Siloxane-modified polyester resin and cured product thereof

Abstract

To provide a siloxane-modified polyester resin enabling impartation of sufficient flexibility to a cured body along with heat resistance.SOLUTION: A siloxane-modified polyester resin having carboxyl groups and (meth)acryloyl groups in side chains.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a siloxane-modified polyester resin and a cured product thereof. [Background technology]

[0002] Siloxane-modified polyimide resins are known to not only have excellent heat resistance but also give flexible cured products, making them suitable for applications such as protective insulating films for semiconductor elements, insulating films for multilayer printed circuit boards, solder protective films, and coverlay films (Patent Document 1).

[0003] However, in recent years, there has been active development of flexible devices, especially for medical applications, and the flexibility of the cured product has yet to be achieved for application in such devices, so further improvement is required. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-217490 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a siloxane-modified polyester resin that is capable of imparting sufficient flexibility to the cured product in addition to heat resistance. [Means for solving the problem]

[0006] As a result of extensive research into achieving the above-mentioned object, the present inventors discovered that a siloxane-modified polyester resin having a carboxyl group and a (meth)acryloyl group in the side chain gives a cured product having high heat resistance and flexibility, and thus completed the present invention.

[0007] That is, the present invention provides the following siloxane-modified polyester resin and a thermoset product thereof. 1. Siloxane-modified polyester resin with carboxyl and (meth)acryloyl groups in the side chains. 2. A siloxane-modified polyester resin 1, which is represented by the following formula (1): [ka] (In the formula, R 1 are each independently a hydrogen atom or a methyl group. R 2 are each independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom. R 3 are each independently a hydrocarbyl having 1 to 8 carbon atoms. Each X is independently a single bond or a divalent organic group. Each Y is independently a trivalent organic group. Z is a tetravalent organic group. Each m is independently an integer of 0 to 4. n is a number whose average is 0 to 100. p is an integer of 1 to 30. q is an integer of 0 to 30. 3. The siloxane-modified polyester resin of 2, wherein Y is a group represented by any one of the following formulas: [ka] (In the formula, R 4 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 8 carbon atoms. * represents a bond. 4. The siloxane-modified polyester resin of 2 or 3, wherein X is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 5. The siloxane-modified polyester resin of any one of 2 to 4, wherein q is an integer of 1 to 30, and Z is a group represented by any one of the following formulae: [ka] (In the formula, * represents a bond.) 6. The siloxane-modified polyester resin of any one of 1 to 5, having a weight average molecular weight of 3,000 to 500,000. 7. A cured product obtained by thermally curing any one of the siloxane-modified polyester resins 1 to 6. [Effects of the Invention]

[0008] By using the siloxane-modified polyester resin of the present invention, it is possible to obtain a cured product that has sufficient flexibility in addition to heat resistance and chemical resistance. DETAILED DESCRIPTION OF THE INVENTION

[0009] [Siloxane-modified polyester resin] The siloxane-modified polyester resin of the present invention is a siloxane-modified polyester resin having a carboxyl group and a (meth)acryloyl group in the side chain.

[0010] Such a siloxane-modified polyester resin is preferably one represented by the following formula (1). [ka]

[0011] In formula (1), R 1 are each independently a hydrogen atom or a methyl group. 2 are each independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom. 3 are each independently a hydrocarbyl group having 1 to 8 carbon atoms. Each X is independently a single bond or a divalent organic group. Each Y is independently a trivalent organic group. Each Z is a tetravalent organic group. Each m is independently an integer of 0 to 4. n is a number whose average is 0 to 100. p is an integer of 1 to 30. q is an integer of 0 to 30.

[0012] R 2Specific examples of the alkyl group having 1 to 5 carbon atoms represented by R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and structural isomers thereof. 2 Specific examples of the aryl group having 6 to 12 carbon atoms represented by R include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. 2 Specific examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0013] R 3 The hydrocarbyl group having 1 to 8 carbon atoms represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, and hexyl groups, and structural isomers thereof; cyclic saturated hydrocarbyl groups such as cyclohexyl; and aryl groups such as phenyl. Of these, methyl and phenyl groups are preferred because of the ease of availability of raw materials.

[0014] The trivalent organic group represented by Y is not particularly limited, but is preferably a saturated hydrocarbon group having 2 to 20 carbon atoms. The saturated hydrocarbon group may be linear, branched, or cyclic, and may contain at least one heteroatom selected from an oxygen atom and a sulfur atom. Such a group is preferably a group represented by any of the following formulas: [ka]

[0015] In the above formula, R 4 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 8 carbon atoms. * represents a bond. R 4 The hydrocarbyl group having 1 to 8 carbon atoms represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, and hexyl groups, and structural isomers thereof; cyclic saturated hydrocarbyl groups such as cyclohexyl; and aryl groups such as phenyl.

[0016] The divalent organic group represented by X is not particularly limited, but is preferably a saturated hydrocarbylene group having 1 to 20 carbon atoms and optionally containing a halogen atom, or an arylene group having 6 to 30 carbon atoms and optionally containing a halogen atom. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the saturated hydrocarbylene group include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, and a propane-2,2-diyl group. Specific examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a naphthylene group, and a fluorene-9,9-diyl group. X is preferably a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group.

[0017] p is an integer of 1 to 30, and more preferably an integer of 1 to 20. q is an integer of 0 to 30, and more preferably an integer of 1 to 20. When q is 1 or more, the tetravalent organic group represented by Z is not particularly limited, but is preferably a tetravalent group having an aromatic ring and 6 to 12 carbon atoms or a tetravalent group having an unsaturated alicyclic ring and 6 to 12 carbon atoms. Such a group is particularly preferably a group represented by any of the following formulas: [ka] (In the formula, * represents a bond.)

[0018] The siloxane-modified polyester resin of the present invention preferably has a weight-average molecular weight (Mw) of 3,000 to 500,000, more preferably 5,000 to 200,000. When the Mw is within this range, a siloxane-modified polyester resin can be obtained that exhibits sufficient solubility in common organic solvents and can provide a cured film that has heat resistance, solvent resistance, and sufficient flexibility. In the present invention, the Mw is a polystyrene-equivalent value measured by gel permeation chromatography (GPC) using tetrahydrofuran as the elution solvent.

[0019] [Method for producing siloxane-modified polyester resin] The method for producing the siloxane-modified polyester resin is not particularly limited, but for example, a method of reacting a siloxane modified with carboxylic acid anhydrides at both ends as raw material compounds with a diol compound having a (meth)acryloyl group can be mentioned. In this case, the acid anhydride moiety of the former reacts with the alcohol moiety of the latter to form an ester bond, resulting in a high molecular weight, and at the same time, carboxyl groups are generated in the side chains.

[0020] The siloxane modified at both ends with carboxylic acid anhydrides is not particularly limited, but is preferably a compound represented by the following formula (2). [ka] (In the formula, R 3 , Y and n are the same as above.)

[0021] The diol compound having a (meth)acryloyl group is not particularly limited, but is preferably a compound represented by the following formula (3). [ka] (In the formula, R 1 , R 2 , X and m are the same as above.

[0022] Furthermore, a tetracarboxylic dianhydride other than the siloxane modified at both ends with a carboxylic acid anhydride may be used as the raw material compound. The tetracarboxylic dianhydride is preferably one represented by the following formula (4). [ka] (wherein Z is the same as defined above.)

[0023] Although it is not necessary to use a catalyst when synthesizing the above-mentioned raw materials, a catalyst such as an organic amine compound can be used to promote the reaction. Specific examples of such catalysts include primary amines such as methylamine, ethylamine, butylamine, s-butylamine, t-butylamine, amylamine, octylamine, cyclohexylamine, vinylmethylamine, allylamine, and ethoxymethylamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, diallylamine, dihexylamine, and didodecylamine; tertiary amines such as trimethylamine, triethylamine, and tripropylamine; alkanolamines such as ethanolamine, diethanolamine, and triethanolamine; aliphatic amines having a benzene ring such as phenylpropylamine, phenylethylamine, methoxybenzylamine, diethylbenzylamine, benzylamine, and dimethylbenzylamine; monoamines such as methylamine, ethylamine, methylbenzylamine, methylbenzylamine, and dimethylbenzylamine; and diamines containing methylbenzylamine. Examples of catalysts include morpholine derivatives such as morpholine and methylmorpholine; aniline derivatives such as t-butylaniline; aromatic amines such as dimethyltoluidine; pyridine derivatives such as 2-hydroxypyrimidine, 2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine; piperidine derivatives such as piperidine, methylpiperidine, and benzylpiperidine; pyrrolidine derivatives such as methylpyrrolidine; pyrrole derivatives such as pyrrole; quinoline derivatives such as 2-hydroquinoline, 3-hydroquinoline, 4-hydroquinoline, 2-methylquinoline, and 4-methyl-8-hydroquinoline; imidazole derivatives such as benzimidazole, methylimidazole, and imidazole; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Organotin compounds such as dibutyltin laurate and butyltin oxyacetate can also be used as catalysts to promote the reaction.

[0024] The amount of the catalyst used is preferably 0.005 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, relative to 100 parts by mass of the total of the tetracarboxylic dianhydride compound and the diol compound having a (meth)acryloyl group, which are raw materials. The catalyst may be used alone or in combination of two or more.

[0025] When synthesizing from the above-mentioned raw materials, an organic solvent can be used to homogenize the reaction system and facilitate the reaction. Examples of such organic solvents include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine oil, Solvesso (registered trademark) #100 and #150 (manufactured by Exxon Chemical Co., Ltd.); ethers such as dioxane and tetrahydrofuran; esters and ether esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, propylene glycol monomethyl ether, and methoxybutyl acetate; acetone, methyl ethyl ketone, diisobutyl ketone, diethyl ketone, methyl propyl ketone, diisopropyl ketone, methyl amylhexanone, isophorone, mesityl oxide, methyl isoamyl ketone, ethanol, and the like. Examples of suitable solvents include ketones such as ethyl n-butyl ketone and ethyl amyl ketone; phosphate esters such as trimethyl phosphate, triethyl phosphate and tributyl phosphate; aprotic polar solvents such as dimethyl sulfoxide and N,N-dimethylformamide; and glycol derivatives such as triethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, dipropylene glycol, diethylene glycol-2-ethylhexyl ether and tetraethylene glycol dimethyl ether. Among these, propylene glycol monomethyl ether acetate is particularly preferred.

[0026] The amount of the organic solvent used is not particularly limited, but is preferably an amount such that the concentration of the reaction raw materials in each reaction stage is 10 to 80 mass %, more preferably an amount such that the concentration is 20 to 60 mass %. The organic solvents may be used alone or in combination of two or more.

[0027] The reaction method is not particularly limited, but the target siloxane-modified polyester resin can be obtained by mixing the above-mentioned raw material compounds together with a catalyst in an organic solvent and heating at 80 to 140°C for about 3 to 30 hours.

[0028] When a siloxane modified at both ends with a carboxylic acid anhydride and a diol compound having a (meth)acryloyl group are used as raw materials, the amount of the raw material used is preferably 0.70 to 0.98 moles, more preferably 0.80 to 0.95 moles, of the siloxane modified at both ends with a carboxylic acid anhydride per mole of the diol compound having a (meth)acryloyl group. When a siloxane modified at both ends with a carboxylic acid anhydride, a diol compound having a (meth)acryloyl group, and a tetracarboxylic acid dianhydride other than the siloxane modified at both ends with a carboxylic acid anhydride per mole of the diol compound having a (meth)acryloyl group, the amount of the raw material used is preferably 0.70 to 0.98 moles, more preferably 0.80 to 0.95 moles, of the siloxane modified at both ends with a carboxylic acid anhydride and the tetracarboxylic acid dianhydride other than the siloxane modified at both ends with a carboxylic acid anhydride per mole of the diol compound having a (meth)acryloyl group. In this case, the siloxane modified at both ends with a carboxylic acid anhydride and the tetracarboxylic acid dianhydride other than the siloxane modified at both ends with a carboxylic acid anhydride are preferably used in such a manner that the molar ratio of the siloxane modified at both ends with a carboxylic acid anhydride to the tetracarboxylic acid dianhydride other than the siloxane modified at both ends with a carboxylic acid anhydride is 100:0 to 100:1000.

[0029] The siloxane-modified polyester resin of the present invention can be made into a composition containing the resin and a curing agent, and by applying the composition to a substrate and then heating it, a cured film having excellent heat resistance, chemical resistance, and flexibility can be obtained.

[0030] The curing agent may be an isocyanate curing agent, such as an aliphatic isocyanate such as methyl isocyanate, tetramethylene diisocyanate, or hexamethylene diisocyanate, an alicyclic isocyanate such as isophorone diisocyanate, an aromatic isocyanate such as toluene diisocyanate, diphenylmethane diisocyanate, or metaphenylene diisocyanate, or a modified version of any of these.

[0031] The content of the curing agent in the composition is preferably 5 to 50 parts by mass, more preferably 5 to 45 parts by mass, per 100 parts by mass of the siloxane-modified polyester resin of the present invention. The curing agents may be used singly or in combination of two or more.

[0032] The composition may contain a solvent, if necessary. Examples of the solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone. These solvents may be used alone or in combination of two or more. The content of the solvent in the composition is preferably 50 to 2000 parts by mass, more preferably 50 to 1000 parts by mass, and even more preferably 50 to 100 parts by mass, relative to 100 parts by mass of the polymer of the present invention. The solvent may be used alone or in combination of two or more.

[0033] The composition can be applied to the substrate by a known method, such as dipping, spin coating, or roll coating. The amount of coating can be appropriately selected depending on the purpose, but an amount that results in a film thickness of 0.1 to 100 μm after evaporation of the solvent is preferred.

[0034] By heating and curing the applied composition, a coating having excellent heat resistance, chemical resistance, and flexibility can be obtained. The heating conditions are appropriately selected depending on the type of siloxane-modified polyester resin of the present invention and the type of curing agent used, but it is usually preferable to perform heating at 50 to 250°C for about 10 minutes to 6 hours. [Example]

[0035] The present invention will be further explained below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, Mw was measured by GPC using a TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as a GPC column under analytical conditions of a flow rate of 0.6 mL / min, tetrahydrofuran as an eluent, and a column temperature of 40°C, with monodisperse polystyrene as the standard. FT-IR measurements were also performed using a Nicolet FT-IR spectrometer (manufactured by Thermo Fisher Scientific Co., Ltd.). TM iS TM The measurements were carried out using a 50FT-IR spectrophotometer.

[0036] The compounds used in the synthesis of the siloxane-modified polyester resin of the present invention are shown below. [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] [Example 1] Synthesis of polymer P-1 A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 46.18 g (0.094 mol) of compound (S-1) and 53.82 g (0.105 mol) of compound (O-1). Then, 150 g of propylene glycol monomethyl ether acetate and 1.0 g of tripropylamine were added, and the mixture was heated at 110°C for 10 hours and then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain polymer P-1. FT-IR analysis of polymer P-1 revealed peaks of the C=O stretching vibration (1815, 1760 cm) derived from the carboxylic acid anhydride. -1 ) and the peak of the C=O stretching vibration (1710 cm ) derived from the carboxyl group. -1 ), the C=C stretching vibration peak (1650 cm ) derived from the (meth)acryloyl group -1 ), and the C=O stretching vibration peak (1740 cm ) derived from the ester bond. -1 ), and the peak of the Si-O-Si antisymmetric stretching vibration (1010 cm) derived from siloxane. -1 ) and confirmed to be the siloxane-modified polyester resin of the present invention. Furthermore, GPC measurement revealed that the Mw was 6,000.

[0041] [Example 2] Synthesis of polymer P-2 A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser was charged with 63.20 g (0.061 mol) of compound (S-2) and 36.80 g (0.068 mol) of compound (O-2), followed by 150 g of propylene glycol monomethyl ether acetate. The mixture was heated at 130°C for 30 hours and then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain polymer P-2. FT-IR analysis of polymer P-2 revealed peaks of the C=O stretching vibration (1815, 1760 cm) derived from the carboxylic acid anhydride. -1 ) and the peak of the C=O stretching vibration (1710 cm ) derived from the carboxyl group. -1 ), the C=C stretching vibration peak (1650 cm ) derived from the (meth)acryloyl group -1 ), and the C=O stretching vibration peak (1740 cm ) derived from the ester bond. -1 ), and the peak of the Si-O-Si antisymmetric stretching vibration (1010 cm) derived from siloxane. -1 ) and confirmed to be the siloxane-modified polyester resin of the present invention. Furthermore, GPC measurement revealed that the Mw was 20,000.

[0042] [Example 3] Synthesis of polymer P-3 A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 66.62 g (0.034 mol) of compound (S-3), 3.03 g (0.010 mol) of compound (P-1), and 30.35 g (0.049 mol) of compound (O-3). Then, 150 g of propylene glycol monomethyl ether acetate and 1.0 g of tripropylamine were added. The mixture was heated at 110°C for 10 hours and then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain polymer P-3. FT-IR analysis of polymer P-3 revealed peaks of the C=O stretching vibration (1815 and 1760 cm) derived from the carboxylic acid anhydride. -1 ) and the peak of the C=O stretching vibration (1710 cm ) derived from the carboxyl group. -1 ), the C=C stretching vibration peak (1650 cm ) derived from the (meth)acryloyl group -1), and the C=O stretching vibration peak (1740 cm ) derived from the ester bond. -1 ), and the peak of the Si-O-Si antisymmetric stretching vibration (1010 cm) derived from siloxane. -1 ) and confirmed to be the siloxane-modified polyester resin of the present invention. Furthermore, GPC measurement revealed that the Mw was 50,000.

[0043] [Example 4] Synthesis of polymer P-4 A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 70.00 g (0.020 mol) of compound (S-4), 5.26 g (0.016 mol) of compound (P-2), and 24.74 g (0.041 mol) of compound (O-4). Then, 150 g of propylene glycol monomethyl ether acetate was added, heated at 130°C for 30 hours, and then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain polymer P-4. FT-IR analysis of polymer P-4 revealed peaks of the C=O stretching vibration (1815, 1760 cm) derived from the carboxylic acid anhydride. -1 ) and the peak of the C=O stretching vibration (1710 cm ) derived from the carboxyl group. -1 ), the C=C stretching vibration peak (1650 cm ) derived from the (meth)acryloyl group -1 ), and the C=O stretching vibration peak (1740 cm ) derived from the ester bond. -1 ), and the peak of the Si-O-Si antisymmetric stretching vibration (1010 cm) derived from siloxane. -1 ) and confirmed to be the siloxane-modified polyester resin of the present invention. Furthermore, GPC measurement revealed that the Mw was 100,000.

[0044] [Example 5] Synthesis of polymer P-5 A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 66.30 g (0.013 mol) of compound (S-5), 4.81 g (0.013 mol) of compound (P-3), 5.96 g (0.013 mol) of compound (P-4), and 22.93 g (0.045 mol) of compound (O-1). Then, 150 g of propylene glycol monomethyl ether acetate and 1.0 g of tripropylamine were added, heated at 110 °C for 10 hours, and then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain polymer P-5. FT-IR analysis of polymer P-5 revealed peaks of the C=O stretching vibration (1815 and 1760 cm) derived from the carboxylic acid anhydride. -1 ) and the peak of the C=O stretching vibration (1710 cm ) derived from the carboxyl group. -1 ), the C=C stretching vibration peak (1650 cm ) derived from the (meth)acryloyl group -1 ), and the C=O stretching vibration peak (1740 cm ) derived from the ester bond. -1 ), and the peak of the Si-O-Si antisymmetric stretching vibration (1010 cm) derived from siloxane. -1 ) and confirmed to be the siloxane-modified polyester resin of the present invention. Furthermore, GPC measurement revealed that the Mw was 150,000.

[0045] [Example 6] Synthesis of polymer P-6 A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 45.87 g (0.007 mol) of compound (S-6), 8.48 g (0.028 mol) of compound (P-5), 7.46 g (0.028 mol) of compound (P-6), and 38.18 g (0.071 mol) of compound (O-2). Then, 150 g of propylene glycol monomethyl ether acetate was added, heated at 130 °C for 30 hours, and then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain polymer P-6. FT-IR analysis of polymer P-6 revealed peaks of the C=O stretching vibration (1815, 1760 cm) derived from the carboxylic acid anhydride. -1) and the peak of the C=O stretching vibration (1710 cm ) derived from the carboxyl group. -1 ), the C=C stretching vibration peak (1650 cm ) derived from the (meth)acryloyl group -1 ), and the C=O stretching vibration peak (1740 cm ) derived from the ester bond. -1 ), and the peak of the Si-O-Si antisymmetric stretching vibration (1010 cm) derived from siloxane. -1 ) and confirmed to be the siloxane-modified polyester resin of the present invention. Furthermore, GPC measurement revealed that the Mw was 200,000.

[0046] [Example 7] Synthesis of polymer P-7 A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 25.44 g (0.052 mol) of compound (S-1), 28.94 g (0.015 mol) of compound (S-3), 23.07 g (0.037 mol) of compound (O-3), and 22.55 g (0.037 mol) of compound (O-4). Then, 150 g of propylene glycol monomethyl ether acetate and 1.0 g of tripropylamine were added. The mixture was heated at 110 °C for 10 hours and then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain polymer P-7. FT-IR analysis of polymer P-7 revealed peaks of the C=O stretching vibration (1815 and 1760 cm) derived from the carboxylic acid anhydride. -1 ) and the peak of the C=O stretching vibration (1710 cm ) derived from the carboxyl group. -1 ), the C=C stretching vibration peak (1650 cm ) derived from the (meth)acryloyl group -1 ), and the C=O stretching vibration peak (1740 cm ) derived from the ester bond. -1 ), and the peak of the Si-O-Si antisymmetric stretching vibration (1010 cm) derived from siloxane. -1 ) and confirmed to be the siloxane-modified polyester resin of the present invention. Furthermore, GPC measurement revealed that the Mw was 30,000.

[0047] [Example 8] Synthesis of polymer P-8 A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 23.20 g (0.022 mol) of compound (S-2), 25.72 g (0.007 mol) of compound (S-4), 11.62 g (0.037 mol) of compound (P-1), 19.20 g (0.037 mol) of compound (O-1), and 20.26 g (0.037 mol) of compound (O-2). Then, 150 g of propylene glycol monomethyl ether acetate was added. The mixture was heated at 130 °C for 30 hours and then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain polymer P-8. FT-IR analysis of polymer P-8 revealed peaks of the C=O stretching vibration (1815 and 1760 cm) derived from the carboxylic acid anhydride. -1 ) and the peak of the C=O stretching vibration (1710 cm ) derived from the carboxyl group. -1 ), the C=C stretching vibration peak (1650 cm ) derived from the (meth)acryloyl group -1 ), and the C=O stretching vibration peak (1740 cm ) derived from the ester bond. -1 ), and the peak of the Si-O-Si antisymmetric stretching vibration (1010 cm) derived from siloxane. -1 ) and confirmed to be the siloxane-modified polyester resin of the present invention. Furthermore, GPC measurement revealed that the Mw was 80,000.

[0048] [Comparative Example 1] Synthesis of Comparative Polymer CP-1 (Siloxane-Modified Polyimide Resin) A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 58.32 g (0.119 mol) of compound (S-1) and 41.68 g (0.133 mol) of compound (Q-1), followed by the addition of 150 g of diglyme and heating at 50 °C for 10 hours. A reflux condenser with a water receiver was then attached to the flask, and 50 g of toluene was added. The mixture was heated at 150 °C for 6 hours and then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain comparative polymer CP-1. GPC analysis revealed that the Mw was 6,000.

[0049] [Comparative Example 2] Synthesis of Comparative Polymer CP-2 (Siloxane-Modified Polyimide Resin) A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 71.72 g (0.070 mol) of compound (S-2) and 28.28 g (0.077 mol) of compound (Q-2), followed by the addition of 150 g of diglyme and heating at 50 °C for 10 hours. A reflux condenser with a water receiver was then attached to the flask, and 50 g of toluene was added. The mixture was heated at 150 °C for 6 hours and then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain comparative polymer CP-2. GPC analysis revealed that the Mw was 20,000.

[0050] [Comparative Example 3] Synthesis of Comparative Polymer CP-3 (Siloxane-Modified Polyimide Resin) A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 78.35 g (0.040 mol) of compound (S-3), 3.57 g (0.012 mol) of compound (P-1), and 18.08 g (0.058 mol) of compound (Q-1). Then, 150 g of diglyme was added and heated at 50 °C for 10 hours. After attaching a reflux condenser with a water receiver to the flask, 50 g of toluene was added and heated at 150 °C for 6 hours. The mixture was then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain comparative polymer CP-3. GPC analysis revealed that the Mw was 50,000.

[0051] [Comparative Example 4] Synthesis of Comparative Polymer CP-4 (Siloxane-Modified Polyimide Resin) A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 77.61 g (0.023 mol) of compound (S-4), 5.83 g (0.018 mol) of compound (P-2), and 16.56 g (0.045 mol) of compound (Q-2). Then, 150 g of diglyme was added and heated at 50 °C for 10 hours. After attaching a reflux condenser with a water receiver to the flask, 50 g of toluene was added and heated at 150 °C for 6 hours. The mixture was then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain comparative polymer CP-3. GPC analysis revealed that the Mw was 50,000.

[0052] [Comparative Example 5] Synthesis of Comparative Polymer CP-5 (non-siloxane-modified polyester resin) A 500 mL flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 35.26 g (0.114 mol) of compound (P-1) and 64.74 g (0.126 mol) of compound (O-1). Then, 150 g of propylene glycol monomethyl ether acetate and 1.0 g of tripropylamine were added. The mixture was heated at 110°C for 10 hours and then cooled to room temperature. The mixture was then poured into methanol, and the resulting precipitate was filtered and dried to obtain comparative polymer CP-5. GPC analysis revealed that the Mw was 50,000.

[0053] [Heat resistance test] To 100 parts by weight of each of polymers P-1 to P-8 and comparative polymers CP-1 to CP-4, 30 parts by weight of isophorone diisocyanate was added as an isocyanate curing agent, and 75 parts by weight of cyclopentanone was added to dissolve the mixture until homogeneous. Each solution was spin-coated onto a substrate with a sputtered copper layer, prebaked at 120°C for 5 minutes, and then thermally cured at 180°C for 1 hour to produce a cured film (50 μm thick) on the copper substrate. This sample was subjected to a heat resistance test at 150°C for 1000 hours and then to a cross-cut peel test (JIS K 5400). The values ​​(A / B) in the table represent the number of peeled fractions (A) per 100 fractions (B). A ratio of 100 / 100 indicates no peeling, and 0 / 100 indicates complete peeling. The results are shown in Table 1.

[0054] [Flexibility evaluation] Before the heat resistance test, the Cu-sputtered substrates with the cured films were immersed in an aqueous solution of 20% phosphoric acid and 10% hydrogen peroxide for 1 hour to etch the Cu sputtered layer, yielding short films of each cured film. The resulting cured film was wrapped around a plastic cylinder with an outer diameter of 10 mm and left to stand for 10 seconds. The film was then returned to its original position and inspected for any abnormalities. If cracks or other defects were found, the result was marked "X," and if no changes were found, the result was marked "O." The results are shown in Table 1.

[0055] [Table 1]

[0056] From the above results, it is clear that the present invention can synthesize and provide siloxane-modified polyester resins having carboxyl groups and (meth)acryloyl groups in the side chains, such as polymers P-1 to P-8, and the cured coatings produced thereby exhibit excellent heat resistance and flexibility.

Claims

1. Siloxane-modified polyester resin with carboxyl and (meth)acryloyl groups on the side chains.

2. 2. The siloxane-modified polyester resin according to claim 1, which is represented by the following formula (1): 【Chemical 1】 (In the formula, R 1 are each independently a hydrogen atom or a methyl group. R 2 are each independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom. R 3 are each independently a hydrocarbyl having 1 to 8 carbon atoms. Each X is independently a single bond or a divalent organic group. Each Y is independently a trivalent organic group. Z is a tetravalent organic group. Each m is independently an integer of 0 to 4. n is a number whose average is 0 to 100. p is an integer of 1 to 30. q is an integer of 0 to 30.

3. 3. The siloxane-modified polyester resin according to claim 2, wherein Y is a group represented by any one of the following formulas: 【Chemistry 2】 (In the formula, R 4 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 8 carbon atoms. * represents a bond.

4. 3. The siloxane-modified polyester resin according to claim 2, wherein X is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group.

5. 3. The siloxane-modified polyester resin according to claim 2, wherein q is an integer of 1 to 30, and Z is a group represented by any one of the following formulas: 【Chemistry 3】 (In the formula, * represents a bond.)

6. 2. The siloxane-modified polyester resin according to claim 1, which has a weight average molecular weight of 3,000 to 500,000.

7. A cured product obtained by thermally curing the siloxane-modified polyester resin according to any one of claims 1 to 6.

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