JP2949566B2 - Polyamide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin composition having excellent heat resistance which can be used in a wide range of fields as a paint, an adhesive, a coating agent and the like. In particular, the present invention
The present invention relates to a composition comprising a reaction product of a polyamide resin and an isocyanate compound, which is excellent in processability before use and excellent in heat resistance, mechanical properties and adhesiveness after use.

[0002]

2. Description of the Related Art Polyamide resins, particularly aromatic polyamide resins, are widely used as engineering plastics because they are thermoplastic resins having not only excellent heat resistance but also excellent film-forming properties. However, although having such excellent characteristics, the workability, particularly the solvent solubility is poor, so that the processing method is limited, and it is difficult at present to make full use of the excellent characteristics. For this issue,
The present inventors have found that a polyamide resin having a specific molecular structure synthesized by a polycondensation reaction of a dicarboxylic compound containing a phenolic hydroxyl group with a diamino compound can easily be used in non-amide solvents such as alcohols. (Japanese Patent Application No. 7-23201).

[0003]

However, the excellent solvent solubility of the polyamide resin in a solvent such as alcohol is exhibited even after use, that is, after forming a coating film on a substrate. Also, when used as a coating film, it is difficult to sufficiently adhere to the substrate due to having high elasticity,
There was also a problem that it was difficult to obtain sufficient adhesiveness. For this reason, a polyamide resin having excellent workability before use, having solvent resistance after use, and having excellent adhesiveness is desired.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by reacting a phenolic hydroxyl group of a polyamide resin with a bifunctional or more isocyanate compound after film formation. I found it. The present invention provides at least an alkyl-substituted aromatic diamine represented by the following general formula:

[0005]

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(Provided that R ₁ and R ₂ each represent a group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and an isopropyl group, but are not hydrogen atoms at the same time). A phenolic hydroxyl group-containing polyamide resin obtained from a diamine component containing at least 50 mol% of a diamine component containing at least 50 mol% of a phenolic hydroxyl group-containing aromatic dicarboxylic acid, and an isocyanate compound having two or more functional groups. The above problem has been solved by a polyamide resin composition characterized by the above.

Further, the present invention comprises a diamine component containing at least 50 mol% of an alkyl-substituted aromatic diamine represented by the above general formula (I) and at least 50 mol% of a phenolic hydroxyl group-containing aromatic dicarboxylic acid. After forming a phenolic hydroxyl group-containing polyamide resin obtained from a dicarboxylic acid component and a polyamide resin composition comprising an isocyanate compound having two or more functional groups on a substrate, the hydroxyl group of the polyamide resin and the isocyanate compound The above object has been achieved by a method for producing a thin film made of a polyamide resin, which is characterized by reacting with an isocyanate group having the same.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The phenolic hydroxyl group-containing polyamide resin of the present invention has a molecular weight of 5,000 to 15
Of the glass transition temperature (T.
g) is preferably 180 ° C. or higher. Molecular weight 150,000
If it is larger than 0, the workability deteriorates, which is not preferable.
On the other hand, when the molecular weight is smaller than 5,000, the function as a resin cannot be maintained, which is not preferable. Tg is 18
When the temperature is lower than 0 ° C., heat resistance, which is one of the objects of the present invention, cannot be obtained, which is not preferable.

The phenolic hydroxyl group-containing polyamide resin of the present invention can be easily produced by a condensation reaction between a dicarboxylic acid component containing a dicarboxylic acid having a hydroxyl group and a diamine component containing diaminodiphenylmethane having an alkyl group. Can be. This condensation reaction can be performed by carrying out a known method. For example, the method can be carried out according to the method described on page 183, “Polymer Functional Material Series 2 Synthesis and Reaction of Polymer”, edited by The Society of Polymer Science, 1991. In particular, a production method by a direct polycondensation reaction using a dehydration catalyst is preferable since a desired polyamide resin containing the repeating unit represented by the general formula (I) can be easily obtained without protecting the phenolic hydroxyl group.

Specifically, a dicarboxylic acid component containing at least 50 mol% or more of an aromatic dicarboxylic acid having a phenolic hydroxyl group and a diamine component containing at least 50 mol% or more of diaminodiphenylmethane having an alkyl group are dehydrated. Solvent and an organic solvent in an inert atmosphere such as nitrogen at room temperature to 160 ° C.
A polyamide resin can be easily produced by directly stirring the polycondensation reaction for a few minutes to several hours. In addition, a phosphite and a pyridine derivative are typical examples of the dehydrating solvent, and N-methyl-2-pyrrolidone and the like can be exemplified as the organic solvent. Further, if necessary, lithium chloride, calcium chloride, or the like can be added as a stabilizer.

The carboxylic acid having a phenolic hydroxyl group includes 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid, and 3-hydroxyisophthalic acid.
Examples include, but are not limited to, hydroxyphthalic acid and 2-hydroxyterephthalic acid.

Further, in addition to the carboxylic acid having a phenolic hydroxyl group, it is also possible to adjust the concentration of the phenolic hydroxyl group in the polyamide resin used in the present invention, the solubility of the solvent, and the polymerization degree of the polyamide resin. Therefore, a carboxylic acid having no phenolic hydroxyl group can be used. Examples of the carboxylic acid having no phenolic hydroxyl group include phthalic acid, isophthalic acid, terephthalic acid,
4'-biphenyldicarboxylic acid, 3,3'-methylene dibenzoic acid, 4,4'-methylene dibenzoic acid, 4,4'-
Oxydibenzoic acid, 4,4′-thiodibenzoic acid, 3,
3′-carbonyldibenzoic acid, 4,4′-carbonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 1,4-
Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2-6-naphthalenedicarboxylic acid, ethylenediaminebisphthalimide-4,4′-dicarboxylic acid, 3,
3'-bis- (4-carboxyphenyl) propane, 3
-3'-bis (4-carboxyphenyl) hexafluoropropane, bis (4-carboxyphenyl) methane,
1,4-cyclohexanedicarboxylic acid and 1,3-
Examples thereof include cyclohexanedicarboxylic acid.

As the diamine, bis (2-methyl-4-aminophenyl) methane, bis (2-ethyl-4)
-Aminophenyl) methane, bis (2-propyl-4-)
Aminophenyl) methane, bis (2-isopropyl-4)
-Aminophenyl) methane, bis (2,5-dimethyl-
4-aminophenyl) methane, bis (2,4-diethyl-4-aminophenyl) methane, bis (2,4-dipropyl-4-aminophenyl) methane, bis (2,4-diisopropyl-4-aminophenyl) Methane, bis (2
-Methyl-5-ethyl-4-aminophenyl) methane,
Bis (2-methyl-5-propyl-4-aminophenyl) methane, bis (2-methyl-5-isopropyl-4)
-Aminophenyl) methane, dis (2-ethyl-5-propyl-4-aminophenyl) methane, bis (2-ethyl-5-isopropyl-4-aminophenyl) methane,
And bis (2-propyl-5-isopropyl-4-aminophenyl) methane and the like, but are not limited thereto.

Further, if necessary, for example, in the case of adjusting the solubility of the solvent and the degree of polymerization, etc., m-phenylenediamine, p-phenylenediamine, metatolylenediamine, 4,4'-diaminodiphenyl ether,
3,3′-dimethyl-4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,
4′-diaminodiphenyl ether, 4,4′-diaminodiphenylthioether, 3,3′-dimethyl-4,
4′-diaminodiphenylthioether, 3,3′-diethoxy-4, 4′-diaminodiphenylthioether, 3,3′-diaminodiphenylthioether, 4,
4'-diaminobenzophenone, 3-3'-dimethyl-
4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 2,2'-bis (3-aminophenyl )
Propane, 2,2′-bis (4-aminophenyl) propane, 4,4′-diaminodiphenylsulfoxide,
4,4′-diaminodiphenyl sulfone, benzidine,
3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 3,3′-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, 3,3′-
A diamine component such as bis (3-amino-4-hydroxyphenyl) hexafluoropropane or 3,3′-bis (4-amino-phenyl-4-phenoxy) hexafluoropropane can be used in combination.

If the amount of the diamine component used is too large, the workability of the resulting composition may be deteriorated, so that the amount of the diamine component must be carefully monitored. Generally, the diaminodiffe
It is not preferable to use 50 mol% or more based on nilmethane .

The above isocyanate includes aliphatic, alicyclic, aromatic and aromatic resin isocyanates, and modified products thereof. As the aliphatic isocyanate, hexamethylene diisocyanate (HD
I), trimethylhexamethylene diisocyanate (T
MDI) or lysine diisocyanate (LDI)
Examples of alicyclic isocyanates include dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), 1,4-cyclohexane diisocyanate (CHDI), hydrogenated xylene diisocyanate (HXDI), and hydrogenated tolylene diisocyanate (HTDI). Examples of the aromatic isocyanate include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate, or 2-4′-diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), and tolidine diisocyanate (TODI). ,
Or p-phenylene diisocyanate (PPDI)
And araliphatic isocyanates, α,
α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like can be exemplified, but the present invention is not limited to these.

Further, as the modified products of aliphatic, alicyclic, aromatic and araliphatic isocyanates, a part or all of the isocyanurate group of the above-mentioned isocyanate compound may be a carbodiimide group, a uretdione group or a uretoimine group. , A buret group, or an isocyanurate group. These isocyanate-modified compounds can be used alone or in combination of two or more. Further, among the above isocyanate compounds, a blocked isocyanate compound in which part or all of the isocyanurate group is blocked by a blocking agent is particularly preferable. This is because, when compared with the non-blocked isocyanate, the composition containing the blocked isocyanate can obtain stable storage properties over a long period of time.

Examples of the blocking agent for blocking the isocyanurate group include oxime compounds, kratams, alkylphenol compounds, dialkylphenol compounds, trialkylphenol compounds, active methylene compounds, acetylacetone, acetoacetate, alcohols and hydroxyl-containing compounds. Ethers, hydroxyl-containing esters, mercaptans, acid amides, imidazoles,
And acid imides. Of these, oxime compounds and lactams are preferred, and methyl ethyl ketoxime and ε-caprolactam are more preferred. This is because it has a relatively high dissociation temperature and promotes the thermal stability of the composition. These blocking agents may be used alone or in combination of two or more.

In the present invention, if necessary, the composition of the present invention may contain a blocking agent dissociation catalyst. For example, when a blocked isocyanate is used, it is preferable to add the above catalyst. Examples of the blocking agent dissociation catalyst include dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dimaleate, dibutyldibutoxytin, bis (2-ethylhexyl) tin oxide, 1,1,3,3-tetrabutyl-1,3-dibutyltin Organotin compounds such as acetoxydistannoxane, organic acid potassium such as alkylsulfuric acid and alkylphosphonic acid, sodium metal salt, sodium fatty acid having 8 to 20 carbon atoms,
Salts such as potassium, nickel, cobalt, cadmium, barium, calcium, and zinc, and mixtures of two or more thereof. Among these catalysts, dibutyltin dilaurate and dioctyltin dimaleate having high catalytic activity are preferable. The amount of the blocking agent dissociation catalyst to be used is generally 0.05 parts to 10 parts, preferably 0.01 to 5 parts, per 100 parts of the blocked isocyanate. If the amount is less than 0.05 part, the effect of the catalyst is not exhibited.

In the composition of the present invention, the blending of the polyamide resin and the isocyanate compound is not limited at all. However, if the number of moles of isocyanate group is more than the number of moles of hydroxyl group contained in the polyamide resin, the It is not preferable because compounds are generated. In consideration of the generation of unreacted compounds, it is preferable to mix the polyamide resin and the isocyanate compound such that the isocyanate group is mixed at a ratio of 1 to 80 mol% with respect to 100 mol% of the hydroxyl group. When the amount is more than 80 mol%, the crosslink density of the obtained composition becomes high, and the composition becomes brittle.
Not preferred. If the amount is less than 1%, the effect of the crosslinking reaction does not appear and the object of the present invention cannot be achieved, which is not preferable.

Additives can be added to the obtained polyamide resin composition, if necessary. For example, in the case of producing a molded article, long-chain aliphatic acids and metal salts, acid amides, esters, release agents such as paraffins, silicone rubber, nitrile rubber, butadiene rubber, stress relaxation agents such as polysiloxane, Flame retardants such as chlorinated paraffin, protoluene, hexabromobenzene, antimony trioxide, etc .; adhesives to glass, metals, etc .; silane coupling agents, titanate coupling agents when forming protective layers, aluminum Coupling agents such as system coupling agents, fused silica, crystalline silica, glass flakes, glass beads, glass balloons, talc, alumina, calcium silicate, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, ferrite, etc. fillers, gold, silver, nickel, copper, zinc, iron, iron powder, iron oxide,
Inorganic conductive materials such as iron sand, conductive polymers, coloring materials such as dyes and pigments, oxidation stabilizers, light stabilizers, moisture resistance improvers, thixotropic agents, diluents, defoamers, and liquid or solid resins. It can also be blended.

The polyamide resin composition of the present invention may be used after being pulverized, but may also be used as a solution. Use as a solution is preferable in terms of handleability and applicability since the viscosity of the composition can be adjusted. In this case, as long as the obtained polyamide resin composition can be dissolved, the solvents used may be used alone or as a mixture. For example, N-methyl-2-pyrrolidone,
Amide solvents represented by dimethylacetamide, and dimethylformamide, dimethylsulfoxide, pyridine solvents, and halogen solvents represented by chlorobenzene and dichloroethane, ether solvents represented by ethyl ether, etc., acetone, and Ketone solvents such as cyclohexanone, aliphatic solvents such as n-hexane, aromatic solvents such as benzene and toluene, nitro group-containing solvents such as nitrobenzene and nitromethane, acetonitrile And nitrile solvents such as benzonitrile, and alcohol solvents typified by methanol and ethanol.

Among the above solvents, alcohol solvents are preferred. The alcohol solvent is a good solvent for the polyamide resin and the isocyanate compound, and is economically excellent. Furthermore, when the composition of the present invention is used as a varnish, it is preferable to use an alcohol-based solvent because it volatilizes at low temperatures and the toxicity of the volatile components is low.

Further, in the present invention, among the alcohol solvents, methanol, ethanol, or propanol is preferable. These alcohols, besides having the above-mentioned advantages, can also make the viscosity of the composition lower, so that a thinner film can be formed. Furthermore, since the content of the polyamide resin component can be increased, the cost can be reduced. When the polyamide resin composition is used by dissolving it in the above solvent, the composition concentration is not particularly limited in the present invention, and the concentration can be selected so as to obtain a solution viscosity according to the purpose.

In the method for producing a thin film comprising a polyamide resin of the present invention, the polyamide resin composition obtained as described above is formed on a substrate or the like, and then a phenolic hydroxyl group and an isocyanate compound of the polyamide resin are formed. Is characterized by reacting with an isocyanate group possessed by In order to accelerate the above reaction, it is preferable to heat. In the method for producing a thin film made of the polyamide resin, the polyamide resin and the isocyanate compound coexist, but are separated and stored without coexistence,
It can be mixed at the time of use and used as a composition.

[0026]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 Synthesis of Polyamide Resin 3.642 g of 5-hydroxyisophthalic acid (20 in a 200 mL three-necked round bottom flask equipped with a mechanical stirrer, a cooling tube, a calcium chloride tube, and a nitrogen inlet tube was used.
Mmol) 3,3 ', 5,5'-tetraethyl-4,
6.209 g (20 mmol) of 4'-diaminodiphenylmethane, 2.02 g of calcium chloride, 0.66 g of lithium chloride, 120 mL of N-methyl-2-pyrrolidone,
6 mL of pyridine and 12.4 of triphenyl phosphite
1 g (40 mmol) and 120
The reaction was carried out with stirring at 4 ° C. for 4 hours. After completion of the reaction, the reaction solution was introduced into a mixed solution having a water: methanol ratio of 8: 2 to precipitate a resin. The produced resin was repeatedly washed twice using a mixed solution of methanol and water as a washing solvent, and dried to obtain 9.02 g of an aromatic polyamide resin. The obtained aromatic polyamide resin has a phenolic hydroxyl group content of about 100 mol% and an intrinsic viscosity of 0.1 mol%.
It was 60 dl / g (calculated from viscosity measurement of a dimethylacetamide solution having a concentration of 0.5 g / dl at 30 ° C.). Moreover, the obtained resin was soluble in ethanol.

Synthesis Example 2: Synthesis of polyamide resin 3.6 of 5-hydroxyisophthalic acid used in Synthesis Example 1
42 g (20 mmol) are obtained from 2.185 g (12 mmol) of 5-hydroxyisophthalic acid and 1.3 of isophthalic acid.
Instead of a mixture with 29 g (8 mmol), 3, 3 ',
6.209 g (20 mmol) of 5,5'-tetraethyl-4,4'-diaminodiphenylmethane was converted to 5.668 g (20 mmol) of 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminophenylmethane. 8.15 g of a polyamide resin was obtained in the same manner except that the above procedure was repeated. The phenolic hydroxyl group content of the obtained polyamide resin was about 60 mol%, and the intrinsic viscosity value was 0.58 dl / g. This resin was soluble in a 1: 5 mixed solvent of ethanol and toluene.

Example 1 2 g of the polyamide resin obtained in Synthesis Example 1 and 0.244 g (0.876 mmol) of 4,4'-diisocyanate-3,3'-dimethylphenylmethane were mixed with ethanol and ethyl methyl ketone. Was dissolved in 25 g of a solvent in which 1: 1 was mixed to obtain a polyamide resin composition. The polyamide resin composition was well dissolved in the mixed solvent. Then, the obtained solution was cast on an aluminum plate. Then, after removing this solvent under vacuum,
The film was gradually heated to react the phenolic hydroxyl group and the isocyanate group contained in the polyamide resin, thereby obtaining a film made of the polyamide resin composition. This film is heated at 200 ° C for 4 hours.
After heating for an hour, peeling from the aluminum plate was not observed, and it was confirmed that the adhesiveness was excellent. Further, even if this film was impregnated with a dimethylformamide solvent, it did not dissolve, and it was confirmed that the film had excellent solvent resistance.

Example 2 The 4,4'-diisocyanate 3, used in Example 1,
0.244 g of 3'-dimethyldiphenylmethane (0.8
76 mmol) in the form of blocked isocyanate, diphenylmethane-bis (4-ethyleneurea) 0.302 g
(0.876 mmol), and a polyamide resin composition was obtained in the same manner as in Example 1. The polyamide resin composition was well dissolved in the mixed solvent. Next, a phenolic hydroxyl group and an isocyanate group contained in the polyamide resin were reacted at 150 ° C. for 1 hour to obtain a polyamide resin composition film. Although this film was heated at 200 ° C. for 4 hours, no peeling from the aluminum plate was observed, and it was confirmed that the adhesiveness was excellent. Further, even if this film was impregnated with a dimethylformamide solvent, it did not dissolve, and it was confirmed that the film had excellent solvent resistance.

Example 3 2 g of the polyamide resin obtained in Synthesis Example 2 and 0.338 g (0.796 mmol) of a methyl oxime block of 4,4'-diisocyanate-3,3'-diphenylmethane were mixed with ethanol and ethyl. 1: 1 with methyl ketone
Was dissolved in 25 g of a mixed solvent to obtain a polyamide resin composition. The polyamide resin composition was well dissolved in the mixed solvent. Then, the obtained solution was cast on an aluminum plate. Then, after removing this solvent under vacuum, a film of the polyamide resin composition was obtained in the same manner as in Example 2. Although this film was heated at 200 ° C. for 4 hours, no peeling from the aluminum plate was observed, and it was confirmed that the adhesiveness was excellent. Further, even if this film was impregnated with a dimethylformamide solvent, it did not dissolve, and it was confirmed that the film had excellent solvent resistance.

Example 4 In Example 2, 4,4'-diisocyanate-3
Example 2 was repeated except that 0.338 g (0.796 mmol) of the methyl oxime block of 3'-diphenylmethane was replaced by 0.302 g (0.876 mmol) of diphenylmethane-bis (4-ethyleneurea) as a blocked isocyanate. Similarly, a polyamide resin composition was obtained. The polyamide resin composition was well dissolved in the mixed solvent. Next, a phenolic hydroxyl group and an isocyanate group contained in the polyamide resin were reacted in the same manner as in Example 2 to obtain a polyamide resin composition film. Although this film was heated at 200 ° C. for 4 hours, no peeling from the aluminum plate was observed, and it was confirmed that the adhesiveness was excellent. Further, even if this film was impregnated with a dimethylformamide solvent, it did not dissolve, and it was confirmed that the film had excellent solvent resistance.

Comparative Example 1 The polyamide resin obtained in Synthesis Example 1 was dissolved in ethanol to obtain a solution. The polyamide resin was well dissolved in the above solvent. Then, the obtained polyamide resin composition was cast on an aluminum plate. Then, ethanol was removed under vacuum to form a film on an aluminum plate. When this aluminum plate was heated at 200 ° C. for 4 hours, this film was peeled off from the aluminum plate. Thereby, it was confirmed that it did not have sufficient adhesiveness. When this film was impregnated with dimethylformamide solvent, it was dissolved. From this, it was confirmed that the solvent resistance was insufficient.

Comparative Example 2 A polyamide resin composition was obtained in the same manner as in Comparative Example 1 except that the polyamide resin obtained in Synthesis Example 2 was used. The obtained polyamide resin was well dissolved in the solvent. Then, the obtained polyamide resin composition was cast on an aluminum plate. When heated in the same manner, the film was peeled off from the aluminum plate. Thereby, it was confirmed that it did not have sufficient adhesiveness. When this film was impregnated with dimethylformamide solvent, it was dissolved. From this, it was confirmed that the solvent resistance was insufficient.

From Examples 1 to 4, the polyamide resin composition comprising a polyamide resin containing a phenolic hydroxyl group in a proportion of 90 mol% or more and an isocyanate compound having two or more functional groups is excellent in alcohol solvents. Was confirmed to have solubility. Further, it was confirmed that the film made of the polyamide resin composition had excellent adhesiveness to the substrate and also had solvent resistance. On the other hand, although the polyamide resin obtained from Comparative Examples 1 and 2 has excellent solvent solubility, the film obtained by processing the resin does not have sufficient adhesiveness, and It was confirmed that the solvent properties were also insufficient.

[0035]

The polyamide resin composition of the present invention comprises at least a diamine component containing at least 50 mol% of an alkyl-substituted aromatic diamine represented by the above general formula (I) and at least a phenolic hydroxyl group-containing aromatic dicarboxylic acid. 5
A polyamide resin composition comprising a polyamide resin obtained from a dicarboxylic acid component containing at least 0 mol% and an isocyanate compound having two or more functional groups. The polyamide resin is excellent in heat resistance and also has excellent dissolution characteristics in a solvent such as alcohol, so that it is excellent in processability. Further, the urethane bond obtained by reacting the isocyanate group of the isocyanate compound with the hydroxyl group of the polyamide resin is rich in flexibility. Therefore, the adhesion between the film obtained by the above reaction and the substrate is improved, and the adhesion is improved.
Further, since the obtained film has already reacted, it is hardly dissolved in a solvent and has a solvent resistance. Therefore, the polyamide resin composition of the present invention has excellent processability before use, has solvent resistance after use, and has excellent adhesiveness, and has a surface protective agent, a coating agent, and an adhesive. It is useful as a sealant.

The method for producing a thin film comprising a polyamide resin according to the present invention is a method for producing a thin film comprising reacting a hydroxyl group of a polyamide resin with an isocyanate group of an isocyanate compound on a substrate.
The above reaction forms a urethane bond. Since a flexible urethane bond is formed on the substrate, the adhesion between the substrate and the polyamide resin is improved. Therefore,
According to the method for producing a thin film made of a polyamide resin of the present invention, a film having excellent solvent resistance and excellent adhesiveness to a substrate can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 18/00-18/87 C08G 69/26-69/36 C08L 75/04-75/16 C08L 77 / 06-77 / 12 C09D 175/04-175/16 C09D 177/06-177/12 C09J 175/04-175/16 C09J 177/06-177/12 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] At least an alkyl-substituted aromatic diamine represented by the following general formula: (However, R ₁ and R ₂ each represent a group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and an isopropyl group. However, they are not hydrogen atoms at the same time.) A phenolic hydroxyl group-containing polyamide resin obtained from a diamine component containing the above, a dicarboxylic acid component containing at least 50 mol% of a phenolic hydroxyl group-containing aromatic dicarboxylic acid, and an isocyanate compound having two or more functional groups. Characteristic polyamide resin composition. 2. The polyamide resin composition according to claim 1, wherein the isocyanate compound is a blocked isocyanate compound. 3. The polyamide resin composition according to claim 1, further comprising an alcohol solvent. 4. The method according to claim 1, wherein the alcohol solvent is methanol,
The polyamide resin composition according to claim 3, which is at least one alcohol selected from the group consisting of ethanol and propanol. 5. The polyamide resin composition according to claim 1, wherein a phenolic hydroxyl group in the polyamide resin is reacted with the isocyanate compound. 6. An alkyl group-substituted aromatic diamine represented by at least the following general formula: (However, R ₁ and R ₂ each represent a group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and an isopropyl group. However, they are not hydrogen atoms at the same time.) A polyamide resin comprising a phenolic hydroxyl group-containing polyamide resin obtained from a diamine component containing the above, a dicarboxylic acid component containing at least 50 mol% of a phenolic hydroxyl group-containing aromatic dicarboxylic acid, and an isocyanate compound having two or more functional groups A thin film made of a polyamide resin obtained by reacting a hydroxyl group of the polyamide resin with an isocyanate group of an isocyanate compound after forming the composition on a substrate. 7. An alkyl group-substituted aromatic diamine represented by at least the following general formula: (However, R ₁ and R ₂ each represent a group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and an isopropyl group. However, they are not hydrogen atoms at the same time.) A polyamide resin comprising a phenolic hydroxyl group-containing polyamide resin obtained from a diamine component containing the above, a dicarboxylic acid component containing at least 50 mol% of a phenolic hydroxyl group-containing aromatic dicarboxylic acid, and an isocyanate compound having two or more functional groups A method for producing a thin film comprising a polyamide resin, comprising reacting a hydroxyl group of the polyamide resin with an isocyanate group of an isocyanate compound after forming the composition on a substrate.