JP2002256040A - Polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition excellent in transparency, heat resistance, solvent resistance, resistance to the liquid crystal, adhesivity to an organic/inorganic film which can be used suitably as a liquid crystal display substrate and the like. SOLUTION: The composition comprises (a) a polyester resin of 99-1 pts.wt. being a polyester polymer comprising a dicarboxylic acid or its ester-forming derivative and a dihydroxy compound in which the acid contains a 2-7C aliphatic or alicyclic dicarboxylic acid and the compound contains a compound represented by the formula (1) [R1 , R2 , R3 and R4 are each a hydrogen or a 1-7C alkyl group, aralkyl group and they may be the same or different] and (b) a polyfunctional monomer having an unsaturated group of 2 or more of 1-99 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to transparency, heat resistance,
The present invention relates to a polyester resin composition having excellent solvent resistance and liquid crystal resistance, and can be suitably used for an optical element substrate such as a liquid crystal display element substrate.

[0002]

2. Description of the Related Art As a polyester having a fluorene skeleton, there is a patent relating to an aromatic polyester comprising 9,9-bis (hydroxyphenyl) fluorene as an aromatic diol and terephthalic acid and / or isophthalic acid as an aromatic dicarboxylic acid component. Many applications have been filed (Japanese Patent Laid-Open No. 57-192432). Also, for the purpose of improving moldability and optical anisotropy, patents and the like have been filed for polyesters using aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, etc. in addition to the aromatic dicarboxylic acid component (Japanese Patent Publication No. 4-22931). Such). It is described that polyesters having these fluorene skeletons are excellent in heat resistance and optical properties.

However, in order to use these resins for an optical element substrate such as a plastic liquid crystal display element substrate, dimethyl sulfoxide (DMS) used for removing resist is used.
O) and not desirably attacked by solvents such as alignment agents,
It is desired to improve solvent resistance without impairing excellent transparency and heat resistance. Furthermore, since these substrates are provided with an organic / inorganic film such as a gas / water vapor impermeable barrier and a transparent electrode, it is also desired that the substrates have improved adhesion with these organic / inorganic films.

[0004]

The problem to be solved by the present invention is that it is excellent in transparency, heat resistance, solvent resistance, and liquid crystal resistance which can be applied to a liquid crystal display element substrate and the like, and has a problem with organic / inorganic films. An object of the present invention is to provide a polyester polymer composition having excellent adhesion.

[0005]

That is, the present invention provides:
(1) (a) a polyester polymer comprising a dicarboxylic acid or an ester-forming derivative thereof and a dihydroxy compound, wherein the dicarboxylic acid contains an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid having 2 to 7 carbon atoms, and A polyester resin composition comprising 99 to 1 part by weight of a polyester resin containing the compound represented by the general formula (1), (b) 1 to 99 parts by weight of a polyfunctional monomer having two or more unsaturated groups,

[0006]

Embedded image

(R ₁ , R ₂ , R ₃ , and R ₄ represent hydrogen or an alkyl group or an aralkyl group having 1 to 7 carbon atoms, and may be the same or different.) The polyester resin composition according to item (1), wherein the unsaturated group of the polyfunctional monomer (b) having at least one is at least one selected from an allyl group, a vinyl group, an acryl group, and a methacryl group, (3) The polyester resin composition according to (1), wherein the compound (b) having two or more unsaturated groups is dicyclopentadienyl diacrylate, (4) an organic peroxide, The polyester resin composition according to the above (1), (2) or (3), which has been crosslinked by one or more crosslinking methods selected from electron beams and ultraviolet rays.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin of the present invention is represented by the general formula (1)

[0009]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ , and R ₄ are the same as described above). Here, various bisphenols (c) represented by the general formula (1) can be applied. Specific examples include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5 -Dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, and the like. Among these, 9,9-bis (4-hydroxyphenyl) fluorene is particularly preferred. These bisphenols may be used alone,
Also, two or more kinds may be used in combination.

The polyester resin of the present invention may be a copolymer of bisphenol (c) represented by the general formula (2) and another bisphenol. Other bisphenols include bis (4-hydroxyphenyl) methane [commonly known as bisphenol F], 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A] , 1,1
-Bis (4-hydroxyphenyl) cyclohexane,
4,4-dihydroxydiphenyl ether, 4,4-dihydroxydiphenylsulfone [commonly known as bisphenol S], 4,4-dihydroxydiphenylsulfide,
4,4-dihydroxybiphenol and the like.
Further, the polyester resin of the present invention may contain an unsaturated group in order to improve crosslinkability. Examples of the polyester resin containing an unsaturated group include those having an unsaturated group added to the terminal and those copolymerized with bisphenol containing an unsaturated group. Examples of the terminal unsaturated group include an allyl group, an acryl group, a methacryl group, and a maleimide group. Examples of bisphenols containing an unsaturated group include bis (3-allyl-4-hydroxyphenyl) methane (commonly called diallyl bisphenol F), 1,1
-Bis (3-allyl-4-hydroxyphenyl) ethane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane (commonly called diallyl bisphenol A), bis (3-allyl-4-hydroxyphenyl) ether, Bis (3-allyl-4-hydroxyphenyl) sulfone (commonly called diallyl bisphenol S), bis (3-allyl-4-hydroxyphenyl) sulfide, 3,3-diallyl-4, and 4-hydroxybiphenol can be exemplified.

The aliphatic or alicyclic dicarboxylic acids and ester-forming derivatives thereof used in the present invention include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, Aliphatic dicarboxylic acids such as ethyl malonic acid, monocyclic alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, and polycyclic alicyclic dicarboxylic acids such as tricyclodecene dicarboxylic acid An acid or the like is used. The total amount of the dicarboxylic acid component can be arbitrarily included in the range of 1 to 99 mol%, with 100 being the total.

For the purpose of further improving heat resistance, an aromatic dicarboxylic acid component such as a polycyclic aromatic dicarboxylic acid or biphenyldicarboxylic acid can be used together. At this time, the content of the aliphatic or alicyclic dicarboxylic acid component is desirably 50 mol% or more so as not to deteriorate the optical anisotropy. Examples of the aromatic dicarboxylic acid component used in this case include aromatic monocyclic dicarboxylic acids such as terephthalic acid and isophthalic acid, and polycyclic aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, anthracene dicarboxylic acid and phenanthylene dicarboxylic acid. And biphenyl dicarboxylic acids such as 2'-biphenyl dicarboxylic acid.

These dicarboxylic acids and their ester-forming derivatives may be used alone or in combination of two or more, if necessary. The polyester resin of the present invention can be produced by a known method used when producing a polyester resin. For example, it can be produced by a so-called interfacial polymerization method in which an alkaline aqueous solution of bisphenol and a dicarboxylic acid chloride dissolved in an organic solvent incompatible with water are mixed and synthesized. It can also be produced by a melt polymerization method in which a phenyl ester of an aromatic dicarboxylic acid and bisphenol are heated. However, in the case of the melt polymerization method, it is necessary to heat to a high temperature, and there is a problem that the polymer is easily colored. Therefore, the interfacial polymerization method is preferable.

In the case of production by an interfacial polymerization method, for example, a mixed aqueous solution of bisphenol and sodium hydroxide is added to a methylene chloride solution of succinic chloride, and 5-2
It is obtained by polymerizing at 5 ° C. with stirring for about 5 minutes to 5 hours. Examples of the organic solvent incompatible with water include methylene chloride, chloroform, 1,2-dichloroethane,
Chlorobenzene, xylene and the like are used. As the alkaline aqueous solution, an aqueous solution of potassium hydroxide, pyridine or the like is used in addition to sodium hydroxide.

In the polymerization reaction, in order to activate the polymerization reaction, a phase transfer catalyst such as a tertiary amine or a quaternary ammonium salt, for example, triethylamine, triethylbenzylammonium chloride, tetrabutylammonium bromide or the like is used. it can. Further, in order to obtain a polymer having a predetermined molecular weight, the molecular weight may be adjusted using a molecular weight regulator. As the molecular weight regulator, a monovalent phenol compound is used. For example, pt-butylphenol and the like can be used.

The number average molecular weight of the polyester resin of the present invention is preferably 5,000 to 200,000, more preferably 10,000 to 150,000, and most preferably 15,000 to 100,000. If the number average molecular weight is less than 5,000, the polymer tends to be brittle, and if it exceeds 200,000, the viscosity tends to be too high and the moldability tends to be poor.

As the polyfunctional monomer (b) having two or more unsaturated groups used in the present invention, various compounds having two or more unsaturated groups can be applied. As the unsaturated group, an allyl group, a vinyl group, an acryl group, a methacryl group and the like are preferable. Specific examples of the polyfunctional monomer having two or more unsaturated groups used in the present invention, such as triallyl isocyanurate, diallyl isophthalate, polyfunctional allyl compounds such as diallyl terephthalate, divinyl biphenyl, divinyl benzene, trivinyl cyclohexane and the like Polyfunctional vinyl compound, isocyanuric acid triacrylate, isocyanuric acid triethoxy triacrylate, trimethylolpropane triacrylate, trimethylolpropane triethoxy triacrylate, trimethylolpropane tripropoxy triacrylate, glycerylpropoxy triacrylate, pentaerythritol triacrylate, penta Erythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pen Acrylate, alkoxy Ray Ted bisphenol A diacrylate, propoxy Ray Ted bisphenol A diacrylate, alkoxy Ray Ted hydrogenated bisphenol A diacrylate,
Multifunctional acrylate compounds such as propoxylated hydrogenated bisphenol A diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dialkoxy diacrylate, and dicyclopentadienyl diacrylate; Examples include a polyfunctional methacrylate compound in which an acrylic group of a functional acrylate compound is replaced with a methacryl group, and among them, dicyclopentadienyl diacrylate is particularly preferable.

The ratio of the polyester resin (a) used in the present invention to the multifunctional monomer (b) having two or more unsaturated groups is 99/1 to 1 / (b) by weight% of (a) / (b). 99
Is preferable, 98/2 to 10/90 is more preferable, and 95/5 to 50/50 is particularly preferable. (A)
If the ratio is less than 1% by weight, the adhesion to the organic / inorganic film tends to be inferior. If it exceeds 99% by weight, the effect of adding (b) is not recognized, and the solvent resistance may be insufficient. .

The polyester resin and the composition of the present invention can be crosslinked by any method as long as it can be polymerized by the reaction of unsaturated groups. Among them, from the viewpoint of transparency, organic peroxides, electron beams, and ultraviolet rays are preferred, and crosslinking using ultraviolet rays is particularly preferred.

The polyester resin composition of the present invention becomes a member having excellent solvent resistance by cross-linking with an organic peroxide, an electron beam, ultraviolet light or the like. The method for forming the member can be selected according to the viscosity of the composition comprising the polyester resin (a) and the polyfunctional monomer (b) having two or more unsaturated groups. For example, casting a resin composition dissolved in a solvent, after evaporating the solvent, electron beam or ultraviolet irradiation, or crosslinking and molding by heating, or directly cast on a roll or belt,
Furthermore, using two opposing flat plates that can transmit an electron beam or ultraviolet light made of polished glass or the like, a cavity is formed by a spacer or the like, and injected into an injection mold having a peripheral portion sealed, and the electron beam or It can be molded by cross-linking by ultraviolet irradiation or heating. Alternatively, after the resin composition is extruded, the resin composition may be cross-linked by electron beam, ultraviolet light, or heating to be molded.

(Crosslinking of Organic Peroxide) Crosslinking with an organic peroxide can be carried out by a usual method of crosslinking with an organic peroxide applied to an unsaturated polyester or the like. As the organic peroxide used in the present invention, known compounds such as dialkyl peroxide, acyl peroxide, hydroperoxide, ketone peroxide and peroxyester can be used. Specifically, dicumyl peroxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane,
2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, di-t-hexyl peroxide,
1,1-bis (t-butylperoxy) -3,3,5-
Trimethylcyclohexane, t-butylperoxy-2
-Ethylhexanoate, t-butylperoxyisopropyl monocarbonate and the like. The compounding amount of the organic peroxide is preferably from 0.1 to 10 parts by weight, more preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of (a) + (b). If the amount of the organic peroxide is less than 0.1 part by weight, sufficient crosslinking cannot be obtained and the solvent resistance tends to be poor. If the amount is more than 10 parts by weight, the appearance of the crosslinked product tends to deteriorate.

(Crosslinking by Electron Beam) The polyester resin composition of the present invention can be crosslinked by radiation such as an electron beam. The irradiation amount of the electron beam is 100 kGy to 2000 kG.
The range of y is preferable, and the range of 500 kGy to 1500 kGy is more preferable, but there is no particular problem even if the value deviates from this range as long as the properties of the obtained crosslinked product do not deviate from the intended range. As the radiation, electron beams from various electron beam accelerators are preferable, but radiation such as α-rays, β-rays, and γ-rays from radioisotopes can also be used.

(Crosslinking by Ultraviolet Ray) The polyester resin composition of the present invention can be crosslinked even by ultraviolet ray by adding a photopolymerization initiator. Examples of the photopolymerization initiator include benzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, and 2,4,6-trimethyl. Benzoyldiphenylphosphine oxide and the like. Two or more of these photopolymerization initiators may be used in combination.

The addition amount of the photopolymerization initiator is (a) + (b)
The amount is preferably 0.02 to 5 parts by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight. If the amount of the photopolymerization initiator is less than 0.02 parts by weight, the crosslinking tends to be insufficient, and if it exceeds 5 parts by weight, the hue tends to deteriorate. The irradiation amount of the ultraviolet ray is arbitrary as long as the photopolymerization initiator generates radicals, but it is preferable to irradiate the ultraviolet light in the range of 0.1 to 200 J in accordance with the type and amount of the photopolymerization initiator.

In the present invention, irradiation with an electron beam or ultraviolet rays and thermal polymerization may be used in combination for the purpose of promptly completing crosslinking. That is, the composition is heated to 30 to 300 ° C. simultaneously with or after the irradiation with the electron beam or ultraviolet light. in this case,
An organic peroxide may be added. In the present invention, the completion of the polymerization reaction and the internal strain generated during the polymerization can be reduced by heating the crosslinked product after the crosslinking by irradiation with an electron beam or an ultraviolet ray. The heating temperature is preferably selected as appropriate according to the composition of the crosslinked product and the glass transition temperature.

In order to improve thermal stability, weather resistance, durability, water resistance, corrosion resistance and the like, the polyester resin composition of the present invention further comprises an ultraviolet absorber, a light stabilizer,
Additives such as an antioxidant, an antifoaming agent, a leveling agent, a release agent, and an ion scavenger can be added to further improve the performance.

[0028]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

Synthesis Example 1 [Synthesis of Polyester Resin A] In a 1 L four-necked flask (with a stirrer, a reflux tube, a gas inlet tube, and a dropping funnel) was added 163.2 ml of a 1M aqueous sodium hydroxide solution.
Dissolve 28.0 g of bisphenolfluorene and 0.48 g of benzyltetraethylammonium chloride,
This was mixed with 11.8 g of succinic chloride and 16 ml of methylene chloride.
A solution dissolved in 0 ml was added and stirred vigorously at room temperature for 30 minutes. After completion of the reaction, the organic phase was separated, washed with water, and then poured into acetone. The precipitate was filtered, washed with acetone and dried. As a result, the number average molecular weight was 20,
000 polyester resin A was obtained.

Synthesis Example 2 [Synthesis of Polyester Resin B] In a 1 L four-necked flask (with a stirrer, a reflux tube, a gas introduction tube, and a dropping funnel) was added 163.2 ml of a 1M aqueous sodium hydroxide solution.
Dissolve 28.0 g of bisphenolfluorene and 0.48 g of benzyltetraethylammonium chloride,
A solution of 6.96 g of adipoyl chloride and 7.72 g of a 5/5 mixture of terephthalic acid chloride / isophthalic acid chloride in 160 ml of methylene chloride was added thereto, followed by vigorous stirring at room temperature for 30 minutes. After completion of the reaction, the organic phase was separated, washed with water, and then poured into acetone.
The precipitate was filtered, washed with acetone and dried. As a result, polyester resin B having a number average molecular weight of 28,000
I got

Example 1 5 g of synthesized polyester resin A and 5 g of cyclopentadienyl diacrylate (DCPDA) were dissolved in 10 g of chloroform, and 1-hydroxycyclohexyl phenyl ketone [Irgacure manufactured by Ciba Geigy Co., Ltd.] was used as a photopolymerization initiator in the solution. 184 "], after dissolving 0.05 g, the solution was cast on a release-treated glass plate,
After irradiating 1000 mJ / cm ² of ultraviolet rays to crosslink, the sheet was further heated under reduced pressure in a nitrogen oven at 250 ° C. * 1 hour to obtain a sheet having a thickness of 0.2 mm.

Example 2 A sheet was obtained in the same manner as in Example 1 except that the polyester resin A in Example 1 was changed to the polyester resin B. Example 3 A sheet was obtained in the same manner as in Example 1, except that 8 g of the synthesized polyester resin A and 2 g of dicyclopentadienyl diacrylate (DCPDA) were used. Example 4 A solution prepared by dissolving 8 g of the synthesized polyester resin A and 2 g of divinyl biphenyl (DVBP) in 20 g of chloroform was cast on a glass plate subjected to a mold release treatment, and 1000 kG.
After irradiating with electron beam of y to crosslink, it was further heated in a reduced pressure oven at 250 ° C. * 1 hour under reduced pressure for a thickness of 0.2 m.
m of sheets were obtained.

Example 5 8 g of the synthesized polyester resin A and 2 g of divinylbiphenyl (DVBP) were dissolved in 20 g of chloroform, and bis (t-butylperoxy) as an organic peroxide was dissolved therein.
After dissolving 0.2 g of diisopropylbenzene [“Perbutyl P” manufactured by NOF CORPORATION], this solution is cast on a glass plate subjected to a mold release treatment, and is heated at 150 ° C. * 1 hour + 175 in an oven under a nitrogen atmosphere. ° C * 1 hour + 200 ° C *
After heating for 1 hour for cross-linking, the sheet was further heated under reduced pressure in an oven under reduced pressure at 250 ° C. * 1 hour to obtain a sheet having a thickness of 0.2 mm.

Comparative Example 1 10 g of the synthesized polyester resin A was mixed with chloroform 10
g was cast on a release-treated glass plate and placed in an oven under a nitrogen atmosphere at 150 ° C. * 1 hour +
After heating and drying at 175 ° C. * 1 hour + 200 ° C. * 1 hour, the sheet was further heated under reduced pressure in an oven under reduced pressure at 250 ° C. * 1 hour to obtain a sheet having a thickness of 0.2 mm.

Comparative Example 2 Bis (t-butylperoxy) diisopropylbenzene ["Perbutyl P" manufactured by NOF Corporation] as an organic peroxide in 10 g of dicyclopentadienyl diacrylate
After mixing 0.2 g, the mixture was cast on a release-treated glass plate and placed in an oven under a nitrogen atmosphere for 15 minutes.
0 ° C. * 1 hour + 175 ° C. * 1 hour + 200 ° C. * 1 hour for cross-linking, followed by 25 minutes in an oven under reduced pressure.
The mixture was heated under reduced pressure at 0 ° C. * 1 hour. For the sheet created as described above, by the following method, color, light transmittance,
Solvent resistance (DMSO, NMP), liquid crystal resistance, heat resistance (T
g) was evaluated.

<Evaluation Method> Color: The appearance was visually observed. Light transmittance: The light transmittance at 550 nm was measured with a U3200 type spectrophotometer manufactured by Hitachi, Ltd. DMSO resistance: Dimethyl sulfoxide (DM at 40 ° C)
After immersing the sample in SO) and leaving it to stand for 60 minutes, the sample was taken out and its appearance was visually observed. Alignment agent resistance: A sample is placed on a spin coater. After dripping CRD-8201 (manufactured by Sumitomo Bakelite) on the surface, spin coating was performed at 2500 rpm. 180
After drying at 60 ° C. for 60 minutes, the appearance was visually observed. Liquid crystal resistance: ZIL-47 manufactured by Merck on the surface of the sheet
One drop of 92 was left and left for 1 hour in an oven at 120 ° C., after which the sample was taken out and the appearance was visually observed. Heat resistance (Tg): DMS-2 manufactured by Seiko Denshi Co., Ltd.
The maximum value of tan δ at 1 Hz using a 10-year-old male measuring apparatus was defined as a glass transition point (Tg). Adhesion with inorganic film: After repeating the treatment of the sheet on which the inorganic film has been formed by sputtering twice at 210 ° C. for 2 hours and at 95 ° C. for 30 minutes in hot water, the occurrence of cracks in the inorganic film is observed by an electron microscope (SEM). Was observed.

The evaluation results are shown in Tables 1 and 2. As is clear from these results, in Examples 1 to 5, DMSO resistance and orientation agent resistance, which were disadvantages of the conventional polyester made of bisphenolfluorene, were improved, and T
A sheet suitable for a liquid crystal display substrate having heat resistance of 200 ° C. or more and transparency and liquid crystal resistance of a light transmittance of 88% or more can be obtained.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

The polyester resin composition of the present invention is excellent in transparency, solvent resistance, liquid crystal resistance, heat resistance, and adhesion to inorganic films, and can be suitably used for a liquid crystal display substrate instead of a glass substrate. Can be.

Continuation of front page (72) Inventor Sumio Shibahara 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. F-term (reference) 2H090 JB03 4J011 QA11 QA15 QA22 QA27 RA07 SA06 SA16 SA22 SA32 SA84 UA01 UA03 VA04 WA07 4J026 AB08 BA21 BA22 BA28 DB05 DB11 DB36 FA09 GA06 GA07 GA08 4J029 AA03 AB01 AC01 AD09 AE18 BD08 CA03 CA04 CA05 CA06 CB05A CB06A CB10A CC05A CC09 CD03

Claims (4)

[Claims] 1. A polyester polymer comprising (a) a dicarboxylic acid or an ester-forming derivative thereof and a dihydroxy compound, wherein the dicarboxylic acid comprises an aliphatic or alicyclic dicarboxylic acid having 2 to 7 carbon atoms, Is a polyester resin composition comprising 99 to 1 parts by weight of a polyester resin containing the compound represented by the general formula (1), and (b) 1 to 99 parts by weight of a polyfunctional monomer having two or more unsaturated groups. Embedded image (R ₁ , R ₂ , R ₃ and R ₄ represent hydrogen or an alkyl group or aralkyl group having 1 to 7 carbon atoms, and may be the same or different.) 2. The polyfunctional monomer having two or more unsaturated groups (b), wherein the unsaturated group is at least one selected from an allyl group, a vinyl group, an acryl group and a methacryl group. 2. The polyester resin composition according to item 1. 3. Compound (b) having two or more unsaturated groups
Is a dicyclopentadienyl diacrylate. The polyester resin composition according to claim 1, wherein 4. The crosslinking treatment according to claim 1, wherein the crosslinking treatment is carried out by at least one crosslinking method selected from organic peroxides, electron beams and ultraviolet rays.
Or the polyester resin composition according to 3.