JPH09316345A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting resin compsn. capable of forming a thermoset product having excellent surface properties by compounding a thermosetting resin with a specified aromatic polyester. SOLUTION: This compsn. comprises 100 pts.wt. thermosetting resin and 0.1 to 50 pts.wt. solvent-soluble and/or hot-melt aromatic polyester comprising a main chain having an aromatic polyester structure and side chains of two or more carbon atoms in at least a part of the aromatic rings in the main chain. At least a part of the side chains of the aromatic polyester are preferably an aliphatic side chain. At least a part of the side chains of the aromatic polyester are preferably a fluorine-containing side chain; and/or at least a part of the side chains of the aromatic polyester are preferably a dialkylsiloxane- containing side chain.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermosetting resin composition comprising a thermosetting resin and an aromatic polyester, which is useful as a coating film, a coating material, a molding material and the like.

[0002]

2. Description of the Related Art In recent years, with the sophistication of industries such as electronics, electricity, automobiles and construction fields, the required characteristics of thermosetting resin materials have been increasing more and more. It has been widely studied to blend and use other organic molecules or polymers.

In particular, it is necessary to improve the mechanical brittleness, which is a drawback of thermosetting resins, and to improve the surface characteristics when used in coatings and coatings, and in particular, to improve the surface properties so as to have water repellency and oil repellency. It is a big issue to improve. Conventionally, regarding the addition of a modifier for improving the surface characteristics of a thermosetting resin, for example, a low molecular weight material that is easy to handle has been used as a surface modifier. There is a problem such as deterioration of mechanical properties of the thermosetting resin due to blending of low molecular weight compounds.

On the other hand, blending with a thermoplastic polymer has also been studied in order to improve the surface characteristics and mechanical properties of the thermosetting resin. However, thermoplastic polymers generally do not have good compatibility with thermosetting resins and are likely to undergo phase separation and aggregation during the curing process, so that it is possible to obtain a good composite having a finely dispersed state and a closely attached interface. Often difficult.

For example, an aromatic polyester having a melted liquid crystal property, which is known as a thermoplastic polymer having excellent mechanical properties, has extremely poor solvent solubility and has a strong self-aggregating property, so that it is forcibly blended. Even in this case, only a blend having a large dispersed particle size and having poor interface adhesion was obtained, and a good composite with a thermosetting resin was not obtained.

[0006]

The problem to be solved by the present invention is that a thermosetting product such as a coating film, film or molded product obtained by using the present invention has good morphology and homogeneity, and It is intended to provide a thermosetting resin composition having excellent surface characteristics such as a high contact angle with water and a low surface free energy.

[0007]

Means for Solving the Problems The inventors of the present invention have been engaged in earnest research toward solving the above problems, and in particular, as a thermoplastic polymer, the main chain has an aromatic polyester structure,
Use of an aromatic polyester having a side chain in the main chain aromatic ring and having solvent solubility and / or heat melting property or melt liquid crystallinity, and a thermosetting resin composition comprising the same and a thermosetting resin have excellent performance They have found the present invention and completed the present invention.

That is, in the present invention, 100 parts by weight of a thermosetting resin, a main chain having an aromatic polyester structure, and a side chain having 2 or more carbon atoms are bonded to at least a part of aromatic rings in the main chain. A thermosetting resin composition containing 0.1 to 50 parts by weight of an aromatic polyester having solvent solubility and / or heat melting property.

The thermosetting resin composition of the present invention is also characterized in that at least a part of the side chains of the aromatic polyester is an aliphatic side chain, and the side of the aromatic polyester is a side chain of the aromatic polyester. Thermosetting resin composition characterized in that at least part of the chain is a fluorine-containing side chain, and thermosetting characterized in that at least part of the side chain of the aromatic polyester is a dialkylsiloxane-containing side chain Resin composition.

Further, the thermosetting resin composition of the present invention is characterized in that the side chain of the above-mentioned aromatic polyester has a branched structure in particular, and that of the aromatic polyester. It includes a thermosetting resin composition whose main chain has a wholly aromatic polyester structure, and more particularly, a thermosetting resin composition whose aromatic polyester has a melt liquid crystallinity.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As the thermosetting resin used in the present invention, for example, a general-purpose thermosetting resin for molding, coating, bonding, paint, etc. is used. Specific examples thereof include thermosetting epoxy resins, alkyd resins, acrylic resins, melamine resins, polyester resins, phenol resins, urethane resins, fluoroolefin copolymer resins, and one or more of them. A thermosetting resin mixed with a curing agent is used.

It is preferable that the thermosetting resin can be mixed homogeneously with the side chain-containing aromatic polyester of the present invention in the coexistence of an organic solvent or alone without an organic solvent, and a transparent homogeneous resin is particularly preferable. A mixture is good.

In order to react the thermosetting resin, usually,
When a solvent is contained, the solvent is cast and removed, and then heated to the curing reaction temperature. Here, it is also possible to use a curing reaction accelerator usually used in the thermosetting reaction in combination. The aromatic polyester used in the present invention has a main chain having an aromatic polyester structure, and at least a part of aromatic rings in the main chain has an aliphatic side chain and / or a fluorine-containing side chain and / or a dialkylsiloxane-containing side. It is essential that the chains are bound and that they have solvent solubility and / or heat melting properties.

The main chain structure of the aromatic polyester used in the present invention includes a wholly aromatic polyester structure consisting only of an aromatic ring and an ester bond, and an aromatic polyester structure containing an aliphatic chain in its main chain. Further, those having an aromatic polyester structure showing a melted liquid crystallinity only in the main chain are also included. Here, as the side chain substituted or unsubstituted main chain aromatic ring, various aromatic rings such as a phenylene ring, a biphenylene ring and a naphthalene ring are used.

The side chain of the aromatic polyester used in the present invention is preferably an aliphatic side chain having 2 or more carbon atoms, particularly preferably 4 or more carbon atoms, a fluorine-containing side chain or a dialkylsiloxane-containing side chain, and Those having a chain structure or a branched structure are used. Those having only 1 side chain or no side chain have solvent solubility and / or
Alternatively, it often has no heat-melting property or does not have good fine dispersibility or interfacial adhesion in a thermosetting resin, and effectively achieves composite with a thermosetting resin, which is the object of the present invention. Not done.

The aromatic polyester used in the present invention does not have the aromatic polyester which has two or more carbons in the side chain and has neither solvent solubility in an organic solvent nor thermal melting property. However, even if it partially contains an aromatic ring having a side chain carbon number of 1 or an aromatic ring having no side chain, by using it together with various side chains having 2 or more carbon atoms in the copolymer, solubility in an organic solvent Alternatively, it can be used in the present invention as long as it has heat melting property.

The aliphatic side chain of the aromatic polyester used in the present invention has 2 or more carbon atoms, preferably 2 to 20 carbon atoms, and has a linear or branched structure. The aliphatic side chain may be substituted on all the aromatic rings in the main chain, or may be substituted on a part of the aromatic rings in the main chain. The number of side chains substituted by one aromatic ring is one or two or more.

As the aliphatic side chain having a branched structure, one or a plurality of secondary or tertiary carbons are contained in the side chain.
Those having at the end or in the middle are used, and specifically,
One side chain is branched into two chains, three chains, etc.,
Examples thereof include those having an isopropyl group or a tert-butyl group at the end of the aliphatic side chain. Those in which the aliphatic side chain has a branched structure are effective in improving the surface characteristics of the thermosetting resin composition. Among the following fluorine-containing side chains and dialkylsiloxane-containing side chains, those having a similar branched structure can be effectively used.

As the fluorine-containing side chain, one having 2 or more carbon atoms, preferably 2 to 30 carbon atoms in which at least a part of hydrogen in the side chain is substituted with fluorine is used. It is preferable that the terminal side is fluorine-substituted, and / or the fluorine-containing side chain has a branched structure.
Examples of the terminal group having a fluorine-containing group at the terminal side of the side chain include those having the following structures.

-X (CH ₂ ) _n (CF ₂ ) _m F, or -X
_{(CH 2) n (CF 2} ) m H ( wherein, n represents 1 to 10, m is an integer of 1 to 20, X is e - represents an ether or ester bond.)

The fluorine-containing side chain may be substituted on all the aromatic rings in the main chain, or may be substituted on a part of the aromatic rings in the main chain. The number of side chains substituted by one aromatic ring is one or two or more. Those having such a fluorine-containing side chain are effective in improving the surface characteristics of the thermosetting resin composition.

The aromatic polyester in the present invention includes those having an aliphatic side chain together with a fluorine-containing side chain. For example, a fluorine-containing side chain is bonded to a part of the aromatic ring in the main chain. , Those in which an aliphatic side chain is bonded to a part or all of the remaining aromatic ring in the main chain.

Here, the ratio of the fluorine-containing side chain to the aliphatic side chain differs depending on the length of each side chain and cannot be unconditionally specified,
(Number of fluorine-containing side chains / Number of aliphatic side chains) = 0.05-
Those in the range of 1 are preferably used. Here, if the ratio is less than 0.05, the effect of the fluorine-containing side chain is small and 1
In the above cases, the performance is often the same as when the fluorine-containing side chain is used alone, and the effect of using the aliphatic side chain together is diminished.

As the dialkylsiloxane structure-containing side chain of the aromatic polyester used in the present invention, one having a dialkylsiloxane structure in at least a part of the side chain is used, and the number of siloxanes is preferably 2 or more, Particularly preferably, the siloxane number is 2 to 10
0. Further, it is more preferable that the terminal side of the side chain has a dialkylsiloxane structure and / or the side chain containing the dialkylsiloxane has a branched structure.

Examples of the side chain having a dialkylsiloxane structure at the terminal side include those having the following structures. _{-X (CH 2) n (Si} (R) 2 O) m R ( where, n represents an integer of 1 or more, m is 2-100 integer,
X represents an ether or ester bond, and R represents an alkyl group having 1 or 2 carbon atoms. )

The dialkylsiloxane-containing side chain may be substituted on all the aromatic rings in the main chain, or may be substituted on a part of the aromatic rings in the main chain. The number of side chains substituted by one aromatic ring is one or two or more. Those having such a dialkylsiloxane-containing side chain are effective in improving the surface characteristics of the thermosetting resin composition.

The aromatic polyesters used in the present invention include those having an aliphatic side chain and / or a fluorine-containing side chain together with a dialkylsiloxane-containing side chain. For example, some aromatic rings in the main chain A dialkylsiloxane-containing side chain is bonded, and an aliphatic side chain and / or a fluorine-containing side chain is bonded to a part or all of the remaining aromatic ring in the main chain.

The ratio of the dialkylsiloxane-containing side chain to the other side chain varies depending on the length of each side chain and cannot be specified unconditionally, but (number of dialkylsiloxane-containing side chains / number of other side chains) = 0.001 Those in the range of to 1 are preferably used. Here, if the ratio is less than 0.001, the effect of the dialkylsiloxane-containing side chain is small, and if the ratio is 1 or more, the effect of using other side chains together is small.

The aromatic polyester used in the present invention may have various bonding modes between the aliphatic side chain, the fluorine-containing side chain, the dialkylsiloxane-containing side chain and the main chain. The bond between the main chain aromatic ring and the side chain by a ter bond (-O-) or an ester bond (-COO-) is preferably used because the side chain can be easily introduced. In the present invention, the carbon contained in the above-mentioned bond connecting the main chain and the side chain is not included in the carbon number of the side chain.

Specific examples of the aromatic polyester having an aliphatic side chain and / or a fluorine-containing side chain and / or a dialkylsiloxane-containing side chain in the present invention include:
Aromatic polyesters obtained by using aromatic dicarboxylic acids having one or more such side chains and side chain-unsubstituted aromatic diols as monomers, and conversely side chain-unsubstituted aromatic dicarboxylic acids and An aromatic polyester obtained by using an aromatic diol having a side chain as a monomer, or an aromatic polyester obtained by using both monomers having the above side chains, and a hydroxycarboxylic acid having a side chain as a monomer. Examples thereof include aromatic polyesters and the like.

As the aromatic polyester in the present invention, in addition to a homopolymer having a fixed chemical structure, plural kinds of aromatic monomers are used, and the main chain has a different bonding property such as a paraphenylene ring or a metaphenylene ring. A copolymer obtained by using an aromatic ring is also included.

For example, those containing an aliphatic side chain or a metaphenylene ring in the main chain can control surface characteristics, thermal characteristics, solvent solubility, etc. more broadly, and can obtain a high molecular weight aromatic polyester. If possible, the use of the meta isomer monomer is excellent in cost and production yield. Further, as one kind of such an aromatic polyester copolymer, it is also possible to use one in which an amide bond or an ether bond is partially introduced into an ester bond of the main chain.

Further, a copolymer having a plurality of types of aliphatic side chains and / or fluorine-containing side chains and / or dialkylsiloxane-containing side chains having different side chain lengths and structures, and an unsubstituted monomer may be used together. The copolymer obtained by the above is also used. In any of the copolymers, the copolymerization ratio and block property, and the copolymerization ratio of the main chain portion and the side chain portion are not limited as long as they have solvent solubility and / or heat melting property.

Copolymerization in the main chain and / or side chain as described above controls and improves the surface characteristics, mechanical characteristics, solvent solubility, melting temperature and liquid crystallinity of the aromatic polyester itself, as well as thermosetting. It is possible to improve the miscibility with the thermosetting resin and is effective in improving the surface characteristics and mechanical characteristics of the thermosetting resin composition obtained.

It is not appropriate to use an aromatic polyester having neither solvent solubility in an organic solvent nor heat melting property in the present invention. Further, an aromatic polyester having no solvent solubility is often inferior in surface properties and mechanical properties of the resulting thermosetting resin composition because it is not easily compounded with a thermosetting resin using a solution. .

On the other hand, those having both solubility in an organic solvent and thermal melting property are preferable in terms of blending property with a thermosetting resin, and those exhibiting liquid crystallinity at the time of melting are capable of controlling orientation, and thus thermosetting. It is also excellent in improving the mechanical properties of the resin composition.

The amount of the aromatic polyester used in the present invention is 0.1 to 100 parts by weight of the thermosetting resin.
It is preferably 50 parts by weight, particularly preferably 0.
It is 2 to 20 parts by weight. If it is less than 0.1 part by weight, the blending effect of the aromatic polyester may be reduced, and if it is 50 parts by weight or more, the curability of the thermosetting resin may be deteriorated. The present invention is characterized in that excellent modifying effects such as surface characteristics can be obtained by adding a small amount of aromatic polyester.

As a method for preparing the thermosetting resin composition containing the thermosetting resin and the aromatic polyester of the present invention, various methods are possible depending on the characteristics of both resins to be used and are not particularly limited. Specifically, a method of directly mixing a thermosetting resin and an aromatic polyester, a method of mixing one or both dissolved in a suitable organic solvent soluble in both resins, or a solution thereof. After the preparation, a method of removing at least a part of the organic solvent, a method of mixing with another dispersion promoter, and the like can be mentioned.

Various methods can be used for obtaining a good thermosetting resin coating film or molded article using the thermosetting resin composition of the present invention. As an example, the above-mentioned thermosetting resin composition or a solution of the thermosetting resin composition dissolved in a solvent is prepared, and the composition is applied, cast or injected onto a predetermined substrate or in a mold. Next, select conditions such as temperature, gas flow, and vacuum, remove the solvent as necessary, and appropriately advance the curing reaction of the thermosetting resin to obtain a coating film, film, or molding with good physical properties. You can get the body.

In addition, for example, the thermosetting resin and the aromatic polyester are dissolved in a common organic solvent to form a solution, which is once dried, or by melt-kneading the thermosetting resin and the aromatic polyester. A curable resin composition can be obtained. An effective molding method is also a method of molding the thermosetting resin composition by a method such as injection, extrusion, pressing or spinning, and at the same time advancing thermosetting of the resin.

In any of the methods, it is possible to add an aromatic polyester to the thermosetting resin in advance or in the middle of a curing reaction accelerator or other conventionally known physical property improver, and a filler such as glass fiber. It can be performed unless it is separated and precipitated from the system.

According to the present invention, the aromatic polyester is finely dispersed in the resin cured product which is thermoset in the form of a coating film, a film or a molded product, so that the surface of the cured product is higher than that of the cured thermosetting resin alone. The properties and mechanical properties are improved. In addition, when the coating film or film is formed or when the resin is heat-cured, the aromatic polyester is concentrated on the surface of the molded product, or side chains of the aromatic polyester are aggregated on the surface. The properties of the thermosetting resin are improved to have excellent surface properties such as low surface free energy.

Further, since aromatic polyester is finely dispersed in a resin cured product which is cured by heat into a molded product such as a coating film or a film, the aromatic polyester is mechanically more mechanically than a cured product of a thermosetting resin alone. The properties are improved. For the present invention,
For example, when a commercially available aromatic polyester having a melted liquid crystallinity represented by a trade name Vectra (manufactured by Ceranizu Co., Ltd.) is used, since it does not have solvent solubility, it can be melt-kneaded into A good composite with the thermosetting resin of the present invention cannot be obtained due to its poor dispersibility in water and interfacial adhesion.

[0044]

The present invention will be further described with reference to examples.

(Production Example 1) 0.1 mol of diethyl 2,5-dihydroxyterephthalate was added to 100 mL under a nitrogen atmosphere.
Of 0.3 mol of dry K ₂ CO ₃ and 1 g of KI were added to a solution of cyclopentanone of 10% and heated for 10 minutes.
0.2 mol of 1-bromopentane was added dropwise and the mixture was heated under reflux for 24 hours. After removing the generated salt such as KBr by heating filtration, cyclopentanone was distilled off to obtain a side chain-substituted monomer into which two aliphatic side chains were introduced.

This monomer was mixed with 20 mL of ethanol and 5
After treatment for 24 hours in a boiling solution of 250 mL of an aqueous KOH solution, the mixture was cooled and filtered to obtain a potassium salt of a monomer. After dissolving this salt again in heated water, hydrochloric acid was added to obtain an aliphatic side chain-substituted dicarboxylic acid monomer,
Purified with dichloromethane. 0.1 mol of the obtained aliphatic side chain-substituted dicarboxylic acid monomer was dissolved in 40 mL of thionyl chloride by heating, 6 mL of pyridine was added dropwise, and the mixture was refluxed for 24 hours, then the solvent was removed, and then petroleum ether was used. And purified to obtain a monomer chloride.

The obtained aliphatic side chain-substituted monomer chloride was dissolved in tetrachloroethane, and 4,4'-biphenol (70 mol%) and 1,5-dihydroxynaphthalene (were dissolved with vigorous stirring of the solution. (30 mol%) mixture is added in an equimolar amount with the monomer chloride, and then pyridine is added dropwise.
The mixture was heated under reflux under a nitrogen atmosphere for 24 hours. The resulting viscous solution was added to methanol to precipitate and filter the polymer, and the dissolution and reprecipitation were repeated using a chloroform solvent and methanol,
Finally, it was washed with methanol and dried to obtain a polymer.

By the above method, an aromatic polyester copolymer A having an aliphatic side chain, in which a side chain of-(CH ₂ ) ₄ CH ₃ was bonded to the main chain aromatic ring by an ether bond, was obtained. . The obtained aromatic polyester copolymer A (polymer A) was dissolved in chloroform. Also, in heating by heating, 27
It became a molten liquid crystal at 0 ° C (Tm) and became an isotropic melt at 320 ° C (Ti).

(Production Example 2) In the same manner as in Example 1 except that 1-bromohexadecane was used instead of 1-bromopentane in Example 1,-(CH ₂ ) ₁₅ C was prepared.
The side chain of H ₃ is bonded to the main chain aromatic ring by an ether bond,
An aromatic polyester copolymer B having an aliphatic side chain was obtained. The obtained aromatic polyester copolymer B (polymer B) was dissolved in chloroform or dichloromethane. Also, when heated by heating, it becomes a liquid crystal at 32 ° C (Tm).
It became an isotropic melt at 42 ° C (Ti).

(Production Example 3) 0.1 mol of pyromellitic dianhydride and 0.2 mol of 1-hexadecanol were stirred in a dry inert gas atmosphere while slowly raising the temperature to 150 ° C. and stirring for 45 minutes. Held After cooling, 400 mL of acetone was added, and the mixture was stirred for 12 hours and then filtered to obtain a para-form dicarboxylic acid monomer into which two aliphatic side chains were introduced.

To 0.05 mol of the obtained monomer, 10 times mol of thionyl chloride was added, and the mixture was refluxed at 80 to 90 ° C. for 20 minutes, and then excess thionyl chloride was removed to obtain the chloride of the monomer. . A solution of 0.04 mol of 4,4'-biphenol and twice its equivalent amount of triethylamine in 30 mL of tetrahydrofuran was strongly stirred, while a monomer chloride of equimolar amount to biphenol was dissolved in tetrahydrofuran. The allowed solution was added dropwise.

After the solution became viscous and the reaction was completed, the solution was added to 500 mL of methanol to precipitate the polymer, which was then filtered and dissolved and re-used with a tetrahydrofuran solvent and methanol. Precipitation was repeated, and finally, the polymer was washed with methanol and dried to obtain a polymer C. The polymer obtained by the above method is an aromatic polyester having an aliphatic side chain in which the side chain of (CH ₂ ) ₁₅ CH ₃ is bonded to the main chain aromatic ring by an ester bond, and chloroform, N- Dissolved in methylpyrrolidone. In addition, it is 87 ℃ in heating
It became a molten liquid crystal at 1, and became an isotropic melt at 123 ° C.

(Production Example 4) 0.1 mol of trimellitic anhydride and 0.1 mol of 1-dodecanol were stirred in a dry inert gas atmosphere, and the temperature was slowly raised to 150 ° C.
It was kept stirring for 5 minutes. After cooling, 300 mL of acetone /
Hexane mixed solvent was added, and the mixture was stirred for 12 hours and then filtered.
The filtered product was washed again with a mixed solvent of acetone / hexane to obtain a para-form dicarboxylic acid monomer in which one aliphatic side chain having 12 carbon atoms was introduced into the paraphenylene ring.

To 0.05 mol of the obtained monomer, 10 times mol of thionyl chloride and 80 mL of tetrahydrofuran were added, and the mixture was refluxed at 80 to 90 ° C. for 20 minutes.
Tetrahydrofuran and excess thionyl chloride were removed to obtain the chloride of the above monomer.

0.02 mol of 4,4'-biphenol,
A solution prepared by dissolving twice the equivalent amount of triethylamine in 30 mL of tetrahydrofuran was stirred vigorously, and a solution prepared by dissolving biphenol and an equimolar amount of monomer chloride in tetrahydrofuran was added dropwise. After the solution became viscous and the reaction was completed, the solution was added to 500 mL of methanol to precipitate a polymer, which was then filtered and repeatedly dissolved and reprecipitated using a tetrahydrofuran solvent and methanol, Finally, it was washed with methanol and dried to obtain a polymer.

By the above method, an aromatic polyester D (-) having one aliphatic side chain per repeating unit structure, in which the side chain of-(CH ₂ ) ₁₁ CH ₃ is bonded to the main chain aromatic ring by an ester bond, Polymer D) was obtained. Here, the side chain is bonded to the main chain aromatic ring by an ester bond. The resulting polymer
D was dissolved in chloroform and N-methylpyrrolidone. Further, in the heating by heating, it became a molten liquid crystal at 150 ° C. (Tm) and became an isotropic melt at 330 ° C. (Ti).

Production Example 5 0.1 mol of pyromellitic dianhydride and 3- (perfluorohexyl) propanol 0.1.
While stirring 2 mol and 2 mol in a dry inert gas atmosphere, the temperature was slowly raised to 150 ° C., and the mixture was kept stirring for 45 minutes. After cooling, 450 mL of an acetone / dichloromethane mixed solution was added, and the mixture was stirred for 12 hours and then filtered. The filtered product was washed with chloroform to obtain a para-form dicarboxylic acid monomer having two fluorine-containing side chains.

To 0.05 mol of the obtained monomer, 10 times mol of thionyl chloride and 10 mL of tetrahydrofuran were added, and the mixture was refluxed for 20 minutes. Then, tetrahydrofuran and excess thionyl chloride were removed, and the chloride of the monomer was removed. Obtained. While stirring vigorously a solution prepared by dissolving 0.02 mol of 4,4'-biphenol and twice its equivalent amount of triethylamine in 30 mL of tetrahydrofuran, the monomer chloride in an equimolar amount of biphenol was added to tetrahydrofuran. The solution dissolved in was added dropwise.

After the solution became viscous and the reaction was completed, the solution was added to 500 mL of methanol to precipitate a polymer, which was then filtered, and the solvent was dissolved in tetrahydrofuran and methanol.
Polymer was repeatedly dissolved and reprecipitated using a solvent, and finally washed with methanol and dried to obtain a polymer E. By the method described _{above, - (CH 2) 3 (} CF 2) 6 side chains of the F was coupled to the main chain an aromatic ring in the ester bond, an aromatic polyester E having two fluorine-containing side chain per repeating unit structure ( Polymer E) was obtained. The obtained polymer E was dissolved in chloroform. Further, when heated at elevated temperatures, it became a liquid crystal at 170 ° C. (Tm) and became an isotropic melt at 235 ° C. (Ti).

Production Example 6 0.1 mol of pyromellitic dianhydride and 0.2 mol of 1-pentanol were slowly heated to 150 ° C. with stirring in a dry inert gas atmosphere.
It was kept stirring for 0 minutes. After cooling, 450 mL of toluene was added to recrystallize. The filtered product was washed with toluene several times to obtain a para-substituted aliphatic side chain-substituted monomer.
After adding 10 times mol of thionyl chloride to 0.05 mol of the obtained monomer and refluxing the mixture at 80 to 90 ° C. for 60 minutes, excess thionyl chloride was removed to obtain a chloride of the monomer.

On the other hand, 0.1 mol of pyromellitic dianhydride,
Dimethyl siloxane oligomer of terminal alkyl alcohol (X-22-170AX: manufactured by Shin-Etsu Chemical Co., Ltd .:
The chemical formula is HO (CH ₂ ) ₁₀ (OSi (CH ₃ ) ₂ ) ₂₀ C
0.2 mol of H ₃ ) and a catalytic amount of dimethylformamide were slowly heated to 150 ° C. while stirring in a dry inert gas atmosphere, and the mixture was kept stirring for 60 minutes. Monomers are mixtures of meta and para substitutions.

After adding 10 times mole of thionyl chloride to 0.05 mole of the obtained monomer and refluxing at 80 to 90 ° C. for 60 minutes, excess thionyl chloride was removed to obtain a chloride of the monomer.

0.0002 mol of the dimethylsiloxane-containing side chain-substituted monomer chloride, 0.0198 mol of the above-mentioned para-substituted aliphatic side chain-substituted monomer chloride, 4,4 '
-Biphenol 0.02 mol and tetrahydrofuran 3
To the solution dissolved in 0 mL, pyridine in an amount 4 times that of biphenol was added dropwise with vigorous stirring. After the solution became viscous and the reaction was completed, the solution was added to 500 mL of methanol to precipitate a polymer, which was then filtered and repeatedly dissolved and reprecipitated using a tetrahydrofuran solvent and methanol, Finally, it was washed with methanol and dried to obtain a polymer.

By the above method,-(CH ₂ ) ₁₀ (OS
i (CH _{3) 2) 20} CH ₃ and the side chain of the - (CH ₂₎ to obtain an aromatic polyester copolymer F (polymer F) having _four side chain of CH ₃ in pair 99 (the number of side chain ratio) It was Here, both side chains are bonded to the main chain aromatic ring by an ester bond. The obtained polymer F was soluble in chloroform and tetrahydrofuran. Further, it melted at 150 ° C. (Tm) in heating at elevated temperature, and thereafter showed optical anisotropy under shear stress at 150 to 260 ° C.

Production Example 7 0.002 mol of a dimethylsiloxane-containing side chain-substituted monomer chloride prepared by the same method as in Production Example 4 and para-substituted aliphatic side chain-substituted monomer chloride 0.018 mol of the product and 0.02 mol of 4,4'-biphenol were dissolved in 30 mL of tetrahydrofuran, and 4 times equivalent amount of pyridine of biphenol was added dropwise with vigorous stirring.

After the solution became viscous and the reaction was completed, the solution was added to 500 mL of methanol to precipitate a polymer, which was then filtered, and the solvent was dissolved in tetrahydrofuran and methanol.
The polymer was repeatedly dissolved and reprecipitated, and finally washed with methanol and dried to obtain a polymer.

By the above method,-(CH ₂ ) ₁₀ (OS
An aromatic polyester copolymer G (polymer G) having a side chain of i (CH ₃ ) ₂ ) ₂₀ CH _{3 and} a side chain of-(CH ₂ ) ₄ CH _{3 in} a ratio of 10:90 (side chain number) is obtained. It was Here, both side chains are bonded to the main chain aromatic ring by an ester bond. The obtained Polymer-G was soluble in chloroform and tetrahydrofuran. Further, it melted at 130 ° C. (Tm) in heating at elevated temperature, and thereafter showed optical anisotropy under shear stress at 130 to 180 ° C.

Example 1 The polymer obtained in Production Example 1
A and a thermosetting polyester polyol-based urethane resin (Dainippon Ink and Chemicals Co., Ltd., Barnock D750
And Barnock D400-70 were mixed at a liquid weight ratio of 60:40) so that the resin solid content weight ratio became 5:95 to prepare a homogeneous solution using chloroform as a solvent.

This solution was cast on a clean glass plate, the solvent was evaporated at room temperature, heat-treated at 60 ° C. for 60 minutes, and then kept at 30 ° C. for 14 days to obtain a uniform coating film having a thickness of 50 μm. It was The surface free energy of the obtained coating film and the contact angle with water were measured by using a contact angle measuring device (FACE contact angle meter manufactured by Kyowa Interface Science Co., Ltd.) and measuring liquids such as water, iodine methane and ethylene glycol. It was obtained by using. Here, the contact angle with water was 95.4 degrees and the surface free energy was 33.4 mN / m.

Example 2 The polymer obtained in Production Example 1
A and thermosetting fluoroolefin copolymer resin (Dainippon Ink & Chemicals Co., Ltd. Fluorone K700 and Ver.
Knock DN980 mixed at a liquid weight ratio of 100: 12) was used at a resin solid content weight ratio of 2:98 to prepare a homogeneous solution using chloroform as a solvent.

This solution was cast on a clean glass plate, the solvent was evaporated, and the mixture was kept at 30 ° C. for 7 days to give a thickness of 5
A uniform coating of 0 μm was obtained. The surface free energy of the obtained coating film and the contact angle with water were measured in the same manner as in Example 1. Contact angle with water is 97.8 degrees, surface free energy
Was 31.4 mN / m.

Example 3 The polymer obtained in Production Example 2
50 μm in thickness as in Example 1 except that B is used.
A uniform coating film was obtained. The surface free energy of the obtained coating film and the contact angle with water were measured in the same manner as in Example 1.
The contact angle with water is 100.5 degrees and the surface free energy is 3
It was 5.7 mN / m.

Example 4 Polymer obtained in Production Example 3
C, a thermosetting acrylic melamine resin (Acrydic A405 manufactured by Dainippon Ink and Chemicals, Inc., Super-Beckamine G821-60, and Epicron 1050 mixed in a solid content weight ratio of 7 to 2: 1. ) Was used at a resin solid content weight ratio of 10:90 to prepare a homogeneous solution using chloroform as a solvent. This solution was cast on a clean glass plate, the solvent was evaporated, and the mixture was heated at 140 ° C. for 20 minutes to obtain a uniform coating film having a thickness of 80 μm. The surface free energy of the obtained coating film and the contact angle with water were measured in the same manner as in Example 1. Contact angle with water is 9
The surface free energy was 7.3 degrees and 35.0 mN / m.

(Example 5) The polymer obtained in Production Example 4
The thickness is 80 μm in the same manner as in Example 4 except that D is used.
A uniform coating film was obtained. The surface free energy of the obtained coating film and the contact angle with water were measured in the same manner as in Example 4.
The contact angle with water is 94.1 degrees and the surface free energy is 3
It was 4.0 mN / m.

Example 6 The polymer obtained in Production Example 5
90 μm in thickness as in Example 4 except that E is used.
A uniform coating film was obtained. The surface free energy of the obtained coating film and the contact angle with water were measured in the same manner as in Example 4.
The contact angle with water is 105.1 degrees and the surface free energy is 1
It was 9.0 mN / m.

Example 7 The polymer obtained in Production Example 5
E and a thermosetting alkyd melamine resin (a mixture of Beckosol 1343 manufactured by Dainippon Ink and Chemicals, Inc. and Super Beckamine G821-60 in a solid content weight ratio of 7: 3) as a resin solid. A homogeneous solution using chloroform as a solvent was prepared by using the mixture at a weight-to-weight ratio of 10:90.

This solution was cast on a clean glass plate, the solvent was evaporated and the mixture was heated at 130 ° C. for 20 minutes to obtain a uniform coating film having a thickness of 70 μm. The surface free energy of the obtained coating film and the contact angle with water were measured in the same manner as in Example 1. The contact angle with water was 102.2 degrees and the surface free energy was 17.9 mN / m.

Example 8 The polymer obtained in Production Example 6
F and a thermosetting epoxy resin (a 14: 1 (weight ratio) mixture of Epicron 850 manufactured by Dainippon Ink and Chemicals, Inc. and a curing agent, tetraethylenepentamine) so that the resin solid content weight ratio is 1:99. A homogeneous solution was prepared using chloroform as a solvent. This solution was cast on a clean glass plate, and the solvent was evaporated at room temperature and then heat-treated at 180 ° C. for 60 minutes to obtain a uniform coating film having a thickness of 70 μm. The surface free energy of the obtained coating film and the contact angle with water were measured in the same manner as in Example 1. Contact angle with water is 9
The surface free energy at 3.8 degrees was 34.5 mN / m.

Example 9 The polymer G obtained in Preparation Example 7 was used in place of the polymer F, and the polymer G was used.
A homogeneous coating film having a thickness of 70 μm was obtained in the same manner as in Example 8 except that the thermosetting epoxy resin was used so that the resin solid content weight ratio was 0.2: 99.8. The surface free energy of the obtained coating film and the contact angle with water were measured in the same manner as in Example 8. The contact angle with water was 96.1 degrees and the surface free energy was 34.3 mN / m.

(Comparative Examples 1 to 5) In Comparative Example 1, the thermosetting resin used in Example 1 was used, and in Comparative Example 2, Example 2 was used.
The thermosetting resin used in Example 4, the thermosetting resin used in Example 4 in Comparative Example 3, the thermosetting resin used in Example 7 in Comparative Example 4, and the example 8 in Comparative Example 5. A thermosetting resin coating film (thickness: about 200 μm) was prepared using the thermosetting resin under the same conditions as in the respective examples except that no aromatic polyester was added.

The surface free energy of the obtained coating film and the contact angle with water were measured in the same manner as in Example 1. As a result, the contact angle with water was 79.6 degrees in Comparative Example 1 and Comparative Example 2
Is 87.2 degrees, Comparative Example 3 is 85.7 degrees, Comparative Example 4 is 84.2 degrees, Comparative Example 5 is 76.9 degrees, and the surface free energy is 44.1 mN / m in Comparative Example 1. Comparative Example 2 is 37.7 mN / m, and Comparative Example 3 is 35.7 mN / m.
m, 39.5 mN / m in Comparative Example 4, 5 in Comparative Example 5
It was 3.3 mN / m.

[0082]

EFFECTS OF THE INVENTION The thermosetting product obtained using the thermosetting resin composition of the present invention has a good morphology and / or homogeneity as a coating film, a film or a molded article and has a high contact angle with water. And excellent surface properties such as low surface free energy.

Claims (7)

[Claims] 1. A solvent comprising 100 parts by weight of a thermosetting resin, a main chain having an aromatic polyester structure, and a side chain having 2 or more carbon atoms bonded to at least a part of aromatic rings in the main chain. A thermosetting resin composition comprising 0.1 to 50 parts by weight of an aromatic polyester having solubility and / or heat melting property. 2. The thermosetting resin composition according to claim 1, wherein at least a part of the side chains of the aromatic polyester is an aliphatic side chain. 3. The aromatic polyester is characterized in that at least a part of its side chains is a fluorine-containing side chain.
3. The thermosetting resin composition according to item 1. 4. The thermosetting resin composition according to claim 1, wherein at least a part of the side chain of the aromatic polyester is a dialkylsiloxane-containing side chain. 5. The thermosetting resin composition according to claim 1, wherein the side chain of the aromatic polyester has a branched structure. 6. The main chain of the aromatic polyester has a wholly aromatic polyester structure.
The thermosetting resin composition according to any one of 1. 7. The thermosetting resin composition according to claim 1, wherein the aromatic polyester has a molten liquid crystallinity.