JPH10204145A - Polyurethane urea and compositions thereof - Google Patents

Abstract

(57) [Problem] To produce a polyurethane urea excellent in abrasion resistance, heat resistance, chemical resistance and adhesiveness. SOLUTION: An organic diisocyanate, a polymer diol and 3 (4), 8 (9) -bis (aminomethyl) -tricyclo [5.2.1.0 ^2,6 ] decane are reacted as a chain extender. Number average molecular weight of 2,000 to 10
0000 polyurethane urea.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyurethane urea. More specifically, it has high adhesion to other kinds of plastics, such as polypropylene, polyacrylate, and alkyd resin, and has abrasion resistance,
The present invention relates to a polyurethane urea which is excellent in various properties such as heat resistance and chemical resistance, and is extremely useful for a wide range of uses such as binders for printing inks, resins for coatings, coating agents and adhesives.

[0002]

2. Description of the Related Art Conventionally, polyurethane urea has been produced by reacting a chain extender comprising an organic diisocyanate, a polymer diol, an organic polyamine and, if necessary, a terminal stopper. Among them, a low molecular weight diamine compound is used as a chain extender for the purpose of improving heat resistance and chemical resistance. However, the polyurethane urea using a low molecular weight diamine compound which has been used so far has not been sufficiently satisfactory in abrasion resistance, heat resistance, chemical resistance and mechanical performance, and there is room for improvement. Further, conventional polyurethane ureas have poor adhesion to polyolefin substrates such as polypropylene and polyethylene, and development of polyurethane ureas having improved adhesion has been desired. Hereinafter, the binder will be described in detail using a printing ink binder as an example.

[0003] Today, polyurethane urea, which has a wide suitability for various plastic films such as polyolefin films, polyester films and nylon films, is widely used as a binder for printing ink. Depending on the type of post-processing performed after printing, these printing inks using polyurethaneurea as a binder may be used in a one-pack type or in a two-pack type by mixing a polyisocyanate compound. Especially in food packaging applications, there are applications where boil sterilization and retort sterilization processes are performed, and even in printing inks, the required performance such as adhesiveness, heat resistance, chemical resistance is strict, and usually it is often used in a two-pack type . However, in the case of the two-pack type, the polyisocyanate compound must be mixed immediately before use from the viewpoint of storage stability, so that the working time is limited and the operation is complicated. In addition, there are disadvantages such as lack of stability of the remaining meat, making it difficult to reuse the remaining meat.

[0004] In addition, although the retort sterilization step is not performed,
In the field of packaging materials based on transparent substrates, there is an application in which biaxially oriented polypropylene is used as a substrate film and lamination processing is directly performed with melted polypropylene without using an anchor coating agent (referred to as PP direct lamination). For such applications, conventional polyurethane urea has a disadvantage that sufficient lamination strength cannot be obtained.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present inventors have developed a polyurethane urea having high adhesiveness to various plastics including polyolefins and excellent in various performances such as abrasion resistance, heat resistance and chemical resistance. Intensive investigations to produce. An object of the present invention is to solve the above problems, polyurethane urea, that is, have sufficient adhesion to various plastics including polyolefin even when used in one liquid, abrasion resistance, heat resistance, chemical resistance. It is to provide an excellent polyurethane urea.

[0006]

Means for Solving the Problems The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that a specific diamine compound is used as a polyamine serving as a chain extender used in the production of polyurethane urea. As a result, the present inventors have found that an excellent polyurethane urea that solves the above problems can be obtained, and thus completed the present invention. The main points are (a) organic diisocyanate, (b) polymer diol, (c) 3 (4), 8 (9) -bis (aminomethyl)
Polyurethane urea having a number average molecular weight of 2,000 to 100,000 obtained by reacting tricyclo [5.2.1.0 ^2,6 ] decane and, if necessary, (d) a terminal stopper.

The present invention also relates to (a) an organic diisocyanate, (b) a polymer diol, (c) 3 (4), 8
(9) -Bis (aminomethyl) -tricyclo [5.2.
1.0 ^2,6 ] decane and optionally (d) a terminal terminator, (e) a chlorine content of 5 to 50% by weight, and a number average molecular weight of 1,000 to 50,000. ,
A chlorinated polyolefin having at least one hydroxyl group and / or (f) a number average molecular weight of 500 to 10,000.
The gist of the present invention is a polyurethane urea having a number average molecular weight of 2,000 to 100,000 obtained by adding and reacting a polyolefin compound having at least one hydroxyl group at a molecular terminal.

[0008]

DETAILED DESCRIPTION OF THE INVENTION As the organic diisocyanate of the component (a) used in the present invention, 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, paraphenylene diisocyanate, 2,5-naphthalenediisocyanate, aromatic diisocyanate such as tolidine diisocyanate, aliphatic diisocyanate having an aromatic ring such as α, α, α ′, α′-tetramethylxylylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, 2,
Aliphatic diisocyanate such as 2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexane diisocyanate (hydrogenated TDI), 1-isocyanate-3
Alicyclic diisocyanates such as -isocyanatomethyl-3,5,5-trimethylcyclohexane (IPDI), 4,4'-dicyclohexylmethane diisocyanate, and isopropylidenedicyclohexyl-4,4'-diisocyanate; These may be used alone or in combination of two or more. In addition, as a binder for printing ink, an alicyclic diisocyanate such as IPDI is preferable.

As the high molecular weight diol component (b) used in the present invention, those generally used in the production of polyurethane can be used. For example, polyether diol, polyester diol, polyether ester diol, polycarbonate diol and these two types A mixture of the above is mentioned. As the polyether diol, those obtained by homogenizing or copolymerizing an alkylene oxide,
Examples include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether glycol, and the like.

As the polyester diol, 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-butane) Diol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl- 1,3-propanediol, 2-butyl-2-ethyl-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, 2-butyl-2-hexyl-1,3-propanediol, 1,8-octanediol, 2-methyl-1, 8-octanediol, 1,9
- aliphatic glycols such nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, xylylene glycol, glycol having an aromatic ring such as bishydroxyethoxybenzene, alkyl dialkanolamine such as C _1-18 alkyl diethanolamine) , Such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene propylene adipate, or one or more lactones using the above glycols as an initiator. Polylactone diols obtained by polymerization, for example, polycaprolactone diol, polymethyl valerolactone diol and the like can be mentioned.

The polyetherester diol is obtained by reacting a mixture with an ether group-containing diol or another glycol with the above-mentioned dicarboxylic acid or anhydride thereof, or by reacting a polyester glycol with an alkylene oxide, for example, And poly (polytetramethylene ether) adipate.

Examples of the polycarbonate diol include those obtained by subjecting the above-mentioned glycol or various polymer diols to dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like by a dealcohol or glycol removal reaction, for example, poly (1,6- Hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate and the like.

A part of the glycol is glycerin, trimethylolethane, trimethylolpropane,
It can be substituted by a trihydric or higher polyhydric alcohol such as 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol and pentaerythritol. In this case, the trihydric or higher polyhydric alcohol used is desirably 20 mol% or less of the glycol. When the amount of the trihydric or higher polyhydric alcohol used exceeds 20 mol%, problems such as a decrease in the solubility of the obtained polyurethane urea may occur.

The number average molecular weight of the high molecular weight diol is usually 50
0 to 10,000, preferably 1,000 to 6,000
It is. More preferably, it is 2,000 to 4,000. When the number average molecular weight of the high molecular weight polyol is less than 500, the film strength of the obtained polyurethane urea may be reduced. On the other hand, when it exceeds 10,000, the abrasion resistance, heat resistance and chemical resistance of the obtained polyurethane urea may be reduced.

Component (c) 3 (4), 8 used in the present invention
(9) -Bis (aminomethyl) -tricyclo [5.2.
1.0 ^2,6 ] decane is obtained by reacting dicyclopentadiene with carbon monoxide and hydrogen in the presence of a cobalt or rhodium catalyst to obtain tricyclodecanealdehyde, and then reducing the formyl group by a known method. It is synthesized by amination (for details, see
See No. 8556. ) Having the following structural formula (1).

[0016]

Embedded image

Tricyclodiamine acting as a chain extender,
3 (4), 8 (9) -bis (aminomethyl) -tricyclo [5.2.1.0 ^2,6 ] decane can be used in combination with other chain extenders described below. That is, the molecular weight of 500 used as a raw material of the polyester polyol
Less than low molecular diol compounds, for example, ethylene glycol, propylene glycol, aliphatic glycols such as 1,4-butanediol, xylylene glycol, glycols such as aromatic glycols such as bishydroxyethoxybenzene, and low molecular diamine compounds, for example 2,4
-Or an aromatic diamine such as 2,6-tolylenediamine, xylylenediamine, 4,4'-diphenylmethanediamine, ethylenediamine, 1,2-propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-
1,3-propanediamine, 2-methyl-1,5-pentanediamine, 2,2,4- or 2,4,4-trimethylhexanediamine, 2-butyl-2-ethyl-
Aliphatic diamines such as 1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine; 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane ( IPD
A), 4,4'-dicyclohexylmethanediamine (hydrogenated MDA), isopropylidenecyclohexyl-4,
4'-diamine, 1,4-diaminocyclohexane,
Alicyclic diamines such as 1,3-bisaminomethylcyclohexane; In this case, the amount of the other chain extender used in combination with the tricyclodecanediamine is preferably not more than 60 mol% of the total amount of the chain extender. If it is used in an amount exceeding 60 mol%, it may not be possible to obtain a sufficient effect on the intended abrasion resistance, heat resistance, chemical resistance and the like.

The terminal terminating agent of the component (d) used as necessary includes monoalcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and isobutyl alcohol, monoethylamine, and the like. n-propylamine, diethylamine, di-n-propylamine, di-n
Monoamines such as -butylamine, and alkanolamines such as monoethanolamine and diethanolamine.

In the present invention, polyurethane urea can be produced by the following method. For example, (a) an organic diisocyanate and (b) a polymeric diol, optionally (c)
A prepolymer method of reacting a part of the chain extender with an isocyanate group excess molar ratio to form a prepolymer having terminal isocyanate groups, diluting with a solvent, and then (c) increasing the molecular weight with a chain extender, or For example, a one-shot method in which (a) an organic diisocyanate, (b) a polymer diol, and (c) a chain extender are reacted at once.

In the prepolymer method, there is no particular limitation on the order of addition of the components during the prepolymerization reaction of the terminal isocyanate groups, and the organic diisocyanate monomer can be added again as needed during the prepolymerization reaction. It is. In producing the prepolymer, the reaction ratio between the isocyanate group and the hydroxyl group is 1.1 / 1 to 10/1.
It is preferred that When the reaction ratio is less than 1.1 / 1, heat resistance and film strength may be reduced, and 1
If it is larger than 0/1, the adhesion to various plastics may be reduced.

In producing the polyurethane urea, the total of the hydroxyl group and the amino group of the chain extender is usually 0.1 to 1 equivalent of the isocyanate group of the prepolymer.
It is 5 to 1.2 equivalents, preferably 0.8 to 1.1 equivalents. The total amount of hydroxyl groups and amino groups of the chain extender is 0.5
When it is smaller than the equivalent, heat resistance and film strength may be reduced due to low molecular weight of the polyurethane urea. If the amount is more than 1.2 equivalents, an excessive amount of monomer remains in the solution, which may cause a problem such as a bad smell and a decrease in heat resistance. Further, the equivalent ratio of the glycol or diamine to the monoalcohol or monoamine in the chain extender needs to be in the range of 1/2 to 100/2. If it is smaller than 1/2, the abrasion resistance and chemical resistance may be reduced. If it is larger than 100/2, the molecular weight may be increased and the viscosity of the resin may be increased, resulting in a decrease in workability. The method of adding the terminal terminator used as necessary may be any of reacting before the chain extension reaction, adding at the same time as the chain extension agent, or adding after the completion of the chain extension reaction to complete the reaction. Method may be used.

Examples of the solvent used include alcohols such as ethanol, isopropanol and n-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; dioxane;
Ethers such as tetrahydrofuran, hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons such as chlorobenzene, tricrene, and perchrene; Examples include aprotic polar solvents such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, and dimethylformamide, and mixtures of two or more thereof.

The reaction can use a catalyst. Examples of the catalyst that promotes the urethanization reaction include tertiary amine catalysts such as triethylamine and dimethylaniline, and organometallic catalysts such as organotin and organozinc. The number average molecular weight of the thus obtained polyurethane urea of the present invention is usually preferably in the range of 2,000 to 100,000. More preferably, the lower limit is 5,
000 or more, more preferably 10,000 or more. The upper limit is more preferably 80,000 or less, and even more preferably 50,000 or less. If it is less than 2,000, the drying properties, blocking resistance, film strength, oil resistance, etc. of the printing ink and paint using this as a binder may be reduced. On the other hand, 100,000
When it exceeds, the handling becomes difficult due to the high viscosity of the polyurethane urea solution, the gloss of the obtained printing ink and paint may be reduced, and the resolubility may also be reduced. The resin concentration of the polyurethane urea solution is not particularly limited, but may be appropriately determined in consideration of workability, and is usually 15 to 60% by weight, and the viscosity is 50 to 10%.
000 mPa · s is practically suitable. In order to improve the adhesion to the polyolefin substrate, it is preferable to add a chlorinated polyolefin having at least one hydroxyl group and / or a polyolefin compound having at least one hydroxyl group at a molecular terminal to the reaction component.

Next, the chlorinated polyolefin having at least one hydroxyl group as the component (e) used in the present invention is not particularly limited, but examples of its production 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 chlorinated polyolefin having at least one hydroxyl group is 5 to 5.
It is preferably 50% by weight, more preferably 15 to 4%.
0% by weight. More preferably, the content is 20 to 35% by weight. If the chlorine content is less than 5% by weight, the solubility in organic solvents may decrease. If the chlorine content exceeds 50% by weight, the adhesion to polyolefins and other substrates may decrease. . The molecular weight is preferably from 1,000 to 50,000, more preferably from 3,000 to 30,000, in number average molecular weight. More preferably, it is 5,000 to 20,000. If the number average molecular weight is less than 1,000, the blocking property may decrease. If it exceeds 50,000, the compatibility with the polyurethane urea portion and the solubility in organic solvents may decrease. is there. Particularly preferred for adhesion to polypropylene is chlorinated polypropylene having at least one hydroxyl group.

The polyolefin compound having at least one hydroxyl group at the molecular terminal of the component (f) used in the present invention generally has a molecular weight of 500 to 10,000.
0, preferably 1,000 to 5,000.
When the molecular weight is less than 500, the effect of improving adhesion is poor, and when the molecular weight exceeds 10,000, the compatibility with polyurethaneurea and the solubility in an organic solvent are significantly reduced. As the polyolefin compound having at least one hydroxyl group at the molecular terminal, a butadiene homopolymer or copolymer (styrene butadiene copolymer, acrylonitrile butadiene copolymer) may be used. Hydrogenated polybutadiene, hydroxyl-terminated hydrogenated polyisoprene, and the like. In the present invention, hydrogenated polybutadiene is particularly preferred.

Hydrogenated polybutadiene having at least one hydroxyl group at a molecular terminal is available from Mitsubishi Chemical Corporation under the trade name Polytail Series or Nippon Soda Co., Ltd. under the trade name N
It is available as the ISSO-PB-GI series. The above-mentioned (e) the chlorinated polyolefin having at least one hydroxyl group and (f) the polyolefin compound having at least one hydroxyl group at the molecular terminal each account for 5 to 40% by weight, preferably 10% by weight of the polyurethane urea. -20% by weight.

When both the chlorinated polyolefin having at least one hydroxyl group and the polyolefin compound having at least one hydroxyl group at the molecular terminal are added, the weight ratio of the two is 5/95 to 95/5. , Preferably 35/65 to 85/15. 5 /
If it is less than 95, the suitability for PP direct lamination is poor, and 9
If it is 5/5, the compatibility with polyurethane urea becomes insufficient.

In this case, the total content of the chlorinated polyolefin having at least one hydroxyl group and the polyolefin compound having at least one hydroxyl group at a molecular terminal in the polyurethane urea is preferably 5 to 40% by weight, more preferably. Is 10 to 20% by weight. If the total content is less than 5% by weight, the suitability for PP direct lamination is low, and if it exceeds 40% by weight, the printability of the polyurethane urea is impaired and the properties as a binder for printing inks become poor.

The chlorinated polyolefin having at least one hydroxyl group as the component (e) and / or the polyolefin compound having at least one hydroxyl group at the molecular terminal of the component (f) can be obtained by the above-mentioned methods (a), (b) and (c). (A) an organic diisocyanate,
(B) polymer diol, 3 (4), 8 of component (c)
(9) -Bis (aminomethyl) -tricyclo [5.2.
1.0 ^2,6 ] simultaneously with decane, or by preliminarily reacting an organic diisocyanate with a polymer diol to prepare a urethane prepolymer having a free isocyanate group, which is then reacted with chlorine having at least one hydroxyl group. A polyolefin having at least one hydroxyl group at the molecular terminal and then reacting with the tricyclodecanediamine to extend the chain to obtain a polyurethane urea. Further, an organic diisocyanate, a polymer diol and By reacting the tricyclodecanediamine to prepare a polyurethane urea having a free isocyanate group, a chlorinated polyolefin having at least one hydroxyl group therein, and
Alternatively, various methods such as a method of reacting a polyolefin having at least one hydroxyl group at a molecular terminal may be employed.

When a composition useful for printing inks, paints and adhesives is prepared using the polyurethane urea of the present invention, various resins compatible with the polyurethane urea of the present invention may be used as an auxiliary component, if necessary. Can be compounded and used. Examples of such resins include chlorinated polyethylene, chlorinated polypropylene, chlorinated polyolefins such as chlorinated polyethylene propylene, chlorsulfonated polyolefins, ethylene / acetic acid, nitrated cotton, ethylene / vinyl acetate copolymer or chlorinated products thereof. Or chlorsulfonate, maleic acid resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, polyester resin, polyamide resin, polycarbonate resin, phenol resin, alkyd resin, polyurethane resin and the like.

When the polyurethane urea of the present invention is used as a printing ink or paint, it can be used in place of or in addition to a conventional binder. Colorants, solvents, and, if necessary, surfactants, waxes, and other additives for improving the fluidity and the surface film are appropriately blended with these binders, and ordinary production of dispersers, ball mills, attritors, sand mills, etc. Printing inks and paints can be produced by dispersing using a device.

The binder using the polyurethane urea of the present invention has excellent adhesiveness, abrasion resistance, heat resistance, and chemical resistance, and provides a stretchable and flexible coating film. It is extremely useful as a binder for inks, as a decoration for various synthetic resin molded articles, as a coating resin, an adhesive and a coating agent for surface protection. Further, the tricyclodecanediamine represented by the structural formula (1) used in the present invention is not limited to organic solvent-based ones, but also when used as a chain extender in anionic, cationic, or nonionic aqueous resins. The effect is expected.

[0033]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition,
"Parts" indicates parts by weight, and "%" indicates% by weight. Production Example In a 5 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, 600.0 parts of isophorone diisocyanate (IPDI) and poly 1,4-butylene adipate (Dainippon Ink & Chemicals, Inc.) (Manufactured by Polylite OD-X-668, number average molecular weight: 2,000, hydroxyl value: 56 KOH mg / g), 1,799.4 parts, and reacted at 100 ° C. for 3 hours to obtain a free isocyanate content of 6.28%. Was obtained. Next, 2,399.4 parts of toluene was added to prepare a prepolymer solution having a resin solid content of 50%.

Example 1 799.8 parts of the prepolymer solution obtained in the above preparation example was charged into a three-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, and toluene 131 was further added. After adding 3.1 parts, 318.6 parts of methyl ethyl ketone and 212.4 parts of isopropyl alcohol to make a homogeneous solution, tricyclodecanediamine, 3 (4), 8 (9)
-Bis (aminomethyl) -tricyclo [5.2.1.0
^2,6 ] decane 46.5 parts and n-butylamine 8.7 parts were added with stirring and reacted at 30 ° C. for 5 hours to obtain a resin solid content of 3%.
A 0% polyurethane urea resin solution A was obtained.

Example 2 799.8 parts of the prepolymer solution obtained in the Preparation Example was charged into a three-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, and subjected to hydroxyl-containing chlorination. Polypropylene (chlorine content 30%, number average molecular weight 9,0
00, hydroxyl value 21 KOHmg / g, resin solid content 50%
268.1 parts of a toluene solution were added and reacted at 100 ° C. for 12 hours to obtain a prepolymer (2) having a free isocyanate content of 2.15%. Next, 146.4 parts of toluene, 408.2 parts of methyl ethyl ketone, and 272.1 parts of isopropyl alcohol were added to make a uniform solution. Then, 37.2 parts of the above tricyclodecanediamine, and n-butylamine 1
2.0 parts were added under stirring and reacted at 30 ° C. for 6 hours to obtain a polyurethane urea resin solution B having a resin solid content of 30%.

Example 3 (Synthesis of Modified Polyurethane Urea) In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, a modified chlorinated PP (having a chlorine content of 28%,
Number average molecular weight 12,000, hydroxyl value 14 KOHmg /
g, resin solid content 30% toluene solution) 800 parts, hydrogenated polybutadiene having a hydroxyl group at a molecular terminal (number average molecular weight 2,200, hydroxyl value 52 KOHmg / g) 44
Parts, 1,4-butylene adipate (number average molecular weight 2,0
00) 1,000 parts and 244.5 parts of isophorone diisocyanate (IPDI) were charged (NCO / OH =
2.2 / 1) at 100 ° C. for 10 hours to obtain a prepolymer having a free isocyanate content of 2.13%. Then, 2,097 parts of toluene and 75 of methyl ethyl ketone
9.3 parts and 380 parts of isopropyl alcohol were added to make a homogeneous solution.
3 parts and 16.3 parts of n-butylamine were reacted at 30 ° C. for 5 hours with stirring to obtain a modified polyurethane urea resin solution C.

COMPARATIVE EXAMPLE 1 799.8 parts of the prepolymer solution obtained in the Preparation Example was charged into a three-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel.
After adding 0.7 part, 294.6 parts of methyl ethyl ketone and 196.2 parts of isopropyl alcohol to form a homogeneous solution, 16.2 parts of ethylenediamine and 4.4 parts of n-butylamine are added with stirring, and the mixture is added at 30 ° C. for 5 hours. The reaction was carried out for an hour to obtain a polyurethane urea resin solution D having a resin solid content of 30%.

The composition ratios in Examples 1 to 3 and Comparative Example 1 are shown in Table 1. Examples 1 to 3 and Comparative Example 1
The viscosity, molecular weight and film properties of the polyurethane urea of the polyurethane urea solution obtained in Table 1 are also listed in Table 1.
It is shown in FIG. The measurement of the free isocyanate content, the viscosity of the polyurethane urea solution, the molecular weight, and the physical properties of the film were performed by the following methods.

(Method for measuring free isocyanate content)
The prepolymer was collected in a stoppered Erlenmeyer flask containing 20 ml of a 5N di-n-butylamine / toluene solution.
Back titration was performed with 0.5N HCl aqueous solution. (Measurement method of viscosity) The viscosity of the polyurethane urea solution was measured using a rotational viscometer (VISCONIC EH manufactured by Tokimec Co., Ltd.).
DR) using a standard rotor (1 ° 34 ′) at 25 ° C.

(Method for Measuring Molecular Weight) The molecular weight of the obtained polyurethane urea was measured by measuring the THF of the polyurethane urea.
A solution was prepared, and a GPC device HLC-80 manufactured by Tosoh Corporation was used.
20 (column G3000HXL / G4000HXL / G
6000HXL) and the number average molecular weight in terms of standard polystyrene was defined as the molecular weight. (Method for measuring physical properties of film) According to JIS K6301,
Tensile tester (Tensilon UTM manufactured by Orientec Co., Ltd.)
-III-100) at a tensile speed of 500 mm / min, a temperature of 23 ° C. and a relative humidity of 55%.

[0041]

[Table 1]

(Evaluation Test) Examples 1 to 3 and Comparative Example 1
The polyurethane urea resin solution obtained in the above was kneaded with a glass bead in the following composition using glass beads to prepare a printing ink. Polyurethane urea (solid content) 12 parts Titanium oxide 30 parts Toluene 34 parts Methyl ethyl ketone 12 parts Isopropanol 12 parts

Next, the above printing ink was applied to a bar coater (N
o. 8) to apply to each film (corona discharge-treated biaxially oriented polypropylene film (OPP), polyethylene terephthalate film (PET), corona discharge-treated nylon film (Ny)), and to adhere to each film, The laminate strength was evaluated. Also,
The abrasion resistance was evaluated using a coating film obtained by applying a polyurethane urea resin solution on a polycarbonate plate so as to have a dry film thickness of 100 μm on a Teflon plate and drying at 80 ° C. for 24 hours. Table 2 shows the results.

(1) Adhesiveness After leaving the above-mentioned color-developed material for one day, an adhesive tape made by Nichiban Co., Ltd., a cellophane tape (trade name) was applied, and it was vigorously peeled off at an angle of 90 °. The adhesiveness was evaluated according to the degree. ◎: No peeling at all ○: 80% or more of the remaining coating film Δ: 50% or more to less than 80% of the coating film remaining X: less than 50% of the remaining coating film (2) Abrasion resistance Polyurethane urea coating film Was evaluated using a taper abrasion tester to determine the wear loss after 500 rotations of a worn wheel CS-10, a load of 1 kg.

(3) Heat resistance The polyurethane urea coating film was treated at a temperature of 110 ° C. for 30 minutes.
After leaving for 0 hour, the breaking strength before and after the measurement was measured, and the strength retention ratio (%) after standing with respect to the strength before leaving was evaluated. (4) Chemical Resistance The alkali resistance, acid resistance and oil resistance of the printing ink were evaluated in accordance with JIS K5400. Using 5% sodium hydroxide solution for alkali resistance and 5% acetic acid solution for acid resistance, immersion at 50 ° C. for 2 hours, washing with water,
The state of the dried coating film was judged from the appearance. Oil resistance is JI
Test volatile oil Nos. 1 and 3 specified in SK5400.7
The condition of the coating film after immersion for 72 hours at a temperature of 20 ° C. was judged from the external appearance using the number. ：: No change in appearance ○: Deterioration of coating film surface △: Part of coating film eluted ×: A considerable part eluted (5) PP direct lamination strength Extrusion of OPP developed product among the above developed products The laminated polypropylene is directly laminated by a laminating machine to obtain a laminated product.
The T-peel strength was measured using the sample cut to m width.

[0046]

[Table 2]

[0047]

The polyurethane urea obtained by the present invention has good adhesion to a wide range of plastics such as polyolefins, polyesters and nylons, and has abrasion resistance,
Excellent heat resistance, chemical resistance and mechanical performance, making it extremely useful as a binder for printing inks, decoration for various synthetic resin molded products, coating resins for surface protection, coating agents and adhesives It is.

Claims (6)

[Claims] 1. An organic diisocyanate, (b) a polymer diol, (c) 3 (4), 8 (9) -bis (aminomethyl) -tricyclo [5.2.1.0 ^2,6 ] Polyurethane urea having a number average molecular weight of 2,000 to 100,000 obtained by reacting decane and, if necessary, (d) a terminal stopper. 2. (a) an organic diisocyanate, (b) a polymer diol, (c) 3 (4), 8 (9) -bis (aminomethyl) -tricyclo [5.2.1.0 ^2,6 ] Decane, (e) chlorinated polyolefin having at least one hydroxyl group having a chlorine content of 5 to 50% by weight and a number average molecular weight of 1,000 to 50,000 in the obtained polyurethane urea 5 to 40% by weight
And, if necessary, the number average molecular weight obtained by reacting (d) a terminal terminating agent with 2,000 to 100,000.
Polyurethane urea. 3. (a) an organic diisocyanate, (b) a polymer diol, (c) 3 (4), 8 (9) -bis (aminomethyl) -tricyclo [5.2.1.0 ^2,6 ] Decane, (f) an amount of a polyolefin compound having a number-average molecular weight of 500 to 10,000 and having at least one hydroxyl group at a molecular terminal to be 5 to 40% by weight in the obtained polyurethaneurea, and The number average molecular weight obtained by reacting (d) the terminal stopper is
0-100,000 polyurethaneurea. 4. An organic diisocyanate, (b) a polymer diol, (c) 3 (4), 8 (9) -bis (aminomethyl) -tricyclo [5.2.1.0 ^2,6 ] Decane, (e) a chlorinated polyolefin having at least one hydroxyl group and having a chlorine content of 5 to 50% by weight and a number average molecular weight of 1,000 to 50,000, and (f)
(E) and (f) a polyolefin compound having a number average molecular weight of 500 to 10,000 and having at least one hydroxyl group at a molecular terminal in a weight ratio of 5/95 to 95/5. The amount of the total amount of the components in the obtained polyurethane urea is 5 to 40% by weight, and if necessary, (d) the number average molecular weight obtained by reacting the terminal stopper is 2,000 to 100,000. Polyurethane urea. 5. The polyurethane urea according to claim 3, wherein the polyolefin compound having at least one hydroxyl group at a molecular terminal is a hydrogenated polybutadiene. 6. A printing ink composition comprising the polyurethane urea according to claim 1.