JPH0699619B2 - Polyester resin composition - Google Patents

Description

TECHNICAL FIELD The present invention mainly relates to a polyester resin composition for obtaining a black enamel coating film.

Conventional technology Although lacquer was used to paint high-end furniture for a long time, the production volume of lacquer is limited, and even with a small number of lacquer painting processes, 11 can be used, and with many, 27 can be used for finishing. Industrial production is difficult because it takes weeks to months. But,
The unique jet blackness, high gloss, depth and sharpness of the product obtained by lacquer coating are the most preferable.

Therefore, various developments of paints replacing lacquer painting have been made.

Cashew paint So-called cashew paint is known as one of the paints that replaces lacquer. This paint uses a cashew nut shell liquid or a mono- or polyhydroxyalkyl ether of cardanol, and / or an adduct obtained by the reaction of cardanol glycidyl ether and a dialkanolamine, which is then added to a metal salt such as cobalt octenoate. Is added for oxidative polymerization, and at this time, an isocyanate adduct is added to accelerate the crosslinking reaction.

Unsaturated Polyester Paint As an alternative to lacquer coating, a polybasic acid component containing an unsaturated polybasic acid component is reacted with a polyhydric alcohol component to obtain an unsaturated polyester having air-drying property (air drying property). To ethylenically unsaturated monomer and black dyeing
Attempts have also been made to prepare an unsaturated polyester resin composition by blending a pigment and apply it to coating.

As this type, in producing an unsaturated polyester having air-drying property by reacting a polybasic acid component containing an unsaturated polybasic acid component with a polyhydric alcohol component, cashew nut shell liquid or mono or poly of cardanol is used. A method of compounding and using a hydroxyalkyl ether, and a method of reacting an adduct obtained by the reaction of cardanol glycidyl ether and dialkanolamine have been proposed (Japanese Patent Publication Nos. 45-12873 and 47-23189). reference).

Problems to be Solved by the Invention The above-mentioned cashew paint is made of cashew nuts as a raw material, so that the raw materials are easily available, and the depth of the coating film formed, the sharpness, the water resistance, the alkali resistance, etc. However, there is a problem in that thick coating is limited because the internal curing rate is very slow.

According to the method described in JP-B-45-12873 or JP-B-47-23189, it is possible to impart properties such as preferable air-drying property, internal plasticity, and pigment wettability to a lacquer-coated product while being inexpensive. Although similar quality can be obtained, when painting pianos, there is a strong demand for a unique jet black feeling, high gloss, depth, and sharpness equivalent to lacquered products.

As a result of earnest studies under such circumstances, the present inventors have found a polyester resin composition containing a specific saturated polyester (X) and a cross-linking agent (Y) as main components as described below. Has been completed.

Means for Solving the Problems The polyester resin composition of the present invention comprises a saturated polyester (X) obtained by reacting a saturated polybasic acid component and a polyhydric alcohol component and a crosslinking agent (Y) as a main component. In the resin composition, as the saturated polyester (X), a polyhydric alcohol allyl ether component (a) and a glycidyl group or an alcoholic group derived from a phenolic compound selected from the group consisting of cardanol, cardol or an oligomer thereof. It is characterized in that a saturated polyester introduced with a derivative component (b) having a hydroxyl group is used.

Hereinafter, the present invention will be described in detail.

The polyester resin composition of the present invention comprises a saturated polyester (X) obtained by reacting a saturated polybasic acid component and a polyhydric alcohol component and a crosslinking agent (Y) as main components.

Saturated Polyester (X) Here, the saturated polybasic acid component constituting the saturated polyester (X) includes terephthalic acid, isophthalic acid, phthalic acid, 2,5-norbornanedicarboxylic acid, 1,4-naphthalic acid, 1,5 -Naphthalic acid, diphenic acid, 4,4'-oxybenzoic acid, diglycolic acid, thiodipropionic acid, 4,
4'-sulfonyldibenzoic acid, 2,5-naphthalenedicarboxylic acid, oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, diapinic acid, dodecanedicarboxylic acid, pimelic acid, 2,2-dimethylglutaric acid , Azelaic acid, sebacic acid, 1,3-cyclohexanedicarboxylic acid and the like.

If necessary, unsaturated polybasic acids such as maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, and fumaric acid are used in an amount of 50% by weight or less of the polybasic acid component (40 to 5% by weight of beads).
They can also be used in combination, and the air-drying property can be further improved by such a combination formulation.

Moreover, as the polyhydric alcohol component constituting the saturated polyester (X), ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, bisphenol dioxypropyl ether, 1,3-butylene glycol, 2,3- Butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 1,4 -Cyclohexanedimethanol, trimethylolethane trimethylolpropane, glycerin, pentaerythritol and the like. In some cases, a polyether glycol such as polytetramethylene glycol, polypropylene glycol or polyethylene glycol, or a hydroxyl group-containing liquid polybutadiene can be used in combination.

In the present invention, as the saturated polyester (X), glycidyl derived from a phenolic compound selected from the group consisting of (a) polyhydric alcohol allyl ether component, (b) cardanol, cardol or oligomers thereof. A saturated polyester in which both components of a base group or a derivative component having an alcoholic hydroxyl group are introduced is used. A synergistic effect can be obtained by using both the above components (a) and (b) together. If either one of (a) and (b) is lacking, the internal curability is insufficient, and the coating film In terms of jet-black feeling etc., the desired improvement effect is not sufficiently exerted.

Examples of the polyhydric alcohol allyl ether component (a) include pentaerythritol triallyl ether, pentaerythritol diallyl ether, trimethylolpropane diallyl ether, trimethylolpropane monoallyl ether, trimethylolethane diallyl ether, trimethylolethane monoallyl ether, and glycerin. Diallyl ether, glycerin monoallyl ether, tetramethylol cyclohexanol diallyl monochlorotyl ether, hexamethylol melamine diallyl dicrotyl ether, hexanetriol diallyl ether, pentaerythritol diallyl crotyl ether, tetramethylol cyclohexanol triallyl ether, tetramethylol cyclohexanone diallyl ether, Hexamethylol Mela Allyl ether having at least one hydroxyl group in the molecule, such as emissions tetraallyl ether can be exemplified.

This polyhydric alcohol allyl ether component (a), as an allyl group, is preferably from 0.05 to 1 mol per saturated polybasic acid component.
It is desirable to use it in a proportion of 0.5 mol, and if it is less than 0.05 mol, the curing and drying properties will be insufficient, while if it exceeds 0.5 mol, the bleaching phenomenon on the surface of the coating film will be remarkable. A particularly preferred range is 0.
It is 1 to 0.4 mol.

As the derivative component (b) having a glycidyl group or an alcoholic hydroxyl group derived from a phenolic compound selected from the group consisting of cardanol, cardol or an oligomer thereof, the following compounds are used.

Cardanol, which is a raw material phenolic compound, is obtained by heating and decarboxylating anacardic acid contained in cashew nut shell liquid. Caldor
Since it is contained in the cashew nut shell liquid, it may be isolated by an appropriate means. Cardanol or cardol oligomers are obtained by condensing cardanol or cardol with formaldehyde or a formaldehyde generator. The oligomer means dimer, trimer, tetramer and the like. Among the phenolic compounds that are the raw materials, the chemical formulas of cardanol, cardol, and cardanol dimer are shown below.

By reacting the above phenolic compound with epichlorohydrin in the presence of a basic catalyst, the corresponding glycidyl ether can be obtained. For example, for cardanol, the formula A cardanol glycidyl ether represented by is obtained. At this time, the formula The compound represented by (1) is by-produced, and this compound can also be used as the above-mentioned derivative component (b).

By reacting the cardanol glycidyl ether obtained above with a dialkanolamine such as diethanolamine or dipropanolamine, the formula A dialkanolamine adduct represented by (R is an alkylene group) is obtained.

By reacting the above phenolic compound with an alkylene oxide such as ethylene oxide or propylene oxide, an alkylene oxide adduct in which one or more phenolic hydroxyl groups are converted into O (CH ₂ CH ₂ O) nH can be obtained. n
Is usually 1, but may be 2 or more. The following formula shows an example of an adduct obtained by adding ethylene oxide to cardanol, cardol, or cardanol dimer.

Among the derivative components (b), cardanol glycidyl ether and cardanol alcohol are particularly preferable.

The ratio of the derivative component (b) introduced into the saturated polyester (X) is 0.05 with respect to 1 mol of the saturated polybasic acid component.
To be selected from the range of 0.5 mol. If this ratio is less than 0.05 mol, the image clarity of the black enamel surface will be insufficient, while if it exceeds 0.5 mol, thick coating of the paint will be impossible. A particularly preferred range is 0.1 to 0.4 mol.

Using the above components, that is, the saturated polybasic acid component, the polyhydric alcohol component, and the above-mentioned components (a) and (b), and reacting them in an inert gas atmosphere at a temperature of about 150 to 250 ° C. according to a conventional method. The target saturated polyester (X)
Can be obtained.

The polyester (X) may be modified by reacting it with an isocyanate compound, and the polyester segment portion may be chain-extended through an isocyanate bond.

Crosslinking Agent (Y) As the crosslinking agent (Y), an isocyanate compound, an epoxy compound, an amine compound, a compound having a radical generating ability, an oxidizing agent, a polymerizable monomer, a metal salt or the like is used.

Here, as the isocyanate compound, tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate,
1,4-tetramethylene diisocyanate, triphenylmethane triisocyanate, methylenebis (4-phenylmethane) triisocyanate, isophorone diisocyanate, trimethylolpropane of the above-mentioned isocyanate compound, adduct with triethylene glycol, etc., especially trimethylolpropane- Examples thereof include tolylene diisocyanate adduct, and ketoxime block products and phenol block products thereof.

Examples of epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin di- or triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, and diglycidyl amine. Is exemplified.

Examples of amine compounds include urea, melamine, and their methylol compounds, hexamethylenediamine, triethanolamine and the like.

Examples of the compound capable of generating radicals include carbonyl compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, pivaloin ethyl ether, acetophenone and 1,1-dichloro. Acetophenone, 2-phenylthioacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, ω-bromoacetophenone, benzophenone, dibenzyl, diacetyl, anthraquinone , 2-chloroanthraquinone, 2-bromoanthraquinone, anthraquinone β-sodium sulfonate, 1,5-dinitroanthraquinone, 1,2-benzanthraquinone, fe Trenquinone, naphthoquinone, chloronaphthoquinone, dichloropropyl phenyl ketone, Michler's ketone, 2-chlorothioxanthone, 2-methyloxanthone, etc., organic sulfur compounds such as dibutyl disulfide, dibenzyl disulfide, decyl phenyl disulfide, diphenyl disulfide, mercaptan. Azo compounds such as azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile,
2,2'-azobis (2-amidinopropane) hydrochloride, diazonium salt, tetrazonium salt or complex salt of these with zinc chloride or its condensate, organic peroxide such as benzoyl peroxide, methyl ethyl ketone peroxide, di- t-
Butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc., inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, etc., as well as halogen compounds, organometallic compounds, metal carbonyls, dyes ( Dyes such as methylene blue or a combination thereof with p-toluenesulfonate ion), pyrylium salt or thiapyrylium salt, phenanthrene, thioxanthone, 5-benzoylacenaphthene, 5-nitroacenaphthene, 1,8-phthaloylnaphthalene, 2- Examples include nitrofluorene, p-nitroaniline, picramide, and the like. If necessary, it is also useful to use a metal soap such as a cobalt salt such as octylic acid or naphthenic acid, a lead salt, a calcium salt or a manganese salt together.

Examples of the oxidizing agent include potassium dichromate, ammonium dichromate, calcium perchlorate and the like.

As the polymerizable monomer, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth)
Acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol mono or di (meth) acrylate, diethylene glycol mono or di (meth) acrylate, tetraethylene glycol mono Or di (meth) acrylate, propylene glycol mono or di (meth) acrylate, dipropylene glycol mono or di (meth) acrylate, polypropylene glycol mono or di (meth) acrylate, butylene glycol mono or di (meth)
Acrylate, 1,6-hexanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane di or tri (meth) acrylate, pentaerythritol di or tri (meth) acrylate
Acrylate, glycidyl (meth) acrylate, 2-
Hydroxy methacrylate glycidyl ether, dimethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-
Ethoxymethyl (meth) acrylamide, methylenebisacrylamide, (meth) acrylonitrile, N-vinylpyrrolidone, styrene, α-methylstyrene, vinyltoluene, monochlorostyrene, diallylphthalate,
Examples include triallyl cyanurate, vinyl acetate, vinyl chloride, divinylbenzene, and 2-hydroxymethacrylate glycidyl ether.

Examples of the metal salt include chlorides, bromides, nitrates, sulfates, acetates and the like of polyvalent metals such as aluminum, iron, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, and chromium, specifically, , Cupric chloride, aluminum chloride, ferric chloride, stannic chloride, zinc chloride, nickel chloride, magnesium chloride, aluminum sulfate, copper acetate, chromium acetate and the like.

Among the above-mentioned cross-linking agents (Y), an isocyanate compound (particularly trimethylolpropane-tolylene diisocyanate adduct), an organic peroxide and a metal soap (cobalt octenoate, cobalt naphthenate, etc.) or an amine / amine salt (diethylaniline) is used. Etc.), among the polymerizable monomers, particularly (meth) acrylic monomers, and among the carbonyl compounds, organic sulfur compounds, azo compounds, and organic peroxides having radical generating ability, those having a photosensitizing effect. And the (meth) acrylic monomer among the polymerizable monomers is particularly important. In case of normal temperature or heat curing type,
In the case, it is used as an ultraviolet ray curable type paint, and in the case of an electron beam curable type paint.

As a light source in the case of ultraviolet irradiation, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a plaque light and the like are used. The irradiation time varies depending on the type of the light source, the distance between the light source and the coating surface, and other conditions, but at most several tens of seconds is sufficient, usually several seconds, and in some cases it may be several seconds. After irradiation with ultraviolet rays, heating may be performed as necessary to achieve complete curing.

In the case of electron beam irradiation, for example, an electron beam having an energy in the range of 50 to 1000 KeV may be used, and the irradiation amount may be 2 to 5 Mrad.

Other Components The polyester resin composition of the present invention contains the saturated polyester (X) and the cross-linking agent (Y) as a main component, and usually, in addition to these, a dye / pigment is added.

Although various color tones are used as dyes and pigments, black dyes and pigments such as aniline black, carbon black and synthetic iron black are the most important, and in some cases titanium white,
Jianine blue, chrome yellow, watching red, red iron oxide, manganese blue, ultramarine blue, Hansa red, chrome yellow, chrome green and the like are also used.

In addition, if necessary, fillers (calcium carbonate, kaolin, clay, talc, mica, alumina, asbestos powder, fine silica, barium sulfate, lithopone, gypsum, perlite, etc.), abrasives (zinc stearate, fine talc, etc.) ), Leveling agents (silicone, cellulose acetate butyrate, surfactants, etc.), diluents (ethyl acetate, toluene, xylene, methanol, ethanol,
Butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cellosolves, diacetone alcohol, etc., thermoplastic resin (nitrocellulose, vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, acrylic resin, butylated melamine, butylated urea, etc.) ), An anti-greening agent (phosphoric acid, phosphorous acid, tartaric acid, etc.) and an air-drying aid (oils, paraffin wax, etc.) can also be added.

Action The polyester resin composition of the present invention is used for various coating purposes, but is particularly preferably used for coating high-grade musical instruments such as pianos, furniture, and furniture.

As a coating means, any coating method such as spray coating, brush coating, curtain flow coating, roll coating and dipping can be adopted.

After painting, buffing is performed to develop jet black feeling, high gloss, depth feeling and sharpness. However, this buffing may be omitted.

In the present invention, since the polyhydric alcohol allyl ether component (a) and the specific derivative component (b) are introduced into the saturated polyester (X), suitability for thick coating is exhibited, jet black feeling, high gloss, depth feeling, and vividness In terms of properties, a synergistic quality improving action is exhibited as compared with the case where either one of these components (a) or (b) is introduced.

EXAMPLES Next, the composition of the present invention will be further described with reference to Examples. Hereinafter, “part” and “%” are expressed on a weight basis.

Example 1 A flask equipped with a stirrer, a gas introduction tube and a reflux condenser was charged with 0.7 mol of phthalic anhydride, 0.3 mol of maleic anhydride, 0.30 mol of diethylene glycol, and trimethylolpropane.
0.40 mol was charged, 3% xylene and 0.02% hydroquinone (polymerization inhibitor) were charged, the first stage condensation reaction was carried out at a temperature of 200 ° C. for 5 hours while blowing nitrogen gas, and then trimethylolpropane diallyl ether was added. 0.
20 mol and 0.40 mol of cardanol glycidyl ether were charged and the second stage condensation reaction was carried out at a temperature of 200 ° C. for 3 hours. After completion of the reaction, the reaction was continued under reduced pressure at 150 ° C for 1 hour.

A portion of the saturated polyester (X) thus obtained was taken and 10% of the amount of aniline black was added, and 3
This roll was passed once to prepare a mill base, 35 parts of this mill base was added to 100 parts of the saturated polyester (X), and further diluted with 40 parts of toluene to give a solid content of 52.8.
%, A resin liquid having a viscosity of 350 cps / 20 ° C. was obtained. (The aniline black content is 2%.) To 100 parts of this resin liquid, 20 parts of trimethylolpropane-tolylene diisocyanate adduct (Coronate L-75 manufactured by Sumitomo Bayer Urethane Co., Ltd.) as a crosslinking agent (Y) and Cobalt octenoate (Octex Co manufactured by Nippon Kagaku Sangyo Co., containing 8% cobalt) 0.5% and methyl ethyl ketone peroxide (Permec-N manufactured by NOF Corporation) 1.0% were added, and the composition was diluted to a spray viscosity with toluene to obtain a coating composition. It was used as a material and spray-painted on a wood (piano material) surface and cured at room temperature.

The results are shown in Table 1.

Comparative Example 1 A saturated polyester (X) and a coating composition were produced in the same manner as in Example 1 except that the use of trimethylolpropane diallyl ether was omitted.

The results are also shown in Table 1.

Comparative Example 2 A saturated polyester (X) and a coating composition were produced in the same manner as in Example 1 except that the charging of cardanol glycidyl ether was omitted and the charging amount of diethylene glycol was changed to 0.7 mol.

The results are also shown in Table 1.

Comparative Example 3 A saturated polyester (X) and a coating composition were produced in the same manner as in Example 1 except that the charging of trimethylolpropane diallyl ether was omitted and the charging amount of diethylene glycol was changed to 0.5 mol. .

The results are also shown in Table 1.

The measurements in Table 1 and Tables 2 and 3 described later,
The determination method is as follows.

The hue was in accordance with JIS K-5400,6901.

Turbidity is based on the kaolin turbidity method (according to JIS K-0101).

For 80 ° C stability, 150ml of resin solution was put into a 200ml glass bottle, sealed and left in a constant temperature bath at 80 ° C to measure the number of days until gelation.

The 60 ° specular gloss, lightness L, and Hunter whiteness were measured using a Nippon Denshoku gloss color difference meter. In addition, the lightness L and the whiteness of the hunter show a jet black tendency as the numerical values are smaller.

Spray suitability and longevity are determined by visual inspection.

Mitsubishi Uni is used for pencil hardness.

As is clear from Table 1, the composition of the present invention has suitability for thick coating, and has excellent jet-blackness, high gloss, depth and sharpness, which are equivalent to those of lacquered products. In addition, it can be seen that the general physical properties are excellent.

Examples 2-4 Instead of 0.40 mol of cardanol glycidyl ether, 0.4 mol of cardanol glycidyl ether / diethanolamine adduct (Example 2), 0.13 mol of cardanol dimer alcohol (Example 3), cardanol alcohol
A saturated polyester (X) and a coating composition were produced in the same manner as in Example 1 except that a mixture of 0.20 mol and 0.20 mol of cardol alcohol (Example 4) was used.

The results are shown in Table 2.

Example 5 An experiment was conducted in the same manner as in Example 1 except that carbon black was used in place of aniline black, and excellent results similar to those in Example 1 were obtained.

Example 6 In a flask equipped with a stirrer, a gas introduction tube and a reflux condenser, 0.8 mol of phthalic anhydride, 0.2 mol of maleic anhydride, 0.3 mol of diethylene glycol, trimethylolpropane.
0.4 mol was charged, xylene 3% and hydroquinone (polymerization inhibitor) 0.02% were charged, the first stage condensation reaction was carried out at a temperature of 200 ° C. for 5 hours while blowing nitrogen gas, and then trimethylolpropane diallyl ether was added. 0.
Charge 2 mol, 0.4 mol of cardanol alcohol and temperature
The second stage condensation reaction was carried out at 200 ° C. for 3 hours. After completion of the reaction, the reaction was continued under reduced pressure at 150 ° C. for 1 hour, and xylene was distilled off.

The acid value of the saturated polyester (X) thus obtained was 14 KOHg / kg, and the viscosity of a solution having a resin content of 70% after dilution with toluene was 1500 cps / 20 ° C.

Prepare a resin liquid of the following composition and apply a thickness of 10 with an applicator.
10 μm for heat-treated polyethylene terephthalate film of 0μ
It was applied to a thickness of μ and irradiated with an active mercury lamp (80 w / cm) for 1.5 seconds.

Saturated polyester (X) 50 parts 2-Ethylhexyl acrylate 10 parts 2-Hydroxypropyl methacrylate 10 parts 1,6-Hexane glycol diacrylate 15 parts Trimethylolpropane triacrylate 15 parts Benzoin isopropyl ether 4 parts Film formed by UV irradiation Then, the jet black feeling, the sharpness, the 60 ° specular gloss, and the pencil hardness were judged or measured.

The results are shown in Table 3.

Comparative Example 4 Preparation of a saturated polyester (X), preparation of a coating composition and irradiation of ultraviolet rays were carried out in the same manner as in Example 6 except that the charging of cardanol alcohol was omitted and the charging amount of diethylene glycol was changed to 0.7 mol. It was

The results are also shown in Table 3.

Comparative Example 5 Preparation of a saturated polyester (X), preparation of a coating composition and irradiation with ultraviolet rays were carried out in the same manner as in Example 6 except that the charging of trimethylolpropane diallyl ether was omitted and the charging amount of diethylene glycol was changed to 0.7 mol. I went.

The results are also shown in Table 3.

Example 7 In the resin liquid composition of Example 6, blending of benzoin isopropyl ether was omitted, and carbon black of 2% was kneaded with three rolls.
Was applied to the untreated polyethylene terephthalate film of 5 μm thick, and was cured by irradiating it with an electron beam having an irradiation dose of 150 KeV and 3 Mrad.

The results were favorable as follows.

Cross-cut test 100/100 Jet-black feeling ◎ Gloss ◎ 60 ° mirror gloss Example 8 Experiments were conducted in the same manner as in Example 1 except that the use of maleic anhydride was omitted and the amount of phthalic anhydride charged was changed to 1.07 mol. As a result, results similar to those of Example 1 were obtained.

Effect of the Invention In the polyester resin composition of the present invention, since the polyhydric alcohol allyl ether component (a) and the specific derivative component (b) are introduced into the saturated polyester (X), these components (a) or (b) As compared with the case where either one of them is introduced, a synergistic quality improvement effect is exhibited. That is, it has suitability for thick coating, and provides excellent results equivalent to those of lacquer-coated products in terms of jet black feeling, high gloss, depth feeling, and sharpness, and can also maintain general physical properties.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C09D 167/02 PLB 175/06 PHQ (72) Inventor Tetsuya Kanbara 300-66 Takagi, Omiya City, Saitama Prefecture (56) References JP-B-45-12873 (JP, B1) JP-B-47-23189 (JP, B1)

Claims (6)

[Claims] 1. A polyester resin composition comprising a saturated polyester (X) obtained by reacting a saturated polybasic acid component and a polyhydric alcohol component and a crosslinking agent (Y) as a main component, wherein the saturated polyester (X) is , A polyhydric alcohol allyl ether component (a) and a derivative component (b) having a glycidyl group or an alcoholic hydroxyl group derived from a phenolic compound selected from the group consisting of cardanol, cardol or their oligomers were introduced. A polyester resin composition comprising a saturated polyester. 2. The ratio of the polyhydric alcohol allyl ether component (a) introduced into the saturated polyester (X) is 0.05 to 0.5 mol per 1 mol of the saturated polybasic acid component. The composition as described. 3. The composition according to claim 1, wherein the ratio of the derivative component (b) introduced into the saturated polyester (X) is 0.05 to 0.5 mol per 1 mol of the saturated polybasic acid component. . 4. A cardanol as a derivative component (b),
The reaction product obtained by reacting epichlorohydrin, epichlorohydrin and dialkanolamine, or alkylene oxide with a phenolic compound selected from the group consisting of cardol or oligomers thereof. Composition. 5. The crosslinking agent (Y) is at least one selected from the group consisting of an isocyanate compound, an epoxy compound, an amine compound, a compound having a radical generating ability, an oxidizing agent, a polymerizable monomer and a metal salt. The composition according to claim 1, which is a cross-linking agent. 6. The composition according to claim 1, which is a polyester resin composition for obtaining a black enamel coating film.