coating agent, coating agent for inkjet image receiving sheet, etc. Usually, hydrophilicity and anti-blocking property are required at the same time as the 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 is obtained, it has a problem that it is not suitable for various paints, binders of printing inks, molded articles, films, sheets, etc. due to poor water resistance, causing swelling, whitening, and reduction in strength due to moisture.

  Accordingly, an object of the present invention is to provide a hydrophilic polyurethane system having excellent adhesiveness to various materials, and excellent in water absorbency, anti-fogging property, transparency, flexibility, writing property of water-based ink, and water resistance and blocking resistance. An object of the present invention is to provide a method for producing a resin.

  The above object is achieved by the present invention described below. That is, in producing a hydrophilic polyurethane resin by reacting an organic polyisocyanate with a high molecular weight hydrophilic polyol, at least one active hydrogen group and at least one tertiary amino group are the same molecule. And a polysiloxane compound having at least one active hydrogen group and a compound having at least one reactive group and at least one hydrolyzable silyl group in the same molecule. Wherein the amount of the polysiloxane compound used is such that the content of the segment comprising the compound in the hydrophilic polyurethane-based resin is 0.1 to 10% by mass. Is a manufacturing method.

  The hydrophilic polyurethane-based resin obtained in the present invention has excellent adhesiveness to various materials, and has water absorption, anti-fogging properties, transparency, flexibility, writing properties of water-based inks, and water resistance, blocking resistance, and lubricity. Excellent as a coating agent for the image receiving layer of an inkjet image receiving sheet, as an anti-fog coating for various films, 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 synthetic artificial leather It is very useful as an application material.

  Next, the present invention will be described in more detail by way of preferred embodiments. The method for producing a hydrophilic polyurethane resin of the present invention comprises the steps of: adding an organic polyisocyanate, a high molecular weight hydrophilic polyol and, if necessary, a chain extender to at least one active hydrogen group and at least one tertiary amino group. In the same molecule, a polysiloxane compound having at least one active hydrogen group and a compound having at least one reactive group and at least one hydrolyzable silyl group in the same molecule. It is characteristic.

  In the polyurethane resin obtained in the present invention, a hydrophilic segment, a tertiary amino group (the group-containing segment), a polysiloxane segment, and a hydrolyzable silyl group (the group-containing segment) are introduced. By crosslinking the degradable silyl group with water, excellent adhesion to various materials to hydrophilic polyurethane resin, and excellent water absorption, antifogging property, transparency, flexibility, writing property of water-based ink and water resistance are obtained. Properties and blocking resistance.

  In the present invention, the method for synthesizing the hydrophilic polyurethane resin itself can be a conventionally known method for synthesizing a urethane resin, and is not particularly limited. Hereinafter, raw material components used for synthesizing a hydrophilic polyurethane-based resin (hereinafter, may be simply referred to as “resin”) will be described.

樹脂の架橋には水分を添加してもよいが、本発明の樹脂が親水性の為、空気中の水分を利用することもできる。上記式における架橋形成のシラノール縮合を促進させる為に樹脂中に触媒を添加しておくのが好ましい。かかる触媒としては、一般には錫系のカルボン酸塩や酸性触媒及び塩基性触媒が好ましく、樹脂に対して０．０００１質量％〜１０質量％の範囲で使用される。 (1) Introduction of a hydrolyzable silyl group (hydrolyzable silyl group-containing segment) When a hydrolyzable silyl group is introduced into a resin, the group is cross-linked with water to improve the water resistance of the resin, In addition, 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 at the molecular chain end and / or the molecular side chain of the resin. Crosslinking of the hydrolyzable silyl group introduced into the molecular chain terminal and / or the molecular side chain of the resin with water is represented by the formula (I) and / or (II).

Moisture may be added to the cross-linking of the resin. However, since the resin of the present invention is hydrophilic, water in the air can be used. It is preferable to add a catalyst to the resin in order to promote the silanol condensation of the crosslinking in the above formula. Such a catalyst is generally preferably a tin-based carboxylate, an acidic catalyst or a basic catalyst, and is used in a range of 0.0001% by mass to 10% by mass based on the resin.

  In the present invention, the compound used to introduce a hydrolyzable silyl group into the hydrophilic polyurethane resin is a silane coupling agent having a reactive organic functional group and a reaction between the silane coupling agent and an organic polyisocyanate. Examples of the obtained compound include at least one free isocyanate group-containing compound.

（式中、Ｒ₁は低級アルキル基を、Ｒ₂は低級アルキル基又は低級アルコキシ基を表す。Ｘは２価の有機基を表し、好ましいものはＣ₀〜Ｃ₅₀のアルキレン鎖、芳香族又は脂肪族環であり、これらの基は−Ｎ−、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＮＨＣＯ−、−Ｓ−、−ＳＯ−又は−ＳＯ₂等の連結基で連結されていてもよい。又、ｍ＝０〜３の整数、ｎ＝３−ｍである。） Examples of the silane coupling agent having a reactive 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.

(Wherein, 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, and preferred are a C ₀ -C ₅₀ alkylene chain, an aromatic or aliphatic ring, these groups -N -, - O -, - CO -, - COO -, - NHCO -, - S -, - SO- or are linked by a linking group -SO ₂ such And m is an integer of 0 to 3 and n is 3-m.)

Preferred specific examples of the silane coupling agent having a free isocyanate group are as follows.

（式中、Ｙは−ＮＨ−、−ＮＲ₃−、−Ｏ−、又は−Ｓ−を表し、Ｒ₁、Ｒ₂、Ｘ、ｍ、ｎは前記定義の通りであり、Ｒ₃は低級アルキル基を表す。） [2] A reaction product of a silane coupling agent having a reactive organic functional group and an organic polyisocyanate, wherein the product has at least one free isocyanate group in a 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).

(Wherein, Y represents —NH—, —NR ₃ —, —O—, or —S—, R ₁ , R ₂ , X, m, and n are as defined above, and R ₃ is lower alkyl Represents a group.)

Preferred specific examples of the 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. Accordingly, not only the above-exemplified compounds but also other known currently commercially available compounds which 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 site of introduction of the group is not particularly limited, but is usually a molecular chain terminal and / or a molecular side chain of the resin. It is. An example of a method for introducing a hydrolyzable silyl group into a molecular chain terminal and / or a molecular side chain of a resin is shown below.
1) Introduction to molecular chain terminal

（上記式中のＲ₁、Ｒ₂、Ｘ、Ｙは前記と同じであり、〔Ｐ〕は重合体１分子当たり少なくとも２つのウレタン結合及び／又はウレア結合を含有する親水性ポリウレタン、親水性ポリウレア又は親水性ポリウレタン−ポリウレアを表し、Ｚは、−Ｏ−、−Ｓ−、−ＮＲ₃−、又は−ＮＨ−であり、Ｒ₃は低級アルキレン基、ｍ＝０〜３の整数、ｎ＝３−ｍである。）
上記以外の方法によっても、親水性樹脂の分子鎖末端及び／又は分子側鎖に加水分解性シリル基を導入することができるが、上記例示以外の方法で該基が導入された親水性樹脂も本発明の親水性樹脂に該当することは勿論である。 2) Introduction into molecular side chains

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

(2) Introduction of Tertiary Amino Group (Tertiary Amino Group-Containing Segment) In the present invention, the compound used to introduce a tertiary amino group into the molecular chain constituting the hydrophilic polyurethane resin is a molecule. Having one or more reactive groups therein, for example, an amino 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 A compound having a tertiary amino group in the molecular chain. Depending on the compound, a tertiary amino group is introduced into the main chain and / or into the side chain of the resin.

（式中の、Ｒ₄は炭素数が２０以下のアルキル基、脂環族基、ハロゲンあるいはアルキル基等の置換基を有していてもよい芳香族基を；Ｒ₅、Ｒ₆は低級アルキレン基又は鎖中に−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＮＨＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−等の連結基を有する低級アルキレン基を；Ｘ及びＹは、同じでも異なってもよく、−ＯＨ、−ＣＯＯＨ、−ＮＨ₂、−ＮＨＲ₇、−ＳＨ等、又は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、カルボキシルエステル基を、Ｒ₇は低級アルキル基をそれぞれ表す。） Preferred examples of the tertiary amino group-containing compound having a reactive group include, for example, compounds represented by the following general formulas (3) to (5).

(In the formula, R ₄ represents an alkyl group having 20 or less carbon atoms, an alicyclic group, an aromatic group which may have a substituent such as a halogen or an alkyl group; R ₅ and R ₆ represent lower alkylene -O in groups or chain -, - CO -, - COO -, - NHCO -, - S -, - SO -, - SO 2 - a lower alkylene group having a linking group such as; X and Y are the same But may be _{different, -OH, -COOH, -NH 2,} -NHR 7, -SH , etc., or an epoxy group that can be induced in these groups, an alkoxy group, an acid halide group, acid anhydride group, a carboxyl ester group , R ₇ each represents a lower alkyl group.)

（式中のＲ₄、Ｒ₅及びＲ₆は前記と同じであり、二つのＲ₄同士で環状構造を形成してもよく、Ｒ₈は−（ＣＨ₂）_n−（ｎは０〜２０の整数）、あるいはＲ₅又はＲ₆と同じであり、ＺはＣＨ又は窒素を表す。）

(In the formula, R ₄ , R ₅ and R ₆ are the same as described above, and two R ₄ 's may form a cyclic structure, and R ₈ is-(CH ₂ ) _n- (n is 0 to 20) The same as R ₅ or R ₆ , and Z represents CH or nitrogen.)

（式中のＸ及びＹは前記と同じであり、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。）

(X and Y in the formula are the same 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 compounds represented by the general formulas (3), (4) and (5) include, for example, 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.

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

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

  By introducing the tertiary amino group into the main chain and / or the side chain of the resin using the above-mentioned tertiary amino group-containing compound, the dye molecule of the printing ink or the ink jet ink becomes an anion in the molecule. Carboxylic acid groups and sulfonic acid groups, ionic bonds are formed with the tertiary amino groups in the resin to improve the fixability of the dye, and the introduction of tertiary amino groups It is considered that the intermolecular force of the polyurethane resin is increased, and the water resistance is improved. However, considering the ionic bonding property that 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, but also has a hydrophobic portion in its molecule. After an ionic bond is formed between the dye and the hydrophilic portion and the tertiary amino group in the resin, the hydrophobic portion comes to surround the hydrophilic portion, thereby improving the water resistance. It seems to be.

(3) Introduction of Polysiloxane Segment Introducing a polysiloxane segment which is originally hydrophobic (water repellent) into the resin structure cannot be expected to obtain good results with respect to water absorption and hydrophilicity. The surface of a film made of a resin with a low polysiloxane segment content is completely covered with a polysiloxane component in a dry state, but when immersed in water, the polysiloxane component is buried in the resin. It is known that it has a property (Polymer Transactions, Vol. 48, [No. 4], p. 227 (1991), etc.). The present invention utilizes this phenomenon, by appropriately controlling the polysiloxane content in the resin, when printing with high humidity or aqueous 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, a polysiloxane compound used for introducing a polysiloxane segment into a molecular chain constituting a hydrophilic polyurethane-based resin includes one or more reactive groups such as an amino group and an epoxy group in a molecule. Is a polysiloxane compound having a 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

(2) Epoxy-modified polysiloxane compound

(3) alcohol-modified polysiloxane compound

(4) Mercapto-modified polysiloxane compound

(5) Carboxyl-modified polysiloxane compound

(4) Introduction of hydrophilic segment The high molecular weight hydrophilic polyol used for introducing the hydrophilic segment into the hydrophilic polyurethane-based resin in the present invention includes a weight average molecular weight having a hydroxyl group, an amino group, a carboxyl group and the like. Is preferably in the range of 400 to 8,000. Examples of the terminal having a hydroxyl group and 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 polyol Polyethylene glycol / poly-valerolactone copolymer polyol Examples of the amino group having hydrophilicity include polyethylene oxide diamine, polyethylene oxide propylene oxide diamine, polyethylene oxide triamine, polyethylene oxide propylene oxide triamine, and an ethylene oxide adduct having a carboxyl group or a vinyl group. However, it is also possible to copolymerize other polyols, polyamines, polycarboxylic acids and the like having no hydrophilic chains in order to impart other performances.

  As the organic polyisocyanate used in the present invention, any conventionally 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, 2,2 There are 6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and the like, or obtained by reacting these organic polyisocyanates with low molecular weight polyols or polyamines to become terminal isocyanates. Naturally, polyurethane prepolymers and the like can also be used.

  In the present invention, a hydrophilic polyurethane-based resin having a hydrolyzable silyl group at a molecular chain terminal and / or a molecular side chain and having a tertiary amino group and a polysiloxane segment in the molecular chain, that is, a hydrophilic polyurethane resin, The polyurethane resin, the hydrophilic polyurea resin, and the hydrophilic polyurea-polyurethane resin can be synthesized without a solvent or in an aqueous solution or solvent according to a conventionally known method. The amount of each component used is as follows: the amount of tertiary amino group (the amount of the group containing segment), the amount of the hydrolyzable silyl group (the amount of the group containing segment), the amount of the polysiloxane segment, and the amount of the hydrophilic segment in the resin shown below. Is the amount The thus obtained hydrophilic polyurethane resin having a tertiary amino group, a polysiloxane segment, and a hydrolyzable silyl group in the molecular chain has a preferred weight average molecular weight (in terms of standard polystyrene measured by GPC) of 3,000. To 800,000, and more preferably a weight average molecular weight of 5,000 to 500,000.

  The hydrolyzable silyl group in the hydrophilic polyurethane resin obtained in the present invention may be contained in one or both of the side chain (pendant) and the main chain, and the content in the resin is determined by the amount of the raw material. The compound having a hydrolyzable silyl group, that is, the amount of the group-containing segment is preferably in the range of 1 to 40% by mass. More preferably, the content is 1 to 10% by mass.

  Further, the number of hydrolyzable silyl groups in the resin is preferably about 0.001 to 10, more preferably 0.01 to 1.0 per 1,000 molecular weight of the resin. When the content of the hydrolyzable silyl group is less than the above range, the desired properties of the anti-blocking property, water resistance, and moisture resistance, which are the intended objects of the present invention, become insufficient. The hydrophilic portion is reduced, and the water resistance is increased due to the crosslinked structure of the resin, and the water absorption performance and the antifogging property are deteriorated, which is not preferable.

  The tertiary amino group in the resin may be contained in the main chain or side chain, or in both, and the content in the resin is determined as a tertiary amino compound as a raw material, that is, The range is preferably 1 to 60% by mass, and more preferably 5 to 30% by mass. The number of tertiary amino groups in the resin is preferably about 1 to 50, more preferably 5 to 20, per 1,000 molecular weight of the hydrophilic resin. When the number of the tertiary amino groups is less than the above range, the intended properties of water resistance, blocking resistance, and moisture resistance, which are the intended objects of the present invention, become insufficient. Hydrophobicity is increased due to the decrease in the hydrophilic portion, and the water absorbing performance and the antifogging property are deteriorated.

  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 preferably 0.1 to 10% by mass in the hydrophilic polyurethane-based resin. Preferably it is 0.5 to 10% by mass. When the content of the polysiloxane segment is less than 0.1% by mass, the surface properties such as water resistance, blocking resistance and lubricity, which are the objects of the present invention, become insufficient. It is not preferable because the water repellency of the segments becomes stronger, the environmental responsiveness used by the present invention becomes poor, and the water absorbency, antifogging property and transparency become poor.

  The hydrophilic segment in the resin is contained in the main chain of the resin, and the content in the resin is preferably from 30 to 80% by mass, and more preferably from 50 to 75% by mass. If the content with the hydrophilic segment is less than the above range, the water absorption and antifogging properties will be poor, and if it exceeds the above range, the water resistance and blocking resistance will be poor, which is not preferable.

  In the hydrophilic polyurethane-based resin obtained in the present invention, each of the above segments is randomly connected with at least one bond of a urethane bond, a urea bond, and a urethane-urea bond (when no chain extender is used). When a chain extender is used, there is also a bond in which a short chain which is a residue of the chain extender exists between these bonds together with these bonds. The above bond is also a component of the resin of the present invention, and is generally called a bond portion. The balance of the content of the above-mentioned all segments is the content of the binding portion in the resin.

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

  Next, the present invention will be described more specifically with reference to examples and comparative examples. Parts and% in the following are based on mass unless otherwise specified.

上記構造を有しているポリジメチルシロキサンポリオール（分子量３，２００）５部とポリエチレングリコール（分子量２，０４０）１４５部、１，３−ブチレングリコール７部、Ｎ−メチルジエタノールアミン１２部を、トルエン１３５部と１００部のメチルエチルケトンとの混合溶剤中に溶解し、７０℃でよく攪拌しながら、ジフェニルメタンジイソシアネート６１部を添加する。添加終了後、更にメチルエチルケトン１００部を加え、８０℃で６時間反応させた。 Example 1
(Production of molecular side chain type hydrolyzable silyl group-tertiary amino group-containing 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), 7 parts of 1,3-butylene glycol and 12 parts of N-methyldiethanolamine were added to toluene 135 Dissolve in a mixed solvent of 1 part and 100 parts of methyl ethyl ketone, and add 61 parts of diphenylmethane diisocyanate with good stirring at 70 ° C. After the addition was completed, 100 parts of methyl ethyl ketone was further added, and the mixture was reacted at 80 ° C. for 6 hours.

No hydroxyl group absorption was observed in the infrared absorption spectrum of the obtained resin, and no hydroxyl group was confirmed by the pyridine method (JIS K-0070 2.5). Next, 7 parts of a silane coupling agent having an isocyanate group ((C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NCO) was added and reacted at 80 ° C. for 8 hours to confirm that the isocyanate group had disappeared. After that, the solid content concentration was adjusted to 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.).

７１部の水素添加ＭＤＩを２００部のジメチルホルムアミドに溶解し、内温を２０℃に保ち、よく攪拌しながら、１００部のジメチルホルムアミドに溶解した、ポリエチレンオキサイドジアミン（ジェファーミンＥＤ：テキサコケミカル社製、分子量２，０００）１４５部と上記構造を有しているポリジメチルシロキサンジアミン（分子量：３，８８０）５部を徐々に滴下し、滴下終了後５０℃で１時間反応させた後、さらに５０部のメチルエチルケトンに溶解したメチルイミノビスプロピルアミン１０部を徐々に滴下し、滴下終了後５０℃で３時間反応させイソシアネート末端ポリウレア樹脂を得た。
内温を再び２０℃にして、５０部のメチルエチルケトンに溶解した５．７部の１，４−ジアミノブタンを徐々に滴下し、滴下終了後同温度で１時間反応させた。更に１００部のメチルエチルケトンに溶解した２８部のγ−アミノプロピルトリエトキシシランを徐々に滴下して、３０℃で１時間反応させ、イソシアネート基が消失していることを確認した後、固形分濃度を３５％に調整し本発明の親水性ポリウレア樹脂の溶液を得た。この溶液は２５０ｄＰａ・ｓ（２５℃）の粘度を有していた。 Example 2
(Production of molecular-terminal hydrolyzable silyl group-tertiary amino group-containing silicone polyurea resin)

Polyethylene oxide diamine (Jeffamine ED: manufactured by Texaco Chemical Co., Ltd.) dissolved in 100 parts of dimethylformamide while dissolving 71 parts of hydrogenated MDI in 200 parts of dimethylformamide, maintaining the internal temperature at 20 ° C., and stirring well. 145 parts) and 5 parts of polydimethylsiloxanediamine (molecular weight: 3,880) having the above structure were gradually added dropwise. After the completion of the dropwise addition, the mixture was allowed to react at 50 ° C. for 1 hour, and then 50 parts. 10 parts of methyliminobispropylamine dissolved in 3 parts of methyl ethyl ketone was gradually added dropwise, and after completion of the addition, the mixture was reacted at 50 ° C. for 3 hours to obtain an isocyanate-terminated polyurea resin.
The internal temperature was again raised to 20 ° C., and 5.7 parts of 1,4-diaminobutane dissolved in 50 parts of methyl ethyl ketone were gradually added dropwise. After completion of the dropwise addition, the mixture was reacted at the same temperature for 1 hour. Further, 28 parts of γ-aminopropyltriethoxysilane dissolved in 100 parts of methyl ethyl ketone were gradually added dropwise, and reacted at 30 ° C. for 1 hour. After confirming that the isocyanate group had disappeared, the solid content concentration was reduced. The solution was adjusted to 35% 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-tertiary amino group-containing silicone polyurethane-polyurea resin)
(1) Production of Isocyanate-Terminated Silane Coupling Agent An adduct of hexamethylene diisocyanate and water (Duranate 24A-100; manufactured by Asahi Kasei Corporation, NCO% = 23.5) is mixed well at 25 ° C. while 270 parts are mixed therein. 111 parts of γ-aminopropyltriethoxysilane was gradually added dropwise to the mixture, and reacted to obtain a colorless and transparent liquid product (I). The resulting product has 10.5% of free isocyanate groups [theoretical value (the amount of the groups in the stoichiometrically generated reactants when reacted at 100%): 11.2%]. Theoretically, the following structure is considered.

前記液状生成物（Ｉ）８部とトルエンジイソシアネート５０部を２００部のジメチルホルムアミドに溶解し、１００部のメチルエチルケトンに溶解したポリエチレングリコール（分子量２，０４０）１４５部と上記構造を有するエチレンオキサイド付加型ポリジメチルシロキサン（分子量４，５００）５部、更に４部の１，３−ブチレングリコール及びＮ，Ｎ−ジメチル−Ｎ′，Ｎ′−ジヒドロキシエチル−１，３−ジアミノプロパン９部を添加し、６０℃で６時間反応させてイソシアネート末端ポリウレタン−ポリウレア樹脂を得た。内温を２０℃にして、５０部のメチルエチルケトンに溶解した８部の１，４−ジアミノブタンを徐々に滴下し、滴下終了後同温度で１時間反応させた。更に１００部のメチルエチルケトンに溶解した２０部のγ−アミノプロピルトリメトキシシランを徐々に滴下して、３０℃で１時間反応させイソシアネート基が消失していることを確認した後、固形分濃度を３５％に調整し本発明のポリウレタン−ポリウレア樹脂の溶液を得た。この溶液は３２０ｄＰａ・ｓ（２５℃）の粘度を有していた。 (2) Production of molecular terminal / side chain type hydrolyzable silyl group-tertiary amino group-containing silicone polyurethane-polyurea resin

8 parts of the liquid product (I) and 50 parts of toluene diisocyanate are dissolved in 200 parts of dimethylformamide, and 145 parts of polyethylene glycol (molecular weight 2,040) dissolved in 100 parts of methyl ethyl ketone and an ethylene oxide addition type having the above structure 5 parts of polydimethylsiloxane (molecular weight 4,500) and further 4 parts of 1,3-butylene glycol and 9 parts of N, N-dimethyl-N ', N'-dihydroxyethyl-1,3-diaminopropane are added, The reaction was carried out at 60 ° C. for 6 hours to obtain an isocyanate-terminated polyurethane-polyurea resin. At an internal temperature of 20 ° C., 8 parts of 1,4-diaminobutane dissolved in 50 parts of methyl ethyl ketone were gradually added dropwise, and after the completion of the addition, the mixture was reacted at the same temperature for 1 hour. Further, 20 parts of γ-aminopropyltrimethoxysilane dissolved in 100 parts of methyl ethyl ketone were gradually added dropwise, and reacted at 30 ° C. for 1 hour. After confirming that the isocyanate group had disappeared, the solid content was reduced to 35 parts. % To obtain a solution of the polyurethane-polyurea resin of the present invention. This solution had a viscosity of 320 dPa · s (25 ° C.).

Comparative Example 1
A polyurethane resin solution was obtained using the same materials and formulation as in Example 1 except that polydimethylsiloxane polyol, N-methyldiethanolamine, and a silane coupling agent having an isocyanate group were not used. This solution had a solid content of 35% and a viscosity of 340 dPa · s (25 ° C.).

Comparative Example 2
A polyurea resin solution was obtained by the same material and formulation as in Example 2 except that polydimethylsiloxanediamine, methyliminobispropylamine, and γ-aminopropyltriethoxysilane were not used. This solution had a viscosity of 300 dPa · s (25 ° C.) at a solid content of 35%.

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

Reference Example 1
A 5% aqueous solution of polyvinyl alcohol (degree of polymerization 550) having a saponification degree of 98.5% was prepared.

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

The 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 image receiving layer for ink jet The resin solution obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the resin solution of Reference Example 1 were dried on a PET film having a thickness of 100 μm to have a thickness of 20 μm. And a transparent sheet was prepared, and printed and recorded by a color ink jet printer (Seiko Epson Corporation; PM-750C), and the following items were evaluated.
(1) Blocking resistance An untreated PET film was overlaid on the resin-coated surface, a load of 0.29 Mpa was applied, and the blocking property was evaluated after being left at a temperature of 40 ° C for 1 day. The results are shown below.
：: No blocking property Δ: Slight blocking property X: Blocking property (2) Printer transportability The printer transportability at the time of printing and recording with an inkjet printer was evaluated.
：: Good transportability Δ: Slight noise generation X: Poor transportability (3) Color clarity After printing a color image with an inkjet printer, the color clarity of the obtained color image was visually observed.
：: good △: normal ×: poor (4) Water resistance of the 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 The change in color development was visually observed.
：: No change Δ: Discoloration observed X: Complete dissolution and disappearance are shown in Table 2.

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

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

(2) Application to antifogging / antistatic paint 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, and the antifogging property was obtained. The antistatic property was evaluated.
(1) Antifogging property A sample plate was set at a position of 5 cm on a boiling water bath, and the coating was evaluated for fogging when exposed to steam at 50 ° C for 10 minutes.
：: No fogging Δ: Partly fogging ×: Fogging (2) Water resistance A sample plate was set at a position of 5 cm on a boiling water bath and exposed to water vapor at 50 ° C. for 10 minutes to evaluate the paint state.
：: No change Δ: Slight change in state X: Peeling or dissolution of coating film (3) Antistatic property The adhesion of charged carbon was evaluated by a dust chamber test.
：: no carbon adhesion Δ: partial carbon adhesion ×: carbon adhesion The above results are shown in Table 3.

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

Claims (4)

  In producing a hydrophilic polyurethane resin by reacting an organic polyisocyanate with a high molecular weight hydrophilic polyol, a compound having at least one active hydrogen group and at least one tertiary amino group in the same molecule, at least Copolymerizing a polysiloxane compound having one active hydrogen group and a compound having at least one reactive group and at least one hydrolyzable silyl group in the same molecule with the above components, A method for producing a hydrophilic polyurethane resin, wherein the amount of the compound used is such that the content of the segment comprising the compound in the hydrophilic polyurethane resin is 0.1 to 10% by mass.   The production of the hydrophilic polyurethane-based resin according to claim 1, wherein the amount of the high-molecular-weight hydrophilic polyol used is such that the content of the polyol segment in the hydrophilic polyurethane-based resin is 30 to 80% by mass. Method.   The method for producing a hydrophilic polyurethane resin according to claim 1, wherein the compound having a tertiary amino group in the molecule is contained in a main chain and / or a side chain of the hydrophilic polyurethane resin. The method for producing a hydrophilic polyurethane resin according to claim 1, wherein the compound having a hydrolyzable silyl group in the molecule is contained in a molecular chain terminal and / or in a side chain of the hydrophilic polyurethane resin.