JP2002284865A - Polyester resin composition, curing resin composition and curing coating composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition which is excellent in storage stability and has a hydrogenated bisphenol as the raw material; a curing resin composition using the same; and a curing coating composition which can provide a coating membrane with high hardness, is excellent in weather resistance and has a very low content of a volatile organic component. SOLUTION: The polyester resin composition comprises being obtained from a raw material containing both an isomer mixture of the trans-trans product, the trans-cis product and the cis-cis product of a hydrogenated bisphenol represented by formula (1) (wherein R is hydrogen or a 1-4C alkyl group) and a carboxylic acid or a carboxylate ester, wherein the trans-trans product has a content of 50% by weight or less. The curing resin composition comprises the polyester resin composition and a curing agent that has a functional group reactable with the polyester resin composition to cure. The curing coating composition comprises the curing resin composition as a coating membrane- forming component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyester resin composition having excellent storage stability, a curable resin composition using the same, and a curable coating composition.

[0002]

2. Description of the Related Art In recent years, due to environmental problems, there is a strong demand for a paint having a high solid content, in particular, a reduction in volatile organic components contained in a paint. In this case, it is generally necessary to lower the resin viscosity of the paint, and therefore, a method of reducing the polarity or the molecular weight of the resin component of the paint has been adopted.

[0003] As disclosed in JP-T-2000-511223, alicyclic compounds have low polarities but a rigid structure, so that hardness can be easily obtained even if the molecular weight is reduced. It has attracted attention as a raw material for resin components of coating materials. In addition, the alicyclic structure has an advantage that it has a low ultraviolet absorptivity and can form a coating film having excellent weather resistance.

[0004] In particular, hydrogenated bisphenol has two alicyclic structures that are continuously repeated, and thus such characteristics are easily exhibited. In addition, polyester resins synthesized from hydrogenated bisphenols and polycarboxylic acids contain alicyclic moieties in the resin skeleton, making it easy to lower the polarity and easily obtain a coating hardness even at a low molecular weight. It has characteristics suitable as a resin.

However, when a hydrogenated bisphenol structure is introduced into the resin skeleton, when dissolved in an organic solvent, crystallization of the resin is liable to occur, which often causes cloudiness during storage and causes lumps. Therefore, generally, in order to suppress crystallization, the amount of hydrogenated bisphenol is reduced,
-The reality is that asymmetric raw materials such as propylene glycol are blended to improve storage stability.

However, as a result, the alicyclic structure portion in the resin is reduced, and the above-mentioned characteristics are lost. When the resin is used as a resin for a high solid content paint, a sufficient coating film hardness cannot be obtained.

[0007]

DISCLOSURE OF THE INVENTION The present invention relates to a polyester resin composition containing hydrogenated bisphenol as a raw material, a curable resin composition using the same, and the hardness of a coating film obtained, which is excellent in storage stability. It is an object of the present invention to provide a curable coating composition having a high content and a very low content of volatile organic components having excellent weather resistance.

[0008]

According to the present invention, there is provided a compound represented by the general formula (1):

[0009]

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(Wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), a trans-trans form, a trans-cis form and a mixture of isomers of the cis-cis form of hydrogenated bisphenol And a carboxylic acid or a carboxylic acid ester, wherein the content of the trans-trans form in the isomer mixture is 50% by weight or less in the polyester resin composition. It is. Here, the content of the trans-trans isomer in the isomer mixture is preferably 35 to 50% by weight, and the melting point of the isomer mixture is preferably 70 to 165 ° C.
The content of the isomer mixture in the raw material is preferably from 10 to 80% by weight. The polyester resin composition thus obtained has a number average molecular weight of 400 to 30.
00 is preferred.

[0011] The present invention also provides a curable resin composition comprising the above-mentioned polyester resin composition and a curing agent having a functional group capable of undergoing a curing reaction with the above-mentioned polyester resin composition. is there. Here, the number average molecular weight of the curing agent is preferably from 200 to 3000. Furthermore, the present invention is a curable coating composition comprising the curable resin composition as a coating film-forming component, and has a solid content when the viscosity at 20 ° C. is 100 mPa · s. It is preferably at least 40% by weight.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTSPolyester resin composition  The polyester resin composition of the present invention has the general formula (1)
Trans-tolan of hydrogenated bisphenol represented by
Mixture of isomeric, trans-cis and cis-cis isomers
Compound and a carboxylic acid or a carboxylic acid ester.
In the polyester resin composition obtained from the raw material,
The content of the trans-trans form in the isomer mixture is
It is characterized by being 50% by weight or less.

The raw material of the polyester resin composition of the present invention contains a trans-trans form, a trans-cis form and a mixture of isomers of the cis-cis form of hydrogenated bisphenol. As the trans-trans form, specifically, the general formula (2)

[0014]

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The trans-cis form represented by the general formula (3)

[0016]

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The cis-cis isomer represented by the general formula (4)

[0018]

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(The above general formulas 2, 3 and 4
Wherein R represents a hydrogen atom or a carbon atom number of 1 to 4;
Which is an alkyl group). The hydrogenated bisphenol as the raw material is a mixture of the above three isomers.

The content of the trans-trans isomer in the isomer mixture as a raw material of the polyester resin composition of the present invention is 50% by weight or less. If the content exceeds 50% by weight, the storage stability of the obtained polyester resin composition is low, and the polyester resin composition crystallizes with time and becomes cloudy and precipitates. Further, from the viewpoints of economy and industrial availability, the content is preferably 35 to 50% by weight.

As described above, an isomer mixture of hydrogenated bisphenol having a trans-to-trans content of 50% by weight or less can be prepared by adding hydrogen to bisphenol, for example, as described in JP-A-2000-44503. In the reaction step to be added, it can be obtained by changing reaction conditions and selecting a catalyst.

The melting point of the isomer mixture which is the raw material of the polyester resin composition of the present invention is preferably from 40 to 165 ° C, more preferably from 70 to 150 ° C. When the melting point is less than 40 ° C., the isomer mixture itself softens over time, or when the obtained polyester resin composition is used as a coating material to obtain a coating film, the coating film hardness is insufficient.
When the temperature exceeds 165 ° C., the storage stability of the obtained polyester resin composition is low, and the polyester resin composition crystallizes with time and becomes cloudy.
Precipitates.

The content of the isomer mixture in the raw material of the polyester resin composition of the present invention is preferably from 10 to 80% by weight. When the content is less than 10% by weight, characteristics such as low polarity and high hardness of hydrogenated bisphenol may not be easily exhibited. On the other hand, when the content exceeds 80% by weight, the solubility of the obtained polyester resin composition is lowered, and when it is used in a coating material, it tends to be non-uniform when mixed with other components.

The raw material of the curable resin composition of the present invention further contains a carboxylic acid and / or a carboxylic acid ester. The carboxylic acid is not particularly limited and includes, for example, aliphatic monocarboxylic acids such as lauric acid, versatic acid, stearyl acid, and fatty acids; succinic anhydride, malonic acid, adipic acid, azelaic acid, sebacic acid, and hexahydrophthalic anhydride. Aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; aliphatic unsaturated carboxylic acids such as acrylic acid, propionic acid, maleic anhydride, mesaconic acid, and tetrahydrophthalic anhydride; benzoic acid, p-tert-butylbenzoic acid Acid, salicylic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimetic anhydride,
Aromatic carboxylic acids such as pyromellitic anhydride can be mentioned. These may be used in combination of two or more. The carboxylic acid ester is not particularly limited, for example,
Examples of the carboxylic acid include methyl ester, ethyl ester, and propyl ester. These may be used in combination of two or more.

The content of the carboxylic acid and carboxylic acid ester in the raw material of the polyester resin composition of the present invention is 2
It is preferably from 0 to 90% by weight.

The raw material of the polyester resin composition of the present invention may contain other alcohols for the purpose of adjusting the molecular weight and properties of the obtained polyester resin composition. These alcohols are not particularly limited,
For example, lauryl alcohol, ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, 1,4-cyclohexanedimethanol, bis (hydroxymethyl) Tricyclo [5,2,1,0] decane, 1,3,5-tris (2-
(Hydroxyethyl) cyanuric acid, isopropylidenebis (3,4-cyclohexanediol), and adducts of these alcohols such as ethylene oxide, propylene oxide and caprolactone. These may be used in combination of two or more.

As a method for obtaining the polyester resin composition of the present invention, a method well known by those skilled in the art can be mentioned.
A method of performing a dehydration reaction or a dealcoholization reaction at 30 ° C. can be mentioned.

At that time, if necessary, for example, p-
Sulfonic acids such as toluenesulfonic acid, organic phosphoric acids such as dibutylphosphoric acid, and their salt compounds such as calcium, magnesium, and zinc; and inorganic metal salts such as zinc chloride and tin chloride; aluminum, titanium, cobalt, tin, and zinc. An esterification catalyst such as an organometallic compound can be used.

The number average molecular weight of the polyester resin composition of the present invention is preferably from 400 to 3,000. When the number average molecular weight is less than 400, the curability may be insufficient when used in a coating material, or the performance of the obtained coating film may be insufficient. On the other hand, when it exceeds 3,000, the viscosity becomes high, and when used in a coating material, a large amount of volatile organic solvent may be required.

[0030]Curable resin composition  The curable resin composition of the present invention comprises the polyester resin described above.
Curable reaction with the composition and its polyester resin composition
And a curing agent having various functional groups.
Things.

The curing agent contained in the curable resin composition of the present invention is not particularly limited. When the above-mentioned polyester resin composition has a hydroxyl group, for example, melamine resin, urea resin, benzoquanamine resin, (blocked) Polyisocyanates, alkoxysilane oligomers, carbamate oligomers and the like, when having a carboxylic acid group, for example, an epoxy oligomer, and when having an active methylene group or an active methine group, for example, a (meth) acrylate oligomer and the like. it can. These may be used in combination of two or more. The number average molecular weight of the curing agent is preferably from 200 to 3000, and more preferably from 250 to
More preferably, it is 2000. When the number average molecular weight is less than 200, when used in a coating material, it is liable to volatilize during application or heating, and the curability may decrease.
On the other hand, when it exceeds 3,000, the viscosity becomes high, and when used in a coating material, a large amount of volatile organic solvent may be required.

[0032]Curable coating composition  The curable coating composition of the present invention is the curable resin composition described above.
Is contained as a film-forming component. The present invention
When producing a curable coating composition of
Is not particularly limited, for example, hexane, octane, etc.
Aliphatic hydrocarbons; aromatic hydrocarbons such as toluene and xylene
Hydrogen; various petroleum fractions with a moderate boiling range;
Esters such as tyl and 2-ethylhexyl acetate;
Keto such as methyl ethyl ketone and methyl isobutyl ketone
Compounds: tetrahydrofuran, ethylene glycol dimethyl
Ethers such as butanol, methoxypro
Alcohols such as panol, and mixtures thereof
Can be mentioned.

The curable coating composition of the present invention may further contain, if necessary, an ultraviolet absorber such as a benzophenone type or a benzotriazonol type, a light stabilizer such as a hindered amine type, an antioxidant such as a phenol type or the like. And a viscosity controlling agent such as organic resin particles and a surface conditioner.

The curable coating composition of the present invention contains 20
The solid content is 40% by weight when the viscosity at 100 ° C is 100 mPa · s.
It is preferably at least the above, and more preferably 60 to 90% by weight. When the solid content is less than 40% by weight, the content of the volatile organic solvent in the coating composition may be large. The viscosity can be measured by, for example, a B-type viscometer (model BM manufactured by Tokyo Keiki Co., Ltd.). The above-mentioned organic solvent can be used for adjusting the viscosity.

The curable coating composition of the present invention can be used as a clear coating or a colored coating. When used as the above-mentioned coloring paint, the curable coating composition of the present invention can contain a coloring component. The coloring component is not particularly limited, and examples thereof include inorganic pigments such as iron oxide, lead oxide, titanium dioxide, carbon black, cadmium yellow, cadmium red, and chrome yellow; phthalocyanine blue, phthalocyanine green, carbazole violet, anthrapyridine, and azo. Organic pigments such as orange, flavanthrone yellow, isoindoline yellow, azo yellow, indathrone blue, dibromo anzathrone red, perylene red, azo red, anthraquinone red, and quinacridone red; 1: 2 chromium complex black, 1: 2 chromium complex Dyes such as yellow and 1: 2 cobalt complex yellow; aluminum powder, alumina powder, bronze powder, copper powder, tin powder, zinc powder, iron phosphide, metal-coated mica powder, and titanium dioxide-coated dye Ca powder, mention may be made of bright pigment such as titanium dioxide-coated glass powder. These may be used in combination of two or more. In addition, extenders such as coal dust, talc, and barium sulfate can be included.

The curable coating composition of the present invention can be applied to an object to be coated by spray coating, brush coating, dip coating, roll coating, flow coating, rotary atomization coating, or the like. The film thickness to be applied is not particularly limited and can be appropriately set according to the application, but is generally 10 to 100 μm. After coating, the coating film is cured by heating. In order to obtain a cured coating film having a high crosslinking density, it is preferable to set the heating temperature to 60 to 180C, preferably 120 to 160C. The curing time can be appropriately set according to the curing temperature, but is preferably 10 to 30 minutes at a heating temperature of 120 to 160 ° C.

When the coating composition of the present invention is used as a clear coating, a base coating is applied on an object to be coated to form an uncured base coating film.
On the uncured base coating according to the on-wet coating method,
A so-called two-coat one-bake method in which a clear paint is applied to form an uncured clear coating film, and the uncured base coating film and the clear coating film are simultaneously heated and cured. The base paint may be a so-called water-based paint or a solvent-based paint.However, when a water-based paint is used, it is necessary to apply a clear paint before applying the clear paint in order to obtain a good finished coating film. It is preferable to heat the cured base coating at room temperature to 110 ° C. for 3 to 10 minutes. Such aqueous base paints are disclosed in US Pat. No. 5,151,125 and US Pat. No. 5,183,350.
No. 4 specifically disclosed can be used.

The method for applying the base paint is not particularly limited, and examples thereof include the above-described coating method. Further, the film thickness to be applied is not particularly limited, but is generally 10 to 25 μm.

The object to be coated is not particularly limited and can be used, for example, on wood, metal, glass, cloth, plastic, foam, etc., or on various primer surfaces.
It can be suitably used for plastic and metal surfaces.

[0040]

EXAMPLES The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the following examples. In the following, “parts” means “parts by weight”.

[0041]Production Example 1 Production of aqueous acrylic resin  Condenser, stir bar, thermometer, decanter, nitrogen introduction
In a flask equipped with a tube, add dipropylene glycol methyl
23.9 parts of ether and propylene glycol methyl
16.1 parts of ether was added, and the temperature was raised to 120 ° C. and maintained.
After that, 54.5 parts of ethyl acrylate, methyl methacrylate
12.5 parts, 2-hydroxyethyl acrylate 14.7
Part, styrene 10.0 parts, methacrylic acid 8.5 parts
Mer mixture and dipropylene glycol methyl ether
A mixture consisting of 10.0 parts and 2.0 parts of Kayaester O
Liquid for 3 hours, and then 0.5 hours
Aged for a while. Further, 0.3 part of Kayaester O and
Consists of 5.0 parts of propylene glycol methyl ether
The mixture was added dropwise over 0.5 hour and then aged for 1 hour.
Was. Thereafter, 16.1 parts of the solvent was distilled off under reduced pressure to obtain dimethyl alcohol.
Add ethanol and deionized water to add GP
Number average molecular weight 10,000 by C measurement, solid content 31 weight
%, Solid content acid value 56, hydroxyl value 70 aqueous acrylic resin
I got

[0042]Production Example 2 Production of pigment paste  The aqueous acrylic resin obtained in Production Example 1 was used for 100.
0 parts, 28.9 parts of ion-exchanged water, dimethylaminoethanol
0.3 parts, Degussa Carbon FW-285 (Degussa A
After pre-mixing 5.1 parts of carbon black manufactured by G company,
Add glass bead medium in paint conditioner
And dispersed at room temperature for 1 hour.
I got the best.

[0043]Production Example 3 Production of aqueous base paint  118.8 parts of the aqueous acrylic resin obtained in Production Example 1
134.3 parts of the pigment paste obtained in Preparation Example 2, Cymel
204 (melamine resin manufactured by Mitsui Cytec, solid content 80
29.1 parts by weight) and 161.3 parts of ion exchange water
By stirring, an aqueous base paint was obtained.

[0044]Example 1  Condenser, solvent recovery device, stirring rod, thermometer, decane
And a flask equipped with a nitrogen inlet tube.
Bisphenol sample A (Maruzen Petrochemical Co., Ltd., R is
18. methyl group), 50.7 parts, trimethylolpropane;
2 parts, 41.3 parts of adipic acid and dibutyltin oxide
0.5 part was charged, and the temperature was raised to 150 ° C. Generated water
The temperature was gradually raised to 210 ° C. while distilling off. afterwards,
While maintaining 210 ° C., until the distilled water becomes 10 parts
After continuing the esterification reaction, the mixture was cooled and 67 parts of xylene was added.
By adding, polyester resin composition 1 was obtained.
The solid content and GPC (gel permeation chromatography)
Table 1 shows the number average molecular weight according to (matography).

The obtained polyester resin composition 100
And 25 parts of Cymel 324 (melamine resin manufactured by Mitsui Cytec Co., Ltd., solid content: 83% by weight, number average molecular weight: 850) were mixed with a disper while stirring, and uniformly dissolved to obtain a curable resin composition. Next, this curable resin composition was used as a film-forming component, and 1 part of p-toluenesulfonic acid, 1 part of Tinuvin T-384 (an ultraviolet absorber manufactured by Ciba-Geigy), and Sanol LS-292 (Light manufactured by Sankyo) A clear paint was obtained by mixing 0.5 part of a stabilizer) and 1.0 part of a surface conditioner (manufactured by Nippon Paint Co., Ltd., solid content: 50% by weight) while stirring with a disper and uniformly dissolving.

The obtained clear paint was subjected to a viscosity measurement at 20 ° C. of 100 mP with a model BM (type B viscometer) manufactured by Tokyo Keiki Co., Ltd.
The viscosity was adjusted with xylene so as to obtain a · s. At this time 2
The viscosity at 0.degree. The measurement at 4 was 30 seconds.

The zinc phosphate treated 150 × 300 × 0.
Powertop U, which is a cation electrodeposition on 8mm dull steel plate
-50 (cationic electrodeposition paint manufactured by Nippon Paint Co., Ltd.) was applied by electrodeposition so as to have a dry film thickness of about 25 μm, and was cured by heating at 160 ° C. for 30 minutes to form an electrodeposition coating film. Olga P on it
-2 (Nippon Paint Co., Ltd. intermediate coating) with a dry film thickness of about 40
Air spray coating to a thickness of μm,
The coating was cured by heating for 0 minutes to form an intermediate coating film. Further, the aqueous base paint obtained in Production Example 3 was applied by air spray coating so as to have a dry film thickness of 16 μm, and was set for 10 minutes. Thereafter, the mixture was heated at 80 ° C. for 3 minutes to obtain an uncured base coating film.

Next, the clear paint having the adjusted viscosity was applied on the obtained uncured base coating film by an air spray to a dry film thickness of 40 μm by a wet-on-wet coating method. After setting for 10 minutes, 140 ° C
For 25 minutes to form a coating film, and a test plate was prepared by a two-coat one-bake method.

[0049]Example 2  In the same apparatus as in Example 1, hydrogenated bisphenol shown in Table 1 was added.
Sample B (R is a methyl group) 64.2 parts, trimethyl
9.1 parts of roll propane, dimethyl adipate 41.7
Parts and 0.5 parts of dibutyltin oxide, 13
The temperature was raised to 0 ° C. Meta formed by transesterification
The temperature was gradually raised to 200 ° C. while distilling off the knol. So
After that, while maintaining the temperature at 200 ° C., 1
Continue transesterification until it reaches 5 parts, then cool
By adding 67 parts of xylene, polyester resin
Composition 2 was obtained. Each of the obtained polyester resin compositions
The special values are shown in Table 1.

The obtained polyester resin composition 100
Parts, Sumidur BL3175 (Sumitomo Bayer Urethane Co., Ltd., blocked isocyanate, NCO content 11.3)
%, Solid content 75% by weight, number average molecular weight 910) 60 parts,
0.5 parts of dibutyltin dilaurate was mixed with stirring with a disper and uniformly dissolved to obtain a curable resin composition. Next, this curable resin composition was used as a film-forming component, and 1 part of Tinuvin T-384 (an ultraviolet absorber manufactured by Ciba Geigy), and Sanol LS-292.
(Light stabilizer made by Sankyo) 0.5 part and surface conditioner 1.0
Parts (manufactured by Nippon Paint Co., Ltd., solid content: 50% by weight) were blended while stirring with a disper and uniformly dissolved to obtain a clear paint.

The obtained clear paint was coated with a BM (type B viscometer) manufactured by Tokyo Keiki Co., Ltd. having a viscosity at 20 ° C. of 100 m.
The viscosity was adjusted with xylene so as to obtain Pa · s. At this time, when the viscosity at 20 ° C. was measured by Ford Cup No. 4, it was 30 seconds. Further, in the same manner as in Example 1, a test plate was prepared by a two-coat one-bake method.

[0052]Example 3  In the same apparatus as in Example 1, hydrogenated bisphenol shown in Table 1 was added.
Sample B79.1 parts, dimethyl malonate 15.5
Parts, 20.5 parts of dimethyl adipate and dibutyltin oxide
0.5 part of quiside was charged and the temperature was raised to 130 ° C. S
While distilling off the methanol produced by the tell exchange reaction
The temperature was gradually raised to 200 ° C. After that, keep at 200 ℃
While the amount of methanol distilled off becomes 15 parts.
The mixture was cooled and 67 parts of xylene was added.
As a result, a polyester resin composition 3 was obtained. Get
The characteristic values of the obtained polyester resin compositions are shown in Table 1.
Was.

The obtained polyester resin composition 100
Parts, 43 parts of Sumidur BL3175, 10 parts of pentaerythritol triacrylate (number average molecular weight 298) 10
Parts, tetrabutylammonium chloride 0.5 part,
1.8 parts of 1,2-epoxyhexadecane and 0.5 parts of dibutyltin dilaurate were mixed while being stirred with a disper and uniformly dissolved to obtain a curable resin composition. Next, this curable resin composition was used as a coating film-forming component, and 1 part of Tinuvin T-384 was added to Sanol LS.
-292 were mixed with 1 part of a surface conditioner while dispersing and stirring, and uniformly dissolved to obtain a clear paint.

The obtained clear paint was coated with a BM (type B viscometer) manufactured by Tokyo Keiki Co., Ltd. having a viscosity at 20 ° C. of 100 m.
The viscosity was adjusted with xylene so as to obtain Pa · s. At this time, when the viscosity at 20 ° C. was measured by Ford Cup No. 4, it was 30 seconds. Further, in the same manner as in Example 1, a test plate was prepared by a two-coat one-bake method.

[0055]Example 4  In the same apparatus as in Example 1, hydrogenated bisphenol shown in Table 1 was added.
Sample B49.4 parts, cyclohexyl dimethanone
30.5 parts, dimethyl malonate 38.9 parts and Djibouti
Charge 0.5 parts of lutin oxide and raise the temperature to 130 ° C
Was. Distillation of methanol produced by transesterification
Then, the temperature was gradually raised to 200 ° C. Then 200
While maintaining the temperature at 0 ° C., the distilled methanol was reduced to 18.5 parts.
The transesterification reaction is continued until
By adding 67 parts, the polyester resin composition 4
I got Each special value of the obtained polyester resin composition is
The results are shown in Table 1.

The obtained polyester resin composition 100
Parts, 55 parts of Sumidur BL3175, 26 parts of pentaerythritol triacrylate, 1.2 parts of tetrabutylammonium chloride, 4.4 parts of 1,2-epoxyhexadecane and 0.6 parts of dibutyltin dilaurate were mixed with stirring with a disper. Then, a curable resin composition was obtained by uniformly dissolving. Next, this curable resin composition was used as a film-forming component, and further, Tinuvin T-
1.5 parts of 384, 2.5 parts of Sanol LS-292 and 1 part of a surface conditioner were blended with a disperser and stirred, and uniformly dissolved to obtain a clear paint.

The obtained clear paint was coated with a BM (type B viscometer) manufactured by Tokyo Keiki Co., Ltd. having a viscosity at 20 ° C. of 100 m.
The viscosity was adjusted with xylene so as to obtain Pa · s. At this time, when the viscosity at 20 ° C. was measured by Ford Cup No. 4, it was 30 seconds. Further, in the same manner as in Example 1, a test plate was prepared by a two-coat one-bake method.

[0058]Example 5  In the same apparatus as in Example 1, hydrogenated bisphenol shown in Table 1 was added.
Sample C (R is a methyl group) 54.5 parts and malonic acid
150.0 parts of dimethyl was charged and the temperature was raised to 120 ° C.
Do not distill off the methanol distilled by the transesterification reaction.
Then, the temperature was gradually raised to 150 ° C. After that, 150 ° C
While maintaining, keep the distilled methanol down to 14.5 parts.
After continuing the transesterification reaction in
90 parts of chill were distilled off under reduced pressure. Cool to 67 parts of xylene
To obtain a polyester resin composition 5.
Was. Table 1 shows the special values of the obtained polyester resin composition.
It was shown to.

The obtained polyester resin composition 154
Parts, 68 parts of pentaerythritol triacrylate, 3.2 parts of tetrabutylammonium chloride, and 11.4 parts of 1,2-epoxyhexadecane are mixed with stirring with a disper and uniformly dissolved to obtain a curable resin composition. I got Next, this curable resin composition was used as a film-forming component, and 1.7 parts of Tinuvin T-384, 3.4 parts of Sanol LS-292, and 3 parts of a surface conditioner were further blended while being stirred with a disper. And a uniform coating was obtained to obtain a clear coating.

The obtained clear paint was coated with a BM (type B viscometer) manufactured by Tokyo Keiki Co., Ltd. having a viscosity at 20 ° C. of 100 m.
The viscosity was adjusted with xylene so as to obtain Pa · s. At this time, when the viscosity at 20 ° C. was measured by Ford Cup No. 4, it was 30 seconds. Further, in the same manner as in Example 1, a test plate was prepared by a two-coat one-bake method.

[0061]Comparative Example 1  In the same apparatus as in Example 1, hydrogenated bisphenol shown in Table 1 was added.
54.5 parts of sample D (R is a methyl group) and malonic acid
150.0 parts of dimethyl was charged and the temperature was raised to 120 ° C.
Do not distill off methanol produced by transesterification.
Then, the temperature was gradually raised to 150 ° C. After that, 150 ° C
While maintaining, keep the distilled methanol down to 14.5 parts.
After continuing the transesterification reaction in
90 parts of chill were distilled off under reduced pressure. Cool to 67 parts of xylene
To obtain a polyester resin composition 6.
Was. Table 1 shows the special values of the obtained polyester resin composition.
It was shown to.

[0062]Evaluation test  Polyester tree obtained in Examples 1 to 5 and Comparative Example 1
Fat compositions 1 to 6 and each clear paint and each test plate
The following evaluation test was conducted. The evaluation results are shown in Table 1.
Indicated. <Storage stability of polyester resin composition> Examples 1 to 5
And the polyester resin compositions 1 to 1 obtained in Comparative Example 1.
6 was stored at 25 ° C and the number of days until cloudiness occurred was evaluated.
did. The evaluation criteria were as follows. ：: The number of days until the occurrence of cloudiness is one month or more. ×: The number of days until the occurrence of cloudiness is within one month.

<Measurement of Weight of Solid Content of Clear Coating> 1 g of each clear coating obtained in Examples 1 to 5 was weighed to obtain 11
The mixture was heated at 0 ° C. for 1 hour, and the heating residue was measured.

<Pencil hardness of coating film> The coating film of each test plate obtained in Examples 1 to 5 was measured according to JIS K5400.
The pencil hardness was evaluated according to 4.2.

<Evaluation of Appearance> The coating film of each test plate obtained in Examples 1 to 5 was visually evaluated for the finished state.

[0066]

[Table 1]

As is clear from the results in Table 1, the polyester resin composition of the present invention has excellent storage stability. Further, a paint using the curable resin composition as a coating film-forming component using the same is a high solid paint having a small content of a volatile organic compound even in viscosity at the time of application. Further, the obtained coating film has good pencil hardness and appearance.

[0068]

The polyester resin composition of the present invention has a storage stability by controlling the content of the trans-trans form in the isomer mixture of hydrogenated bisphenol, which is one of the raw materials, to a specific range. Becomes better. this is,
By defining the content of the trans-trans isomer having a small steric hindrance in the isomer mixture, the ratio of the large cis-cis isomer becomes relatively high, and the crystallization of the resin during storage is inhibited by the steric hindrance. It is thought that it can be done. Further, by defining the melting point of the isomer mixture, it is possible to suppress softening and crystallization over time, and furthermore, decrease in hardness of a coating film obtained when used for a coating material. In addition, since the curable resin composition of the present invention contains the polyester resin composition described above, a curable coating composition using the same is a paint having a sufficiently high solid content even in the viscosity for application. The amount of the volatile organic compound contained can be reduced, and the hardness and appearance of the obtained coating film can be improved.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshifumi Ichinose 19-17 Ikedananakacho, Neyagawa-shi, Osaka Inside Nippon Paint Co., Ltd. F term (reference) in the company 4J002 CC182 CC212 CD002 CF031 CF041 CP032 ER006 FD142 FD146 GH01 4J029 AA03 AB01 AC01 AD01 AE11 BD10 CA02 CA03 CA04 CA06 CB05A CB06A GA23 GA42 GA74 HA01 HB01 HB02 4J038 CG141 DA142 DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DD052 DG261 DG262 DG301 DG302 DL021 DL022 KA03 KA06 MA12 MA14 NA03 NA11 NA24 NA26 NA27 PA19 PC02 PC03 PC06 PC08 PC10

Claims (9)

[Claims] 1. A compound of the general formula (1) (Wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), a trans-trans form, a trans-cis form and a cis-form of hydrogenated bisphenol represented by
In a polyester resin composition obtained from a raw material containing a cis isomer mixture and a carboxylic acid or a carboxylic acid ester, the content of the trans-trans isomer in the isomer mixture is 50% by weight or less. Polyester resin composition. 2. The polyester resin composition according to claim 1, wherein the content of the trans-trans isomer in the isomer mixture is 35 to 50% by weight. 3. The melting point of the isomer mixture is 40-16.
The polyester resin composition according to claim 1, which is at 5 ° C. 4. The polyester resin composition according to claim 1, wherein the content of the isomer mixture in the raw material is 10 to 80% by weight. 5. The polyester resin composition according to claim 1, which has a number average molecular weight of 400 to 3,000. 6. A polyester resin composition according to claim 1, further comprising a curing agent having a functional group capable of undergoing a curing reaction with the polyester resin composition. Curable resin composition. 7. The curing agent having a number average molecular weight of 200 to 3
The curable resin composition according to claim 6, which has a molecular weight of 000. 8. A curable coating composition comprising the curable resin composition according to claim 6 as a coating film-forming component. 9. The curable coating composition according to claim 8, wherein the solid content when the viscosity at 20 ° C. is 100 mPa · s is 40% by weight or more.