JPH11130854A - Polyester resin and its production and composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester resin capable of giving molded products such as flexible films of excellent toughness and elastic properties by including a specific aromatic residue having phenolic hydroxyl group and polyoxyalkylene glycol unit. SOLUTION: This polyester resin is obtained by including (A) an aromatic dibasic acid residue bearing phenolic hydroxyl group (e.g. 3-hydroxyorthophthalic acid) and (B) a polyoxyalkylene glycol unit with a number-average molecular weight of pref. 500-4,000 or so (e.g. polyoxyethylene glycol); wherein it is preferable that the amounts of the component A and the component b are 0.05-1.0 mol and 500-900 g per 1,000 g of the above resin on a solid basis.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a new and useful polyester resin, a method for producing the polyester resin, and a composition containing the polyester resin, respectively.

More specifically, the present invention relates to a polyester resin having a phenolic hydroxyl group and a polyoxyalkylene glycol unit in a polymer main chain, and a method for producing the same. Polyester resin, a resin solution composition comprising an organic solvent, moreover, such a polyester resin, a curable resin composition comprising a cross-linking agent component, further, such a polyester resin, a cross-linking agent component And an organic solvent.

[0003] The polyester resin according to the present invention reacts with various cross-linking agent components and has excellent properties such as flexibility, high mechanical strength, and low permanent set. It provides a sheet, film or various molded articles, and the resin solution composition of the present invention is also useful mainly as an adhesive or as a component of various coating agents.

Further, the polyester resin according to the present invention comprises:
As a curable resin composition in a form containing a cross-linking agent component, or, alternatively, as a curable resin solution composition in a form containing a cross-linking agent component and an organic solvent, mainly for the uses described above, It can be used advantageously.

The cured product obtained from the polyester resin according to the present invention has a form in which it has both a flexible polyoxyalkylene glycol unit and a constraint point due to crosslinking.
It has a multi-dimensional network structure and exhibits characteristics as a so-called elastomer.

[0006]

2. Description of the Related Art A polyester elastomer is an elastomer in which an aromatic polyester is used as a hard segment and a polyoxyalkylene glycol or an aliphatic polyester is used as a soft segment.
Widely used mainly for molding applications.

[0007] Such polyester-based elastomers generally have characteristics such as a higher usable temperature and excellent oil resistance, as compared with polyurethane-based elastomers. In addition, the polyester-based elastomer does not have the problem that the polyurethane-based elastomer fatefully generates toxic hydrogen cyanide upon burning.

[0008] However, the properties of the molded product of the polyester-based elastomer are limited because the constraint point of the molecular chain is the crystal phase of the aromatic polyester segment, which is a so-called hard segment. Often.

That is, such a hard segment is
A form containing a relatively large number of segments is superior in strength, but does not have a soft feel, while a form containing a relatively small number of such hard segments is flexible. However, it cannot be tough. Further, the conventional polyester-based elastomer also has a drawback that the elastic recovery is inferior to the polyurethane-based elastomer.

[0010] Up to now, studies have been made to overcome these problems, and many such techniques have been disclosed. That is, first, JP-A-48-48
No. 96693 discloses a hard segment,
A technique relating to a method for producing a polyester elastomer containing a polyester component obtained from 2,6-naphthalenedicarboxylic acid and tetraethylene glycol or hexamethylene glycol is disclosed, which is excellent in properties such as elastic recovery. Is obtained.

Japanese Patent Application Laid-Open No. 2-88632 discloses that
As a soft segment, for example, a technique relating to a polyester-based elastomer using a polyoxyalkylene glycol which is a copolymer of a 3-methyltetramethylene oxide unit and a tetramethylene oxide unit is disclosed. It is an elastomer with excellent properties such as low permanent set.

Next, Japanese Patent Application Laid-Open No. Hei 4-285563 discloses a technique relating to a polyester elastomer containing a polyester unit as a hard segment containing a component represented by an ethylene oxide adduct of bisphenol-A. It has been shown to be excellent in properties such as elastic recovery.

Furthermore, Japanese Patent Application Laid-Open No. 6-87951 discloses that a polyoxyalkylene glycol which is a copolymer composed of a neopentylene oxide unit and a tetramethylene oxide unit is used as a soft segment. A technique relating to a method for producing a polyester-based elastomer is disclosed, in which an article having excellent properties such as elastic recovery can be obtained.

[0014] The composition of the polyester-based elastomer as shown by these various techniques is devised, and depending on such devises, although various properties can be improved,
Breakthrough improvements can be difficult in nature.

Attempts to improve various properties by crosslinking polyester-based elastomers have also been made.
Various things have been done. That is, JP-A-54-131
No. 688 discloses, for example, using hexahydrophthalic anhydride, 2-butene-1,4-diol, etc.
There is disclosed an invention relating to a method for producing a crosslinked polyester by irradiating an electron beam to a polyester elastomer having an unsaturated group introduced therein.

As described above, in the case of cross-linking by irradiating an electron beam, of course, the shape of the obtained molded product is a film, an extremely thin sheet, or a fibrous material. Otherwise, the effect cannot be sufficiently obtained, and furthermore, there is a drawback that molding cannot be performed unless the place is provided with an electron beam irradiation device.

Even if the above-mentioned improvement is included, the polyester-based elastomer is generally hardly soluble in a solvent, and a film or a sheet is formed by an operation such as coating or casting. Often, they are inappropriate to obtain.

On the other hand, the polyester resin having a phenolic hydroxyl group is a powder coating material which forms a cured coating film in combination with a so-called crosslinking agent component such as aminoplasts or polyfunctional epoxy compounds. There is also known a technique of using as a solvent-type or water-based paint.

That is, Japanese Patent Publication No. 56-5275 discloses that a polyester resin having a form in which a phenolic hydroxyl group is introduced into a molecular terminal by using parahydroxybenzoic acid and the like, and a polyfunctional epoxy compound. And a technique relating to a resin composition for powder coatings comprising: a phenolic hydroxyl group using parahydroxybenzoic acid or hydroxyisophthalic acid in Japanese Patent Publication No. 53-42341. There is disclosed a technique relating to a resin composition for powder coating, which comprises a polyester resin in an introduced form and an aminoplast.

Further, Japanese Patent Publication No. 62-9263 discloses a technique relating to a coating composition for a paint comprising a polyester resin containing polyhydric phenolcarboxylic acid as an essential raw material component and aminoplast. However, JP-A-4-9625 discloses a technique relating to a liquid resin composition comprising a polymer having a phenolic hydroxyl group at a terminal and an aminoplast.

Further, Japanese Patent Application Publication No. Hei 8-503984 discloses a polyester resin having a side chain phenolic hydroxyl group introduced by using hydroxyisophthalic acid and the like, an aminoplast, a polyfunctional epoxy compound and the like. There is disclosed a technique relating to a resin composition for a solvent-type paint, a water-based paint, or a powder paint, comprising:

Incidentally, the polyester resin having a phenolic hydroxyl group has been proposed to be applied to various uses other than the above-mentioned use as a resin composition for coatings.
That is, for example, Japanese Patent Application Laid-Open No. 50-32297 discloses a technique in which a phenolic hydroxyl group-containing polyester resin is used as a linear polyester having excellent light stability for a fiber or a film.

In the technique described in Japanese Patent Application Laid-Open No. 50-32297, a compound containing a phenolic hydroxyl group is disclosed.
-Hydroxy-5-alkylisophthalic acid residues have been reported to function as light stabilizers incorporated into polyester molecules.

However, the phenolic hydroxyl group-containing polyester resin obtained by or used in the conventional techniques as described above is cured together with a crosslinking agent component to obtain a hard coating. Or for itself, or amorphous or crystalline, is a hard polyester resin, such as the above-mentioned polyester-based elastomer, such as exhibiting elastic properties Of course, it is not something that can form a flexible, tough film, sheet or other various molded articles.

[0025]

Thus, as far as the prior art is concerned, it is absolutely necessary, especially, to be flexible.
In addition, extremely high practicality, such as polyester resin having excellent properties such as high mechanical strength and low permanent set, is not limited to the above. A novel and useful production method of a high polyester resin, and also a curable resin composition containing such an extremely practical polyester resin as an essential base resin component, It is also very difficult to provide a resin solution composition and a curable resin solution composition as main components.

Therefore, the problem to be solved by the present invention is, on the one hand, that it is more flexible and tougher than conventional polyester-based elastomers as described above, and that it has excellent elastic properties. Providing a polyester resin capable of forming a film, sheet or other various molded articles, and providing a curable resin composition containing the polyester resin as a main component, and further, such as coating or casting It is an object of the present invention to provide a resin solution composition and a curable resin solution composition which can form a film or sheet which is flexible and tough by operation.

In the present invention, the term “film or sheet” refers to not only the crosslinked form of the polyester resin of the present invention formed into a film or sheet, but also the crosslinked form of the present invention. Polyester resin according to, various synthetic resin films, sheets, or non-woven fabric, woven fabric or knitted fabric as a base material, a laminated film or sheet, furthermore, It also includes a coating film, a coating material layer, and an adhesive layer, respectively, formed on the surface of various substrates.

[0028]

SUMMARY OF THE INVENTION The present inventors have, in order to solve the above-mentioned various drawbacks or defects in the conventional technology, have additionally provided a solution to the problems to be solved by the above-mentioned invention. Aiming, aiming, as a result of repeated investigations, a polyester resin in the form of having both an aromatic dibasic acid residue having a phenolic hydroxyl group and a polyoxyalkylene glycol unit was crosslinked by various crosslinking agents. Flexible, tough, film,
In finding that sheets or various other molded articles can be formed,

Further, the present inventors have found a method which can advantageously produce such a polyester resin without gelation, and furthermore, by appropriately setting the composition of the polyester resin, it is possible to use an organic solvent. A soluble polyester resin is obtained, and furthermore, by mixing an appropriate crosslinking agent component into an organic solvent solution of such a polyester resin, by an operation such as coating or casting,
The present invention has been completed by finding that a curable resin solution composition which is flexible and tough and can form a film or a sheet can be obtained.

[0030]

DETAILED DESCRIPTION OF THE INVENTION That is, according to the present invention, first, an aromatic dibasic acid residue having a phenolic hydroxyl group (a) [hereinafter referred to as a phenolic hydroxyl group-containing aromatic dibasic acid residue ( Also referred to as a). And a polyoxyalkylene glycol unit (b).

A form containing a phenolic hydroxyl group-containing aromatic dibasic acid residue (a), a polyoxyalkylene glycol unit (b), and an aliphatic glycol residue having 2 to 4 carbon atoms (c). The polyester resin of

The phenolic hydroxyl group-containing aromatic dibasic acid residue (a), the polyoxyalkylene glycol unit (b), the aliphatic glycol residue having 2 to 4 carbon atoms (c), A polyester resin characterized by containing a glycol residue (d) having 5 or more carbon atoms other than the alkylene glycol unit (b),

A phenolic hydroxyl group-containing aromatic dibasic acid residue (a), a polyoxyalkylene glycol unit (b), and a phenolic hydroxyl group-free dibasic acid residue (e) are contained. In addition to the characteristic polyester resin,

A phenolic hydroxyl group-containing aromatic dibasic acid residue (a), a polyoxyalkylene glycol unit (b), an aliphatic glycol residue having 2 to 4 carbon atoms (c), and a phenolic hydroxyl group And a polyester resin characterized by containing a dibasic acid residue (e) not having the same.

Next, a phenolic hydroxyl group-containing aromatic dibasic acid or its ester-forming derivative (a '), a polyoxyalkylene glycol (b'), and a compound having 2 carbon atoms.
An aliphatic glycol (c ′) having a carbon number of 5 or more and / or a phenolic hydroxyl group other than polyoxyalkylene glycol, if necessary. Not dibasic acid or its ester-forming derivative (e ')

In producing a polyester resin by using the polyester resin in such an amount as to satisfy the following conditional expressions (I) and (II), the ester compound is first reacted by reacting these various raw material components. Get, and then,
A polycondensation reaction for removing an excess glycol component from the dibasic acid component under heating and reduced pressure conditions, characterized by having a weight average molecular weight of 20,000 to 400,000, and A method for producing a polyester resin containing a phenolic hydroxyl group-containing aromatic dibasic acid residue (a) and a polyoxyalkylene glycol unit (b),

[0037]

Equation 5 1.2 ≦ (C ′ + D ′) / (A ′ + E ′) ≦ 5. O: Conditional expression (I)

[0038]

(6) (B '+ D') / (A '+ E') <1.0 ... Conditional expression (II)

[However, A ', B', C ', D' in the formula
And E ′ are (a ′), (b ′),
The ratio of the number of moles of (c ′), (d ′) and (e ′) is represented. ]

In addition, a phenolic hydroxyl group-containing aromatic dibasic acid or its ester-forming derivative (a '), a polyoxyalkylene glycol (b'), and a compound having 2 carbon atoms
An aliphatic glycol (c ′) having a carbon number of 5 or more and / or a phenolic hydroxyl group other than polyoxyalkylene glycol, if necessary. Not dibasic acid or its ester-forming derivative (e ')

(A ′) and (b ′) may be used, if necessary, in preparing a polyester resin by using them in an amount that satisfies the following conditional expressions (I) and (II). , (E ′) and (d ′) are also reacted to obtain an ester compound, and then a polyoxyalkylene glycol (b ′) is further added. Characterized by performing a polycondensation reaction to remove excess glycol components to
A phenolic hydroxyl group-containing aromatic dibasic acid residue and a polyoxyalkylene glycol unit are included, and it is intended to provide a method for producing a polyester resin,

[0042]

[Equation 7] 1.2 ≦ (C ′ + D ′) / (A ′ + E ′) ≦ 5. O: Conditional expression (I)

[0043]

[Equation 8] (B '+ D') / (A '+ E') <1.0 ... conditional expression (II)

[However, A ', B', C ', D' in the formula
And E ′ are (a ′), (b ′),
The ratio of the number of moles of (c ′), (d ′) and (e ′) is represented. ]

Next, another object of the present invention is to provide a resin solution composition comprising the above-mentioned respective polyester resins and an organic solvent,

It is also an object of the present invention to provide a curable resin composition comprising each polyester resin and a crosslinking agent component.

It is another object of the present invention to provide a curable resin solution composition comprising each of the polyester resins, a crosslinking agent component, and an organic solvent.

Hereinafter, the present invention will be described in detail.

First, the polyester resin according to the present invention comprises:
Basically, it has a weight average molecular weight of 20,000 to 400,000, and further has a phenolic hydroxyl group-containing aromatic dibasic acid residue (a) and a polyoxyalkylene glycol unit ( b) as an essential constituent unit.

The polyester resin is ultimately used as a film, a sheet or other various molded products, and further as an adhesive or the like. Means that the polyester resin according to the present invention is in the range of 20,000 to 400,000, preferably in the range of 30,000 to 300,000, and more preferably in the range of 50,000 to 250,000.
It should have a weight average molecular weight in the range of 00.

If the molecular weight is not sufficiently large, even if the polyester resin is crosslinked, a flexible and tough film cannot be formed.
If the molecular weight is too large, the operation for forming a film or the like may be difficult to perform.

Examples of particularly typical phenolic hydroxyl group-containing aromatic dibasic acid residues (a) contained in the polyester resin include 3-hydroxy orthophthalic acid and 4-hydroxy orthophthalic acid. Orthophthalic acid, 3,4-dihydroxyorthophthalic acid, 3,5-dihydroxyorthophthalic acid, 2-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, 4,5-dihydroxyisophthalic acid, 2- Such as hydroxyterephthalic acid, 2,3-dihydroxyterephthalic acid or 2,5-dihydroxyterephthalic acid,
Various dibasic acid residues derived from various phenolic hydroxyl group-containing aromatic dibasic acids. These may be used alone or in combination of two or more.

The phenolic hydroxyl group-containing aromatic dibasic acid residue (a) is used in an amount of 0.05 to 1.0 mol per 1,000 g (g) of the solid content of the polyester resin. More preferably, it is contained in the range of 0.1 to 0.6 mol.

When the content of the phenolic hydroxyl group-containing aromatic dibasic acid residue is too small than 0.05 mol, a film, sheet or other various kinds of products obtained by crosslinking the polyester resin can be obtained. Molded articles may not be tough due to low crosslink density.

Conversely, if the content of the phenolic hydroxyl group-containing aromatic dibasic acid residue exceeds 1.0 mol and is too large, the film or the like obtained by crosslinking the polyester resin will have a cross-linking point. Because there are too many,
It may not be flexible, or the storage stability of the curable resin composition in which the crosslinking agent component is mixed may be inferior, or severely, it may gel during the production of the polyester resin. In some cases, this is undesirable.

The polyester resin according to the present invention has a phenolic hydroxyl group-containing aromatic dibasic acid residue content of 0.1 g per 1,000 g of solid content of the polyester resin.
When the amount is about 1 to 0.6 mol, a film or the like obtained by crosslinking the resin becomes very flexible and tough, which is particularly desirable.

Another unit, polyoxyalkylene glycol unit (b), contained in the polyester resin
If we only exemplify especially typical ones,
Polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol or polyoxy-2-alkyltetramethylene glycol;

Further, it is derived from various polyoxyalkylene glycols, such as polyoxyalkylene glycol in a form in which two or three or more kinds of the monomers (monomers) constituting them are copolymerized. And polyoxyalkylene glycol units. These may be used alone or in combination of two or more.

The polyoxyalkylene glycol unit (b) contained in the polyester resin according to the present invention
Is in the range of 50 to 90% by weight based on the solid content weight of the polyester resin,
A range from 0 to 90% by weight is suitable.

When the content of the polyoxyalkylene glycol unit is too small than 50% by weight, a film or the like obtained by crosslinking the polyester resin tends to be less flexible, On the other hand, the content of the polyoxyalkylene glycol unit is
If the amount exceeds 90% by weight and becomes too large, the resulting polyester resin tends to be unable to form a tough film or the like, and in the extreme case, it contains a phenolic hydroxyl group-containing aromatic dibase. In any case, it is difficult to produce a polyester resin containing a sufficient amount of an acid residue.

When the content of the polyoxyalkylene glycol unit in the polyester resin is about 70 to 90% by weight, the film or the like obtained by crosslinking the resin becomes very flexible. It is particularly preferable because it becomes tough.

The polyoxyalkylene glycol unit (b) contained in the polyester resin according to the present invention
Should have a number average molecular weight of about 500 to 4,000, and more preferably about 500 to 3,000. When the number average molecular weight of such a polyoxyalkylene glycol unit is much smaller than 500, a film or the like obtained by crosslinking the polyester resin,
In some cases, it is not flexible and yet tough.

On the other hand, when the number average molecular weight of the polyoxyalkylene glycol unit exceeds 4,000 and becomes too large, it may be difficult to produce a polyester resin having a sufficiently large molecular weight. Yes,
May not be preferred.

The polyester resin has a polyoxyalkylene glycol unit having a number average molecular weight of 500 to 3,
When it is about 000, a film or the like obtained by cross-linking it is very flexible and tough, which is particularly preferable.

The preferred polyoxyalkylene glycol unit contained in the polyester resin is a polyoxytetramethylene glycol unit or polyoxy-2-methylene glycol unit among the various polyoxyalkylene glycol units described above. It is a polyoxyalkylene glycol unit in the form of a methyltetramethylene glycol unit or in a form in which a monomer constituting the unit is copolymerized.

These polyoxyalkylene glycol units are particularly excellent in heat resistance and the like as compared with the other polyoxyalkylene glycol units, and the polyester resin having such preferable polyoxyalkylene glycol units was used. In such a case, a film or the like obtained by crosslinking the polyester resin is often particularly excellent in both heat resistance and durability, and is particularly preferable. These preferred units may also be included in a form in which two or more kinds are used in combination.

It has a weight-average molecular weight of 50,000 to 250,000, and the content of phenolic hydroxyl group-containing aromatic dibasic acid residue is 0.1 to 1,000 g of solids.
About 1 to 0.5 mol and a number average molecular weight of 5
A polyester resin containing 70 to 90% by weight of about 00 to 3,000 polyoxyalkylene glycol units is particularly desirable as the polyester resin according to the present invention.

The polyester resin has only the above-mentioned phenolic hydroxyl group-containing aromatic dibasic acid residue as the dibasic acid residue and only the polyoxyalkylene glycol unit as the glycol residue, and The polyester resin may be such that each content is within the above-mentioned range.

One of the preferred polyester resins according to the present invention is a phenolic hydroxyl group-containing aromatic dibasic acid residue (a) having a weight average molecular weight of 20,000 to 400,000, and a polyoxyalkylene. Glycol units (b) are contained in a ratio within the above-mentioned range, and further include an aliphatic glycol residue (c) having 2 to 4 carbon atoms.

In the polyester resin containing (a), (b) and (c), only the aliphatic glycol residue (c) having 2 to 4 carbon atoms which is particularly representative will be exemplified. If it stops, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-
Various, such as butylene glycol, 1,4-butylene glycol or diethylene glycol, having 2 to 2 carbon atoms
And glycol residues derived from the aliphatic glycols No. 4. These may be used alone or in combination of two or more.

In order for the polyester resin containing (a), (b) and (c) to have a sufficiently large molecular weight, and in particular to form a soft and tough film,
The total number of moles of (b) and (c) is substantially equal to the number of moles of (a), and the ratio of the number of moles of (c) to the total number of moles of glycol residues is 0.1 to 0.9. In the range of, further, in the range of 0.3 to 0.8,
Those containing (c) are preferred.

One of the preferred polyester resins according to the present invention is a phenolic hydroxyl group-containing aromatic dibasic acid residue (a) having a weight average molecular weight of 20,000 to 400,000, and a polyoxyalkylene. The glycol unit (b) is contained at a ratio within the above-mentioned range, and further has an aliphatic glycol residue (c) having 2 to 4 carbon atoms and a carbon number other than the polyoxyalkylene glycol unit. One containing 5 or more glycol residues (d) is also included.

In the polyester resin containing (a), (b), (c) and (d), a glycol residue (d) having 5 or more carbon atoms other than polyoxyalkylene glycol is particularly typical. If only examples are given, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, Diols derived from various diols having 5 or more carbon atoms, such as 3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2-butyl-2-ethyl-1,3-propanediol or dimer diol. Residues. These may be used alone or in combination of two or more.

Further, in the polyester resin according to the present invention, the glycol residue derived from a polyoxyalkylene glycol having a trimer or less such as dipropylene glycol, triethylene glycol or tripropylene glycol is also used as the ethylene residue of bisphenol-A. Among the oxide or propylene oxide adducts, glycol residues derived from those having an average addition mole number of ethylene oxide or propylene oxide of 6 or less are also carbon atoms other than polyoxyalkylene glycol units which can be introduced into the polyester resin. It can be treated as a glycol residue (d) having a number of 5 or more.

Such a polyester resin is capable of forming a flexible and tough film by being crosslinked, and has excellent solubility in an organic solvent. It is a polyester resin which can form a film or a sheet by operation, and is particularly suitable.

The polyester resin containing (a), (b), (c) and (d) has a sufficiently large molecular weight,
In particular, in order to form a flexible and tough film or the like, the total number of moles of (b), (c) and (d) is substantially equal to the number of moles of (a), The ratio of the total number of moles of (c) and (d) to the total number of moles of the residue is in the range of 0.1 to 0.9, and further,
It is desirable to contain (c) and (d) at a ratio within the range of 0.3 to 0.8.

Further, in the polyester resin containing (a), (b), (c) and (d), the ratio of the number of moles of (c) to the number of moles of (d) is as follows:
When the ratio is in the range of 1: 9 to 9: 1, a film or the like obtained by crosslinking the polyester resin becomes very flexible, or the obtained polyester resin has a solubility in an organic solvent. Is particularly favorable, and is more preferable.

As one of the preferred polyester resins of the present invention, a phenolic hydroxyl group-containing aromatic dibasic acid residue (a) having a weight average molecular weight of 20,000 to 400,000 and polyoxyalkylene glycol And a polyester resin containing the unit (b) at a ratio within the above-mentioned range and also containing a dibasic acid residue (e) having no phenolic hydroxyl group. .

In the polyester resin containing (a), (b) and (e), only the typical dibasic acid residue (e) having no phenolic hydroxyl group is exemplified. If stopped, o-phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
2,7-naphthalenedicarboxylic acid or 4,4'-biphenyldicarboxylic acid, or various aromatic dicarboxylic acids represented by sodium sulfoisophthalic acid or lithium sulfoisophthalic acid;

Various aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, itaconic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid and dimer acid. Acid; 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or 1,4
-Various dibasic acid residues derived from various dicarboxylic acids such as various alicyclic dicarboxylic acids represented by cyclohexanedicarboxylic acid and the like. These may be used alone or in combination of two or more.
Of course.

In order for the polyester resin containing (a), (b) and (e) to have a sufficiently large molecular weight and to form a flexible and tough film, The total number of moles of a) and (e) is substantially equal to the number of moles of (b), and the ratio of the number of moles of (e) to the total number of moles of dibasic acid residues is 0.2 to 0. 0.95, and further within a range of 0.4 to 0.9,
It is desirable to contain (e).

One of the preferred polyester resins according to the present invention is a phenolic hydroxyl group-containing aromatic dibasic acid residue (a) having a weight average molecular weight of 20,000 to 400,000, and a polyoxyalkylene. And a glycol residue (c) having 2 to 4 carbon atoms and a dibasic acid residue having no phenolic hydroxyl group. And a polyester resin containing the group (e).

The polyester resin containing (a), (b), (c) and (e) has a sufficiently large molecular weight,
In order to form a flexible and tough film, the total number of moles of (a) and (e) must be (b)
And approximately equal to the total number of moles of (c), and the ratio of the number of moles of (c) to the total number of moles of glycol residues is 0.1 to
(C) is contained at a ratio within the range of 0.9, further within the range of 0.3 to 0.8, and the number of moles of (e) relative to the total number of moles of dibasic acid residues The ratio is between 0.2 and 0.
It is desirable that (e) be contained at a ratio within the range of 95, and more preferably within the range of 0.4 to 0.9.

The dibasic acid residue (e) having no phenolic hydroxyl group to be introduced into the polyester resin containing (a), (b), (c) and (e) is as described above. Although various compounds as described above may be mentioned, among them, if only particularly desirable ones are exemplified, a terephthalic acid residue or a 2,6-naphthalenedicarboxylic acid residue may be used. May be introduced alone, or two or more of them may be introduced in combination.

As the dibasic acid residue (e) having no phenolic hydroxyl group, in addition to terephthalic acid residue and / or 2,6-naphthalenedicarboxylic acid residue, other aromatic dicarboxylic acid residues It is an acid residue,
An aliphatic dicarboxylic acid residue or an alicyclic dicarboxylic acid residue may be used in combination.

In this case, the introduction amount of the terephthalic acid residue and / or the 2,6-naphthalenedicarboxylic acid residue is set to 50 to 80 mol% of (e) to the organic solvent. Is particularly desirable also in that the balance between the solubility and the mechanical strength is good.

As described above, (a), (b) and (c)
The polyester resin containing (e) and (e) forms a flexible and tough film or the like by being crosslinked, and has excellent solubility in an organic solvent. Alternatively, it is particularly preferable because it is a polyester resin which can form a film or a sheet by an operation such as casting.

The polyester resin according to the present invention may be obtained by any known and commonly used production method as long as it has the composition described above. However, the phenolic hydroxyl group contained in the phenolic hydroxyl group-containing aromatic dibasic acid component has low reactivity under ordinary polyester resin synthesis conditions, but does not react at all. If an attempt is made to obtain a resin having a high weight average molecular weight of 20,000 to 400,000, such as a resin, there is a risk of gelation during the reaction.

In this respect, according to the manufacturing method of the present invention,
The polyester resin can be advantageously produced without gelling.

That is, (1) a phenolic hydroxyl group-containing aromatic dibasic acid or its ester-forming derivative (a ′) and a polyoxyalkylene glycol (b ′)
And an aliphatic glycol (c ′) having 2 to 4 carbon atoms as an essential raw material. If necessary, glycols (d ′) having 5 or more carbon atoms other than polyoxyalkylene glycol and / or Or a dibasic acid having no phenolic hydroxyl group or an ester-forming derivative thereof (e ')
Are also used to react these in advance to obtain an ester compound, and subsequently, under heating and reduced pressure conditions,
It is a method based on a polycondensation reaction in which excess glycol is distilled off with respect to the dibasic acid component,

Or (2) a phenolic hydroxyl group-containing aromatic dibasic acid or its ester-forming derivative (a ′) and an aliphatic glycol having 2 to 4 carbon atoms (c ′) as essential raw materials And, if necessary,
Other than the polyoxyalkylene glycol, a glycol having 5 or more carbon atoms (d ') and / or a dibasic acid having no phenolic hydroxyl group or an ester-forming derivative thereof (e') is also used, After reacting them to obtain an ester compound, a polyoxyalkylene glycol (b ') is further added, and then, under heating and reduced pressure conditions, excess glycol is distilled off with respect to the dibasic acid component. In producing by any of the methods such as a method by a polycondensation reaction in the form of

The polyester resin according to the present invention can be produced without gelation by using each raw material in such an amount as to satisfy the following conditional expressions (I) and (II). Can be done.

[0093]

[Equation 9] 1.2 ≦ (C ′ + D ′) / (A ′ + E ′) ≦ 5. O: Conditional expression (I)

[0094]

(Equation 10) (B ′ + D ′) / (A ′ + E ′) <1.0... Condition (II)

[However, A ', B', C ', D' in the formula
And E ′ are (a ′), (b ′),
The ratio of the number of moles of (c ′), (d ′) and (e ′) is represented. ]

In the production method according to the present invention as described above, the polycondensation reaction in the form of distilling off excess glycol with respect to the dibasic acid component is carried out at 180 to 240 ° C.
And more preferably within a range of 180 to 220 ° C.

The method for producing a polyester resin according to the present invention can be broadly divided into two steps. First, as the first step, a dibasic acid component, a glycol component in excess of the dibasic acid component, and a low molecular weight ester compound derived by reacting a polyoxyalkylene glycol with the polyoxyalkylene glycol. Is carried out. In the above method (2), the polyoxyalkylene glycol is charged into the reaction vessel after the completion of the first-stage reaction.

In the subsequent second step, the ester compound is used in the method (1), and the ester compound is used in the method (2). A so-called polycondensation reaction is carried out by extracting a glycol component excessively used in the first-stage reaction from the mixture with the oxyalkylene glycol under a transesterification temperature under reduced pressure.

In the method for producing a polyester resin according to the present invention, the first-stage reaction can be carried out by various methods known in the art. For example, when the dibasic acid component to be used is a dibasic acid having a carboxyl group as a functional group, together with the glycol component, in a reaction vessel having a suitable fractionating device and a stirring device, 180
At a temperature of about 240 ° C., water produced by the esterification reaction can be removed outside the reaction system.

In the case where the dibasic acid component used is a dialkyl ester derived from a dibasic acid and a lower alcohol, a transesterification reaction is carried out by the same operation as described above. The reaction can be carried out by withdrawing the resulting lower alcohol out of the reaction system.

When the dibasic acid component used is, for example, 3-
Hydroxy orthophthalic anhydride, even in the case of an acid anhydride such as succinic anhydride or phthalic anhydride, by the same operation as described above, the acid anhydride and the addition reaction of the glycol component, Furthermore, the first-stage reaction can be performed by an esterification reaction between the carboxyl group generated thereby and the glycol component.

As described above, it is needless to say that the polyoxyalkylene glycol may be used together with the glycol component in the first-stage reaction, or may be added after the completion of the first-stage reaction.

However, care must be taken especially when different types of dibasic acid components are used in combination. That is, the dibasic acid and the acid anhydride may be simultaneously reacted with the glycol component,
In the case where a dialkyl ester of a dibasic acid and a dibasic acid and / or an acid anhydride are used in combination, after completing the reaction of either one with the glycol component, By charging the other dibasic acid component and reacting with the glycol component,
In many cases, it is better to carry out the first-stage reaction in a divided form.

If these are to be reacted simultaneously with the glycol component, the reaction time may be very long.

In the method for producing a polyester resin according to the present invention, the reaction temperature in the second stage reaction is 180 °.
Within the range of ~ 240 ° C, further 180 ~ 220 ° C
Is appropriate.

When the reaction temperature is much lower than 180 ° C., it is difficult to extract the glycol component present in excess from the dibasic acid component from the inside of the reaction vessel. The required time may be very long, or the molecular weight of the obtained polyester resin may be too small to be practically used, or more severely, the reaction may hardly proceed. On the other hand, if the reaction temperature exceeds 240 ° C. and becomes too high, the risk of gelation increases.

The term "reaction temperature" as used herein refers to the maximum value of the average temperature of the polyester resin in the liquid or molten state during the reaction. In addition, it is desirable that the reaction temperature be gradually increased from a relatively low temperature of, for example, about 120 to 160 ° C. to a target temperature over time.

In the method for producing a polyester resin according to the present invention, in order to obtain a polyester resin having a sufficiently large molecular weight, an aliphatic glycol (c ′) having 2 to 4 carbon atoms must be used. Must.

As shown in the conditional expressions (I) and (II) as described above, the amount of each raw material component used is an aliphatic glycol (c ') having 2 to 4 carbon atoms, The total of the glycol (d ') having 5 or more carbon atoms other than the alkylene glycol is about 1.2 to 5 times the number of moles of the dibasic acid component, and (b') and (d ') )
Is required to be set so that the total number of moles does not exceed the total number of moles of the dibasic acid components (a ′) and (e ′).

If the amount of the glycol component used is much smaller than 1.2 times the dibasic acid component, the reaction time or the reaction temperature must be increased in the first-stage reaction. In some cases, the risk of gelation increases, and the amount of unreacted dibasic acid components increases. As a result, a polyester resin having a sufficiently large molecular weight may not be obtained.

When the total number of moles of the polyoxyalkylene glycol and the other glycol having 5 or more carbon atoms is equal to or more than the number of moles of the dibasic acid component, the amount of the glycol component in the second stage reaction is reduced. Extraction may be incomplete and a polyester resin having a sufficiently large molecular weight may not be obtained.

In the method for producing a polyester resin according to the present invention, the method for producing a polyester resin other than the polyoxyalkylene glycol includes
Glycols having 5 or more carbon atoms are not necessarily required to be used, but may be used as needed in order to match various properties of the obtained polyester resin to the intended use.

In the production method according to the present invention, the reaction in the second stage is performed under reduced pressure. The pressure is preferably 5 mm or less, more preferably 1 mm of mercury. Should be:

If the pressure in the reaction vessel is not sufficiently low, the extraction of the glycol component is difficult to proceed, and the reaction time may be prolonged, or a polyester resin having a sufficiently large molecular weight may not be obtained. It is desirable that the pressure in the reaction vessel be adjusted from a relatively high pressure, such as about the atmospheric pressure, to a target pressure continuously or gradually and slowly over time.

In the method for producing a polyester resin according to the present invention, the reaction apparatus used in the second-stage reaction is not particularly limited, but the temperature and pressure conditions as described above are achieved. In addition to what is obtained, it is desirable that the fluid has excellent stirring performance for a high-viscosity fluid.

[0116] If only a typical example of such a reactor is exemplified, a vertical reactor having a ribbon-type stirring blade or a twisted-grating-type stirring blade, for example, "VIVOLAC" [Sumitomo, Ltd.] Product of Heavy Machinery Co., Ltd .; "Vaivolak" is a registered trademark of the company. ], And a horizontal twin-screw reactor.

The phenolic hydroxyl group-containing aromatic dibasic acid or its ester-forming derivative (a ′) to be used in carrying out the production method is not particularly limited to phenolic hydroxyl group. Various dibasic acids, dialkyl esters thereof and the like, and in some cases, acid anhydrides thereof as described above for deriving the hydroxyl group-containing aromatic dibasic acid residue (a) Is mentioned. These can be used alone or 2
It goes without saying that more than one kind may be used in combination.

If only typical examples of the polyoxyalkylene glycol (b ') used in the production method according to the present invention are given as examples, the polyoxyalkylene glycol unit (b) is derived as described above. And various polyoxyalkylene glycols, which may be used alone or in combination of two or more.

[0119] The compound having 2 to 4 carbon atoms used in the production method is used.
Various glycols, such as those listed above as those for deriving a glycol residue (c) having 2 to 4 carbon atoms, may be mentioned only as typical examples of the glycol (c '). These may be used alone or in combination of two or more.

[0120] If only glycols having 5 or more carbon atoms (d ') other than polyoxyalkylene glycols used in the production method are specifically exemplified, only glycols other than polyoxyalkylene glycols may be used.
Various glycols and the like as described above for deriving the glycol residue (d) having 5 or more carbon atoms can be used alone or in combination of two or more. is there.

The phenolic hydroxyl group is not particularly limited to the dibasic acid having no phenolic hydroxyl group or its ester-forming derivative (e ′) used in the production method. Various dibasic acids, dialkyl esters thereof, and the like as described above for deriving the dibasic acid residue (e) having no acid anhydride. Objects may be used, and these may be used alone or in combination of two or more.

In the production method, various known and commonly used catalysts each suitable for the first-stage reaction and the second-stage reaction can be used. Antimony trioxide, if only a typical example among them is exemplified,
Barium oxide, zinc acetate, manganese acetate, cobalt acetate, zinc succinate, zinc borate, cadmium formate, lead monoxide, calcium silicate, dibutyltin oxide, butylhydroxytin oxide, tetraisopropyl titanate, tetrabutyl titanate, magnesium methoxide or Sodium methoxide and the like, which may be used alone or in combination of two or more.

In the production method, various known antioxidants can be used in order to suppress the thermal oxidative decomposition of the polyoxyalkylene glycol during the reaction. Hindered phenol compounds and the like are only examples of particularly preferable antioxidants.

Next, the resin solution composition according to the present invention comprises:
Basically, it is obtained by dissolving the above-described polyester resin according to the present invention in an organic solvent.

The organic solvent used in the preparation of the resin solution composition is not particularly limited, but if only typical ones among them are exemplified, methanol, ethanol, normal ( n-) propanol, iso- (iso-) propanol, n-butanol,
Various lower alcohols such as isobutanol, secondary (sec-) butanol or tertiary (tert- or t-) butanol;

Various ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether, ethylene glycol monoethyl ether, ethylene glycol mononormal butyl ether, ethylene glycol dinormal butyl ether, propylene glycol monomethyl ether or propylene glycol Various ether compounds such as mono-n-butyl ether; various cyclic ether compounds such as tetrahydrofuran or dioxane;

Ethyl acetate, n-butyl acetate, iso acetate
-Various ester compounds such as butyl, ethylene glycol monoacetate or ethylene glycol diacetate; various aliphatic hydrocarbon compounds such as hexane, heptane or octane; various aromatic compounds such as toluene or xylene. Group hydrocarbon compounds; or N, N-dimethylformamide, N, N-
Dimethylacetamide, dimethylsulfoxide or N
Various aprotic polar compounds such as -methyl-2-pyrrolidone and the like.

These may be used alone or in combination of two or more. Among these organic solvents, particularly preferred are ketone compounds, aromatic hydrocarbon compounds, aprotic polar compounds, and the like, and mixtures mainly containing them.

As the resin solution composition according to the present invention, 5
It is particularly desirable that the composition contains the polyester resin according to the present invention as described above in the range of from 70 to 70% by weight, and more preferably in the range of from 10 to 50% by weight. The content of the polyester resin may be appropriately adjusted according to the purpose of use. However, when the content is less than 5% by weight, a large amount of an organic solvent must be used when preparing a film or the like. In the case where it must be evaporated and there are many disadvantages, while if it is too much more than 70% by weight, the viscosity of the resin solution becomes
The operation may be extremely high, and operations such as coating and casting are difficult to perform, which is not preferable in some cases.

The resin solution composition according to the present invention includes, in addition to the polyester resin according to the present invention and an organic solvent, various colorants such as pigments or dyes, fillers, and the like. Further, it may be in a form containing other various additives.

The resin solution composition according to the present invention as described above is coated or cast, then dried after addition of a crosslinking agent component. It is capable of forming a film or sheet which is flexible and tough.

The curable resin composition is basically in the form of containing the polyester resin according to the present invention and the crosslinking agent component as described above.

As the cross-linking agent component used in the preparation of the curable resin composition, only particularly representative ones are exemplified, and alkoxide type, acylate type, chelate type or polyvalent metal may be used. Metal-containing compounds composed of these mixed types; aminoplasts; polyfunctional epoxy compounds; polyfunctional isocyanate compounds;

A functional group which reacts with a phenolic hydroxyl group, such as a so-called polyfunctional block isocyanate compound, an aziridine compound, or an epoxy group-containing silane coupling agent, in which isocyanate group is generated by stimulation such as heat. And various kinds of compounds, and further, resins and the like, and these may be used alone or in combination of two or more.

One preferred crosslinking agent component used in the preparation of the curable resin composition according to the present invention is a metal-containing compound of an alkoxide type, an acylate type or a chelate type of a polyvalent metal or a mixed type thereof. Can be shown. Among these polyvalent metals, particularly preferable ones include aluminum, titanium, zirconium and zinc.

As the above-mentioned aluminum compounds, only typical ones are exemplified. Aluminum triethylate, aluminum tri-iso-isopropylate, aluminum mono-sec-butylate diisopropylate, aluminum tri-sec- Butyrate, aluminum monoethylacetoacetate di-is
Various compounds such as o-propylate, aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate) or aluminum tris (acetylacetonate).

As typical examples of the above titanium compounds, only typical ones are exemplified. Titanium tetraethylate, titanium tetra-n-propylate,
Titanium tetra-iso-propylate, titanium tetra-n-butylate, titanium tetra-iso-
Butyrate, titanium tetra-sec-butyrate,
Titanium tetra-tert-butylate, titanium tetra-2-ethylhexylate, titanium tetrastearylate, titanium di-iso-propylate bis (acetylacetonate), titanium di-n-butylate bis (triethanolamine), titanium dihydroxy Dobis (lactide), titanium tetraoctylene glycolate or titanium di-iso
Various compounds such as propylate bis (ethyl acetoacetate);

As typical examples of the above-mentioned zirconium compounds, zirconium tetraethylate, zirconium tetra-iso-propylate, zirconium tetra-sec-butylate,
Such as zirconium tetra (ethylacetoacetate) or zirconium tetra (acetylacetonate),
Various compounds and the like. Of course, the above-mentioned various metal-containing compounds may be used alone or in combination of two or more.

Of these metal-containing compounds, particularly preferred are aluminum tris (ethyl acetoacetate), aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (acetylacetonate), and zirconium tetra (ethyl acetoacetate). ) Or zirconium tetra (acetylacetonate) and other chelate-type metal-containing compounds of various polyvalent metals with β-diketone or ketoester.

One preferred crosslinking agent component used for preparing the curable resin composition according to the present invention is a group consisting of aminoplasts, polyfunctional epoxy compounds, polyfunctional isocyanate compounds and polyfunctional block isocyanate compounds. And at least one compound selected from the group consisting of:

The above-mentioned aminoplasts include, for example, all of the amino groups of compounds having various amino groups such as urea, melamine, acetoguanamine, benzoguanamine, cyclohexanecarboguanamine, steloguanamine or spiroguanamine or glycouril. Alternatively, a part thereof is alkylated with various aldehyde compounds such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde or butyraldehyde or glyoxal, and further, all or a part of the alkylol group is obtained. It is a compound in the form of being obtained by etherification with a lower alcohol having about 1 to 4 carbon atoms, and furthermore, a condensate thereof, a dimer or a multimer thereof or the like. And mixtures of the form include those referred finger.

For preparation of the curable resin composition according to the present invention, various known and commonly used aminoplasts are used.
Can be used. Among them, particularly typical ones are exemplified, and tetramethoxymethylolurea, hexamethoxymethylolmelamine,
For example, tetramethoxymethylol benzoguanamine or tetraisobutoxymethylol benzoguanamine.

Further, if only typical examples of the above-mentioned polyfunctional epoxy compounds are given as examples, various bisphenols such as bisphenol-A or bisphenol-F and epichlorohydrin can be used. Various epoxy resins of the so-called bisphenol-A type or bisphenol-F type; or various polyglycidyl ethers of various aliphatic polyhydric alcohols such as glycerin triglycidyl ether or sorbitol tetraglycidyl ether.

If only typical examples of the above-mentioned polyfunctional isocyanate compounds are given as examples, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate,
Various diisocyanates such as xylylene diisocyanate, tolylene diisocyanate or diphenylmethane diisocyanate; or polyisocyanates having an isocyanurate ring which is a cyclic trimer thereof; further, these diisocyanates and trimethylolpropane And adducts with various polyhydric alcohols.

In the above-mentioned polyfunctional blocked isocyanate compounds, the isocyanate groups of the above-mentioned various polyfunctional isocyanate compounds are represented by various oximes represented by methyl ethyl ketoxime; phenol or cresol; Various phenols; various tertiary alcohols represented by tert-butanol and the like;

Various lacram compounds such as ε-caprolactam; various active methylene compounds such as acetylacetone or ethyl acetoacetate; Can be used.

Further, a compound having a plurality of uretdione structures formed by cyclization and dimerization of two isocyanate groups can also be used as one of such polyfunctional block isocyanate compounds.

In preparing the curable resin composition according to the present invention from such various cross-linking agents and the polyester resin according to the present invention, the amount of the cross-linking agent used is determined based on the final film or the like. Depending on the properties to be obtained, it may be appropriately set, but in the case where the crosslinking agent component is a metal-containing compound, a polyfunctional epoxy compound, a polyfunctional isocyanate compound or a polyfunctional block isocyanate compound, With respect to 1 mol of the phenolic hydroxyl group of the polyester resin, the number of moles of the functional group of the crosslinking agent component is generally about 0.2 to 20 times, preferably about 0.5 to 10 times. It is appropriate to set.

When aminoplasts are used as the crosslinking agent, the ratio of the crosslinking agent is 1 to 60 parts by weight with respect to 100 parts by weight of the polyester resin.
Preferably, the crosslinking agent is blended at a ratio of 5 to 40 parts by weight.

In the curable resin composition according to the present invention,
By changing the amount of the crosslinking agent component used,
One of the great features of the curable resin composition according to the present invention is that various properties such as a film finally obtained can be adjusted widely.

The curable resin composition according to the present invention is basically produced by mixing the polyester resin according to the present invention and a crosslinking agent component, respectively.
The mixing method is not particularly limited. However, attention must be paid to the mixing conditions, especially the temperature and time.

That is, the conditions under which the used crosslinking agent component reacts with the polyester resin to cause gelation must be avoided by all means. For this purpose, for example, various known kneaders such as a kneader are used to mix at a low temperature, or various known kneaders such as an extruder are used for short mixing. Various methods such as mixing with time can be employed.

The curable resin composition according to the present invention comprises:
In addition to the polyester resin according to the present invention and the crosslinking agent component, various colorants such as pigments or dyes,
It may be a form containing other various additives such as a filler, a plasticizer, or a catalyst for accelerating a crosslinking reaction.

As described above, the curable resin composition according to the present invention is formed into a film, a sheet or other various molded articles to give a flexible and tough article. Included in the curable resin composition according to the present invention,
The reaction between the polyester resin according to the present invention and the cross-linking agent component often proceeds sufficiently only with the heat given during molding, and in some cases, after molding, heat treatment is performed. May be advanced.

The curable resin solution composition according to the present invention basically comprises the polyester resin according to the present invention, a crosslinking agent component, and an organic solvent.

The crosslinker component used in the preparation of the curable resin solution composition according to the present invention is not particularly limited to representative ones. If the alkoxide type, the acylate type or the polyvalent metal is used. Including chelate-type or mixed-type metal-containing compounds and the like, and further,
Amino plasts, polyfunctional epoxy compounds, polyfunctional isocyanate compounds, polyfunctional block isocyanate compounds, aziridine compounds or epoxy group-containing silane coupling agents and the like, as described above, the curable resin composition according to the present invention. The compounds used for the preparation include the same compounds as those already exemplified, and these may be used alone or in combination of two or more.

One preferred crosslinking agent component used for preparing the curable resin solution composition according to the present invention comprises a polyvalent metal of an alkoxide type, an acylate type, a chelate type or a mixed type thereof. Metal-containing compounds may be mentioned, and among them, particularly preferred are
A polyvalent metal, a chelate-type metal-containing compound such as β-diketone or ketoester, and aluminum, titanium, zirconium, and aluminum. At least one metal selected from the group consisting of zinc; various metal-containing compounds exemplified as those used for preparing the curable resin composition according to the present invention. Is similar to

Other preferable crosslinking agents used for preparing the curable resin solution composition according to the present invention include aminoplasts, polyfunctional epoxy compounds, polyfunctional polyisocyanates and polyfunctional polyisocyanates. Blocked isocyanates are exemplified, and if only particularly typical examples of such cross-linking agents are exemplified, they are exemplified as those used in preparing the curable resin composition as described above. And various substances.

The organic solvent used for preparing the curable resin solution composition according to the present invention is not particularly limited, and may be lower alcohols, ketone compounds, ether compounds, cyclic ether compounds, ester compounds. Compounds, such as aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds or aprotic polar compounds, such as those listed above as organic solvents used in the preparation of the resin solution composition according to the present invention, Various compounds can be mentioned. These may be used alone or in combination of two or more.

Of these compounds, particularly desirable compounds include ketone compounds, aromatic hydrocarbon compounds, aprotic polar compounds, and mixtures mainly composed of these.

In preparing the curable resin solution composition according to the present invention, the amount of the cross-linking agent component to be used is appropriately set according to various characteristics required for a finally obtained film or the like. In the case where the crosslinking agent component is a metal-containing compound, a polyfunctional epoxy compound, a polyfunctional isocyanate compound or a polyfunctional block isocyanate compound, one mole of the phenolic hydroxyl group of the polyester resin is crosslinked. The number of moles of the functional groups contained in the agent component is generally about 0.2 to 20 times, preferably 0.1 to 20 times.
It is preferable to set so as to be about 5 to 10 times.

When aminoplasts are used as the cross-linking agent, the cross-linking agent is used in an amount of 1 to 60 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of the polyester resin. It is preferable to add a crosslinking agent in such a ratio as to be 40 parts by weight.

In the curable resin solution composition, by changing the amount of the crosslinking agent component used, it is possible to control various properties of the finally obtained film and the like in a wide range. This is one of the great features of the curable resin solution composition according to the above.

The curable resin solution composition according to the present invention contains the polyester resin according to the present invention and a cross-linking agent component in an active ingredient in a proportion of 5 to 70% by weight.
It is preferable that the content is 10 to 50% by weight.

The content of the active ingredient in the curable resin solution composition composed of the polyester resin and the crosslinking agent component may be appropriately adjusted according to the purpose of use. When the amount is less than 5% by weight, a large amount of an organic solvent must be evaporated when preparing a film or the like, which has many disadvantages.

On the other hand, when the content exceeds 70% by weight, the viscosity of the curable resin solution composition may become extremely high, and it becomes difficult to perform an operation such as coating or casting. There are cases.

The curable resin solution composition according to the present invention may contain, in addition to the polyester resin according to the present invention, a crosslinking agent component and an organic solvent, various coloring agents such as pigments or dyes, It may contain fillers, a catalyst for accelerating a crosslinking reaction, and the like, and may also contain other various additives.

The curable resin solution composition according to the present invention is produced by mixing the polyester resin according to the present invention, a crosslinking agent component, and an organic solvent, but the method is not particularly limited. Absent. For example, the polyester resin according to the present invention may be mixed with a cross-linking agent component in a composition in a form dissolved in an organic solvent, or the cross-linking agent component may be already contained. Even when the above-mentioned curable resin composition is dissolved in an organic solvent, the curable resin solution composition according to the present invention can be obtained.

The curable resin solution composition according to the present invention as described above is coated or cast, dried, and, if necessary, further subjected to a heat treatment to obtain a flexible and tough film. Alternatively, it can form a sheet or the like, and is useful as an adhesive or various coating agents.

The curable resin composition and the curable resin solution composition according to the present invention are mainly
Forming a laminated film on various fibrous base materials such as woven fabric, knitted fabric or nonwoven fabric to give a composite sheet that has a soft texture and is tough. And can be suitably used for the production of so-called synthetic leather.

[0171]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following, all parts are by weight unless otherwise specified, and pressures are indicated by absolute pressure.

The various measurements were made in the following manner.

(1) Composition analysis of polyester resin The analysis was performed by proton NMR measurement.

(2) Measurement of Weight Average Molecular Weight The measurement was performed using polystyrene as a standard sample by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase.

(3) Measurement of strength and elongation of film A film having a width of 5 mm and a test length of 20 mm was used as a test piece and subjected to elongation deformation at a speed of 300 mm / min. is there. The unit of the breaking strength and the 100% modulus is indicated by MPa (megapascal), and the unit of the elongation is indicated by%.

(4) Evaluation of elastic properties A film having a width of 10 mm and a test length of 100 mm was used as a test piece.
At a speed of 1 minute, the film was elongated and deformed to an elongation of 100%, and was held for 1 minute in this state. At this time, the moving distance of the movable end is L. Continue for 100m
By relaxing at a speed of m / min,
It was noted that the stress on the film was zero. The moving distance of the movable end at this time is defined as L ′.

As described above, the value of (L '/ L) × 100 is referred to as an elastic recovery rate and is used as an index of elastic characteristics. The unit of the elastic recovery rate is indicated by%.

(5) Measurement of Gel Fraction A test was conducted in which a 2 to 3 cm square film was immersed in methyl ethyl ketone at room temperature for 24 hours, and drying of the film after the test with respect to the weight of the film before the test. The weight ratio is used as the gel fraction. The unit of the gel fraction is shown by%.

(6) Measurement of Viscosity of Resin Solution Composition, etc. 100 g of the resin solution was collected in a glass bottle having a capacity of about 120 ml and left in a constant temperature water bath at 25 ° C. for 2 hours. , Using a BM type rotational viscometer,
The viscosity was measured. The unit of the viscosity is mPa · s
(Milli-pascal second).

Example 1 136 parts of ethylene glycol, 155 parts of dimethyl terephthalate and 19 parts of dimethyl isophthalate,
674 parts of polyoxytetramethylene glycol having a number average molecular weight of 2,000 as determined by a terminal group assay and 1,3,5-trimethyl-2,4,6-tris (3,5-ditertiary) as an antioxidant 3.5 parts of butyl-4-hydroxybenzyl) benzene, 0.1 part of zinc acetate dihydrate as a catalyst, and 0.1 part of tetraisopropyl titanate as a catalyst were mixed with a fractionator and a ribbon. Into a reaction vessel equipped with a mold stirrer, thermometer and nitrogen piping,
The temperature was increased by heating while passing dry nitrogen.

When the temperature of the contents reached about 170 ° C., the temperature at the top of the fractionator became about 60 ° C., and it was confirmed that the distillation of methanol started. In addition, 180
The temperature was raised to 200 ° C and the reaction was continued.
90 minutes after the temperature reached ° C, it was observed that the temperature of the uppermost stage of the flow separator reached 55 ° C, and the distillation of methanol became slow.

Therefore, from 180 ° C. to 210 ° C., 6
The temperature was raised over 0 minutes, and the reaction was continued. As the temperature began to rise, the temperature at the top of the fractionator reached about 60 ° C. and methanol began to come out again. 210 ℃ reached 3
After 0 minutes, the temperature at the top of the fractionator dropped to 40 ° C. or less, and the distillation of methanol stopped, so the heating was stopped and the temperature was lowered to 160 ° C.

The fractionator was removed from the reaction vessel, and the apparatus was reassembled so that components distilled out of the reaction vessel were directly collected.

Next, 55 parts of 5
-Addition of hydroxyisophthalic acid, from 160 ° C. to 2
Raise the temperature to 20 ° C over 60 minutes, 220 ° C
After the reaction was performed for 60 minutes,
And the first-stage reaction was completed.

Thereafter, a pressure reducing pipe was set in the reaction vessel, and further, the nitrogen pipe was closed and a pressure gauge was connected.

Subsequently, the contents of the reaction vessel were heated to increase the temperature from 160 ° C. to 200 ° C. over 60 minutes, and at the same time, the pressure in the reaction vessel was slowly decreased to 200 ° C. ℃ and at the same time the pressure is 2mm
It was operated so as to be Hg.

After that, while keeping the temperature at 200 ° C.,
The pressure was further increased to 0.8 mmHg for 30 minutes.
Down to. Further, the reaction was continued for 120 minutes in that state, and then the reaction was stopped by blowing dry nitrogen into the reaction vessel to terminate the second-stage reaction. The polyester resin thus obtained was taken out on a Teflon resin plate and cooled in air.

The proton NMR of this polyester resin
Table 1 shows the composition ratio obtained from the composition analysis according to the above and the design value calculated from the charged composition.

The analytical value of the composition ratio of this polyester resin almost coincided with the design value calculated from the charged composition.
The analysis value and the design value of the content of the 5-hydroxyisophthalic acid residue and the content of the polyoxytetramethylene glycol unit were almost the same.

The weight average molecular weight of this polyester resin determined by gel permeation chromatography was
The molecular weight in terms of polystyrene was 123,000.

[0191]

[Table 1]

<< Footnotes to Table 1 >> EG: abbreviation of ethylene glycol PTMG: abbreviation of polyoxytetramethylene glycol TPA: abbreviation of terephthalic acid IPA: abbreviation of isophthalic acid HIPA: 5- Abbreviation for hydroxyisophthalic acid

HIPA content: 5- in polyester resin
Hydroxyisophthalic acid residue content (mol / kg)

PTMG content: content of polyoxymethylene glycol unit in polyester resin (% by weight)

Mw × 10 ^-3 : weight average molecular weight in terms of polystyrene by GPC

Examples 2 to 5 Except that the types of raw materials to be used, the amounts used, the maximum temperature of the second-stage reaction, and the reaction time at that temperature were changed as shown in Table 2, In the same manner as in Example 1,
Various polyester resins of Examples 2 to 5 were prepared.

Table 3 summarizes the composition ratio estimated from the charged composition of each resin and the weight average molecular weight in terms of polystyrene measured by GPC.

In each of the examples, the desired polyester resin was obtained without any gelation.

[0199]

[Table 2]

<< Footnotes to Table 2 >> BG: abbreviation of 1,4-butanediol DMT: abbreviation of dimethyl terephthalate

PTMG-2: Number average molecular weight is 2,000
Polyoxytetramethylene glycol PTMG-1 ... Polyoxytetramethylene glycol having a number average molecular weight of 1,000

[0202]

[Table 3]

<< Footnotes to Table 3 >> HIPA content: content of 5-hydroxyisophthalic acid residue in polyester resin (mol / kg)

PTMG content: content of polyoxymethylene glycol unit in polyester resin (% by weight)

Mw × 10 ^-3 : weight average molecular weight in terms of polystyrene by GPC

Comparative Examples 1 to 4 The same procedures as in Example 1 were carried out except that the kind of raw materials used, the amount used, the reaction temperature of the second stage reaction, and the reaction time at that temperature were changed as shown in Table 4. In the same manner as in Example 1, the polyester resins of Comparative Examples 1 to 4 were prepared. Table 5 shows the composition ratio of these resins estimated from the charged composition and the weight average molecular weight of polystyrene equivalent measured by gel permeation chromatography.

The polyester resin of Comparative Example 1 had a very low viscosity despite the reaction time of 150 minutes. The polyester resin of Comparative Example 3 had a hard touch, was hardly soluble in a solvent, and could not be measured for molecular weight distribution. The polyester resin of Comparative Example 4 gelled and could not be obtained.

[0208]

[Table 4]

<< Fourth Footnote >> HG: abbreviation of 1,6-hexanediol DMI: abbreviation of dimethyl isophthalate

Reaction temperature: reaction temperature of the second-stage reaction (° C.) Reaction time: reaction time of the second-stage reaction at a set reaction temperature (minutes)

[0211]

[Table 5]

<< Footnote to Table 5 >> HIPA content: content of 5-hydroxyisophthalic acid residue in polyester resin (mol / kg)

PTMG content: content of polyoxymethylene glycol unit in polyester resin (% by weight)

Mw × 10 ^-3 : weight average molecular weight in terms of polystyrene by GPC

Example 6 First, 100 parts of the polyester resin prepared in Example 2 and 15 parts of aluminum tris (ethyl acetoacetate) were kneaded with a kneader to obtain the desired curability. A resin composition was prepared. At this time, the heating medium was adjusted through the outer jacket of the kneader so that the temperature of the mixture during kneading was 90 ° C.

Next, the composition thus obtained was mixed with 12
Pressed with a hot press heated to 0 ° C. to produce a film having a thickness of about 100 microns (μm), which was subsequently dried in a hot air dryer at 150 ° C. for 5 minutes. It was heat-treated and further cured at room temperature for one week.

Thereafter, this film was made flexible and showed a good elastic touch feeling.
% Modulus is 1.5 MPa and breaking strength is 25 MPa
And elongation at break was 950%. The elastic recovery was 91%.

Example 7 A target film was produced in the same manner as in Example 6, except that the polyester resin prepared in Example 4 was used. The 100% modulus of this film was 1.7 MPa, the breaking strength was 27 MPa, the breaking elongation was 900%, and the elastic recovery was 88%, which made it soft and suitable. It had a certain tactile sensation.

Comparative Example 5 A control film was prepared in the same manner as in Example 6, except that the polyester resin prepared in Comparative Example 2 was used. The 100% modulus of this film was 0.8 MPa, the breaking strength was 16 MPa, the breaking elongation was 1,100%, and the film had a sticky feel. The elastic recovery of this film was 80%.

Comparative Example 6 The polyester resin prepared in Comparative Example 3 was pressed by a hot press heated to 200 ° C.
A μm thick control film was prepared. The 100% modulus of this film is 8 MPa and the breaking strength is 2
0 MPa, elongation at break is 600%, and
The elastic recovery was 78%, which was a hard touch.

Example 8 25 parts of the polyester resin prepared in Example 2 was
The desired resin solution composition was prepared by dissolving in 5 parts of N, N-dimethylformamide. Further, 3.4 parts of a 50% by weight toluene solution of aluminum tris (ethyl acetoacetate) was added to obtain a target curable resin solution composition. The viscosity of this curable resin solution composition is 4,500
mPa · s.

Next, this curable resin solution composition was applied on release paper to a thickness of about 0.25 mm,
160 ° C. for 4 minutes in a hot air dryer
In a hot air dryer for 4 minutes.
It was allowed to cure for one week at room temperature to produce the desired film.

This film is soft and shows a good elastic feeling. The film has a 100% modulus of 1.7 MPa when measured for the film elongation. Strength is 28 MPa, elongation at break is 800%, and elastic recovery is 85%
Met.

Further, the gel fraction of this film was 60%. Then, the viscosity of the curable resin solution composition obtained here on the next day after preparation is 6,000 mP.
and the viscosity after one week was 6,000 m
Pa · s, and no tendency for gelation was observed. These physical properties are summarized in Table 6.

Examples 9 to 11 The objective films were produced in the same manner as in Example 8, except that the polyester resin to be used was changed as shown in Table 6. Collectively, the physical properties of this film,
It is shown in the table.

Any of the curable resin solution compositions is capable of forming a tough film.
The stability was also good.

[0227]

[Table 6]

<< Footnotes in Table 6 >> 100% M: 100% modulus (MPa)

Breaking strength: (MPa) Breaking elongation: (%) Elastic recovery: (%)

Gel fraction: (%)

Viscosity: (mPa · s)

Comparative Examples 7 and 8 Control films were prepared in the same manner as in Example 8, except that the polyester resin to be used was changed as shown in Table 7. The physical properties of each film are shown in the same table.

The solution composition of Comparative Example 7 gives only a fragile film to the extent that it is difficult to measure the film elongation. After a while, the solution composition hardens and becomes fluid. Was to lose. On the other hand, the solution composition of Comparative Example 8 had good stability but did not give a film which could be said to be tough.

[0234]

[Table 7]

<< Footnotes in Table 7 >> 100% M: 100% modulus (MPa)

Breaking strength: (MPa) Breaking elongation: (%) Elastic recovery: (%)

Gel fraction: (%)

Viscosity: (mPa · s)

Examples 12 and 13 and Comparative Example 9 The same procedure as in Example 8 was carried out except that the blending amount of a 50% by weight toluene solution of aluminum tris (ethylacetoacetate) to be used was changed as shown in Table 8. In this way, various target films and control films were produced. The physical properties of each film are shown in the same table.

The resin solution composition of Comparative Example 9 in which the crosslinking agent component was not blended did not give a film which could be said to be tough. On the other hand, the curable resin solution compositions of Examples 12 and 13 both exhibited good stability and gave a tough film.

[0241]

[Table 8]

<< Footnote to Table 8 >> Compounding amount: Compounding amount (parts by weight) of a 50% by weight toluene solution of aluminum tris (ethylacetoacetate)

100% M: 100% modulus (MP
a)

Breaking strength: (MPa) Breaking elongation: (%) Elastic recovery: (%)

Gel fraction: (%)

Viscosity: (mPa · s)

Examples 14 and 15 The type of the crosslinking agent component to be used and the amount thereof were
Various target films were produced in the same manner as in Example 8, except that the film was changed as shown in the table. The physical properties of each film are shown in the same table.

However, in Example 15, the measured value of the viscosity was obtained for a solution composition containing no crosslinking catalyst.

Each of the curable resin solution compositions of Examples 14 and 15 formed a tough film. Both the stability of the solution composition obtained in Example 14 and the stability of the solution composition containing no crosslinking catalyst obtained in Example 15 were good.

[0250]

[Table 9]

<< Footnote to Table 9 >> ALA2E: Abbreviation for a 75% solution of aluminum acetylacetonate bis (ethylacetoacetate) in isopropanol

L117: "Super Beckamine L-
117-60 ", a trade name of n-butyl etherified methylolmelamine resin manufactured by Dainippon Ink and Chemicals, Incorporated; non-volatile content = 60%

Compounding amount: Compounding amount of crosslinking agent component (parts by weight)

PTS: Abbreviation of paratoluenesulfonic acid

Catalyst blending amount: blending amount of cross-linking catalyst PTS (parts by weight)

100% M: 100% modulus (MP
a)

Breaking strength: (MPa) Breaking elongation: (%) Elastic recovery: (%)

Gel fraction: (%)

Viscosity: (mPa · s)

[0260]

The polyester resin according to the present invention reacts with various cross-linking agents to make it flexible, has high mechanical strength, and has excellent properties such as low permanent set. It mainly provides a sheet, a film or various molded articles, and the resin solution composition according to the present invention is further useful as a component such as an adhesive or various coating agents. .

In addition, the polyester resin according to the present invention may be used as a curable resin composition containing a crosslinking agent component or as a curable resin solution composition containing a crosslinking agent component and an organic solvent. , Respectively, can be mainly used for the preparation of sheets, films or various molded products, and further, adhesives,
They are also useful as various coating agents.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 63:00)

Claims (20)

[Claims] 1. A polyester resin comprising an aromatic dibasic acid residue (a) having a phenolic hydroxyl group and a polyoxyalkylene glycol unit (b). 2. An aromatic dibasic acid residue having a phenolic hydroxyl group (a), a polyoxyalkylene glycol unit (b), and an aliphatic glycol residue having 2 to 4 carbon atoms (c). A polyester resin characterized by: 3. An aromatic dibasic acid residue (a) having a phenolic hydroxyl group, a polyoxyalkylene glycol unit (b), an aliphatic glycol residue having 2 to 4 carbon atoms (c), A polyester resin characterized by containing a glycol residue (d) having 5 or more carbon atoms other than the polyoxyalkylene glycol unit (b). 4. It contains an aromatic dibasic acid residue (a) having a phenolic hydroxyl group, a polyoxyalkylene glycol unit (b), and a dibasic acid residue (e) having no phenolic hydroxyl group. A polyester resin characterized by: 5. An aromatic dibasic acid residue having a phenolic hydroxyl group (a), a polyoxyalkylene glycol unit (b), an aliphatic glycol residue having 2 to 4 carbon atoms (c), and phenol A dibasic acid residue (e) having no hydroxyl group. 6. The content of the above-mentioned aromatic dibasic acid residue (a) having a phenolic hydroxyl group in the range of 0.05 to 1.0 per 1,000 g of solid content of the polyester resin.
The polyester resin according to claim 1, wherein the amount is 0 mol. 7. The method according to claim 1, wherein the content of the polyoxyalkylene glycol unit (b) is in the range of 50 to 90% by weight based on the solid content of the target polyester resin. Polyester resin described in Crab. 8. The method according to claim 1, wherein the polyoxyalkylene glycol unit (b) has a number average molecular weight in the range of 500 to 4,000. Polyester resin. 9. An aromatic dibasic acid having a phenolic hydroxyl group or an ester-forming derivative thereof (a ′), a polyoxyalkylene glycol (b ′), and a compound having 2 to 2 carbon atoms.
An aliphatic glycol (c ′) of 4 as an essential raw material component, if necessary, having no glycol (d ′) having 5 or more carbon atoms and / or a phenolic hydroxyl group other than polyoxyalkylene glycol. In producing a polyester resin using a dibasic acid or its ester-forming derivative (e ′) in an amount that satisfies the following conditional expressions (I) and (II), ,
An ester compound is obtained by reacting these various raw material components, and subsequently, a polycondensation reaction for distilling off an excess glycol component relative to the dibasic acid component is performed under heating and reduced pressure conditions. Yes, 20,0
An aromatic dibasic acid residue (a) having a weight average molecular weight of 00 to 400,000 and having a phenolic hydroxyl group, and a polyoxyalkylene glycol unit (b)
And a method for producing a polyester resin. [Formula 1] 1.2 ≦ (C ′ + D ′) / (A ′ + E ′) ≦ 5. O: conditional expression (I) [Equation 2] (B '+ D') / (A '+ E') <1.0 ... conditional expression (II) A ', B', C ', D' and E '
Represents the ratio of the number of moles of (a ′), (b ′), (c ′), (d ′) and (e ′), respectively. ] 10. An aromatic dibasic acid having a phenolic hydroxyl group or an ester-forming derivative thereof (a ′), a polyoxyalkylene glycol (b ′), and a compound having 2 carbon atoms.
An aliphatic glycol (c ′) having a carbon number of 5 or more and / or a phenolic hydroxyl group other than polyoxyalkylene glycol, if necessary. In preparing a polyester resin, a dibasic acid or its ester-forming derivative (e ′) is also used in an amount that satisfies the following conditional expressions (I) and (II).
(A '), (b') and optionally (e '),
After reacting (d ′) to obtain an ester compound, a polyoxyalkylene glycol (b ′) is further added, and then, under heating and reduced pressure conditions, an excess glycol component relative to the dibasic acid component A method for producing a polyester resin comprising a polyoxyalkylene glycol unit and an aromatic dibasic acid residue having a phenolic hydroxyl group, comprising performing a polycondensation reaction for distilling off a polycondensation residue. [Equation 3] 1.2 ≦ (C ′ + D ′) / (A ′ + E ′) ≦ 5. O ... Conditional expression (I) [Equation 4] (B '+ D') / (A '+ E') <1.0 ... Conditional expression (II) A ', B', C ', D' and E '
Represents the ratio of the number of moles of (a ′), (b ′), (c ′), (d ′) and (e ′), respectively. ] 11. The process for producing a polyester resin according to claim 9, wherein the polycondensation reaction for removing an excess glycol component from the dibasic acid component is carried out at a temperature in the range of 180 to 240 ° C. 12. A resin solution composition comprising the polyester resin according to claim 1 and an organic solvent. 13. A curable resin composition comprising the polyester resin according to claim 1 and a crosslinking agent component. 14. The curing method according to claim 13, wherein the crosslinking agent component is at least one compound selected from the group consisting of an alkoxide type, an acylate type, a chelate type and a mixture thereof of a polyvalent metal. Resin composition. 15. The method according to claim 13, wherein the crosslinking agent component is at least one compound selected from the group consisting of an aluminum chelate compound, a titanium chelate compound, a zirconium chelate compound and a zinc chelate type compound. The curable resin composition according to the above. 16. The method according to claim 13, wherein the crosslinking agent component is at least one compound selected from the group consisting of aminoplasts, polyfunctional epoxy compounds, polyfunctional isocyanate compounds, and polyfunctional blocked isocyanate compounds. The curable resin composition according to the above. 17. A curable resin solution composition comprising the polyester resin according to claim 1, a crosslinking agent component, and an organic solvent. 18. The method according to claim 18, wherein the crosslinker component is at least one selected from the group consisting of an alkoxide type, an acylate type, a chelate type and a mixed type of a polyvalent metal.
18. The curable resin solution composition of claim 17, which is a species compound. 19. The cross-linking agent component is at least one compound selected from the group consisting of an aluminum chelate compound, a titanium chelate compound, a zirconium chelate compound, and a zinc chelate compound.
The curable resin solution composition according to claim 17. 20. The cross-linking agent component is at least one compound selected from the group consisting of aminoplasts, polyfunctional epoxy compounds, polyfunctional isocyanate compounds, and polyfunctional blocked isocyanate compounds.
8. The curable resin solution composition according to 7.