JPH0782337A - Modified polyurethane-urea and its use - Google Patents

Abstract

PURPOSE:To obtain a modified polyurethane-urea improved in the suitability of direct lamination with PP by making it from a hydroxy chlorinated polypropylene, a specified polyhydroxyhydrocarbon polymer, a diol, a diisocyanate and a chain extender. CONSTITUTION:A modified polyurethane-urea having a number-average molecular weight of 5000-100000 is obtained by effecting the urethane formation reaction by a prepolymer process comprising reacting an organic diisocyanate with a chlorinated polypropylene having at least one hydroxyl group (hereinbelow referred to as modified chlorinated PP) with a polyhydroxyhydrocarbon polymer having at least one terminal hydroxyl group and a polymer diol and optionally part of the chain extender in an isocyanate-excess molar ratio to form an isocyanate-terminated prepolymer, diluting this prepolymer with a solvent and chain-extending it with a chain extender or by a one-shot process comprising reacting an organic diisocyanate with a modified chlorinated PP, a polyhydroxyhydrocarbon polymer having at least one terminal hydroxyl group, a polymer diol and a diamine in a solution.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a modified polyurethane urea, and more particularly to a modified polyurethane urea useful as a binder for printing inks or paints for various plastics, or as an adhesive or coating agent.

[0002]

2. Description of the Related Art With the diversification and high functionality of plastic products, plastic films, plastic sheets,
Printing inks, adhesives, paints, and various coating agents used for decoration, adhesion, coating, etc. of plastic molded products are required to have various and high performances.

In the case of printing ink, for example, when a plastic film is used as a packaging material, printing is performed for decoration or surface protection. Printing inks for such printing are required to have a wide range of adhesiveness and high printability. The printed plastic film is often subjected to dry laminating or extrusion laminating after printing. For example, a film of polyester or nylon is laminated with a polyethylene film or a polypropylene film in order to improve heat sealability and moisture resistance. In this case, a polyisocyanate adhesive or the like is used in the dry laminating process. On the other hand, in the extrusion laminating process, various anchor coating agents such as polyisocyanate type, polyethyleneimine type and organic titanate type are used. Further, an aluminum foil is interposed between the plastic films to make a packaging material that can be boiled or retort processed. In addition, in the field of packaging materials based on transparent base materials, strength is not required until retort processing, but in the field of packaging materials based on transparent base materials, oriented polypropylene (OPP) is used as the base material film, and a laminate in which molten polypropylene is directly coated without using an anchor coating agent. A processing method (PP direct laminating) is performed.

In carrying out such post-processing, various performances such as adhesiveness, printability and suitability for post-processing are required for printing inks of various plastic films. Performance is primarily determined by the binder used in the printing ink. Generally used printing inks with polyurethane urea as a binder have excellent adhesion to polyester films and nylon films, but sufficient adhesion to polyolefin films such as polyethylene films and polypropylene films. In addition, there is a problem that the PP direct laminating suitability is insufficient.

On the other hand, a printing ink containing chlorinated polypropylene and a chlorinated ethylene vinyl acetate copolymer as a main binder does not have sufficient adhesiveness to a polyester film or a nylon film, and has boilability and retortability. However, there is a problem that the use is limited because it is low. Therefore, it is necessary to select and use a binder suitable for each type according to the adhesiveness to various plastic films, various laminating or boiling, retort processing, etc. It took a lot of effort to manage inventory.

As a method for solving these problems, methods using polyurethane-modified chlorinated polypropylene (Japanese Patent Laid-Open Nos. 64-85226 and 64-85227) have been proposed. However, since the chlorinated polypropylene and polyurethane used in these methods have poor compatibility, white turbidity or two-layer separation occurs, the resulting printing ink is inferior in stability over time, and satisfies the PP direct laminating suitability. When the obtained amount of chlorinated polypropylene is reacted with polyurethane, it has the drawback of impairing the printability, boil resistance, retort resistance, etc. of the original polyurethane, and it has the drawback of being used for printing inks. Alternatively, it was not sufficiently satisfactory as a binder for paints, and was not necessarily satisfactory as an adhesive.

[0007]

The object of the present invention is particularly excellent in PP direct laminating suitability, and adhesiveness to various plastic films such as polyester film, nylon film, polyolefin film, printability, laminating processability, and resistance to laminating. It is an object of the present invention to provide a modified polyurethane urea which is useful as a binder for printing inks and has a property of satisfying boilability and storage stability, and also useful as a binder for paints.

Further, another object of the present invention is to provide a modified polyurethane urea useful as an adhesive or coating agent having a performance capable of satisfying the adhesiveness, decorativeness and covering property for various plastic films, sheets and molded products.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, the compatibility with chlorinated polypropylene was ensured by blocking the polyolefin skeleton in the polyurethane urea main chain. Has been improved, a transparent resin solution can be obtained, and further, since the content of chlorinated polypropylene can be reduced, it has been found that the harmful effects derived from chlorinated polypropylene can be minimized and the present invention has been achieved. . The gist is that it is formed from chlorinated polypropylene having at least one hydroxyl group, polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, other high molecular weight diol, organic diisocyanate and chain extender. Average molecular weight is 5
000 to 100,000, which is a modified polyurethane urea.

The present invention will be described in detail below. The chlorinated polypropylene having at least one hydroxyl group (hereinafter, also referred to as modified chlorinated PP) used in the present invention is not particularly limited, but its production examples include, for example, chlorinated polypropylene and hydroxyl group. And reacting a compound having a radical-polymerizable double bond by a known method. The chlorine content of the modified chlorinated PP is preferably 5 to 50 wt%, more preferably 15 to 40 wt%. Chlorine content is 5
If it is less than wt%, the solubility in an organic solvent tends to decrease, and if it exceeds 50 wt%, the adhesion to polyolefins and other substrates tends to deteriorate. The number average molecular weight is preferably 1,000 to 50,000, more preferably 3,000 to 30,000. When the molecular weight is less than 1000, the blocking resistance is low,
PP direct laminating suitability is also poor, molecular weight 5000
If it exceeds 0, the compatibility with the polyurethaneurea moiety and the solubility in organic solvents tend to decrease.

The polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end used in the present invention preferably has a molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. . When the molecular weight is less than 500, the effect of improving the compatibility is poor, and when the molecular weight exceeds 10,000, the compatibility with the polyurethaneurea portion and the solubility in the organic solvent tend to decrease. Examples of the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end include a butadiene polymer having at least one hydroxyl group at the molecular end, a styrene-butadiene copolymer having at least one hydroxyl group at the molecular end, and a At least one of the molecular terminals is obtained by hydrogenating a hydroxyl group-terminated butadiene-based polymer such as an acrylonitrile-butadiene copolymer having at least one hydroxyl group, or a hydroxyl group-terminated butadiene-based polymer by a known method using a Raney nickel catalyst, a ruthenium catalyst or the like. Examples thereof include hydrogenated butadiene-based polymers having one hydroxyl group and hydrogenated isoprene-based polymers having at least one hydroxyl group at the molecular end. Of these, hydrogenated butadiene-based polymers having at least one hydroxyl group at the molecular end are preferable, and hydrogenated polybutadiene having at least one hydroxyl group at the molecular end is particularly preferable.

The hydrogenation rate is 10 g based on the iodine value of the polymer.
/ 100 g or less is preferable, and 5 g / 100 g is particularly preferable. Examples of hydrogenated polybutadiene having at least one hydroxyl group at the molecular end include Polytail (trade name) manufactured by Mitsubishi Kasei Co., Ltd. and NISS manufactured by Nippon Soda Co., Ltd.
O-PB-GI (brand name) etc. are mentioned.

The total of constituent components derived from chlorinated polypropylene having at least one hydroxyl group in modified polyurethane urea and constituent components derived from polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end. The content is 5 to 40 wt%, preferably 10 to 20 wt%. If the total content is less than 5 wt%, the PP direct laminating suitability is low and 40 wt%
If it exceeds%, the adhesiveness and printability are impaired. Further, the weight ratio of the component derived from the chlorinated polypropylene to the component derived from the polyhydroxy hydrocarbon polymer is 25/75 to 95/5, preferably 4
It is 5/55 to 85/15. PP less than 25/75
The direct laminating property is poor, and if it is 95/5 or more, the compatibility between the modified chlorinated PP portion and the polyurethane urea portion becomes insufficient.

Other polymeric diols used in the present invention are other than chlorinated polypropylene having at least one hydroxyl group or polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end. Then, those usually used in the production of polyurethane can be used, and examples thereof include polyether diol, polyester diol, polyether ester diol, and a mixture of two or more kinds thereof.

The polyether diol is obtained by homopolymerizing or copolymerizing alkylene oxide, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether. Examples thereof include glycol and a mixture of two or more thereof.

The polyester diols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, Neopentyl glycol, 2-methyl-2-propyl-1,3
-Propanediol, 1,5-pentanediol, 1,
6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol,
2,5-dimethyl-2,5-hexanediol, 1,8
-Aliphatic glycols such as octanediol and 1,9-nonanediol; Alicyclic glycols such as bishydroxymethylcyclohexane; Aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; C1-1
(8) alkyldialkanolamine such as 8 alkyldiethanolamine) and the like, for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, or the above diols are used as an initiator. Examples of the polylactone diol thus obtained include polycaprolactone diol, polymethylvalerolactone diol, and mixtures of two or more of these.

The polyether ester diol is obtained by reacting a mixture of an ether group-containing diol or another glycol with the above dicarboxylic acid or an anhydride thereof, or by reacting a polyester glycol with an alkylene oxide. Examples thereof include poly (polytetramethylene ether) adipate and the like. Besides, polycarbonate diols can also be used.

A part of the polymer diol is replaced with a polyol such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol and pentaerythritol. You can also do it. The number average molecular weight of the polymer diol is usually 500 to 6000, preferably 1000 to 4000.

The organic diisocyanate used in the present invention includes 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, methylene diisocyanate, isopropylene diisocyanate, 1,4- Cyclohexane diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, methylcyclohexane diisocyanate, 1-isocyanate-3-isocyanate methyl-3,5,5 Trimethylcyclohexane (hereinafter IPD
I or isophorone diisocyanate),
4,4'-dicyclohexylmethane diisocyanate,
Examples include isopropylidene dicyclohexyl-4,4'-diisocyanate. These may be used alone or in combination of two or more. In addition, isophorone diisocyanate is preferable for obtaining a polyurethane urea having excellent solubility and printability.

Examples of the chain extender used in the present invention include diamines and low molecular weight diols commonly used in polyurethane production. Examples of diamines include aliphatic diamines such as ethylenediamine, 1,2-propylenediamine, and hexamethylenediamine, 1-amino-3-
Aminomethyl-3,5,5-trimethylcyclohexane (hereinafter also referred to as IPDA or isophoronediamine), dicyclohexylmethane-4,4'-diamine (hydrogenated MDA), isopropylidenedicyclohexyl-
Alicyclic diamines such as 4,4′-diamine, 1,4-diaminocyclohexane and 1,3-bisaminomethylcyclohexane can be used. Moreover, you may use these in mixture of 2 or more types.

The low molecular weight diol has a molecular weight of 500.
Low molecular weight diols below are preferred, for example aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and xylylene glycol,
Examples thereof include aromatic glycols such as bishydroxyethoxybenzene. The amount of the chain extender used is determined by the relationship between the total amount of the chain extender, which will be described later, and the isocyanate group.

Further, as the terminal terminator used as necessary, monoalcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and isobutyl alcohol; monoethylamine, n-propylamine, Examples include monoamines such as diethylamine, di-n-propylamine, and di-n-butylamine; alkanolamines such as monoethanolamine and diethanolamine.

The modified polyurethane urea of the present invention can be produced by the following method. For example, an organic diisocyanate, a modified chlorinated PP, a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, a polymer diol, and optionally a part of a chain extender are reacted in a molar ratio of excess isocyanate groups. To produce a prepolymer having a terminal isocyanate group, dilute it with a solvent, and then extend the chain with a chain extender, organic diisocyanate, modified chlorinated PP, polyhydroxy carbon having at least one hydroxyl group at the molecular end. A one-shot method in which a hydrogen-based polymer, a polymeric diol, and a diamine are reacted in a solvent solution in a single step may be used. The method of adding the terminal terminator in the case of using the terminal terminator may be added before the chain extension reaction, may be added at the same time as the chain extender, or may be added after the end of the chain extension reaction. . When the terminal terminator is not used, the method of adding the prepolymer to the solvent containing the chain extender is preferable. The prepolymer method in the prepolymer method is a method in which an organic diisocyanate, a modified chlorinated PP, a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, and a polymer diol are reacted at once. Alternatively, a method may be used in which each component is reacted separately and then these are mixed to produce a prepolymer.

In producing the prepolymer, the equivalent amount of the isocyanate group of the organic diisocyanate and the modified chlorinated P
The NCO / OH ratio, which is the ratio of P, the total equivalent of the hydroxyl groups of the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, the polymer diol, etc., is 1.1 / 1.
Preferably in the range of ~ 3/1, NCO / OH
When the ratio is less than 1.1 / 1, it is difficult to obtain sufficient physical properties, and when the NCO / OH ratio is greater than 3/1, adverse effects such as a decrease in resolubility are likely to occur.

The ratio of the total equivalent of amino groups and hydroxyl groups of the chain extender and the terminal terminator to the equivalent of isocyanate groups of the prepolymer is usually 0.95 to 1.1, preferably 0.98.
Is about 1.05. When the amount of the chain extender or the end terminator used is large, the chain extender and the end terminator remain unreacted, and odor tends to remain. Further, the equivalent ratio of the amino group (hydroxyl group) of the chain extender and the terminal terminator is 1/2 to 1
The range of 5/2 is preferable. If it is less than this, problems may occur in sufficient drying property, blocking resistance, film strength and the like. Further, in the case of less than this, since the polymer has a high molecular weight, there is a possibility that adverse effects such as a decrease in re-solubility may occur. The above reaction is preferably carried out in the presence of a solvent, and examples of the solvent include ethanol, isopropanol,
Alcohols such as n-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethers such as dioxane and tetrahydrofuran; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate Included are halogenated hydrocarbons such as chlorobenzene, trichlene, and perklene, and mixtures of two or more thereof. As the solvent, those capable of dissolving the modified polyurethane urea and its raw materials are preferable.

It is also possible to use a catalyst in the urethanization reaction. Examples of the catalyst include tertiary amine catalysts such as triethylamine and dimethylaniline, and metal catalysts such as tin and zinc. The modified polyurethane urea preferably has a number average molecular weight of 5,000 to 100,000. When the number average molecular weight is less than 5,000, the drying property, blocking resistance, film strength, oil resistance, etc. are likely to decrease, and when it exceeds 100,000, the viscosity of the polyurethane urea solution is high and handling tends to be difficult. . The modified polyurethane urea solution obtained by the reaction may be used as it is for the production of printing inks or paints, or the above-mentioned solvent may be further added to the modified polyurethane solution. The solid content concentration in the modified polyurethane urea solution may be appropriately determined in consideration of workability and the like, and is usually 15 to 60 wt%.
Further, a viscosity of 50 to 100,000 mPa · s is practically suitable.

When the modified polyureaurethane of the present invention is used as a binder for printing ink or paint,
A resin compatible with the modified polyurethane urea may be used as an auxiliary component. Examples of such resins include:
Nitrified cotton, chlorinated polyethylene, chlorinated polypropylene,
Chlorinated polyolefins such as chlorinated polyethylene / propylene, chlorsulphonated polyolefins, ethylene vinyl acetate copolymers Chlorinated or chlorsulphonated products thereof, maleic acid resins, vinyl chloride / vinyl acetate copolymers, other polyurethane resins, etc. To be

To produce a printing ink, the modified polyurethaneurea of the present invention is provided with a colorant, a solvent, and if necessary, a surfactant, a wax and other additives for improving the ink fluidity and the ink surface film. The ingredients are appropriately blended and kneaded by using an ordinary ink manufacturing device such as a ball mill, an attritor, or a sand mill. The amount of the modified polyurethane urea of the present invention in the printing ink is 3 to 20 w.
It is preferably within the range of t%.

The printing ink using the modified polyurethane urea of the present invention can be used as a so-called two-component printing ink in combination with a polyisocyanate curing agent. Two
Examples of the polyisocyanate-based curing agent that can be used in the liquid printing ink include, for example, an adduct of 1 mol of trimethylolpropane and 3 mol of diisocyanate such as tolylene diisocyanate, 1,6-hexamethylene diisocyanate or isophorone diisocyanate, tolylene diisocyanate, Isocyanurate compounds synthesized by cyclic trimerization of isocyanate groups such as 1,6-hexamethylene diisocyanate or isophorone diisocyanate, partial buret reaction products synthesized from 1 mol of water and 3 mol of 1,6-hexamethylene diisocyanate, and these Mixtures are preferred. In this case, the addition amount of the polyisocyanate-based curing agent is 0.5 to 10 wt% with respect to the main agent. The modified polyurethane urea of the present invention is excellent not only as a binder for printing inks or paints, but also as an adhesive for coating agents such as woven fabrics and non-woven fabrics because it has excellent properties such as adhesiveness, appearance and heat resistance. Alternatively, it is also useful as a coating agent for decoration and protection of synthetic resin molded products.

[0030]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, "part" is a weight part,
"%" Indicates% by weight.

Example 1 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, modified chlorinated PP (chlorine content 28%, number average molecular weight 12000, hydroxyl value 14 KOHmg / g, Resin solid content 30% toluene solution) 445.7 parts, hydrogenated polybutadiene having at least one hydroxyl group at the molecular end (Mitsubishi Kasei Co., Ltd.)
Polytail HA number average molecular weight 2200, hydroxyl value 52
KOHmg / g) 44.6 parts, 3-methyl-1,5-pentylene adipate (number average molecular weight 2000) 100
0.0 parts and isophorone diisocyanate (IPD
I) 255.5 parts was charged and reacted at 100 ° C. for 10 hours to obtain a prepolymer having a free isocyanate content of 2.81%. Then, after adding 2185 parts of toluene, 535.1 parts of methyl ethyl ketone and 535.1 parts of isopropanol to form a uniform solution, isophorone diamine (IPD
A) 84.5 parts and 10.5 parts of monoethanolamine were reacted with stirring at 30 ° C. for 5 hours to obtain a modified polyurethane urea solution A.

Example 2 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, modified chlorinated PP (chlorine content 30%, number average molecular weight 9000, hydroxyl value 21 KOHmg / g, Resin solid content 50% toluene solution) 372.2 parts, hydrogenated polybutadiene having at least one hydroxyl group at the molecular end (Mitsubishi Kasei Co., Ltd. Polytail HA number average molecular weight 2200, hydroxyl value 52K
OHmg / g) 32.8 parts, poly 1,4-butylene adipate (number average molecular weight 2000) 1000.0 parts and isophorone diisocyanate (IPDI) 240.1 parts were charged and reacted at 100 ° C. for 10 hours to contain free isocyanate. An amount of 2.41% prepolymer was obtained. Next, toluene 1962.9 parts, methyl ethyl ketone 107
After adding 4.4 parts and 358.1 parts of isopropanol to make a uniform solution, isophorone diamine (IPDA) 72.
5 parts of 4 parts and 3.5 parts of n-butylamine under stirring at 30 ° C
The reaction was carried out for a time to obtain a modified polyurethane urea solution B.

Example 3 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, modified chlorinated PP (chlorine content 30%, number average molecular weight 9000, hydroxyl value 21 KOHmg / g, Resin solid content 50% toluene solution) 306.4 parts, hydrogenated polybutadiene having at least one hydroxyl group at the molecular end (number average molecular weight 15
00, hydroxyl value 75 KOHmg / g) 229.8 parts, polycaprolactone polyol (number average molecular weight 2000)
1000.0 parts and isophorone diisocyanate (I
(PDI) (256.8 parts) was charged and reacted at 100 ° C. for 10 hours to obtain a prepolymer having a free isocyanate content of 1.78%. Then, toluene 2322.4 parts, methyl ethyl ketone 795.2 parts, isopropanol 795.
After adding 2 parts to make a uniform solution, 61.4 parts of isophoronediamine (IPDA) and 2.8 parts of n-butylamine were reacted at 30 ° C. for 5 hours with stirring to obtain a modified polyurethane urea solution C.

Example 4 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, modified chlorinated PP (chlorine content 40%, number average molecular weight 20000, hydroxyl value 20 KOHmg / g, Resin solid content 30% toluene solution) 1716.7 parts, hydrogenated polybutadiene having at least one hydroxyl group at the molecular end (number average molecular weight 1500, hydroxyl value 75 KOHmg / g) 57.2 parts,
Charge 1000.0 parts of poly-3-methyl-1,5-pentylene adipate (number average molecular weight 3000) and 263.8 parts of isophorone diisocyanate (IPDI), and 1
The reaction was carried out at 00 ° C for 10 hours to obtain a prepolymer having a free isocyanate content of 1.59%. Then toluene 15
After adding 01.1 parts, 1351.4 parts of methyl ethyl ketone and 450.5 parts of isopropanol to form a uniform solution,
86.1 parts of isophoronediamine (IPDA) and 8.4 parts of monoethanolamine were reacted at 30 ° C. for 5 hours with stirring to obtain a modified polyurethane urea solution D.

Example 5 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, modified chlorinated PP (chlorine content 28%, number average molecular weight 12000, hydroxyl value 14 KOHmg / g, Resin solid content 30% toluene solution) 253.7 parts, hydrogenated polybutadiene having at least one hydroxyl group at the molecular end (number average molecular weight 3
000, hydroxyl value 37 KOHmg / g) 50.7 parts, poly 1,4-butylene adipate (number average molecular weight 100
0) 1000.0 parts and isophorone diisocyanate (IPDI) 514.7 parts were charged and reacted at 100 ° C. for 10 hours to obtain a prepolymer having a free isocyanate content of 5.75%. Next, toluene 2001. 3 parts, methyl ethyl ketone 1743.1 parts, isopropanol 4
After adding 35.8 parts to make a uniform solution, 106.0 parts of isophoronediamine (IPDA), 104.7 parts of dicyclohexylmethane-4,4'diamine (hydrogenated MDA), and 15.4 parts of monoethanolamine were stirred. The reaction was carried out at 30 ° C. for 5 hours to obtain a modified polyurethane urea solution E.

Example 6 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, modified chlorinated PP (chlorine content 30%, number average molecular weight 9000, hydroxyl value 21 KOHmg / g, Resin solid content 50% toluene solution) 1300 parts Hydrogenated polybutadiene having at least one hydroxyl group at the molecular end (number average molecular weight 150
0, hydroxyl value 75 KOHmg / g) 216.7 parts, IP
DI (236.9 parts) was charged and reacted at 100 ° C. for 12 hours to obtain a prepolymer having a free isocyanate content of 2.48%. Separately, 1000 parts of polybutylene adipate (number average molecular weight 2000) and 222.3 parts of IPDI were charged and reacted at 100 ° C. for 5 hours to obtain a prepolymer having a free isocyanate content of 3.38%. These prepolymers were mixed and then 3428.1 parts of toluene,
873.9 parts of methyl ethyl ketone and 873.9 parts of isopropyl alcohol were added to form a uniform solution, and then 156.0 parts of isophoronediamine (IPDA) and 14.9 parts of n-butylamine were reacted with stirring at 30 ° C. for 5 hours for modification. A polyurethane urea resin solution F was obtained.

[Comparative Example 1] In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, modified chlorinated PP (chlorine content 30%, number average molecular weight 9000, hydroxyl value 21 KOHmg / g, Resin solid content 50% toluene solution) 300.0 parts, poly 1,4-butylene adipate (number average molecular weight 2000) 1000.0 parts and isophorone diisocyanate (IPDI) 247.3 parts were charged and reacted at 100 ° C. for 10 hours. A prepolymer having a free isocyanate content of 2.95% was obtained. Next, toluene 1933.8 parts, methyl ethyl ketone 1041.9.
And 347.3 parts of isopropanol to form a uniform solution, 83.2 parts of isophoronediamine (IPDA),
A modified polyurethane urea solution G was obtained by reacting 7.9 parts of n-butylamine with stirring at 30 ° C. for 5 hours.

Comparative Example 2 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, modified chlorinated PP (chlorine content 28%, number average molecular weight 12000, hydroxyl value 14 KOHmg / g, Resin solid content 30% toluene solution) 1981.8 parts, poly 1,4-butylene adipate (number average molecular weight 2000) 1000.0 parts and isophorone diisocyanate (IPDI) 288.2 parts were charged and reacted at 100 ° C. for 10 hours. A prepolymer having a free isocyanate content of 1.55% was obtained. Next, toluene 1387.4 parts, methyl ethyl ketone 1387.4.
And isopropanol 462.5 parts were added to obtain a uniform solution, and then isophoronediamine (IPDA) 90.4 parts,
A modified polyurethane urea solution H was obtained by reacting 8.8 parts of monoethanolamine with stirring at 30 ° C. for 5 hours.

Comparative Example 3 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, modified chlorinated PP (chlorine content 30%, number average molecular weight 9000, hydroxyl value 21 KOHmg / g, Resin solid content 50% toluene solution) 2250.0 parts, hydrogenated polybutadiene having at least one hydroxyl group at the molecular end (number average molecular weight 2
200, hydroxyl value 52 KOHmg / g) 375.0 parts,
Poly 1,4-butylene adipate (number average molecular weight 200
0) 1000.0 parts and isophorone diisocyanate (IPDI) 564.0 parts were charged and reacted at 100 ° C. for 10 hours to obtain a prepolymer having a free isocyanate content of 2.52%. Next, toluene 3455.5 parts, methyl ethyl ketone 2290.3 parts, isopropanol 7
After adding 63.4 parts to make a uniform solution, 171.1 parts of isophoronediamine (IPDA) and n-butylamine 3
The modified polyurethane urea solution I was obtained by reacting 6.7 parts with stirring at 30 ° C for 5 hours.

Comparative Example 4 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, hydrogenated polybutadiene having at least one hydroxyl group at the molecular end (number average molecular weight 2200, hydroxyl value 52 KOHmg
/ G) 323.9 parts, poly 1,4-butylene adipate (number average molecular weight 2000) 1000.0 parts and isophorone diisocyanate (IPDI) 355.8 parts were charged and reacted at 100 ° C. for 10 hours to give a free isocyanate content. 3.95% prepolymer was obtained. Next, toluene 2534.6 parts, methyl ethyl ketone 1267.3.
And 422.4 parts of isopropanol to form a uniform solution, and then isophoronediamine (IPDA) 107.6.
Parts and 23.1 parts of n-butylamine at 5 ° C. with stirring at 5 ° C.
The reaction was carried out for a time to obtain a modified polyurethane urea solution J.

Table 1 shows the reaction conditions in Examples 1 to 6 and Comparative Examples 1 to 4. Further, Examples 1 to 6 and Comparative Examples 1 to
The viscosity of the modified polyurethane urea solution obtained in Example 4 and the molecular weight of the modified polyurethane urea are also shown in Table 1. The free isocyanate content, the viscosity of the modified polyurethane urea solution and the molecular weight of the modified polyurethane urea were measured by the following methods.

[Method for measuring free isocyanate content] 1
/ 2N-di-n-butylamine / toluene solution 20 ml
Collect the prepolymer into a conical Erlenmeyer flask with a stopper,
Back titration with 1 / 2N-HCl.

[Viscosity Measuring Method] The viscosity of the modified polyurethane urea solution is measured by a rotational viscometer (VISC manufactured by Tokyo Keiki Co., Ltd.).
ONIC EHD-R), the rotation speed was 20 rpm, the standard rotor (1 ° 34 '), and 25 ° C.

[Molecular Weight Measuring Method] The molecular weight of the modified polyurethane urea was measured by preparing a THF solution having a resin content of 0.2% by weight, and using a Tosoh GPC device HLC-8020, column G3000HXL / G4000HXL / G6000H.
XL was used. Injection volume 20 μl, flow rate 1.0 ml / m
in, pressure 40 kg / cm 2, RI detector RANGE3
The number average molecular weight in terms of standard polystyrene was used as the molecular weight.

[Evaluation Test] Examples 1 to 6 and Comparative Examples 1 to 4
The modified polyurethaneurea solution obtained in 1. was kneaded with a paint shaker in the following formulation to prepare a printing ink.

[0046]

[Table 1] Modified polyurethane urea (solid content) 12 parts Titanium oxide 30 parts Toluene 34 parts Methyl ethyl ketone 12 parts Isopropanol 12 parts

Next, each film of the above printing ink (corona discharge treated polypropylene (OPP), polyethylene terephthalate (PET), corona discharge treated nylon (N
Y)) was evaluated for adhesion, laminate strength, boil resistance and storage stability. The results are shown in Table 2.

(1) Adhesiveness A printed matter prepared by using the above-mentioned printing ink is left on each of the above-mentioned films for 1 day, and then a cellophane tape is attached thereto, and the temperature is kept at 90 ° C.
Was peeled off vigorously at an angle of, and the adhesiveness was evaluated by the degree of peeling on the printed portion. ⊚: No peeling at all ◯: 80% or more of the coating film remains Δ: 50 to 80% of the coating film remains ×: 50% or less of the remaining coating film

(2) Extrusion laminating strength Among the above-mentioned printed matters, polyethyleneimine-based anchor coating agent is used for OPP printed matter and polyisocyanate-based anchor coating agent is used for PET printed matter and NY printed matter, and molten polyethylene is laminated by an extrusion laminating machine. Obtain a laminated product, and after 3 days,
The T-type peel strength was measured using a sample cut into a width of 5 mm.

(3) PP Direct Lamination Strength Of the above-mentioned printed matter, the OPP printed matter is directly laminated with molten polypropylene by an extrusion laminating machine to obtain a laminated product, and after 2 days, the laminated product is 15 m.
The T-type peel strength was measured using a sample cut into m widths.

(4) Boil resistance The laminated product used in the above test (2) was made into a bag,
Put a mixture of water / vinegar / salad oil inside and seal it, then
After heating at 0 ° C./30 minutes, the state of the printed matter was judged from the appearance. ⊚: The appearance has not changed at all. ○: Some blister has occurred. Δ: Blister is generated. X: Delamination has occurred.

(5) Storage stability The stability of the printing ink prepared by the above formulation after 1 week was judged from the solution properties. ◯: No change with time is observed. X: Thickening of ink, two-layer separation, or precipitation occurred.

[0053]

The modified polyurethane urea obtained in the present invention is useful as a binder for printing inks or coatings, and printing inks using the binders of the present invention include polyolefin films, polyester films,
It has good adhesion to various plastic films such as nylon film, excellent laminate strength and boil resistance, and excellent storage stability. Compared with conventional binders, printing inks suitable for a wide range of purposes can be used. Can be created. Further, since the modified polyurethane urea of the present invention has excellent adhesiveness and appearance to various plastics, it is also useful as a decorative coating agent for various plastic films, plastic sheets, plastic molded articles, etc., a protective coating agent, and an adhesive agent. .

[0054]

[Table 2]

[0055]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C09J 175/04 JFC

Claims (7)

[Claims] 1. A chlorinated polypropylene having at least one hydroxyl group, a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, another polymeric diol, an organic diisocyanate and a chain extender, A modified polyurethane urea having a number average molecular weight of 5,000 to 100,000. 2. The chlorine content of chlorinated polypropylene is 5
˜50 wt%, number average molecular weight is 1000-500
The modified polyurethaneurea according to claim 1, wherein the modified polyurethaneurea is 00. 3. The modified polyurethane urea according to claim 1, wherein the polyhydroxy hydrocarbon polymer has a number average molecular weight of 500 to 10,000. 4. The polyhydroxy hydrocarbon polymer is hydrogenated polybutadiene.
The modified polyurethane urea described. 5. The weight ratio of chlorinated polypropylene to polyhydroxy hydrocarbon polymer is 25/75 to 95/5, and the total content of both is 5 to 40 wt%. The modified polyurethane urea according to any one of claims 1 to 4. 6. A binder for printing inks or paints, which comprises the modified polyurethaneurea according to any one of claims 1 to 5. 7. An adhesive or coating agent comprising the modified polyurethaneurea according to claim 1.