JP2002194069A - Aromatic polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aromatic polyester resin composition excellent in transparency, thermal resistance, solvent resistance and liquid crystal resistance, and capable of very suitably using for a substrate for a crystal displaying element, a substrate for an organic EL element, and the like. SOLUTION: This aromatic polyester resin composition is composed of repeating units given by formula (1), and does not dissolve or does not swell greater than twice, even if heated at 60 deg.C and for 1 hr in dimetyl sulfoxide(DMSO).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to transparency, heat resistance,
The present invention relates to an aromatic polyester resin composition having excellent solvent resistance and liquid crystal resistance.
It can be suitably used for an element substrate or the like.

[0002]

2. Description of the Related Art An aromatic polyester having a fluorene skeleton relates 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 patents have been filed (JP-A-57-192432 and the like). These aromatic polyesters are described as having excellent heat resistance and optical properties. However, when these resins are used for a plastic liquid crystal display element substrate, an organic EL element substrate, or the like, it is desirable that the resin is not affected by a solvent such as dimethyl sulfoxide (DMSO) or a solvent in an alignment agent, and has excellent transparency and heat resistance. It is desired to improve the solvent resistance without impairing the solvent.

[0003]

The problem to be solved by the present invention is that an aromatic compound having excellent transparency, heat resistance, solvent resistance and liquid crystal resistance which can be applied to a liquid crystal display element substrate, an organic EL element substrate and the like. An object of the present invention is to provide an aromatic polyester resin composition.

[0004]

That is, the present invention provides:
(1) an aromatic polyester resin composition containing a repeating unit represented by the following general formula (1), and does not dissolve or swell twice or more in dimethyl sulfoxide (DMSO) at 60 ° C. for 1 hour;

[0005]

Embedded image

(R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen or a compound having 1 carbon atom.
To 7 represent an alkyl group and an aralkyl group, which may be the same or different. (2) (a) 99 to 1 part by weight of an aromatic polyester resin containing a repeating unit represented by the general formula (1),
(B) Polyfunctional monomers 1 to 9 having two or more unsaturated groups
9 parts by weight of an aromatic polyester resin composition,
(3) The unsaturated group of the polyfunctional monomer (b) having two or more unsaturated groups is an allyl group, a vinyl group, an acryl group,
The aromatic polyester resin composition according to item (2), wherein the aromatic polyester resin composition is at least one member selected from a methacryl group.
(5) The aromatic polyester resin composition according to (2), wherein the compound (b) having two or more unsaturated groups is divinyl biphenyl, and (5) a compound having two or more unsaturated groups. The aromatic polyester resin composition according to item (2), wherein the polyfunctional monomer (b) is dicyclopentadienyl diacrylate (6), selected from organic peroxides, electron beams, and ultraviolet rays. The aromatic polyester resin composition according to any one of the items (1) to (5), which has been crosslinked by one or more crosslinking methods.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The aromatic polyester resin of the present invention is represented by the general formula (2)

[0008]

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 (2) can be applied. As a specific example, 9,9′-bis (4-hydroxyphenyl)
Fluorene, 9,9′-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9′-bis (4-hydroxy-3,5-dimethylphenyl) fluorene,
9′-bis (4-hydroxy-3-ethylphenyl) fluorene, and the like. Among them, 9, 9 '
-Bis (4-hydroxyphenyl) fluorene is particularly preferred. These bisphenols may be used alone or in combination of two or more.

[0010] The aromatic 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] and 1,1′-bis (4-
(Hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A], 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′- Examples thereof include dihydroxydiphenylsulfone [commonly known as bisphenol S], 4,4′-dihydroxydiphenylsulfide, and 4,4′-dihydroxybiphenol. Further, the aromatic polyester resin of the present invention may contain an unsaturated group in order to improve crosslinkability. Examples of the aromatic 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. Bisphenols containing an unsaturated group include bis (3-
Allyl-4-hydroxyphenyl) methane (commonly called diallylbisphenol F), 1,1′-bis (3-allyl-
4-hydroxyphenyl) ethane, 2,2′-bis (3
-Allyl-4-hydroxyphenyl) propane (commonly called diallylbisphenol A), bis (3-allyl-4-hydroxyphenyl) ether, bis (3-allyl-4-)
Examples thereof include (hydroxyphenyl) sulfone (commonly called diallyl bisphenol S), bis (3-allyl-4-hydroxyphenyl) sulfide, and 3,3′-diallyl-4,4′-hydroxybiphenol.

The acid component used in the present invention is isophthalic acid and / or terephthalic acid. Isophthalic acid and terephthalic acid are preferably used as a mixture in a molar ratio of 3/7 to 7/3, and most preferably a molar ratio of 4/6 to 6/4. The aromatic polyester resin of the present invention can be produced by a known method used for producing an aromatic polyester resin. For example, an alkaline aqueous solution of bisphenol,
It can be produced by a so-called interfacial polymerization method in which an aromatic dicarboxylic acid chloride dissolved in an organic solvent incompatible with water is 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 the interfacial polymerization method, for example, a mixed aqueous solution of bisphenol and sodium hydroxide is added to a methylene chloride solution of isophthalic acid dichloride and terephthalic acid dichloride, and the mixture is stirred at 5 to 25 ° C. under stirring.
It is obtained by polymerizing for about 1 minute 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, 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 to activate the polymerization reaction. 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 aromatic polyester resin of the present invention is preferably 5,000 to 200,000, and 10,000 to 1
It is more preferably 50,000, and most preferably 15,000 to 100,000. When the number average molecular weight is 5,000 or less,
The polymer tends to be brittle, and if it exceeds 200,000, the viscosity tends to be too high and the moldability tends to deteriorate.

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, dicyclopentadienyl diacrylate, etc. Examples include a polyfunctional methacrylate compound in which the acryl group of the functional acrylate compound is replaced with a methacryl group. Among them, divinyl biphenyl and dicyclopentadienyl diacrylate are particularly preferable. As divinyl biphenyl, 4,4′-divinyl biphenyl, 3,4 ′
-Divinylbiphenyl, 3,3'-divinylbiphenyl, 2,2'-divinylbiphenyl and the like, which may be used alone or as a mixture thereof,
It may be used as a mixture containing a biphenyl compound such as monovinyl biphenyl. The content of divinyl biphenyl in the biphenyl compound is preferably at least 30%, more preferably at least 50%.

The ratio of the aromatic polyester resin (a) used in the present invention to the multifunctional monomer (b) having two or more unsaturated groups is 99/99 by weight% of (a) / (b).
It is preferably from 1/1/99, and from 98/2 to 10 /
90 is more preferred, and 95/5 to 50/50 is particularly preferred. When the proportion of (a) is 1% by weight or less, the crosslinked product tends to become brittle. When the proportion exceeds 99% by weight, the effect of adding (b) is not recognized, and the solvent resistance may be insufficient.

The method for crosslinking the aromatic polyester copolymer and the composition of the present invention can be applied by any method as long as it can be polymerized by the reaction of unsaturated groups. Above all, from the viewpoint of transparency, organic peroxides, electron beams and ultraviolet rays are preferred, and crosslinking by heating using an organic peroxide and crosslinking by ultraviolet rays are particularly preferred.

The aromatic polyester resin composition of the present invention becomes a member having excellent solvent resistance by being crosslinked with an organic peroxide, an electron beam, ultraviolet rays, or the like. The method of forming the member can be selected according to the viscosity of the composition comprising the aromatic polyester resin (a) and the polyfunctional monomer (b) having two or more unsaturated groups (b). For example,
Cast a solution of the resin composition in a solvent, after evaporating the solvent, irradiate with an electron beam or ultraviolet light, or cross-link and mold by heating, or directly cast on a roll or belt, and even from a polishing glass etc. Using two opposing flat plates through which an electron beam or ultraviolet light can pass, a cavity is formed by a spacer or the like, and the periphery is sealed and injected into an injection mold. It can be molded by crosslinking. Also, after extrusion molding of the resin composition, an electron beam or ultraviolet light,
Alternatively, it may be molded by crosslinking by heating.

(Crosslinking of Organic Peroxide) Crosslinking with an organic peroxide can be carried out by a usual crosslinking method using 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 (a) + (b)
Is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight. 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 aromatic 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 200 kGy.
The range of 0 kGy is preferable, and 500 kGy to 1500 k
The range of Gy is more preferable, but there is no particular problem if 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 α-rays, β-rays from radioisotopes,
Radiation such as gamma rays can also be used.

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

The amount of the photopolymerization initiator added 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, etc., the aromatic polyester resin composition of the present invention further comprises an ultraviolet absorber, a light stabilizer, Further, additives such as an antioxidant, an antifoaming agent, a leveling agent, a release agent, and an ion scavenger may be added to further improve the performance.

[0027]

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 aromatic polyester resin] 1-L four-necked flask (with stirrer, reflux tube, gas inlet tube, dropping funnel)
163.2 ml of 1 M aqueous sodium hydroxide solution
28.0 g of bisphenolfluorene and 0.48 g of benzyltetraethylammonium chloride were dissolved therein, and a solution prepared by dissolving 15.48 g of a 1/1 mixture of terephthalic acid dichloride and isophthalic acid dichloride in 160 ml of methylene chloride was added thereto. Stir vigorously for hours. 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 4
An aromatic polyester resin having a glass transition temperature Tg = 320 ° C. of 2,000 was obtained.

Example 1 8 g of an aromatic polyester resin and divinyl biphenyl (D
VBP) (2 g) was dissolved in chloroform (20 g), and 0.1 g of bis (t-butylperoxy) diisopropylbenzene [“Perbutyl P” manufactured by NOF Corporation] was dissolved therein as an organic peroxide. The solution was cast on a release-treated glass plate and placed in an oven under a nitrogen atmosphere at 150 ° C. * 1 hour + 175 ° C. * 1 hour + 200 ° C. * 1
After heating for a time to crosslink, it 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.

Example 2 A sheet was obtained in the same manner as in Example 1, except that 6 g of the aromatic polyester resin and 4 g of divinyl biphenyl were used. Example 3 5 g of an aromatic polyester resin and dicyclopentadienyl diacrylate (DCPDA) [M-20 manufactured by Toagosei Co., Ltd.
3] A sheet was obtained in the same manner as in Example 1 using 5 g. Example 4 A sheet was obtained in the same manner as in Example 1 using 5 g of an aromatic polyester resin and 5 g of triacrylisocyanurate (TAIC).

Example 5 8 g of aromatic polyester resin and 2 g of divinyl biphenyl
Was dissolved in 20 g of chloroform, cast on a release-treated glass plate, irradiated with an electron beam of 1000 kGy to crosslink, and then further dried in an oven under reduced pressure.
The film was heated under reduced pressure for 1 hour to obtain a sheet having a thickness of 0.2 mm.

Example 6 5 g of an aromatic polyester resin and 5 g of dicyclopentadienyl diacrylate were dissolved in 20 g of chloroform, and 1-hydroxycyclohexyl phenyl ketone [Irgacure 1 manufactured by Ciba Geigy Co., Ltd.] was added as a photopolymerization initiator.
84 "], after dissolving 0.05 g, casting this solution on a release-treated glass plate, irradiating with 500 mJ / cm ² to crosslink, and further heating at 275 ° C. * in an oven under a nitrogen atmosphere. After heating for 3 hours, a sheet having a thickness of 0.2 mm was obtained. Example 7 A sheet was obtained in the same manner as in Example 6, except that 8 g of the aromatic polyester resin and 2 g of dicyclopentadienyl diacrylate were used. Example 8 A sheet was obtained in the same manner as in Example 6, except that 6 g of the aromatic polyester resin and 4 g of dicyclopentadienyl diacrylate were used. Example 9 A sheet was obtained in the same manner as in Example 6, except that 4 g of the aromatic polyester resin and 6 g of dicyclopentadienyl diacrylate were used. Example 10 A sheet was obtained in the same manner as in Example 6, except that 1 g of the aromatic polyester resin and 9 g of dicyclopentadienyl diacrylate were used.

Comparative Example 1 A solution obtained by dissolving 10 g of an aromatic polyester resin in 20 g of chloroform was cast on a glass plate subjected to a release treatment.
150 ° C * 1 hour + 175 in an oven under nitrogen atmosphere
C. * 1 hour + 200.degree. C. * 1 hour, dried by heating, and further heated under reduced pressure in an oven at 250.degree. C. * 1 hour to obtain a sheet having a thickness of 0.2 mm.

Comparative Example 2 10 g of triallyl isocyanurate was mixed with 0.1 g of bis (t-butylperoxy) diisopropylbenzene [“Perbutyl P” manufactured by NOF Corporation] as an organic peroxide, and the mixture was added to the mixture. After casting on a release-treated glass plate and heating and crosslinking in an oven under a nitrogen atmosphere at 150 ° C. * 1 hour + 175 ° C. * 1 hour + 200 ° C. * 1 hour, it is further heated in an oven under reduced pressure at 250 ° C. * Heated under reduced pressure for 1 hour. The obtained crosslinked product was very brittle and could not be formed into a sheet.

With respect to the sheet prepared as described above, the color, light transmittance, and solvent resistance (D
(MSO), alignment agent resistance, liquid crystal resistance, and heat resistance (Tg) were evaluated. <Evaluation method> Color: The appearance was visually observed. Light transmittance: The light transmittance at 500 nm was measured with a Hitachi U3200 type spectrophotometer. DMSO resistance: 60 ° C. dimethyl sulfoxide (D
(MSO) and left for 60 minutes, the sample was taken out, and the appearance was visually observed. Alignment agent resistance: A sample was placed on a spin coater, and an alignment agent CRD-8201 (manufactured by Sumitomo Bakelite) was dropped on the surface thereof, and then spin-coated at 2500 rpm. After drying at 180 ° 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 in an oven at 80 ° C. for 1 hour, then the sample was taken out and the appearance was visually observed. Heat resistance (Tg): Examples 1-5 and Comparative Examples 1-2
The glass transition temperature (Tg) was measured with a DSC-220 differential scanning calorimeter manufactured by Seiko Electronics Co., Ltd. according to JIS K7121. In Examples 6 to 10, the maximum value of tan δ at 1 Hz with a DMS-210 type viscoelasticity measurement device manufactured by Seiko Electronics Co., Ltd. was defined as the glass transition temperature (Tg).
In addition, it has been confirmed that the temperature and the processing conditions regarding DMSO resistance and liquid crystal resistance do not affect the evaluation result even if there are some differences.

The evaluation results are shown in Tables 1 and 2. As is clear from these results, Examples 1 to 10 all have improved DMSO resistance and alignment agent resistance, which were the drawbacks of the conventional aromatic polyester made of bisphenolfluorene, and have a heat resistance of Tg of 250 ° C. or more. 8 and light transmittance
A sheet suitable for a liquid crystal display element substrate or an organic EL display element substrate having a transparency and liquid crystal resistance of 8% or more can be obtained.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

The aromatic polyester resin composition of the present invention is excellent in transparency, solvent resistance, liquid crystal resistance and heat resistance, and is suitable for a liquid crystal display element substrate or an organic EL display element substrate instead of a glass substrate. Can be used.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideki Kubo 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. (72) Inventor Hiromitsu Kuramoto 2-5-2 Higashishinagawa, Shinagawa-ku, Tokyo F-term in Sumitomo Bakelite Co., Ltd. (reference) 4J029 AA01 AA06 AB01 AC01 AE01 AE18 BB13 BB18 BD01 BH02 CB03 DB09 DB10 DB11 HA01 HB01 KE11 KH01 KH08

Claims (6)

[Claims] 1. A resin containing a repeating unit represented by the following general formula (1) and containing dimethyl sulfoxide (DMSO) at 60 ° C.
Aromatic polyester resin compositions that do not dissolve or swell more than twice when heated for 1 hour. 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. (a) 99 to 1 part by weight of an aromatic polyester resin containing a repeating unit represented by the general formula (1), and (b) a polyfunctional monomer 1 having two or more unsaturated groups.
To 99 parts by weight of an aromatic polyester resin composition 3. The polyfunctional monomer (b) having two or more unsaturated groups, 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 aromatic polyester resin composition according to item 2. 4. A compound (b) having two or more unsaturated groups
Is divinyl biphenyl.
Aromatic polyester resin composition as described 5. The aromatic polyester resin composition according to claim 2, wherein the polyfunctional monomer (b) having two or more unsaturated groups is dicyclopentadienyl diacrylate. 6. The cross-linking treatment by one or more cross-linking methods selected from organic peroxides, electron beams and ultraviolet rays.
The aromatic polyester resin composition according to any one of the above.