JPH06256666A - Resin solution composition and resin film made therefrom - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a resin solution composition suitable for coating or coating, which has a good surface finish during coating and is excellent in heat resistance, and a resin film formed from the composition. To do. [Structure] (A) A resin composition composed of a polyphenylene ether resin and a polyamide, and (B) a resin solution composition comprising a mixed solvent of methylene chloride and m-cresol, and a resin formed from the composition. film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin solution composition prepared by blending a specific mixed solvent with a resin composition comprising an amorphous resin and a crystalline resin, and a resin film formed from the solution composition. It is a thing. More specifically, a resin composition composed of a non-crystalline resin and a crystalline resin, which are hardly completely compatible when originally blended, is dissolved in a mixed solvent prepared by mixing a specific amount of a good solvent for each resin. The present invention relates to a resin solution composition obtained by dissolving or dispersing a part or all of each resin, and a high-performance resin film formed from the resin solution composition.

[0002]

2. Description of the Related Art Conventionally, it has been widely practiced to dissolve a resin in a solvent capable of dissolving the resin and use it as a resin film such as a paint or a coating film. However, paints and coat films made from a single resin reflect the characteristics of each resin as they are, and the drawbacks of the resin are the same as those of the resin film such as the coating film. However, the applicable application range was limited.

For example, crystalline thermoplastic resins such as polyamide, polyester, polypropylene, polyethylene and polyphenylene sulfide generally have a low glass transition temperature, even though they show good solvent resistance, and are scratched when used at high temperatures. In addition, when coated or coated products are piled up and stored at a high temperature, there is a problem that the coating surfaces adhere to each other or scratches occur. In order to solve this problem, for example, a paint obtained by mixing a crystalline resin as a base with a non-crystalline resin excellent in heat resistance and durability has been considered, but the non-crystalline resin to be mixed is However, the crystalline resin had no solubility in a good solvent, and even when the mixed paint was applied to the product, the surface was remarkably rough and only a product that could not be used was produced.

[0004]

DISCLOSURE OF THE INVENTION The present invention contains different types of resins as a resin-based coating composition, and improves the characteristics thereof as compared with conventionally used resin-based coating compositions.
It is to provide a resin solution composition which has a good surface finish during coating and is effective in improving the performance of a resin film for coating or coating which has practical utility, and a resin film formed from the composition. .

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above situation, and as a result, have shown that a resin composition is mixed with a solvent in which two or more different resins to be mixed are dissolved. It was found that by dissolving, a defect such as the heat resistance of a single resin can be improved, and a product having a uniform resin film appearance such as a coated product and the like can be obtained and which has practicality. I arrived.

That is, the present invention comprises (A) 1 to 99 parts by weight of a non-crystalline resin A1 and a crystalline resin A2 99.
100 parts by weight of a resin composition consisting of 1 part by weight and (B) a good solvent B1 of resin A1 and a good solvent B2 of resin A2, and the weight ratio represented by solvent B1 / solvent B2 is 0.0.
Mixed solvent of 01 to 1000 100 parts by weight to 100
The present invention relates to a resin solution composition comprising 0000 parts by weight.

The present invention also relates to a resin film formed from these resin solution compositions.

The (A) non-crystalline resin A1 referred to in the present invention is 10 ° C./min. After heating the resin to a temperature at which it is melted by a differential scanning calorimeter (DSC). A resin in which no exothermic peak due to crystallization is observed when the temperature is lowered at. The resin A1 may be a single resin or a combination of two or more compatible resins that exhibit a uniform phase by melt blending.

Preferred resins A1 are polymethylmethacrylate, polycarbonate, polyarylate, polyester carbonate, polyethersulfone, polyetherimide, polyphenylene ether resin (hereinafter abbreviated as PPE) and polystyrene resin (hereinafter abbreviated as PS). When melt-kneading alone or in the case of melt-kneading such as a combination of PPE and PS, there are combinations such that they are compatible with each other at an arbitrary ratio to form one phase. As one of the preferable resins A1,
There is a resin composition consisting of 0 to 100 parts by weight of PPE and 100 to 0 parts by weight of PS.

The term PPE as used herein means a compound represented by the general formula 1 (wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are selected from hydrogen, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group). A polymer obtained by oxidatively polymerizing one or more phenol compounds represented by the formula (1) or two or more of the phenol compounds represented by the formula (1) are oxygen atoms with an oxygen or oxygen-containing gas. Is.

[0011]

[Chemical 1]

R ₁ , R ₂ in the general formula 1 above,
Specific examples of R ₃ , R ₄ and R ₅ include hydrogen, chlorine,
Bromine, fluorine, iodine, methyl, ethyl, n- or i
so-propyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl,
Methoxycarbonylethyl, cyanoethyl, phenyl,
Chlorophenyl, methylphenyl, dimethylphenyl,
Examples include ethylphenyl and allyl.

Specific examples of the above general formula 1 include phenol, o-, m-, or p-cresol, 2,6-,
2,5-, 2,4- or 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2
-Methyl-6-ethylphenol, 2,3,5-, 2
3,6- or 2,4,6-trimethylphenol, 3
-Methyl-6-t-butylphenol, thymol, 2-
Methyl-6-allylphenol and the like can be mentioned. Furthermore, a phenol compound other than the above general formula 1, for example,
Bisphenol-A, tetrabromobisphenol-
Copolymerization of a polyvalent hydroxyaromatic compound such as A, resorcin, hydroquinone, and novolak resin with the above-mentioned general formula may also be used.

Preferred among these compounds are homopolymers of 2,6-dimethylphenol or 2,6-diphenylphenol and a large amount of 2,6-xylenol and a small amount of 3-methyl-6. A copolymer of -t-butylphenol or 2,3,6-trimethylphenol may be mentioned. The oxidative coupling catalyst used when oxidatively polymerizing the phenol compound is not particularly limited, and any catalyst having a polymerization ability can be used.

Further, the PPE in the present invention includes those obtained by grafting the above-mentioned polyphenylene ether with a styrene polymer or another polymer. The styrene-based polymer is specifically a polymer composed of one or more kinds of polymerized units selected from styrene, α-methylstyrene, p-methylstyrene, and the like, and specifically, polystyrene and rubber reinforcement. Examples thereof include polystyrene, poly α-methylstyrene, poly p-methylstyrene, and styrene-acrylonitrile copolymer.

The crystalline resin (A2) referred to in the present invention means
The temperature of the resin was raised to a melting temperature with a differential scanning calorimeter (DSC), and then 10 ° C./min. A resin in which an exothermic peak due to crystallization is observed when the temperature is lowered at.

When the resin A2 is mixed with the resin A1 and melt-kneaded, the resin A2 is incompatible with each other or does not form a single phase because it has no compatibility with each other. Further, the resin A2
Are generally excellent in solvent resistance and have a high melting point.

Examples of the resin A2 include polyamide, polyester such as polyethylene terephthalate and polybutylene terephthalate, polypropylene, polyethylene and polyphenylene sulfide. A2 does not have to be a single resin and may be a combination of two or more resins. Further, in order to improve the affinity between the resin A1 and the resin A2, the block of the resin A1 may be copolymerized with the resin A2. Further, the block copolymer of the resin A1 and the resin A2 may be added to the resin A1 and the resin A2 in an arbitrary amount. On this occasion,
Any known method may be used for producing the block copolymer. Further, another compatibilizing agent may be added in order to improve the affinity at the interface between the resin A1 and the resin A2.

A preferred resin as the resin A2 is polyamide. The polyamide resin mentioned here is a mixture of one or more polyamides selected from homopolyamides and copolyamides obtained by polymerization of lactam or aminocarboxylic acid and polycondensation of diamine and dicarboxylic acid.

Specifically, nylon 6, nylon 66,
Nylon 64, Nylon 10, Nylon 11, Nylon 12, Nylon MXD6, Nylon 66/6 copolymer, which is a copolymer of metaxylylenediamine and adipic acid,
Copolyamide of para-aminomethylbenzoic acid and ε-caprolactam (nylon AHBA / 6), 2,2,4
-/ 2,4,4-Trimethylhexamethylenediamine
Polyamide containing terephthalate as the main component (nylon T
HDT, THDT / 6I), and the like, but are not limited thereto.

Any method may be used for copolymerizing the resin A1 with the resin A2 in order to improve the affinity between the resin A1 and the resin A2. However, the resin A1 is PPE and the resin A2 is polyamide (PA). In the case of the PPE / PA copolymer-containing composition which is), the methods disclosed in JP-A-56-26913 and JP-A-56-49753, and JP-A-61-502195. However, it is not limited to these.

The ratio of the resin A1 to the resin A2 used in the present invention is 1 to 99 for the resin A1 and 99 to 1 for the resin A2.
Is. When the mixing ratio of the resin A1 is less than 1 and when the mixing ratio of the resin A1 is more than 99, the effect of improving the coating film characteristics by blending the resin A1 and the resin A2 is small and not preferable.

The solvent (B) B1 used in the present invention is a good solvent for the resin A1, and is a resin A1: at least at room temperature.
When 0.1 gram is poured into a solvent of 1000 cc and stirred, 0.05 gram or more of A1 can be dissolved.
For example, when the resin A1 is PPE or polycarbonate, the solvent B1 is methylene chloride, chloroform, carbon tetrachloride, benzene, xylene, toluene, ethylbenzene, tetrahydrofuran or the like.

Further, the (B) solvent B2 used in the present invention
Is a good solvent for the resin A2, and is a resin A2 at least at room temperature.
When 2: 0.1 gram is put into a 1000 CC solvent and stirred, 0.05 gram or more of A2 can be dissolved. For example, when the resin A2 is polyamide, the solvent B2
Include formic acid, m-cresol, hexafluoroisopropanol (HFIP), 2,2,2-trifluoroethanol and the like.

The mixed solvent (B) in the present invention is the solvent B.
1 and solvent B2 in combination, solvent B1 and solvent B
A combination in which both solvents form one phase when two are mixed. If both solvents undergo phase separation when the solvent B1 and the solvent B2 are mixed, distribution of the resin concentration in the solution occurs, which is not preferable.

In the mixed solvent (B) of the present invention,
The mixing ratio of the solvent B1 and the solvent B2 is as follows: solvent B1 / solvent B2
The weight ratio shown by is in the range of 0.001 to 1000. If the mixing weight ratio is less than 0.001, the dissolving ability of the mixed solvent in the resin A1 is significantly reduced, which is not preferable. If the weight ratio exceeds 1000,
This is not preferable because the ability of the mixed solvent to dissolve in the resin A2 decreases. The decrease in the dissolving power is not preferable because the resin does not dissolve when the resin is dissolved and remains as pellets or powder, which makes the mixed solution non-uniform and the appearance after coating remarkably deteriorates. The mixing weight ratio of the solvent is preferably 0.01 to 100, more preferably 0.1 to 10.

In the present invention, the mixing ratio of the resin composition and the mixed solvent (B) is 100 to 100 parts by weight of the sum of the resin A1 and the resin A2, and the mixed solvent of the solvent B1 and the solvent B2 is 100 to 100.
It is used at a rate of 0000 parts by weight. Mixed solvent amount is 100
When the amount is less than the weight part, the solution viscosity becomes high and the handling becomes difficult, which is not preferable. The amount of mixed solvent is 1,000,000
When the amount is more than parts by weight, the concentration is too low, which is not preferable as a coating solution composition. It is preferable to dissolve 100 parts by weight of the total amount of the resin in 200 to 100,000 parts by weight of the mixed solvent, and more preferable to dissolve it in 500 to 100,000 parts by weight of the mixed solvent.

Any method may be used to dissolve the resin composition in the mixed solvent (B).
1, the solvent B2 may be premixed and placed, and then the resin A1 and the resin A2 may be added to the solvent, or the solvent B1 solution of the resin A1 and the solvent B2 solution of the resin A2 may be prepared in advance, You may mix both solutions. Moreover, in order to dissolve the resin mixture in the mixed solvent, heating or stirring may be performed. Further, it is not necessary that the two or more resins are completely dissolved in the mixed solvent, and one or both of them may be partially precipitated.

[0029]

The present invention will be described in detail below with reference to examples, but the examples are merely examples and the present invention is not limited thereto. Each Example and Comparative Example was implemented using the following samples. PPE: A chloroform solution (concentration: 0.5 g / dl) obtained by homopolymerizing 2,6-dimethylphenol, having a logarithmic viscosity of 0.
46 poly (2,6-dimethyl-1,4-phenylene ether). -PS: Nippon Polystyrene Esbright 8K. -Polycarbonate: Mitsubishi Gas Iupilon S20
00.

Polyamide nylon 6: Ube nylon manufactured by Ube Industries
1013B. Nylon 12: Daicel Huls Daiamide L1
801. Nylon 6-12: Daicel Hurus Daiamide D1
4. Nylon 11: Toray Lilsan BM
NO P40.

Composition containing PPE / PA copolymer 5 kg of the PPE and 50 g of maleic anhydride were added to TEX44.
The cylinder temperature was set to 280 ° C. with a twin-screw kneader, and melt kneading was performed. 3 kg of maleic acid-modified PPE thus obtained
Nylon 6 made by Ube Industries (Ube nylon 1013B)
4 kg was mixed and melt-kneaded again at a cylinder temperature of 280 ° C. to form pellets. -Solvent Good solvent for PPE and PS (B1): methylene chloride, chloroform. Good solvent for polycarbonate (B1): Chloroform. Good solvent for nylon (B2): m-cresol, hexafluoroisopropanol (HFIP), formic acid.

Example 1, Comparative Examples 1 to 4 PPE powder and polyamide pellets (1 g in total) were added to 100 ml of solvent in the proportions shown in Table 1 and stirred for about 2 hours,
The appearance of this solution was observed. Then, the solution is dropped on two copper plates, and then hot hot air is blown onto the surface with a hot dryer to dry it. This was repeated 10 times to increase the film thickness. The appearance of the coating film thus obtained was observed, and the case where the surface was smooth was regarded as good, and the case where granular unevenness was observed was regarded as bad. Further, the coating films of the copper plates were put together and the copper plates were stacked, and a weight of 500 g was put on the copper plate, which was then placed in an oven at 50 ° C. and a humidity of 90%. After 5 hours, it was taken out, cooled, and after removing the weight, one copper plate was grasped and lifted. At this time, whether or not the two copper plates were adhered was evaluated as heat resistance. That is, heat resistance was poor when mutual adhesion occurred and adhered, and heat resistance was good when mutual adhesion did not occur.
The evaluation results are shown in Table 1.

Examples 2 to 7 1 g of a mixture of polystyrene and PPE powder and polyamide pellets having the composition shown in Table 2 or a PPE / PA copolymer-containing composition was mixed solvent of m-cresol and methylene chloride (mixing ratio). 50:50) 100 ml, and stirred at 30 ° C. for about 2 hours. After observing the state and dropping the solution on the copper plate, hot hot air is blown onto the surface with a hot drier to dry. This was repeated 10 times to increase the film thickness. The appearance and heat resistance of the coating film thus obtained were observed. The evaluation results are shown in Table 2.

Examples 8 to 10 1 g of a mixture of PPE powder and polyamide pellets having the composition shown in Table 3 was added to 100 ml of a mixed solvent of m-cresol and chloroform (mixing ratio 50:50) and stirred at room temperature for about 2 hours. did. After observing the state and dropping the solution on the copper plate, hot hot air is blown onto the surface with a hot drier to dry. This was repeated 10 times to increase the film thickness. The appearance and heat resistance of the coating film thus obtained were observed.

Examples 11 to 13 A mixture of PPE powder and polyamide pellets having the composition shown in Table 3 or a composition containing PPE / PA copolymer.
1 g was put into 100 ml of a mixed solvent of hexafluoroisopropanol and chloroform (mixing ratio 50:50) and stirred at room temperature for about 2 hours. After observing the state and dropping the solution on the copper plate, hot hot air is blown onto the surface with a hot drier to dry. The appearance of the thin film thus obtained was observed.

Examples 14 to 15 and Comparative Example 5 1 g of a mixture of PS, polycarbonate and polyamide having the composition shown in Table 4 was added to 100 ml of a solvent and stirred at room temperature for 2 hours, and the same evaluation was performed.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

As described above, according to the present invention, a resin composition composed of an amorphous resin and a crystalline resin is dissolved in a mixed solvent composed of respective good solvents, so that it can be used conventionally. Provided is a resin solution composition having a better surface finish at the time of coating and excellent heat resistance, which is suitable for coating or coating, and a resin film formed from the resin solution composition, as compared with existing resin-based paints. can do.

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Claims (6)

[Claims] 1. A resin composition comprising 100 parts by weight of (A) 1 to 99 parts by weight of a non-crystalline resin A1 and 99 to 1 parts by weight of a crystalline resin A2, and (B) a good solvent B1 of the resin A1 and a resin. A resin solution composition comprising 100 parts by weight to 1,000,000 parts by weight of a mixed solvent consisting of a good solvent B2 of A2 and having a weight ratio of solvent B1 / solvent B2 of 0.001 to 1000. 2. A resin film formed from the composition according to claim 1. 3. (A) Resin A1 is at least one type of non-crystalline resin selected from polymethyl methacrylate, polycarbonate, polyarylate, polyester carbonate, polyether sulfone, polyether imide, polyphenylene ether resin, and polystyrene resin. The resin solution composition according to claim 1, wherein the resin A2 is a thermoplastic resin, and the resin A2 is at least one crystalline thermoplastic resin selected from polyamide, polyester, polypropylene, polyethylene, and polyphenylene sulfide. 4. The resin A1 comprises 0 to 100 parts by weight of a polyphenylene ether resin and 100 to 100 parts of a polystyrene resin.
The resin solution composition according to claim 3, wherein the resin composition comprises 0 parts by weight, and the resin A2 is a polyamide. 5. The (A) resin A1 is at least one type of non-crystalline resin selected from polymethyl methacrylate, polycarbonate, polyarylate, polyester carbonate, polyether sulfone, polyetherimide, polyphenylene ether resin and polystyrene resin. The resin film according to claim 2, which is a thermoplastic resin and wherein the resin A2 is at least one crystalline thermoplastic resin selected from polyamide, polyester, polypropylene, polyethylene, and polyphenylene sulfide. 6. A resin A1 comprises 0 to 100 parts by weight of a polyphenylene ether resin and 100 to 100 parts of a polystyrene resin.
The resin film according to claim 5, wherein the resin composition comprises 0 parts by weight, and the resin A2 is polyamide.