JPH05117582A - Coating composition - Google Patents

Abstract

PURPOSE:To provide the subject composition composed of a specific polyurethane polyurea resin, a solvent and a polyisocyanate compound and giving a tough coating film having excellent solution stability, dryability, adhesiveness, etc. CONSTITUTION:The objective composition is produced by compounding (A) a polyurethane polyurea resin obtained by reacting (i) a polymeric polyol, (ii) a diisocyanate compound and (iii) a diamine compound as a chain extender with (B) 1-40 pts.wt. (based on 100 pts.wt. of the component A) of a polyisocyanate compound (e.g. carbodiimide-modified diphenylmethane diisocyanate) and (C) a tertiary alcohol of formula I (R<1> is lower alkyl or group of formula II; R<2> and R<3> are lower alkyl) (preferably t-butanol and/or diacetone alcohol are used in an amount of 5-80wt.% based on the total solvent).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to new and useful coating compositions.

[0002]

2. Description of the Related Art Recently, in various industrial fields such as construction industry, automobile industry, packaging industry, audio / video industry,
A wide variety of plastic moldings are used. As a coating agent for these plastic molded products, polyurethane excellent in adhesion and versatility has been favored.

Polyurethane coating agents are roughly classified into the following two types. One is called a reactive type, and is a two-pack type in which a main agent mainly composed of a high molecular weight polyol and an auxiliary agent composed of a polyisocyanate compound are mixed immediately before use, or a one-pack type composed of an isocyanate-terminated prepolymer ( Moisture curing type). This type of coating agent is characterized in that it can be applied with a high solid content and the film after curing is extremely tough, but it has the drawback of requiring a long time for curing, and it is necessary to dry and form a film in a short time. Not suitable for line painting and printing.

Another type is called a polymer type (lacquer type), which has a molecular weight of tens of thousands to which a high molecular polyol, a diisocyanate and a chain extender react with each other.
It is made by dissolving hundreds of thousands of polyurethane in a solvent. Further, this type of coating agent is a so-called pure polyurethane using ethylene glycol or glycol such as 1,6-hexanediol as a chain extender and a so-called polyurethane using diamine such as ethylenediamine or isophoronediamine as a chain extender. Divided into polyurea. The present polymer type coating agent is characterized in that a polymer film can be obtained immediately after the solvent is volatilized by simply coating the polymer type coating agent, and is suitable for the above-mentioned line coating and printing methods. When it is desired to form the film in a longer time and to obtain an extremely tough film, a tolylene diisocyanate or diphenylmethane diisocyanate-based polyisocyanate compound may be blended.

Of the above-mentioned polymer type coating agents, pure polyurethane has a low intermolecular cohesive force, and therefore a highly crystalline one is generally used as a high molecular polyol as a constituent component thereof for the purpose of improving cohesive force. As a result, there is a drawback that the coating film becomes hard easily and sufficient rubber elasticity cannot be obtained. Further, since the molecular weight is usually designed to be 200,000 or more, the viscosity becomes high and the resin solid content when used as a coating agent is also low.

[0006] Polyurethane polyurea, which is the other polymer type coating agent described above, has a urea bond in the molecule and thus has a high intermolecular cohesive force, and can have a high rubber elasticity with a molecular weight of tens of thousands. In comparison with the pure polyurethane type, there is an advantage that a coating agent having high solid content and high elasticity can be obtained. However, due to its high cohesive force, polyurethane polyurea is inferior in stability over time in solution and has a drawback that viscosity increases with time. As a means for improving the stability of the polyurethane polyurea solution over time, a method using a polar solvent such as dimethylsulfoxide or N, N-dimethylformamide, a common solvent such as toluene, methyl ethyl ketone, or ethyl acetate, along with methanol, ethanol, Isopropyl alcohol, cellosolve, butyl cellosolve, etc. primary or secondary
The fact is that any one of the methods of using a relatively large amount of a solvent having a hydroxyl group in the grade is adopted.

However, in the method of 1, the toxicity of the solvent is high,
It is not suitable as a general-purpose coating agent. In the other method, since the solvent itself having a primary or secondary hydroxyl group easily reacts with the combined polyisocyanate compound, the reactivity between the polyurethane polyurea and the polyisocyanate compound is relatively lowered, and the desired physical properties are obtained. I can't.
Paying attention to the reactivity (deactivation of isocyanate group),
Although aliphatic or alicyclic polyisocyanate compounds such as isophorone diisocyanate and hexamethylene diisocyanate are generally used in spite of their low reactivity compared to aromatic polyisocyanate compounds,
As a result, it is difficult to obtain a desired coating agent having high reactivity and excellent physical properties after the reaction, and the coating agent is currently applied only to printing ink having an extremely thin film thickness.

[0008]

DISCLOSURE OF THE INVENTION According to the present invention, the compounded polyisocyanate compound is not deactivated, has good solution stability, and can easily form a tough film excellent in dryness and adhesion. An object of the present invention is to provide a polyurethane polyurea-based coating composition suitable for coating plastic molded products.

[0009]

In view of the above technical background, the inventors of the present invention have made earnest studies to solve the problems of the prior art, and as a result, surprisingly, by using a specific organic solvent, the above problems have been solved. The inventors have found that the above can be solved and completed the present invention.

The present invention relates to a polyurethane polyurea resin obtained by reacting a polymer polyol, a diisocyanate compound and a diamine compound as a chain extender, and a coating composition comprising a solvent and a polyisocyanate compound, wherein the solvent is represented by the following general formula: :

[0011]

[Chemical 1]

[0012] The present invention relates to a coating composition characterized by essentially using a tertiary alcohol represented by That is, by adopting a new solution means using a specific organic solvent called the tertiary alcohol, it is possible to solve the above-mentioned problems that could not be solved by conventional coating agents.

The polyurethane polyurea resin, which is one of the main constituent features of the present invention, is composed of the following components. First, as the polymer polyol component, polyether polyols such as polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, etc .; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1, 3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, diethylene glycol, triethylene glycol,
Saturated and unsaturated various known low-molecular glycols such as dipropylene glycol or n-butyl glycidyl ether, alkyl glycidyl ethers such as 2-ethylhexyl glycidyl ether, monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester, Dimer diol obtained by reducing dimer acid, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid,
Polyester polyols obtained by dehydration condensation of dibasic acids such as malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, or acid anhydrides or dimer acids corresponding thereto; cyclic ester compounds Polyester polyols obtained by ring-opening polymerization;
In addition, various known polymer polyols generally used in the production of polyurethane are exemplified, such as polycarbonate polyols, polybutadiene glycols, glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A, and the like. In the case of a polymer polyol obtained from glycols and a dibasic acid among the above, up to 5 mol% of the glycol component can be substituted with the following various polyols. That is, for example, glycerin,
Trimethylolpropane, trimethylolethane, 1,
Examples thereof include 2,6-hexanetriol, 1,2,4-butanetriol, pentaerythritol, sorbitol and the like.

The molecular weights of the above various polymer polyols are
The solubility, drying property, blocking resistance and the like of the obtained polyurethane polyurea resin are appropriately determined, and it is usually in the range of 500 to 3000. When the molecular weight is less than 500, the printability tends to be poor due to the decrease in solubility, while when it exceeds 3,000, the drying property and the blocking resistance tend to decrease.

Further, a part of the polymer polyol component may be replaced with a low molecular weight polyol within a range not deviating from the performance of the polyurethane polyurea resin, and the amount used in the polyol component is usually used. Is 2
It is 0% by weight or less, preferably 10% by weight or less. Examples of the low molecular weight polyols include various low molecular weight polyols used for producing the high molecular weight polyols. When the use ratio of the low molecular weight polyol exceeds 20% by weight, the adhesiveness of the obtained coating agent to the plastic film and the solubility to the diluting solvent tend to decrease, which is not preferable.

The diisocyanate compound which is another constituent of the polyurethane polyurea resin of the present invention is an aromatic, aliphatic or alicyclic diisocyanate.
For example, 1,5-naphthylene diisocyanate, 4,
4'-diphenylmethane diisocyanate, 4,4'-
Diphenyldimethylmethane diisocyanate, 4,4 '
-Dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4- Trimethylhexamethylene diisocyanate, 2,4,4
-Trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-
Representative examples thereof include diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and methylcyclohexane diisocyanate.

Examples of the chain extender include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine and dimerdiamine. Further, diamines having a hydroxyl group in the molecule, for example, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2
-Hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine and the like can be used as well. Furthermore, if necessary, a dialkylamine such as di-n-butylamine may be used as a polymerization terminator.

As the method for producing the polyurethane polyurea resin of the present invention, first, a polymer polyol component and a diisocyanate compound are reacted under conditions of excess isocyanate groups to prepare a prepolymer having isocyanate groups at both ends of the polymer polyol. A two-step method of preparing and then reacting this with a chain extender and optionally a polymerization terminator in a suitable solvent, and a polymer polyol component, a diisocyanate compound, a chain extender and optionally a polymerization terminator, Although any one-step method of reacting in a suitable solvent at a time can be adopted, the former method is preferable for the purpose of obtaining a uniform polymer solution.

Examples of the tertiary alcohol of the above general formula used in these production methods include t-butanol and t-butanol.
Amyl alcohol, 3-methyl-3-pentanol, 3
-Ethyl-3-pentanol, 2,3-dimethyl-2-
Examples thereof include butanol and diacetone alcohol, and these can be used alone or in combination. Considering availability and price, t-butanol or diacetone alcohol is preferable. In the present invention, the use of the tertiary alcohol is essential, and the essential solvent is an aromatic solvent such as benzene, toluene, xylene, etc. which is generally known as a solvent for coating agents; an ester solvent such as ethyl acetate, butyl acetate; acetone. , Methyl ethyl ketone, methyl isobutyl ketone, and other ketone solvents alone or in combination with two or more. The amount of the tertiary alcohol used in the whole solvent used is usually preferably in the range of 5 to 80% by weight. If it is less than 5% by weight, the stability of the solution over time tends to be poor, and if it exceeds 80% by weight, the solubility tends to decrease. The conventionally used solvents having a primary or secondary hydroxyl group, such as isopropyl alcohol, ethanol, methanol, cellosolve, and butyl cellosolve, deactivate the polyisocyanate compound used together and should not be used.

When the polyurethane polyurea resin used in the present invention is produced by a two-step method, the conditions for reacting the high molecular weight polyol component and the diisocyanate compound are not limited, except that the isocyanate is in excess. Isocyanate groups have an equivalent ratio of 1 / 1.2-
It is preferable that the reaction is carried out in the range of 1/3. The conditions for reacting the obtained prepolymer with a chain extender and optionally a polymerization terminator are also not limited, but when the free isocyanate group at the end of the prepolymer is 1 equivalent, It is preferable that the total equivalent of amino groups capable of reacting with the isocyanate group in the extender is in the range of 0.5 to 1.3 equivalents. When the amino group is less than 0.5 equivalent, the drying property, blocking resistance and film strength are not sufficient, and when the amino group exceeds 1.3 equivalent, the chain extender is unreacted. It remains as it is, and the odor tends to remain after applying the coating agent.

The number average molecular weight of the polyurethane polyurea resin obtained as described above is 5,000 to 100,000.
It is suitable to be within the range. When the molecular weight is less than 5,000, the coating composition containing this as a main component is inferior in drying property, blocking resistance, film strength, oil resistance and the like, while when it exceeds 100,000, the viscosity of the polyurethane polyurea resin solution is low. Tends to be too high.

The concentration of the resin solid content of the polyurethane polyurea resin solution obtained as described above is not particularly limited and is appropriately determined in consideration of workability at the time of coating, and usually 15% to 60% by weight. And the viscosity is 50-1000.
Practically suitable is 0 cP / 25 ° C. Although the above various solvents can be used for viscosity adjustment, a solvent having a primary or secondary hydroxyl group must not be used for the reasons described above.

Examples of the polyisocyanate compound essential to the present invention, which is used in combination with the above-mentioned polyurethane polyurea resin, include the above-mentioned diisocyanate compounds, addition products of these diisocyanate compounds with polyhydric alcohols or water, or the weight of these diisocyanate compounds. Examples include coalescing. More specifically, an adduct of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate, a tolylene diisocyanate trimer by an isocyanurate bond, a carbodiimide-modified diphenylmethane diisocyanate (liquid MDI), polymethylene polyphenyl isocyanate (crude MDI). ), Triphenylmethane 4,4 ′, 4 ″ -triisocyanate, burette-bonded hexamethylene diisocyanate trimer, isocyanurate-bonded hexamethylene diisocyanate trimer, trimethylolpropane 1 mol and hexamethylene diisocyanate 3 mol Addition product, addition product of 1 mol of trimethylolpropane and 3 mol of isophorone diisocyanate, isophorone diisocyanate trimer by isocyanurate bond, trimethylo Examples include an adduct of 1 mol of propane propane and 3 mol of xylylene diisocyanate, an adduct of 1 mol of trimethylolpropane and 3 mol of 1,3-bis (isocyanatomethyl) cyclohexane, etc. Among these, more excellent physical properties are obtained. The aromatic polyisocyanate compound is particularly preferable in that it is added to the polyurethane polyurea resin in an amount of 1 to 40 parts by weight, which is less than 1 part by weight. In this case, the physical properties of the coating cannot be expected to be improved, and if it exceeds 40 parts by weight, the coating becomes too hard and the rubber elasticity is impaired.

The coating composition of the present invention can be applied as it is as a clear varnish, or may be used in combination with a known coating additive such as a pigment, a dispersant, an anti-sagging agent, an ultraviolet absorber, etc. It can also be applied as an enamel paint obtained by kneading.

As the base material to which the coating composition of the present invention is applied, a plastic molded product is suitable, but it can also be applied to paper, wood, metal and the like. When coating the coating composition of the present invention on these substrates, the coating method is not particularly limited, and various known methods such as brush coating, spraying, dipping, and roll coating may be adopted. Other uses of the coating composition of the present invention include printing ink binders, overprint varnishes, adhesives, and magnetic tape binders.

[0026]

EXAMPLES The present invention will be described in detail below with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. In the examples, all parts and% are by weight unless otherwise specified.

Production Example 1 A round-bottomed flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introducing tube was charged with poly (1,2-
Propylene adipate) glycol (1000 parts) and isophorone diisocyanate (222 parts) were charged and reacted under a nitrogen stream at 100 ° C. for 6 hours to give a free isocyanate value of 3.3.
A 6% prepolymer was prepared, and 815 parts of methyl ethyl ketone was added thereto to prepare a uniform solution of urethane prepolymer. Then, 77.6 parts of isophorone diamine, di-n-
2037 parts of the above urethane prepolymer solution was added in the presence of a mixture of 2.1 parts of butylamine, 1214 parts of methyl ethyl ketone and 1018 parts of t-butanol,
Then, the mixture was reacted at 50 ° C. for 3 hours. The polyurethane polyurea resin solution A thus obtained had a resin solid content concentration of 30% and a viscosity of 1800 cP / 25 ° C.

Production Example 2 A reactor similar to that of Production Example 1 was charged with 1000 parts of poly (butylene adipate) glycol having a molecular weight of 2000 and 222 parts of isophorone diisocyanate, and reacted at 100 ° C. for 6 hours under a nitrogen stream to obtain a free isocyanate value. 3.4
A 0% prepolymer was prepared, and 815 parts of methyl ethyl ketone was added thereto to prepare a uniform solution of the urethane prepolymer. Then, 78.6 parts of isophoronediamine, di-n-
2037 parts of the above urethane prepolymer solution was added in the presence of a mixture of 2.0 parts of butylamine, 1216 parts of methyl ethyl ketone and 1018 parts of diacetone alcohol, and then reacted at 50 ° C. for 3 hours. The polyurethane polyurea resin solution B thus obtained had a resin solid content concentration of 30% and a viscosity of 6000 cP / 25 ° C.

Production Example 3 A reactor similar to that of Production Example 1 was charged with 1000 parts of polyoxytetramethylene glycol having a molecular weight of 1000 and 333 parts of isophorone diisocyanate, and the mixture was placed under a nitrogen stream for 10 minutes.
The reaction was carried out at 0 ° C for 10 hours to give a free isocyanate value of 3.10.
% Prepolymer with 8% methyl ethyl ketone
89 parts were added to obtain a uniform solution of urethane prepolymer. Then, 71.5 parts of isophoronediamine, di-n-
Butylamine 18.4 parts, methyl ethyl ketone 1324
2222 parts of the above urethane prepolymer solution was added in the presence of a mixture of 1 part and 1107 parts of diacetone alcohol, and then the mixture was reacted at 50 ° C. for 3 hours. The polyurethane polyurea resin solution C thus obtained had a resin solid content concentration of 30% and a viscosity of 2200 cP / 25 ° C.

Production Example 4 A reactor similar to that of Production Example 1 was charged with 1000 parts of polycaprolactone glycol having a molecular weight of 2000, 52 parts of neopentyl glycol, and 291 parts of 1,3-bis (isocyanatomethyl) cyclohexane, under a nitrogen stream. To 1
The reaction was carried out at 00 ° C for 10 hours to obtain a free isocyanate value of 3.1.
A 0% prepolymer was prepared, and 895 parts of methyl ethyl ketone was added thereto to prepare a uniform solution of urethane prepolymer. Then, 73.3 parts of isophoronediamine, di-n-
Butylamine 10.2 parts, methyl ethyl ketone 1329
2238 parts of the above urethane prepolymer solution was added in the presence of a mixture of 1 part by weight and 1115 parts of diacetone alcohol, and then reacted at 50 ° C. for 3 hours. The polyurethane polyurea resin solution D thus obtained had a resin solid content concentration of 30% and a viscosity of 2500 cP / 25 ° C.

Production Example 5 A polyurethane polyurea resin solution E was obtained in the same manner as in Production Example 1 except that isopropyl alcohol was used instead of t-butanol. Resin solid concentration is 30%,
The viscosity was 680 cP / 25 ° C.

Production Example 6 A polyurethane polyurea resin solution F was obtained in the same manner as in Production Example 2 except that butyl cellosolve was used instead of diacetone alcohol. Resin solid concentration is 30%,
The viscosity was 4600 cP / 25 ° C.

Production Example 7 1000 parts of poly (butylene adipate) glycol having a molecular weight of 2000 were added to a reactor similar to that of Production Example 1,
A moisture-curable urethane prepolymer solution was prepared by charging 250 parts of 4′-diphenylmethane diisocyanate, reacting them at 70 ° C. for 3 hours under a nitrogen stream, and then adding 536 parts of toluene. Resin solid content concentration is 70
%, The viscosity was 650 cP / 25 ° C.

Example 1 Titanium white (rutile type) 30 parts Polyurethane polyurea resin solution A obtained in Production Example 1 50 parts Toluene 30 parts After kneading a mixture of the above composition with a paint shaker,
The viscosity was adjusted by diluting with toluene in an Iwata cup for 15 seconds, and 1 part of an adduct of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate was further mixed,
A coating composition was prepared. This coating composition was spray-coated on a polypropylene sheet having a thickness of 3 mm, and then forcedly dried at 70 ° C. for 15 minutes (film thickness after drying was about 25 μm). The adhesiveness of the obtained coating film (initial adhesiveness) and the adhesiveness after standing for 6 months (durability adhesiveness) were evaluated by a scoring-tape peeling test. Further, for gasoline resistance and alcohol resistance, one week after coating, the change of the surface condition of the coating film was evaluated by rubbing the coating film surface with absorbent cotton impregnated with each of these solvents.
The case where there was almost no change was rated as good, and the case where a part of the coating film was transferred to absorbent cotton was rated as bad. The evaluation results are shown in Table 1.

Example 2 In Example 1, the polyurethane polyurea resin solution A was used.
In place of the polyurethane polyurea resin solution B obtained in Production Example 2, and the addition amount of the adduct of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate was 3
A coating composition was prepared and evaluated in the same manner as in Example 1 except that the parts were used. The results are shown in Table 1.

Example 3 In Example 1, the polyurethane polyurea resin solution A was used.
Was used in place of the polyurethane polyurea resin solution C obtained in Preparation Example 3, and triphenylmethane-4,4 ', 4 "-triisocyanate was used instead of the adduct of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate. A coating composition was prepared and evaluated in the same manner as in Example 1 except that 7.5 parts of a 20% solid content methylene chloride solution was used, and the results are shown in Table 1.

Example 4 In Example 1, polyurethane polyurea resin solution A
In place of the polyurethane polyurea resin solution D obtained in Production Example 4, and 4 parts of 3 mol buretlet conjugate of hexamethylene diisocyanate in place of the adduct of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate. A coating composition was prepared and evaluated in the same manner as in Example 1 except for the above. The results are shown in Table 1.

Comparative Example 1 Polyurethane polyurea resin solution A in Example 1
A coating composition was prepared and evaluated in the same manner as in Example 1 except that the polyurethane polyurea resin solution E obtained in Production Example 5 was used instead of. The results are shown in Table 1.

Comparative Example 2 Polyurethane polyurea resin solution B in Example 2
A coating composition was prepared and evaluated in the same manner as in Example 2 except that the polyurethane polyurea resin solution F obtained in Production Example 6 was used instead of. The results are shown in Table 1.

Comparative Example 3 Polyurethane polyurea resin solution A in Example 1
Using the urethane prepolymer solution obtained in Production Example 7 instead of, a coating composition was prepared in the same manner as in Example 1 without adding an adduct of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate, The polypropylene sheet was spray-painted and then forcedly dried at 70 ° C. for 15 minutes, and the coatings after the forced drying had no stickiness with the coating compositions of Examples 1 to 4 and Comparative Examples 1 and 2 and were completely dried. On the other hand, the coating composition was not cured yet and remained sticky, and finally cured after 3 days. Therefore, evaluations other than initial adhesion were performed. The results are shown in Table 1.

[0041]

EFFECTS OF THE INVENTION According to the present invention, a plastic compound in which a compounded polyisocyanate compound is not deactivated and has good solution stability, and a tough film excellent in drying property and adhesion can be easily formed A polyurethane polyurea-based coating composition suitable for coating molded articles is obtained.

[0042]

[Table 1]

Claims (5)

[Claims] 1. A coating composition consisting of a polymer polyol, a diisocyanate compound and a polyurethane polyurea resin obtained by reacting a diamine compound as a chain extender, and a solvent and a polyisocyanate compound, wherein the solvent is represented by the following formula: 1] A coating composition which essentially uses a tertiary alcohol represented by: 2. The coating composition according to claim 1, wherein the amount of the tertiary alcohol used is 5 to 80% by weight based on the total solvent used. 3. The tertiary alcohol is t-butanol,
At least one selected from the group consisting of t-amyl alcohol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 2,3-dimethyl-2-butanol and diacetone alcohol. The coating composition according to 1. 4. The coating composition according to claim 1, wherein the tertiary alcohol is t-butanol and / or diacetone alcohol. 5. The coating composition according to claim 1, wherein the addition amount of the polyisocyanate compound is 1 to 40 parts by weight with respect to 100 parts by weight of the polyurethane polyurea resin.