TW200804455A - Polyester containing terpene phenol unit - Google Patents

Abstract

Disclosed is a novel polyester to be used as a flexible photosensitive resin, namely a polyester having a terpene skeleton represented by the general formula (1) below. (In the formula below, X represents a terpene diphenoxy group; Y represents a residue obtained by removing a carboxyl group from a tetrabasic acid dianhydride; R represents H or CH3; R' represents H or a residue of a carboxyl group blocking agent; and n represents an integer of 1-40.)

Description

200804455 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION C FIELD OF THE INVENTION The present invention relates to a poly-terpene unit contained in a skeleton, and more specifically, for example, A new polyester for alkaline development of photosensitive resin.

L· iitr U Background Art Conventionally, a photoresist such as a photoresist or a solder resist in a printed wiring board has been made of a photosensitive resin. The photosensitive resin can be cured by light irradiation in the presence of a suitable photopolymerization initiator, for example, a propylene-propylene having a side bond heterocyclic (cardo) resin skeleton as proposed in Patent Document 1 below. Dilute acid compound. Further, as disclosed in Patent Document 2, the photosensitive resin is a compound obtained by subjecting the epoxy acrylate compound of Patent Document 1 to an addition reaction with a carboxylic acid anhydride, and is alkaline in an unhardened state. An alkali-soluble photosensitive resin which is soluble in an aqueous solution and which becomes insoluble after hardening, and which can be subjected to an illustrative development. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The side chain heterocyclic ring is rigid 5 200804455 structure, and is an epoxy acrylate resin with only acrylic or methacrylic acid added to the epoxy resin etherified epoxy resin terminal at both ends, so the flexibility is not good. Disadvantages. SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polymer which can be used as a photosensitive photosensitive resin. Means for Solving the Problem The polyester of the first invention of the present invention is represented by the following formula (1): [Chemical Formula 1] R, 〇_J^ jL0R_ ο ο

(1) In the formula, X is a terpene diphenoxy group represented by the following formula (2) or (3), and may contain a mixture of the formula (2) and the formula (3) in one molecule; The residue of the four carboxyl group organic compounds after removal of the carboxyl group, R represents deuterium or CH3, and R' represents the residue of the indole or carboxyl blocker, and η represents an integer of 1 to 40. [Chemical Formula 2]

Further, the polyester of the second invention of the present invention is an epoxy (meth) acrylate represented by the following formula (4) and an epoxy (meth) acrylate represented by the following formula (5). At least one of them has a weight average molecular weight of 3,000 to 100,000 obtained by condensation polymerization with a tetrabasic acid dianhydride represented by the following general formula (6): 6 15 200804455 (tetrabasic dianhydride). [Chemical Formula 3]

Wherein R represents deuterium or CH3. [Chemical Formula 4]

In the formula, Y represents a residue in which an organic compound having four carboxyl groups has a carboxyl group removed. According to the present invention, the terpene phenol unit contained in the polyester skeleton is flexible, and the tank phenolic unit is linked by an ester bond between four base acid dianhydrides. Therefore, a photosensitive resin having flexibility (flexibility) can be obtained. 7 200804455 [Finance Mode] BEST MODE FOR CARRYING OUT THE INVENTION The polyester of the present invention can be obtained by the above-described formula (4) and/or (5). An esterification reaction (condensation polymerization reaction) between acrylic acid ester and 5-tetrabasic acid dianhydride represented by the above formula (6). The above di(meth)acrylate can be synthesized by etherifying a terpene diphenol, that is, a terpene phenol resin with a diepoxypropyl group, and then adding acrylic acid or methacrylic acid to the epoxy resin. The end is synthesized. In the formulae (4) and (5), when R=H, it is a diacrylate, R=cHy· is a dimethacrylate, and two of them are collectively called a di(meth)acrylate. The epoxy acrylate resin thus obtained preferably has an acid value of less than 10 mgKOH/g and an epoxy equivalent of 10,000 to 20,000. The acid value here is obtained by the following steps: first, we take a sample of lg in a conical flask and dissolve it in 50 ml of dioxane, and then use phenolphthalein as an indicator, using 0.1 MKOH. The aqueous solution was titrated and then measured at the point where no 15 colors turned pink. Further, the epoxy equivalent is obtained by weighing a predetermined amount (~5 g) of the sample in a beaker to dissolve it in 50 ml of chloroform, and then adding 5 ml of a 20% acetic acid solution of tetraethylammonium bromide. Crystal violet (crystal vi〇iet) was used as an indicator, and titration was carried out using a perchloric acid solution of 〇·ιν, and the point at which the purple color became cyan was measured. In the above formula (7) or (8), the 1,3-decene phenol resin represented by the formula (7) and the 2,8-decene represented by the formula (8) are used. The phenol resins may be used singly or as a mixture of the two. Usually, a mixture of the two is used, and the mixing ratio is preferably a weight ratio of the formula (7): formula (8) = 80 to 60: 20 to 40. 8 200804455 [Chemical Formula 5]

The method for synthesizing the above epoxy resin can be carried out by a general epoxy resin synthesis method, for example, by synthesizing the above-mentioned dienol in the presence of a base catalyst with epichlorohydrin 5, whereby An alkenediphenol diglycidyl ether represented by the following formula (9) or formula (10) can be obtained. The epoxy resin thus obtained preferably has an epoxy equivalent of from 260 to 300. [Chemical Formula 6]

The above-mentioned four-base acid dianhydride may, for example, be seven aromatic quaternary acid dianhydrides shown below, but is not limited thereto. In particular, those represented by the following formulas (11), (12), and (13) are preferred. 9 15 200804455 【化7】

Ο Ο

ρ ο oxydiphthalic anhydride Ω 〇 On

Ethylene glycol trimellitic anhydride ester (ethylglycol-bis anhydrotrimellitate)

Glycerin-bis anhydrotrimellitate monoacetate

15 benzophenone tetracarboxylic-dianhydride

Methylcyclohexane tetracarboxylic-dianhydride 20 200804455 The method for the above-described cooling reaction is not particularly limited, for example, by dissolving the above-mentioned di(meth)acrylic acid vinegar in an organic solvent, and then By adding four needles of tetrakisic acid and mixing them to form a reaction, the epoxy group represented by the above formula (1) (the methyl ester of the methyl group and the dianhydride of the dianhydride) can be synthesized. The weight average molecular weight of the vinegar can be adjusted by changing the amount of the solvent and the mass of the reaction group in the above hydration reaction. In the present invention, the weight average molecular weight is preferably 3, _100, _, and 5_~25_ It is preferable that the weight average molecular weight is also related to the above formula (1), and 10 η is preferably from 1 to 40. When the weight average molecular weight is smaller than the above range, sufficient flexibility and adhesion cannot be obtained, and conversely When it is too large, the alkali solubility in the photohardenability and the uncured state becomes poor. The weight average molecular weight here is determined by gel permeation chromatography (GPC, dissolution solvent: tetrazole). Polyphenylene The ethylene-based weight average molecular weight. Further, in order to impart good solubility in the uncured state, the acid value is preferably from 60 to 70 mgKOH/g. The polyester obtained by the above esterification reaction is in the formula ( In the case where R is all Η, that is, the residue portion of each tetrabasic acid dianhydride has two or three carboxyl groups, thereby having excellent solubility for an alkaline aqueous solution. Further, blocking with a blocking agent 2〇 The above-mentioned rebel base can adjust the test solubility. By changing the blocking amount of Weiji, the acid value of the polyester can be controlled. Although not particularly limited, the acid value is 20~80 mgKOH/g. Preferably, it is preferably 30 to 7 〇 mgKOH/g. Further, the type of the tetrakisic acid dianhydride is also good, and in terms of ensuring the basic development property, R' is preferably 5 〇 mol% or more. Further, it is more preferably η at 70 mol% or more. 11 200804455 The thiol blocker is not particularly limited as long as it has a functional group reactive with a terminal carboxyl group, and may be an epoxy propyl group. For example, various known terminal blockers such as carbon di-i-imine are exemplified by phenyl epoxypropyl ketone and butyl phenyl epoxy. It is preferable that the epoxy propylene group such as epoxy propylene and the like is in the form of (b) (10) or more. The polyacetate having the above structure is preferable. The photopolymerized acrylic acid or methyl acrylate moiety can be photopolymerized in the presence of a suitable photopolymerization initiator, and bridged and hardened by photopolymerization, thereby becoming less soluble in the alkaline aqueous solution m. Si can be dissolved in the aqueous solution 10 in an uncured state, so that by partially irradiating light onto the film, alkaline development can be exhibited, and the unhardened portion can be dissolved by the alkaline aqueous solution to leave the hardening. Further, the polyester has good adhesion to various substrates, has small hardening shrinkage, is excellent in heat resistance (high Tg), and can form a hard film. Further, since the unitene phenol unit contained in the polyester skeleton has a relatively soft structure, and the terpene phenol unit is bonded through the ester bond between the four base acid dianhydrides, Flexible. The polyester may be polymerized by itself or may be used in combination with various photopolymerizable monomers, as a coating agent for glass or various films, or as a raw material for coating on glass or various thin coatings. Moreover, 20 can be used as a binder for a photoresist material such as a photoresist for a printed wiring board or a color photoresist. [Examples] Hereinafter, the embodiments of the present invention will be more specifically described, but the present invention is not limited to the following examples. 12 200804455 (Synthesis Example 1: Zestene diphenol diepoxypropyl ether) 1070 g of terpene diphenol (1,3-decenol resin: 2,8-decenol resin = 70:30 (weight ratio) An Anwar ("YP-90" manufactured by Yasuhara Chemical Co., Ltd.), 1520 g of epigas oxide, and 1,700 g of DMSO were placed in a 5 L four-necked flask equipped with a condenser 5 tube and a stirrer, and stirring was started. After heating to 5 ° C to dissolve it, 290 g of caustic soda was added to carry out a heating reaction from 65 ° C to 90 ° C for 10 hours. The progress and the end point of the reaction were carried out by measuring the epoxy equivalent, and after the epoxy equivalent reached the target value, the DMSO was removed under reduced pressure at 90 to 100 °C. Then, it was redissolved in toluene at 50 to 70 ° C, and further added with distilled water to wash with water, and then left to stand for separation. The solvent of the organic layer was removed under reduced pressure to obtain 1260 g of the above formula (9). A mixture of epoxy resins represented by formula (10). The epoxy resin obtained had an epoxy equivalent of 260. As shown in Fig. 1, in the NMR spectrum of the person (1H-NMR: CDC13 solvent, tetramethyl sulphate base, ppm), 15 benzene rings of a terpene skeleton can be found at δ6·8~7.3. The resulting absorption peak (8H), and the absorption peak (6Η) produced by the epoxy moiety was found at δ3.3, δ3·9~4·2, and found from the terpene skeleton at δ0·7~0.9 The absorption peak (6 Η) produced by the two methyl groups of the isopropyl group. Further, as shown in Fig. 2, in the infrared absorption spectrum (ir) of the person, the absorption derived from the aromatic ether or the epoxy ring can be found at 1241 (: 11^1) at 20 1036, 828 cm·1. It was found to be derived from the absorption of aromatic ether. From the above results, it was confirmed that the mixture was a mixture of terpene diphenol diglycidyl ether represented by the formula (9) and the formula (1). (Synthesis Example 2: Xue Diol diol diepoxypropyl dimethacrylate) 1000 g of a mixture of epoxy resins prepared in Synthesis Example 1, l. g g to benzene 13 200804455 hydroquinone monomethyl ether, 350 g methyl group Acrylic acid was placed in a 5 L four-necked flask equipped with a condenser and a stirrer, and mixing was started. After dissolving at 60 ° C, 8 g of tetraethylammonium bromide was added thereto, and the reaction was continued under heating at 70 to 9 Torr. The acid value was 8 mgKOH/g, and the epoxy equivalent reached 17〇〇〇5. After 15 hours, the end point was confirmed by the acid value and the epoxy equivalent, and then cooled to obtain 1300 g of the following formula (14) and formula ( 15) A mixture of epoxy methacrylate resins as shown. The epoxy equivalent of the obtained epoxy methacrylate resin is 17,000, and the acid value is 8mgKOH / g, hydroxide base price i65mgKOH / g. [Chemical Formula 8]

As shown in Fig. 3, in the iH-Nmr spectrum (tetramethylammonium group, ppm) of the person, the double bond of methacrylic acid can be found at δ5·6 and δ6·1. The absorption peak (4Η), and the absorption peak position of δ3·3, δ3·9~4.2 in the above formula (9) and formula (1〇) is found to be shifted by δ3·9~4.4 due to the ring opening of the epoxy. The absorption peak (10Η). Further, as shown in Fig. 4, in the IR spectrum of the person, absorption derived from an ester bond can be found at 172 〇cm-i. From the above results, it was confirmed that the mixture was a mixture of diphenol epoxypropyl dimethacrylate represented by formula (14) and formula (15). (Synthesis Example 3: dinodiene digoxypropyl diacrylate) The methacrylic acid of Synthesis Example 2 was replaced with 293 g of acrylic acid, and the reaction was carried out in the same manner to obtain 1200 g of the following formula (16) and formula. (17) A mixture of 5 epoxy acrylate resins as shown. The obtained epoxy acrylate resin had an epoxy equivalent of 16500, an acid value of 6 mgKOH/g, and a hydroxyl group valence of 171 mgKOH/g. [Chemical Formula 9]

10 (Synthesis Example 4: methacryl fluorenyl group having a terpene skeleton containing a polyester) 670 g of a mixture of the epoxy methacrylate resin obtained in Synthesis Example 2 and 1300 g of methyl isobutyl ketone were charged. Stirring was started in a 5 L four-necked flask of a condenser and a stirrer. After heating and dissolving at 60, 22 g of the pyromic acid dianhydride represented by the above formula (11) (manufactured by 15 companies of Daicel Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 80 ° C. The reaction was carried out until the acid value was 67.9 mgKOH/g. The change in the acid mussels was 2 mgK〇H/g or less. After the completion of the reaction, distilled water was added to the reaction solution, washed with water, and allowed to stand for separation. The organic layer was recovered, and the solvent was distilled off under reduced pressure at 5 Torr to 7 ° C to obtain 860 g of the following formula (18). A polyester resin (wherein X is a terpene diphenoxy group represented by the above formula (2) or (3) 15 200804455, R is CH3, and R is H, n*2〇). The polystyrene-equivalent weight average molecular weight of the resin measured by coagulation-removing chromatography (Gpc, solvent (tetra)··tetrazide) was 18 mm. Further, the acid value was 61.2 mgKOH/g. 5 [Chemical Formula 10]

As shown in Fig. 5, in the 1H_NMR spectrum (CDCI3 solvent, = Weiwei basis, ppm) of the person, the benzene ring of the (tetra) skeleton and the benzene ring of the pyrophoric acid can be found at δ6·9~76. The absorption peak, and the absorption peak generated by the double bond of methacrylic acid was found in δ5·8 and 2, and the absorption peak derived from the cyclohexene skeleton of the terpene was found at δ11~2·2. And an absorption peak derived from two sulfhydryl groups derived from the isopropyl group of the (four) skeleton was found in δ 〇·7~〇·9. Further, as shown in Fig. 6, in the IR spectrum of the person, the absorption derived from the ester bond can be found at 1735 cm_i, and the absorption at 1735, 1241, and 1102 cm·1 is now derived from the absorption of the aromatic ester. . From the above results, it was confirmed that the methacryl fluorenyl group having a terpene skeleton represented by the formula (18) contained a polyester. (Synthesis Example 5: propylene fluorenyl group having a terpene skeleton containing a polyester) A mixture of 660 g of the epoxy acrylate resin obtained in Synthesis Example 3 was charged with 20 parts of the epoxy methacrylate resin used in Synthesis Example 4. Further, the reaction was carried out in the same manner as in Synthesis Example 4 to obtain 840 g of the alkene diphenoxy group represented by the above-mentioned formula (18), wherein R is a resin (wherein X is the above formula (2) or (3). The household is Η, R' is Η, η is 17). The resin was subjected to a gel permeation ▲ decantation method (GPC, dissolution solvent: tetrahydrofuran), and the polystyrene conversion weight was determined to obtain a total molecular weight of 15,000. Further, the acid 5 value was 60.9 mgKOH/g. (Synthesis Example 6: a methyl propyl group having a box-thin skeleton containing a polyacetal cap) 275 g of a polysyl resin prepared in Synthesis Example 4, 275 g of propylene glycol monoacetate (propylene glycol) M〇nomethyl coffee she) was placed in a four-necked flask equipped with a condenser tube and a 10-mixer, and began to stir. After dissolving at 60 ° C, 1.5 g of tetraethylammonium bromide was added, and then 3 〇g was added. The base epoxidized propyl ether (trade name: EPIOL P (manufactured by Sakamoto Oil Co., Ltd.)) was heated and stirred at 80 to 90 ° C as a carboxyl blocker. The reaction is continued until the acid value changes below 2 mg K0H/g, and after the acid value reaches the target value, it is cooled to room temperature, and 15 g of the polyester resin represented by the above formula (18) is obtained (where X is The terpene diphenoxy group represented by the above formula (2) or (3), R is CH3, R, is hydrazine or C6H5〇CH2CH(OH)CH2 (wherein Η is 78%, and the blocker thiol group is 22%), η is 20) 树脂 The resin has a polystyrene-equivalent weight average molecular weight of 21,000 as measured by gel permeation chromatography (GPC, dissolution solvent: tetrahydrogenose 20 mer). Further, the acid value was 52.1 mgKOH/g. As shown in Fig. 7, in the 1H-NMR spectrum (in the CDCU solvent, the tetramethyl sulphate base, ppm), in addition to the polyester resin obtained in the above Synthesis Example 4, it is also possible to be δ6·9~ 7.6 The absorption peaks produced by the benzene ring of the phenyl epoxypropyl scale 17 200804455 used to block the carboxylic acid were found. Further, as shown in Fig. 8, in the IR spectrum of the person, absorption derived from aromatic ether can be found at i〇47 cm-i. Namely, the absorption of 1047 cm·1 was larger than that of the polyester resin 5 obtained in the above Synthesis Example 4 due to the introduction of phenylepoxypropyl ether. (Synthesis Example 7: a carboxy cap having a propylene group having a olefin skeleton and a polyester), 300 g of the polyester resin obtained in Synthesis Example 5 was substituted for the polyester resin obtained in Synthesis Example 4, and the others were synthesized. In the same manner as in Example 6, 340 g of a polyester resin represented by the following formula (18) (wherein X is a terpene diphenoxy group represented by the above formula (7) or (3) 10, and R is H, R, was obtained. Is Η or C 6H5 〇CH2CH(OH)CH2 (wherein Η is 80% and the blocker residue is 20%), η is 17) 树脂 The resin is subjected to gel permeation chromatography (GPC, dissolution solvent: The polystyrene-equivalent weight average molecular weight measured by tetrahydrocethane was 25,000. Further, the acid 15 value was 50.0 mgKOH/g. (Synthesis Example 8: The methacryl group having a fluorene skeleton contains a polyg). A mixture of 670 g of the epoxy methacrylate resin obtained in Synthesis Example 2 and 1470 g of methyl isobutyl ketone were charged and condensed. In the 5L four-necked flask of the tube and the scrambler, the mixing was started. After heating and dissolving at 60 ° C, 313 g of oxydiphthalic anhydride (manac) manufactured by the above formula (12) was added, and the reaction was stirred at 80 ° C to carry out the reaction to an acid value. 53.3 mg KOH / g. After the completion of the reaction, distilled water was added to the reaction solution, and the organic layer was recovered by static washing, and the organic layer was recovered under reduced pressure at 5 Torr to 7 Torr (after distillation to remove the solvent, 800 g of the following formula (19) was obtained. Polyester resin 18 200804455 (wherein X is a terpene diphenoxy group represented by the above formula (2) or (3), R is CH3, R' is Η, and η is 8). The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC, dissolution solvent: tetrahydrofuran) was 9000. 5 [Chemical Formula 11]

19 200804455 (Synthesis Example 9: methacryl fluorenyl group having a terpene skeleton containing a polyester) 670 g of a mixture of epoxy methacrylate resins obtained in Synthesis Example 2, and 1660 g of methyl isobutyl ketone were charged. Stirring was started in a 5 L four-necked flask equipped with a condenser and a stirrer. After heating and dissolving at 60 ° C, 434 g of ethylene glycol trimellitic anhydride ester (manufactured by Nippon Science & Technology Co., Ltd.) represented by the above formula (13) was added, and the mixture was stirred at 80 ° C to carry out the reaction to an acid value. It is 46.2 mgKOH/g. After the completion of the reaction, steamed water was added to the reaction solution, washed with water, and allowed to stand for separation. The organic layer was recovered, and under reduced pressure, at 5 Torr to 7 Torr (after distillation to remove the solvent, 9 〇〇g was obtained. The polyester resin 10 represented by the formula (2) (wherein X is a (tetra)diphenoxy group represented by the above formula (7) or (3), R is CH3, R is ruthenium, and η is 12). The polystyrene-equivalent weight average molecular weight measured by Sasuke (4) (GPC, dissolution solvent: ° South) is 13_. 15 20 20 200804455 Chemical Formula 12] 〇 =

21 200804455 (Example) Each of the resins of the above Synthesis Examples 3 to 9 is added with 100 parts by weight of a solvent of 100% by weight of propylene glycol monomethyl methacrylate and 3 parts by weight of a photopolymerization initiator (Xiba). The pharmaceutical factory (GIBAGEIGY) "irgacurel84"), 5 is applied to the substrate with a film thickness (dried ΜΟΟμηι). Then, after drying at 120 ° C for 5 hours under reduced pressure, a high-pressure mercury lamp of 1 盏 80 W/cm is used as the focus. The distance is 8 cm and the integrated illuminance is 2 〇〇〇mj to perform uv irradiation to harden. The inspectability of the cured film to be cured, the adhesion to the substrate, the hardening shrinkage, the heat resistance, the pencil hardness The flexibility is evaluated. Each evaluation method is as follows: • Qualitative solubility: The film before hardening and the cured film are immersed in a 2.5% NaOH aqueous solution to evaluate the solubility. Slip the thin film on the substrate (glass plate) and the depth of the substrate surface into a checkerboard pattern, then paste the tape on the checkerboard, 15 calculate the number of remaining parts after peeling off (representing the remaining number X relative to 100 chessboards as "χ/100"). ● Hardening shrinkage ratio: The specific gravity of the sample before and after curing was measured according to JIS K0061-1992, and the volume shrinkage ratio was calculated by the following formula: Volume shrinkage ratio (%) = {(weight after hardening) _The specific gravity of 2 硬化 after hardening before hardening} χΙΟΟ • Heat resistance: Using the "Rheogel E-4000" manufactured by UBM, the breaking point (Tg) giving the maximum value of (10) is obtained by the dynamic viscoelasticity measurement method. "As tana = loss of elasticity coefficient / dynamic elasticity coefficient. - Pencil hardness · Based on JIS K5600-5-4, the film was evaluated by pressing a pencil of the size and hardness specified in 22 200804455 on the film. Resistance to scratches or other defective films. • Flexibility: For specimens made using tinplate (15〇χ5〇χ〇.3mm) as the substrate, the bending tester is used to make the coated surface The shaft rod was placed on the outer side 5, and then rapidly bent around the shaft rod by about 180 degrees. Then, the sample was taken out to visually investigate the crack and peeling. When the three samples were not found to have cracked peeling of the coating film, respectively. That is, it has bending resistance and is judged as Grid. Sequentially determined by the large diameter shaft rod, qualified first minimum diameter is shown in Table 10 152,023,200,804,455 [Table 1] To save a Long aunt κ · 40

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E 0 Inmrn 寸 ^ 毖姨Κ - 001 / 001 2 611 0 mm £ (%) 缇 缇 ^ 24 200804455 As shown in Table 1, the adhesion of each polyester and substrate of this example It is good, and has small hardening shrinkage, excellent heat resistance, and a hard film, and is excellent in film flexibility. Further, the unhardened portion is soluble in the aqueous test solution, and is insoluble by photohardening, so that it can be inspected. 5 INDUSTRIAL APPLICABILITY The polyester of the present invention can be used for coating various substrates such as glass or film, and can be used as a raw material for coatings applied to the substrates, and can also be used as a photoresist or colored light for printed wiring boards. A binder for photoresists such as resistants. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the results of measurement of the 1H-NMR spectrum of the epoxy resin of Synthesis Example 1. Fig. 2 is a graph showing the measurement results of the IR spectrum of the epoxy resin of Synthesis Example 1. Fig. 3 is a graph showing the results of measurement of 15 1H-NMR spectrum of the epoxy methacrylate resin of Synthesis Example 2. Fig. 4 is a graph showing the results of measurement of IR spectrum of the epoxy methacrylate resin of Synthesis Example 2. Fig. 5 is a graph showing the results of measurement of the 1H-NMR spectrum of the polyester resin of Synthesis Example 4. 20 Fig. 6 is a graph showing the measurement results of the IR spectrum of the polyester resin of Synthesis Example 4. Fig. 7 is a graph showing the results of measurement of the 1H-NMR spectrum of the polyester resin of Synthesis Example 6. Fig. 8 is a graph showing the measurement result 25 of the IR spectrum of the polyester resin of Synthesis Example 6. [Main component symbol description] None 25

Claims (1)

200804455 X. Patent application scope: 1. A polyester which is represented by the following formula (1), namely: [Chemical Formula 1] 5 (wherein X is a terpene diphenoxy group represented by the following formula (2) or (3), and may contain a mixture of the formula (2) and the formula (3) in one molecule; further, Y represents The residue of the four carboxyl group organic compounds after removing the carboxyl group, R represents hydrazine or CH3, and R' represents the residue of the hydrazine or carboxyl blocker, and η represents the integer 1 to 40) [Chemical Formula 2] 10 〇2. A polyester having at least an epoxy (meth) acrylate represented by the following formula (4) and an epoxy (meth) acrylate represented by the following formula (5) One of the weight average molecular weights obtained by condensation polymerization with a tetrabasic acid dianhydride represented by the following formula (6) is 3,000 to 100,000, 26 15 200804455 [Chemical Formula 3] (wherein R represents Η or CH3) [Chemical Formula 4] (wherein Y represents a residue in which an organic compound having four carboxyl groups has a carboxyl group removed). 27