JP3204244B2 - Non-aqueous coating composition and coating method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a coating composition and a method for coating a substrate using the coating composition. The coating composition of the present invention includes various plastics, glasses, metals, leather materials,
It can be used for coating various base materials such as wood, paper, concrete, rubber, woven fabric, non-woven fabric, etc.
It can be used for coating in various fields as a binder for printing inks, flooring materials, waterproofing materials, fiber processing agents, paper processing agents, and the like.

[0002]

2. Description of the Related Art Conventionally, various organic polymers have been used as coating agents in various fields. For example, polyurethane has been awarded in various coating fields because of its rubber elasticity. The rubber elasticity of the polyurethane is exhibited because the tough hard segment is insolubilized from the matrix of the soft segment having flexibility to form a domain. However, polyurethane is generally a material having low heat resistance, and usually has a problem in that the rubber elasticity is lost due to melting of the hard segment at 100 to 160 ° C., and the polyurethane is liquefied. Particularly, in recent years, with the diversification of technology, improvement in performance has been demanded also in the field of coating, and polyurethane having rubber elasticity even at high temperatures is desired.

[0003] As a method for improving the heat resistance of polyurethane, there are a method of increasing the ratio of a hard segment and a method of introducing many urea bonds into the hard segment. However, such a method is not preferable because the solvent is insolubilized or the viscosity of polyurethane is increased.

As a method of imparting heat resistance to polyurethane, there is a method of synthesizing a hybrid with inorganic glass by applying a sol-gel method. That is, a hybrid in which inorganic glass is dispersed in polyurethane by a so-called filler effect is produced by utilizing hydrolysis and polycondensation of a hydrolyzable alkoxysilane such as tetraethoxysilane. According to such a sol-gel method,
Since the glass particles to be grown are very small with a size of several nanometers, the transparency of the organic polymer is not lost even if the glass particles are dispersed in polyurethane.

However, when an organic / inorganic hybrid of polyurethane is produced by the sol-gel method, the performance such as heat resistance is improved by the filler effect, but the glass particles are dispersed throughout the polyurethane, so the soft segment unique to polyurethane is used. Loses flexibility and becomes brittle.
For example, JP-A-6-136321 discloses the production of an organic-inorganic hybrid using an alcohol sol solution obtained by dissolving a hydrophilic soft segment polyurethane, a hydrolyzable alkoxysilane and, if necessary, a catalyst in a lower alcohol. Although a method is described, the resulting organic-inorganic hybrid is inflexible and brittle.

[0006]

SUMMARY OF THE INVENTION The present invention relates to an organic-inorganic hybrid comprising polyurethane as an organic polymer, wherein the coating has improved properties such as heat resistance without losing the rubber elasticity (flexibility) of the polyurethane. An object of the present invention is to provide a coating composition capable of forming a film on a substrate and a method for coating various substrates using the coating composition.

[0007]

Means for Solving the Problems In order to solve the above problems, the present inventors have proposed an organic polymer comprising polyurethane as an organic polymer.
As a result of intensive studies on a composition capable of forming an inorganic hybrid, among polyurethanes, a polyurethane having a hydrophobic soft segment and a specific contact angle with water was selected, and the polyurethane and a specific hydrolysis were selected. Photopolymerizability containing reactive alkoxysilane
The non-aqueous coating composition was prepared having no, especially this
It has been found that by curing in the presence of a fixed curing catalyst, a coating film meeting the above-mentioned purpose can be formed. In the coating film thus formed, almost all silica generated by the reaction of the hydrolyzable alkoxysilane is introduced into the domain of the hard segment of the polyurethane to form a composite domain, and the composite domain and the hydrophobic soft segment are combined. Is a hybrid that has a two-layer separation (sea-island) structure. Due to such a two-layer separation (sea-island) structure, the soft segment of polyurethane constituting the matrix of the hybrid body does not contain silica, so that its flexibility is maintained as it is. On the other hand, in the hard segment of the polyurethane, the heat resistance of the obtained coating film is improved by toughening only the domain by a composite domain with silica. The present invention has been completed based on such new findings.

That is, the present invention relates to a method for preparing a carbon
Selected from polyoxyalkylene diols with a number of 3 or more
At least one of which has a number average molecular weight of 1500
A polyurethane having a diol of at least 6000 or less as an essential component , wherein the polyurethane is a terminal isocyanate.
No anate group, no photopolymerizability, and water resistant
Simultaneously satisfy the condition that the contact angle is 70 degrees or more.
It has no photopolymerizability characterized by containing a polyurethane (1) and a tetraalkoxysilane and / or a hydrolyzable alkoxysilane (2) which is a condensate thereof.
A non-aqueous coating composition . In addition, the present invention
Is a tetraalkoxysilane and / or a condensate thereof
Hydrolyzable alkoxysilane (2)
The coating comprising a catalyst for condensation
To a composition for use. The present invention relates to a substrate surface, the touch <br/> after medium was coated with the coating composition comprising, cured, method of coating a substrate to form a coating film on the substrate surface; The present invention relates to a coated substrate in which the coating composition is applied to the surface of a substrate and then cured to form a coating film on the surface of the substrate.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a specific polyurethane (1) comprising a hard segment and a hydrophobic soft segment is used as an organic polymer constituting an organic / inorganic composite. Polyurethane (1) is
Polio xylene alkylene carbon atoms of alkylene group is 3 or more
At least one selected from all and a number average molecule
A diol having an amount of from 1500 to 6000 is essential.
A polyurethane as a component, comprising the polyurethane
Has no terminal isocyanate group and is not photopolymerizable.
The condition that the angle of contact with water is 70 degrees or more is the same.
A polyurethane that is sometimes satisfactory. That is, polyure
As a hydrophobic soft segment in tan (1),
It is not only a requirement that the diol be used
Has no terminal isocyanate group, has no photopolymerizability,
In addition, the contact angle with water must be 70 degrees or more.
And do not satisfy these requirements at the same time.
No. The hard segment of the polyurethane (1) refers to a material that contains a large number of hydrogen bond accepting groups such as urethane bonds and urea bonds and forms a domain by aggregation, and a soft segment is a long chain. It refers to one that imparts flexibility to the organic polymer and forms a matrix phase (continuous phase) in which hard segments can exist as a dispersed phase. The soft segment is an alkylene group
Polyoxyalkylene diol having 3 or more carbon atoms
At least one selected from the group consisting of a number average molecular weight of 15
A diol formed from a diol having a size of from 00 to 6000
In other words, the polymer position in the polyurethane (1).
Corresponds to the riol component. In the case of polyurethane having a hydrophilic soft segment, even when an organic / inorganic composite is produced using the same, silica is also introduced into the soft segment, so that the coating film becomes brittle and has excellent properties such as the coating film of the present invention. It is impossible to achieve any of the above-mentioned effects.

The polyurethane (1) comprising such a hard segment and a hydrophobic soft segment includes, for example, a polyurethane which is a reaction product comprising a specific high molecular polyol and an organic polyisocyanate compound as described below; Polyurethane which is a reaction product composed of such a specific high molecular polyol, an organic polyisocyanate compound and a chain extender is exemplified.

In the polyurethane (1), as a specific polymer polyol forming a hydrophobic soft segment, the alkylene group has 3 or more carbon atoms (the alkylene group preferably has 4 or more carbon atoms. Has preferably 8 or less, more preferably 6 or less.)
And a polyoxyalkylene diol having a number average molecular weight of 1500 or more and 6000 or less. The alkylene group may be linear or branched. The polyoxyalkylene diols usually propylene oxide, oxetane, Tetorahi de Rofuran, 3 Mechirutetorahi number of carbon atoms in the alkylene group, such as de Rofuran is obtained by ring-opening polymerization or copolymerization of 3 or more alkylene oxides. Specific examples of the polyoxyalkylene diol include polyoxypropylene diol, polyoxybutylene diol, and the like. When the number of carbon atoms of the alkylene group such as polyoxyethylene diol is 2 or less, the hydrophilicity is so strong that the object of the present invention cannot be achieved.

[0012] Among the essential polymer polyols,
In particular, polyoxybutylene diol and polybutadiene diol are most suitable because silica enters the hard segment to form a composite domain more easily.

Usually, polyester diols, polycarbonate diols and the like do not become hydrophobic high molecular diols due to their high hydrophilicity. However, the high molecular diol shows hydrophobicity and the soft segment of the obtained polyurethane shows hydrophobicity. If it is shown, it can be used in combination with the specific polymer polyol. As such a polymer polyol which can be used in combination, a highly hydrophobic dicarboxylic acid and / or diol having about 20 to 36 carbon atoms, specifically (hydrogenated) dimer acid and / or (hydrogenated) dimer diol, etc. And the like. Number average of these polymer polyols that can be used together
The molecular weight is usually 1500 or more, and more preferably 2000 or more
It is preferred that The number average molecular weight is 6000 or less.
It is preferred to be below.

The organic polyisocyanate compound forms a hard segment of the polyurethane (1). Examples of the organic polyisocyanate compound include various compounds such as a linear aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an aromatic polyisocyanate, an araliphatic polyisocyanate, and a polyisocyanate obtained from an amino acid derivative.

Specific examples of the linear aliphatic diisocyanate include methylene diisocyanate, isopropylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-diisocyanate. Trimethylhexamethylene diisocyanate, dimer isocyanate in which the carboxyl group of dimer acid is replaced with an isocyanate group, and the like can be mentioned. Specific examples of the cycloaliphatic diisocyanate include cyclohexane-
Examples include 1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-di (isocyanatomethyl) cyclohexane, and methylcyclohexane diisocyanate. As specific examples of the aromatic diisocyanate,
Dialkyldiphenylmethane diisocyanate such as 4,4'-diphenyldimethylmethane diisocyanate,
Tetraalkyldiphenylmethane diisocyanate such as 4,4'-diphenyltetramethylmethane diisocyanate, 1,5-naphthylene diisocyanate, 4,4 '
-Diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate and the like. Specific examples of the araliphatic diisocyanate include xylylene diisocyanate, m
-Tetramethylxylylene diisocyanate. Specific examples of the diisocyanate obtained from the amino acid derivative include lysine diisocyanate.

Further, the polyurethane (1) of the present invention
Can also use a chain extender. Poly chain extender
In order to introduce into the hard segment of urethane (1), it is usually preferable to use a low molecular polyol and / or a low molecular polyamine having about 2 to 6 carbon atoms.

Examples of the low molecular polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol and pentane. Diol, 3-
Low molecular weight glycols such as methyl-1,5-pentanediol and 1,6-hexanediol; trihydric alcohols such as glycerin, butanetriol, pentanetriol, hexanetriol, trimethylolethane, and trimethylolpropane; pentaerythritol, sorbitol And the like.

The low molecular weight polyamine includes ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-diamine.
Amine compounds such as 4,4′-diamine; 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine;
Examples thereof include diamine compounds having a hydroxyl group such as 2-hydroxypropylethylenediamine and di-2-hydroxypropylethylenediamine.

These chain extenders are used in an amount of 2 times the total amount of the hydrophobic polymer diol and the organic polyisocyanate compound.
It is desirably 0% by weight or less, and more desirably 15% by weight or less.

[0020] The polyurethane of the present invention (1), the
Polymeric polyol and an organic polyisocyanate compound,
Further, it can be obtained by reacting a chain extender as needed. The reaction can employ a general method of polyurethane, other bulk feed, it may be employed a urethane prepolymer method to be reacted in advance with the polymer polyol and the organic polyisocyanate compound in the case of using a chain extender. In addition, by appropriately adjusting the amount of each component used, the terminal of the polyurethane of the present invention can be any of a hydroxyl group and an amino group (however, excluding an isocyanate group).
It can also be. In addition, a dialkylamine such as di-n-butylamine; and a chain terminator such as a monovalent alcohol such as ethanol and isopropanol may be used in the polyurethane of the present invention, if necessary. The number average molecular weight of the polyurethane thus obtained is 5,000 to 10
It is preferably set to about 0000.

The tetraalkoxysilane used in the present invention and
The hydrolyzable alkoxysilane (2), which is a condensate thereof, is selected from the viewpoint of affinity with the domain formed by the hard segment of the polyurethane (1) used in combination therewith . That is, generally, sol-
One selected from among those used in the gel method
There are, specifically tetraalkoxysilanes or their partial condensation products is applicable. Among them, tetramethoxysilane, tetraethoxysilane or a partial condensate thereof is particularly preferable.

The amount of the hydrolyzable alkoxysilane (2) used is such that when the silica produced by the condensation of the hydrolyzable alkoxysilane exceeds the total amount of the domains formed by the hard segments of the polyurethane (1), the silica becomes Since the coating film is agglomerated and precipitated on the surface of the coating film and the coating film becomes cloudy, it is preferable that the amount of silica generated is about 1 to 30 parts by weight based on 100 parts by weight of the polyurethane (1). It is more preferably at least 3 parts by weight, and even more preferably at most 15 parts by weight.

The coating composition of the present invention comprises the polyurethane (1) and a hydrolyzable alkoxysilane
(2) is contained. Such a coating composition of the present invention can be used as it is as a solventless composition as it is, or as a solution composition in which these are dissolved in an organic solvent capable of dissolving them. Whether the coating composition of the present invention is used in the form of a solvent-free composition or a solution composition may be appropriately determined depending on various applications to which the coating composition of the present invention is applied. . Normally, use as a solution composition is preferred because of good handling.

The organic solvent used in the solution composition includes, for example , aromatic solvents such as benzene, toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; methanol, ethanol, isopropanol and n-
Alcohol solvents such as butanol; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; amide solvents such as dimethylformamide; sulfoxide solvents such as dimethyl sulfoxide;
Examples include ether solvents such as dimethyl ether and diethyl ether. Usually, the solid concentration of the solution composition is 1
It is preferable to adjust to about 0 to 40% by weight.

When the coating composition of the present invention is applied to a substrate and coated, a curing catalyst capable of hydrolyzing and condensing the hydrolyzable alkoxysilane (2) to promote curing is used. Used. Examples of the curing catalyst include organic acid catalysts such as formic acid, acetic acid, propionic acid, paratoluenesulfonic acid, and methanesulfonic acid; inorganic acid catalysts such as boric acid and phosphoric acid; and ammonia, triethylamine, dimethylamine, diethanolamine, and dimethylethanolamine. And amine catalysts such as methyldiethanolamine, and alkali catalysts such as sodium hydroxide and potassium hydroxide. Among them, when an organic acid catalyst or a tertiary amine catalyst is used, it is particularly preferred that silica is particularly likely to be induced only in the domain formed by the hard segment of the polyurethane (1) . By hydrolyzing the hydrolyzable alkoxysilane with an organic acid catalyst or a tertiary amine catalyst, silanol residues are increased, and the hydrogen bonding interaction with the hard segment of the polyurethane (1) is increased. Among these organic acid catalysts, formic acid, acetic acid and p-toluenesulfonic acid are preferable, and among the tertiary amine catalysts, triethylamine, dimethylethanolamine and methyldiethanolamine are more preferable.

The curing catalyst may be used in a so-called catalytic amount. That is, the amount of the catalyst used can be appropriately determined depending on the activity of the catalyst used. Usually, 0.001 to 5 mol% with respect to the hydrolyzable alkoxysilane (2) with paratoluenesulfonic acid having a high catalytic ability, a tertiary amine catalyst or the like
About 0.01 to 5 for formic acid, acetic acid, etc.
About 0 mol% is used. The timing of adding the curing catalyst is not particularly limited, and may be used when preparing a solventless composition from the polyurethane (1) and the hydrolyzable alkoxysilane (2) ,
Polyurethane (1) and hydrolyzable alkoxysilane
(2) may be added when preparing a solution composition by dissolving in an organic solvent, or may be added immediately before applying the composition to a substrate.

The coating composition of the present invention contains a viscosity modifier, a leveling agent, an antifoaming agent, a coloring agent, a stabilizer, and a solvent for adjusting the solubility within a range not to impair the effects of the present invention. Various organic and inorganic additives can be added as necessary. In addition, in applications such as various kinds of binders, it is needless to say that components usually used together with the binder in the application can be used by being blended.

The coating composition of the present invention thus prepared is applied to the surface of a substrate, and then cured (hydrolyzed or condensed) to form a coating film on the surface of the substrate. Perform The substrate can be appropriately selected and used according to various uses. The water necessary for curing can be added as appropriate, and water existing in the air can also be used. Although the curing temperature is sufficient even at room temperature, it can be appropriately heated to a temperature of 300 ° C. or lower while paying attention to evaporation of the silica precursor. As the application method, for example, various ordinary application methods such as dip coating, roll coating, bar coating, curtain flow coating, spray coating, and spin coating can be adopted.

[0029]

According to the present invention, an organic compound having improved heat resistance without losing the rubber elasticity (flexibility) of polyurethane.
A coating film composed of an inorganic hybrid can be formed on a substrate. Further, the coating film made of such an organic / inorganic hybrid is excellent in water resistance, solvent resistance and light resistance.

[0030]

The present invention will be described below in detail with reference to examples and comparative examples. In addition, in each example, parts and% are based on weight.

Production Example 1 Polytetramethylene glycol (number-average molecular weight: 20) was added to a 3-L four-necked corben equipped with a thermometer and a cooling tube.
[0092] 489.9 parts (0.242 mol) and 107.6 parts (0.485 mol) of isophorone diisocyanate were charged and reacted at 80 ° C for 4 hours under a nitrogen stream. Then
After adding 1085 parts of methyl ethyl ketone to the system and cooling to 50 ° C. while stirring well, isophorone diamine 3
7.34 parts (0.2120 mol) and dibutylamine
27 parts (0.0253 mol) of 2-propanol 543
The solution dissolved in the mixture was added dropwise over 10 minutes, and then reacted at the same temperature for 1 hour. Thus, the number average molecular weight is about 500
A polyurethane solution having a solid content of 30% was obtained. The contact angle of the obtained polyurethane with water was 81.5 degrees.

The contact angle of polyurethane with water was determined by dropping 0.03 ml of deionized water on the surface of the coating film.
Kyowa Interface Science Contact Angle Meter CA-S15 at 5 ℃
Measured using 0.

Production Example 2 In Production Example 1, the amounts of the components used were 232.3 parts (0.116 mol) of polytetramethylene glycol, 64.2 parts (0.289 mol) of isophorone diisocyanate and 27.27 parts of isophorone diamine. The reaction was carried out in the same manner as in Production Example 1 except that 34 parts (0.161 mol), 1.68 parts of dibutylamine (0.0129 mol), 868 parts of methyl ethyl ketone, and 434 parts of 2-propanol were used. A polyurethane solution having a molecular weight of about 50,000 and a solid content of 20% was obtained. The contact angle of the obtained polyurethane with water was 82 degrees.

Example 1 25 parts of the polyurethane solution obtained in Production Example 1 was partially condensed with tetramethoxysilane (trade name: M, manufactured by Tama Chemical Co., Ltd.).
S51) 0.735 part, 0.1 part of a 10% aqueous solution of paratoluenesulfonic acid and 25 parts of methyl ethyl ketone were mixed to prepare a coating solution composition.

Examples 2 to 5 A coating solution composition was prepared in the same manner as in Example 1 except that the type of the alkoxysilane or the amount used or the type of the curing catalyst was changed as shown in Table 1. Prepared.

Comparative Example 1 A solution composition for coating was prepared by diluting 25 parts of the polyurethane solution obtained in Production Example 1 with 25 parts of methyl ethyl ketone.

Comparative Example 2 A coating solution composition was prepared by diluting 37.5 parts of the polyurethane solution obtained in Production Example 2 with 12.5 parts of methyl ethyl ketone.

[0038]

[Table 1]

In Table 1, MS-51: Tetramethoxysilane partial condensate (trade name: MS-5, manufactured by Tama Chemical Co., Ltd.)
1), TEOS: tetraethoxysilane (manufactured by Huls, trade name Dynasil A), PTS aqueous solution: 10
% Paratoluenesulfonic acid aqueous solution, DMEA aqueous solution: 1
0% dimethylethanolamine aqueous solution, MEK: methyl ethyl ketone.

The soft segments (hereinafter, referred to as SS) and the hard segments (hereinafter, referred to as HS) based on the polyurethane (1) in the coating films obtained from the coating solution compositions of Examples 1 to 5 and Comparative Examples 1 and 2 described above.
) And silica (alkoxysilanes are all Si
Value approximately determined by the following equation the ratio of O ₂ converted to those assumptions) shown in Table 2. In addition, since almost all silica is introduced into HS and forms a composite domain by hybridization, the total of HS and silica is also shown in Table 2 as the ratio of the domain.

(1) Weight% of SS = (weight of polytetramethylene glycol / weight of solid content of polyurethane) × 100 (2) Weight% of HS = 100− (weight% of SS) (3) Weight of silica % = Amount of alkoxysilane used x
(60.02 / molecular weight of alkoxysilane) × (100
/7.5)

[0042]

[Table 2]

From Table 2, it can be seen that the polyurethane used in Comparative Example 2 (polyurethane of Production Example 2) has a higher proportion of HS than the polyurethane used in Examples 1 to 5 and Comparative Example 1 (polyurethane of Production Example 1). Therefore, it is recognized that it is tough and has excellent heat resistance. Further, Examples 2, 4, and 5 and Comparative Example 2 have the same apparent domain ratio.

(Heat Resistance) A container (length × width × depth = 10 cm × 10 cm × 1.5 cm) coated with the coating solution composition prepared in Examples 1 to 5 or Comparative Examples 1 and 2 was coated with a fluororesin. Poured into
After leaving it to cure for 3 days, it was dried at 100 ° C. for 1 hour to remove the remaining solvent to form a coating film (thickness: about 0.6 mm). The coating film was peeled off from the container, and a viscoelasticity measuring device (DVE-
V4, measurement conditions: amplitude 10 μm, frequency 10 Hz, slope 3 ° C./min), the dynamic storage modulus was measured, and the heat resistance was evaluated. FIG. 1 shows the measurement results.

From FIG. 1, it can be seen that in Comparative Examples 1 and 2, the dynamic storage elastic modulus sharply decreases at around 100 to 150 ° C., but in Examples 1 to 4, a sharp decrease is observed even when the temperature exceeds 200 ° C. Absent. From these, it is recognized that the coating film formed according to the present invention has excellent heat resistance. Also, -70
The remarkable change in the dynamic storage modulus around ℃ is derived from the Tg (glass transition point) of the soft segment which is a continuous phase, and the values of Tg in Examples 1 to 4 and Comparative Example 1 are almost the same. The same is true that silica is a polyurethane SS
Has been introduced, demonstrating that it forms a composite domain with HS. In Comparative Example 2, since the ratio of HS in the polyurethane used was higher than that of Comparative Example 1, the dynamic storage modulus of Comparative Example 2 was higher than that of Comparative Example 1, but was similar to that of Comparative Example 1. The temperature at which the dynamic storage modulus sharply drops is lower than that of Example 2 or Example 4 using polyurethane and having the same apparent domain ratio.
This indicates that by forming a composite domain of silica and polyurethane HS, the effect of improving heat resistance is greater than simply increasing the proportion of HS.

Production Example 3 Polybenzol (number average molecular weight 1800, ethylene oxide content 5
(0%) 481.3 parts (0.2674 mol) and 118.7 parts (0.5347 mol) of isophorone diisocyanate were charged and reacted at 80 ° C. for 4 hours under a nitrogen stream. Next, 1024 parts of dimethylformamide was added to the system, and the mixture was cooled to 50 ° C. with good stirring, and 37.33 parts (0.220 mol) of isophorone diamine and 3.27 parts (0.0311 mol) of dibutylamine were added to 2 parts. -Propanol 5
The solution dissolved in 12 parts was added dropwise over 10 minutes, and then reacted at the same temperature for 1 hour. Thus, the number average molecular weight is about 5
A polyurethane solution of 0000 and a solid content of 20% was obtained. The contact angle of the obtained polyurethane with water was 61.5 degrees.

Production Example 4 491 parts (0.24) of polyester diol (Adeka New Ace F13-35, trade name, manufactured by Asahi Denka Co., Ltd.) was added to the same kolben as in Production Example 1.
55 mol) and 109.1 parts (0.491 mol) of isophorone diisocyanate.
Allowed to react for hours. Next, methyl ethyl ketone 1
After cooling to 50 ° C. with good stirring, 36.33 parts (0.214 mol) of isophoronediamine and 3.26 parts (0.0310 mol) of dibutylamine were added.
Was dissolved in 542 parts of 2-propanol dropwise over 10 minutes, and then reacted at the same temperature for 1 hour. Thus, a polyurethane solution having a number average molecular weight of about 50,000 and a solid content of 30% was obtained. The contact angle of the obtained polyurethane with water was 69 degrees.

Comparative Example 3-1 37.5 parts of the polyurethane solution obtained in Production Example 3, 1.471 parts of a partial condensate of tetramethoxysilane (trade name: MS-51, manufactured by Tama Chemical Co., Ltd.), 10% para. 0.1 parts of toluenesulfonic acid aqueous solution and dimethylformamide 1
2.5 parts were mixed to prepare a coating solution composition.

Comparative Example 3-2 A solution composition for coating was obtained by diluting 37.5 parts of the polyurethane solution obtained in Production Example 3 with 12.5 parts of dimethylformamide.

Comparative Example 4-1 25 parts of the polyurethane solution obtained in Production Example 4 was partially condensed with tetramethoxysilane (trade name: M, manufactured by Tama Chemical Co., Ltd.).
S-51) 1.471 parts, 0.1 part of a 10% aqueous solution of p-toluenesulfonic acid and 25 parts of methyl ethyl ketone were mixed to prepare a coating solution composition.

Comparative Example 4-2 A coating solution composition was prepared by diluting 25 parts of the polyurethane solution obtained in Production Example 4 with 25 parts of methyl ethyl ketone.

(Flexibility) The coating solution compositions prepared in Examples 1 to 5, Comparative Examples 1, 3 and 4 were used as coating films in the same manner as in the heat resistance section. The obtained coating film was cut out with a dumbbell No. 1, and 50 cm in diameter was measured using a Tensilon tester (trade name: UCT-500, manufactured by Orientec).
The film was stretched at a pulling rate of / min, and the film elongation to break (maximum elongation) was measured. 25 ° C
And the tensile test was performed three times in the same manner. The average value is shown in Table 3.

(Water Resistance) The coating solution compositions prepared in Examples 1 to 5, Comparative Examples 1, 3 and 4 were used as coating films in the same manner as in the section of heat resistance. About 0.15 g of the obtained coating film was precisely weighed and immersed in 20 ml of deionized water.
Warmed to 0-100 ° C. The weight of the film in water is measured over time, and when the film contains about 6% of water with respect to the weight of the original coating film, the film is lifted from the warm water bath and the surface is wiped,
The sample was placed on a balance and left at 25 ° C. When the water content reached 5%, the dynamic storage modulus at 25 ° C. was measured with the same viscoelasticity tester as in the heat resistance test, and the elastic retention was determined from the following equation. Elasticity retention = (Dynamic storage modulus at 5% moisture content / weight of coating film) × 100. The appearance of the coating film was visually observed. Table 3 shows the evaluation results.

(Solvent Resistance) The coating solution compositions prepared in Examples 1 to 5, Comparative Example 1, Comparative Example 3 and Comparative Example 4 were coated on a glass plate (3 cm × 5 cm 2).
m) After coating by dipping method, cure at room temperature for 24 hours,
Dried. A few drops of methyl ethyl ketone were dropped on the film surface of the obtained coating film and left for 1 minute, and then the tack generated by the melted resin component was evaluated by finger touch according to the following criteria. ：: no tack. Δ: There is slight tack. ×: There is tack.

[0055]

[Table 3]

As apparent from Table 3, in Comparative Examples 3 and 4, polyurethane (Comparative Example 3-2, Comparative Example 4-2) was used.
Of the hybrid body (Comparative Example 3-1 and Comparative Example 4)
-1), the results are worse.
In No. 5, the same flexibility as in Comparative Example 1 is maintained even when the hybrid body is obtained. In addition, it is recognized that Examples 1 to 5 are also excellent in water resistance and solvent resistance.

Example 6 37.5 parts of the polyurethane solution obtained in Production Example 2, 1.029 parts of a partial condensate of tetramethoxysilane (trade name: MS-51, manufactured by Tama Chemical Co., Ltd.), 10% paratoluene sulfone 11. 0.1 part of an aqueous acid solution and methyl ethyl ketone
Five parts were mixed to prepare a coating solution composition.

(Lightfastness) The coating solution compositions of Example 6 and Comparative Example 2 were
A coating film was prepared in the same manner as in the heat resistance section. The coating film was peeled off from the container, and a super-accelerated weather resistance tester (I-Super UV Tester F-11, manufactured by Iwasaki Electric Co., Ltd., wavelength: 295-450 nm, illuminance: 100)
(mW / cm ² , temperature 70 ° C.). The film after UV irradiation was punched out with a dumbbell No. 1 and a Tensilon tester (Orientec Co., Ltd., trade name UCT-
The film was stretched at 50 cm / min by using (500), and the change in film stress at the time of 100% (double) elongation was measured together with the ultraviolet irradiation time to evaluate light resistance. FIG. 2 shows a graph of the measurement results. As can be seen from FIG. 2, the hybrid of Example 6 is slower in light degradation than the polyurethane of Comparative Example 2 and is excellent in light resistance.

[Brief description of the drawings]

FIG. 1 is a graph of dynamic storage modulus of Examples 1 to 4 and Comparative Examples 1 and 2.

FIG. 2 is a graph of a light resistance deterioration test of Example 6 and Comparative Example 2.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-9-241349 (JP, A) JP-A-8-60094 (JP, A) JP-A-7-331171 (JP, A) JP-A-6-241 136321 (JP, A) JP-A-63-46212 (JP, A) JP-A-60-199072 (JP, A) JP-A-11-35819 (JP, A) JP-A-6-100816 (JP, A) JP-A-3-182573 (JP, A) JP-A-4-500660 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 1/00-201/10

Claims (7)

(57) [Claims] 1. A polyalkylene group having 3 or more carbon atoms.
At least one selected from lioxyalkylene diols
A seed with a number average molecular weight between 1500 and 6000
A polyurethane having a certain component as an essential component,
The polyurethane does not have a terminal isocyanate group,
No polymerizability, and the contact angle with water is 70 degrees or more
Polyurethane (1) that satisfies certain conditions at the same time,
Tetraalkoxysilane and / or a condensate thereof
Containing a hydrolyzable alkoxysilane (2)
A non-aqueous coating composition having no photopolymerizability, characterized by the following . 2. The hydrolyzable alkoxysilane as described above.
(2) hydrolysis, comprising a curing catalyst which may be condensed claim 1 coating composition. 3. The coating composition according to claim 2 , wherein the curing catalyst is an organic acid catalyst or a tertiary amine catalyst. 4. The coating composition according to claim 3 , wherein the organic acid catalyst is at least one selected from formic acid, acetic acid, and p-toluenesulfonic acid. 5. The tertiary amine catalyst is triethylamine,
The coating composition according to claim 3 , wherein the composition is at least one selected from dimethylethanolamine and methyldiethanolamine. 6. After coating the coating composition according to any one of claims 1 to 5 on a surface of a substrate, curing the composition,
A method for coating a substrate, which forms a coating film on the surface of the substrate. 7. After coating the coating composition according to any one of claims 1 to 5 on a surface of a substrate, curing the composition,
A coating substrate with a coating film formed on the substrate surface.