TW201209073A - Polyester-based resin and manufacturing method thereof, and polyester-based resin aqueous solution - Google Patents

Abstract

The present invention provides a polyester-based resin with a high refractive index, which can be easily hydrated in an aqueous solvent. Specifically, the present invention relates to a polyester-based resin consisting of a polyol component (A), which contains 50 mole percent or more of the fluorine-based compound (A1) represented by the following formula (1), and a carboxylic acid component (B), with carboxyl group(s) from a carboxylic acid anhydride (C) bonded to the end of the molecule. (In the formula (1), R1 represents an alkylene group having 1-4 carbon atoms, and R2, R3, R4, and R5, which can be the same or different from each other, represent a hydrogen atom, an alkyl group having 1-4 carbon atoms, an aryl group, or an aralkyl group respectively.)

Description

201209073 VI. Description of the Invention: [Technical Fields of the Invention] Resin, poly-% method, and _, resin water-based group [prior art] Conventionally, it is used in packaging materials, magnetic cards, magnetic The poly(tetra) film, (four) ^ ί Π), etc., the thermoplastic thief, etc., the copolymer, the sputum and the resin, melt extruded and formed, the biaxial 2 to = face 'because of the fine (four) order _, paste In the case of the cover film which is formed by coating the surface of the polyester film with the shovel of the shovel of the shovel, the adhesion of the paint or the like is increased.易年来光薄薄途#t, is formed on the surface of the film to form an optical film with less strain. It is necessary to improve the adhesion: ^ refractive index, and shrink with the poly(tetra) film constituting the substrate ❸ PET, etc. For example, it has been proposed to form a polyester film by forming a poly-alcohol component with a poly(4-(ethoxy)phenyl)-containing polyol. Refer to Patent Document 1). However, the polyester resin obtained by the proposal of Patent Document 1 does not sufficiently satisfy the moisture content associated with the preparation of the film forming material. In order to solve the above problems, it has been proposed to copolymerize a polycarboxylic acid component containing a specific amount of 2,6-naphthalene dicarboxylic acid having a metal sulfonate group with a polyol component containing a specific amount of a compound. A polyester resin is formed (refer to Patent = 2).

S 201209073 PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT (2) The polyg-recommended resin is produced by adding a dicarboxylic acid having a metal sulfonate group or a polyvalent carboxylic acid having a trivalent or higher value together with other carboxylic acid component and diol component. There is a possibility of increase, gelation, etc. during the condensation reaction. Further, since the polyester resin proposed in Patent Document 2 has a large molecular weight, there is a problem in that an aqueous liquid which is difficult to be aqueous when water-based is prepared. The present invention has been made in view of the above circumstances, and an object thereof is to provide a polyester resin, a polyester resin method, and an aqueous polyester resin liquid which have a high refractive index and can be easily aqueousized in an aqueous solvent. [Technical means for solving the problem] Therefore, the inventors of the present invention have a high refractive index in order to obtain a formed film, and it is water-soluble in aqueous solution (4), and it becomes easy to form according to the film to be coated. As a result, it was found that the i-end bond of the poly-S resin which is composed of a specific amount of the polyol component having the specific compound and the ship component is carboxylated, and is provided with a county derived from the phthalic anhydride. When a large amount of a compound is used to make a poly@|-based resin, it is usually because the deuterated &amplifier has a hydrophobicity, so that the obtained (four) trapped and the polyol component are simultaneously added together to carry out a polycondensation reaction: ^^ As a bond at the end of the molecule, a large amount of silk compound is adhered to t« or 201209073, which improves the manufacturing of the product, but the carboxylic anhydride (C) is also determined according to the process of the present invention. Carboxyl group ^τ£Βΐτ:)^ [Chemical 1]

(1) In the formula (1), ' Ri is a stretching group having a carbon number of 1 to 4, and r2, r3, ^ and r5 are hydrogen or a carbon group having 1 to 4 carbon atoms, an aryl group or an aralkyl group, and the same may be the same. Can also be different. Further, the second aspect of the present invention is a method for producing a polyester resin, and a method for producing the polyester resin is to contain 50 moles of a lanthanoid compound (Al) represented by the following formula (丨). % or more of the polyol component (A) and the carboxylic acid component (B) are copolymerized to form a poly (V) polyol (I), by making the carboxylic anhydride (Q addition reaction to the polyester polyol (I)' The carboxylic anhydride (C) is bonded to the molecular end of the polyester polyol (I).

S 6 201209073 [Formula (1)" is an alkylene group having a carbon number of Μ or a alkyl group, an aryl group or an aryl group having a carbon number of 1 to 4, and these 3 are hydrogen and the present invention Two|^ ^ is also different. 〕 The fat is dissolved or dispersed, and the poly-alkali resin aqueous solution, the poly [controlling the efficacy of the prior art] as described above, the present invention is a polyester-based resin first-line compound (_mol% or more of the polyol = In the composition, the aqueous solvent of the silk knives bonded from the neoanhydride (c) at the end of the * can be easily water-based and has a high refractive index. A good coating can be formed by the eight main cloth on the film as a substrate. The difference in refractive index between the polyester film and the polyester film. [Embodiment] The embodiment of the present invention will be described as an example of the embodiment of the present invention (the polyester resin will be described in detail below). It consists of a multi-turn component (A) and a carboxylic acid age (9) on the t-type compound t containing the solution of the general formula (1), and is a sub-terminal bond derived from a carboxylic acid anhydride.

[In the formula (1), the people are carbon numbers! ~4 of the alkyl group, &amp;, heart, private and ruler 5 is nitrogen 201209073 or a hindrance of 1 to 4 of silk, aryl or aramid, and these can also be the same, the clear polyester resin For example, [α] is contained in the following formula; the ruthenium containing the first compound (A1) 5G ϋ represented by the following formula (1) is a component (4) and a carboxylic acid ^, ', 卩^ &lt; 7 long time (2), jj person j person in the 琢 元 ol (I) 'and the __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ modulation. Further, in addition to the above, the "polyphenolic resin (A) is a mixture of the acid-inducing component (8) and the acid-forming compound is reacted with an acid anhydride to form an end of the reaction). The poly-resin of the present invention can be prepared by the reaction. However, in the present invention, the viewpoint of the control of the reaction is particularly preferable. <Polyol component (Α)> The polyol component (Α) contains at least 5 % by mole of the first compound represented by the above formula (1), and preferably contains the first compound 7〇 More than 5% of the molars, more ideally, the yttrium-containing complex is 8 〇 mol%, and the most ideal state is 100% of the silk compound, that is, the polyol component (Α) only "the first When the content of the ruthenium compound is too small, it is difficult to obtain a refractive index. 153 It is preferable to use ruthenium compound (Α1) represented by the formula (1) as Ri. The form, the sulfhydryl group, the ethyl group. Further, R2, R3, K, and R5 are ideally preferred. 5, hydrogen, sulfhydryl, ethyl, and especially hydrogen are preferred. From the viewpoint of the nature and the like, it is preferable to use bisphenoxyethanol. The polyol component (A) may be a polyol component other than the oxime compound represented by the formula (1). The diol is exemplified by ethylene glycol-ethyl alcohol, diethyl glycol, propylene glycol, dipropylene glycol, 1,3-propylene glycol, 2, 4, and 2-2-ethyl-l,3-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-oxime-propanediol, 2 —Ethyl 2-isobutyl-propanediol, hydrazine, 3-butanediol, hydrazine, 4-butanediol, hydrazine, 5-pentanediol, 1,6-hexanol, 3-mercapto- 1 , an aliphatic diol such as 5-pentanediol, 2,2,4-trimethyl--1&gt;6-hexanediol, U-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1&gt;4 one ring

8 S 201209073 , 2?2Λ4_^ Between benzene, bis, 4, 4, Ί) = 2 - diphenyl, phthalic acid, chlorophenol 125 - technology - 醢芬斟 _ m Propofol, 4,4,-iso-propionyl bis (2,6-di is a combination of two oxime and the use of a bipartite aromatic weidiol. The family alone or in particular as an aliphatic diol _ ^ family 1,2-cyclohexanol diethanol of diol 7 7 ^, H, as alicyclic dimethanol, spiro glycerol, tricycloanthracene hexanol, cyclohexane, more important: family, alcohol, ideal The use of 'alcohols, such as neopentyl alcohol, di-n-dipropanol, is less than 5 or more of the ternary combustion, three brewing, ^ <carboxylic acid component (B)> j" Shen Yiszi #. The acid component (B), for example, can be strictly controlled. #二酸,Μ-Cera dicarboxylic acid, 联出出4^^, = acid, aryl propyl acid, malonic acid, malonate, V , Naphthalene acid adipic acid, Sanqimei? _ in the soil, succinic acid, glutaric acid, azelaic acid, Fumar ΐ = bis-glutaric acid, azelaic acid, aliphatic 2 oxo acid 'i, 3 - _ alkane 2 on the sulfur; dichaic acid and other fat burning diterpenic acid, 2 5 - lower it, production - get the lack of, Chen has burned an acid 1,4 - cyclohexene and terephthalic acid diphenyl g. These = day to the present - formic acid dimethyl cool in the above, especially as a scorpion #一独或疋 combined two or more. 2,5- Naphthalene di-, p-acid, as an aliphatic dicarboxylic acid in the amount of bisphenoxy in the aromatic diacid, _ lipid-blocking amount, and more like the low-point ideal Aromatic anhydride. Ί, is the axis ^, the shaft anhydride \ 201209073 Office / then the second one of the two, in addition to the second, you can also use a small amount of more than three yuan of polycarboxy-夂, such as Ben Qiao three T Acid, pyromellitic acid, adamantane tricarboxylic acid, pyromellitic acid, etc. Acid 趟 ̄ ̄ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ For example, there may be mentioned a monocarboxylic acid 5-sodium sulfonate, an isophthalic acid 5-sulfonic acid <polyester polyol (I) > a polyglycol (1), for example, by containing The general formula (1) on the ear can be used as a method of manufacturing acid, for example, the ship component (9): ί常升四至ίί:; 'alcohol,, and catalyst-into the reaction :I hoist, dish 140~280 C, the ideal state is raised like the like is carried out like state is allowed to warm to ⑽~2 pit 'off 5: reaction, optionally an acid material can depend, benzene, _, = an inert solvent. Τ本甲本# The polyester polyol (I), the average molecular weight is ~3_, the most ideal heart ~:: 里+All the knives are too small, the tendency to collapse when coating, and too big ' The right gel reduction, water-based transformation becomes difficult, and the uneven coating is generated. Lida $ has a number average molecular weight WlMOOOx ^ acid value, the polyphenol polyol (1), the base value of soil 20~5〇0mgKO block, more ideally, the state is 3〇~4 ' == ; for 5 Hey, hey (four) g. When the base value is too small, there is a base from the 1 2 3 ^ bond, aqueous solution - aqueous H anhydride (HJ, due to the molecular weight becomes smaller, so the base of the pour polyol (I) collapsed when applied The value can be determined according to ®Κ〇〇7〇. The water is used in the addition of the polyglycol polyol (1) to the acidification Xuan (6), at least 201209073 structure can be used and the use of acid The viewpoint of the reactivity of mono-anhydride, ruthenium carboxylic acid, etc., and the water dispersibility in water-based, especially tetracarboxylic acid =

Specific examples of the acid sf of the iH (C) include, for example, a H-xanthic acid hydride of a hetero acid component (Β), and a 5-benzoic acid dianhydride (Benzene tetra H ^ 3, 3, 4) :^. —π-carboxy anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3 —cyclo^^ anhydride, 5-(2,5-dioxotetrahydrofuranylmethyl)3-burning four rebellion Acid i anhydride, 2^3, ^― 稀稀—U,3—three traits, cyclopentane, ,, naphthalene carboxylic acid dianhydride, 5,6-naphthalene tetracarboxylic acid monoanhydride, 乙^双4 Tri-acid dianhydride, 2, w-diphenyl tetra-resorpene J-tetrater-tetracarboxylic dianhydride, ethylene tetra dianhydride, etc., and especially U4,5 = cinnamic acid 5 - (2,5 dioxotetrahydrofurfurylmethyl) - 3-for two ships are more suitable for immortals. The amount of the _iSf(c) that can be used alone or in the persimmon 1°== relative to the heteropolyol (η, the shape of the two hearts is 1 to 5 〇 mol%, more ideally It is 3~3〇mol% is 5~25mol%. When the carboxylic anhydride (the amount of hydrazine used is too small, the water is two, the tendency is difficult, and when the shirt is used, there is collapse or uneven coating when coating. The tendency is 23 (Τ(: °ΐΛϋ should not necessarily need a solvent' and the reaction is better than ^(10)~boots. Therefore, the viscosity of the reactants in the above temperature is Hi, ^ easy to mix, /, necessary to use The solvent may be used. The solvent may be an ester of ruthenium acetate =, hexaacetate, butyl acetate, acetoacetate, ethyl acetate or the like =|, propyl =, methyl ethyl _, ketone-based solvent such as ketoisobutyl ketone, benzene, agent, 曱5曱f, butyl sulphate, butyl sulphate acetate, etc., aromatics, alcohol, propanol Alcohol solvent, dimethyl decylamine, etc. The addition reaction can also be carried out at room temperature, but it is usually carried out at a temperature of 17 〇 to 21 〇〇c 〇 5 to 4, preferably at a temperature of m. ~篇.c, and the most reasonable response The keeper is 1 to 3 hours. Furthermore, when the molecular weight is increased to some extent, 11 201209073 I think the polyester polyol is 180 to 25 〇. (: After dehydration condensation, the line is cold 郃) The reaction is carried out at 170 to 210 C for 0.5 to 4 hours, and more preferably for 1 to 3 hours at 170 to 200 ° C. 'Heart = the above-obtained invention of the present invention having a filament at the molecular end The optimal average molecular weight of Ju Yue Yu is 3〇〇~1〇〇〇〇, and the towel is more suitable for 'more ideal form 450~2_. When the amount of polyester resin is even / knife 1 is too small There is a tendency to cause collapse or uneven coating during coating. There is a tendency for gelation, water-based conversion, and coating strips, lines, etc.. The state of J is 25~7GmgK(10)g. When the value is too small, g 2 2 ', when it is too large, there is a collapse at the time of coating, water resistance, and the acid value is based on JIS K0G7(). (10) Conversion temperature iA s〇~175t. When the coating film is taken, the tendency to cause cracks is hard, and the roll phase is sticky ===_, after the film is dissolved, it can be The aqueous bathing agent may be exemplified by water or a mixture of ammonia water in a neutralizing agent. The hydrophilic compound is a hydrophilic organic solvent or an alcoholic monotop, an ethylene glycol single; Kesailusu, ethylene glycol monomethyl sulphate, ethylene glycol single. Especially in the use of butyl; organic solvent, it is more ideal than the aqueous solvent in the whole propanol. Make * set, for example, as an aqueous solvent as a whole 30 * Dan ' is suitable for use, etc., the poly gt system of the present invention is more ideal than the following. The disease turns into a water clock, the article is called lifting the vinegar system 12 201209073, the fat aqueous liquid coating is applied to Polyester _ time ion surfactant, non-Iim. , '11 agents, specifically, polyoxyethylene alkyl base i month i acid 酉, sorbitol liver fatty acid 、, glycerol fatty acid 酉, 曰 曰 鲅 属 、 、, alkyl sulfate, Alkyl sulfonate, alkyl hydrazine alkylamine hydrochloride, dodecyl phenylwei sodium, and the like. These ϋ can be used in combination of two or more types. Further, in the aqueous solution of the polyester resin of the present invention, the external agent of the electric agent can be produced, for example, as follows. Specifically, it is possible to hunt the polyester resin obtained by putting the obtained polyester resin into the water solvent to dissolve or disperse it in the temperature of the temperature. The wealth is 1240 minutes 6〇^i2 60^180^4^fa1} Then, the solid of the aqueous solution of the polystyrene resin of the present invention is appropriately adjusted to ensure a good film of the poly-based resin to form a good film, for example, The desert

Sti ff 1G~%, % ° When the concentration of the solid content is too low, the ίί time is lowered to cause a layer separation tendency. Tianji ruler, stable liquid mixture &amp; The use example of the aqueous solution of the polyacetal resin of the present invention is, for example, sadly coated with _ aqueous liquid, and heated and dried to form a film. 13 201209073 Synthetic copolymerization The person's W has the same purpose, and the other copolymerizers can also be made into "臈. The polyester film can be stretched for the unstretched shaft. It is a polyester film which can be used for the magnetic 3 and breaks the f type, and is excellent in heat resistance and water resistance, etc., and is suitable for the image material, the photosensitive material, etc., and the special embodiment is outstanding. In the case of the ship's syllabus, the postal county invention does not exceed the example of the following. In addition, in the example, the "part", "heart [Example 1] into the enemy: thermometer, Hertz, and the tower's reaction In the apparatus, put - ΐίΐ77® naphthene diacetate ^CM) 229.2 parts (0.94 moles), more = into / knife (4) phenoxyethanol (BPEF) 658.3 parts (L5 〇 Mo Er), catalyst Dingxi (DBTO) 0.2 parts, and zinc bismuth · 2 parts, the temperature is raised to 7 〇 ~ 24 ^ hunted by = alcohol or water, and the reaction is carried out for 8 hours to make a multi-component vinegar, cooled to After 200 〇C, 112.6 parts (0.52 moles) of pyromellitic acid di(PMAn) of the carboxylic anhydride (c) was placed, and at the end of the molecule, it was dissolved by simultaneous digestion at 17 ° C for 2 hours. A polyester resin having a carboxyl group. [Example 2] A succinic anhydride of a carboxylic acid component (9) (3^^^47.5 parts (1.48 mol), a poly-alcohol component (A) of bisphenoxyethanol oxime (BPEF) 743.3 parts (1·7〇mol) and diethyl: 31.3 parts of alcohol (DEG) (〇.3〇莫耳), 5′ of (2)5 dioxo-tetra-furanyl group of anhydride (C) a 3-mercapto-3-cyclohexene-i,2-dicarboxylic anhydride (manufactured by DIC Corporation, EP^L〇NB-4400) 77.9 parts (0.30 mol). Similarly, a polyester resin having a carboxyl group at the molecular terminal was obtained. [Example 3]

S 201209073 113.5 parts (0.68 moles) of isophthalic acid (IPA) of carboxylic acid component (B), bisphenoxyethanol burial (BPEF) of polyol component (A) 748.8 parts (1.71 moles) and diethyl 2 Alcohol (DEG) 3.6 parts (0.03 mol), carboxylic anhydride (purine tetrasuccinic dianhydride (0.61 mol). In addition to the same as in the example}, a polyglycol at the molecular end and having a carboxyl group was obtained. Ester-based resin ～ [Example 4] 161.2 parts (0.66 mol) of dicaptanum naphthalate (NDCM) using carboxylic acid component (B), bisphenoxyethanol oxime (BPEF) of polyol component (A) 720.8 parts (1.64 moles) and 2.8 parts of diethylene glycol (DEG) (〇.〇3 mole), carboxylic anhydride (〇 苯 苯 苯 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115 115) In addition to the above, a polyg-type resin having a group of groups at the molecular terminal was obtained. [Comparative Example 1] The content of the funeral compound was less than 5 〇 mol%. In a reactor for introducing a tube, a thermometer, a stirrer, or a rectification column, 286.9 parts (2_87 mol) of succinic anhydride (SuAn) of a carboxylic acid component (8) was placed, and bisphenoxyethanol of the polyol component (A) was placed. (BPEF) 440.0 parts (1 〇〇 Mo Er) Diethylene glycol (DEG) 121.7 parts (1.15 mol), catalyst dibutyltin oxide (DBT〇) 〇 2 parts, and zinc acetate 0.2 parts, by heating to 7 〇 2 thieves, sterol Or the water crane is taken, and the reaction is carried out for 8 hours to prepare polyester polyol 1. Next, it is cooled to 200. (: After the addition of the carboxylic anhydride (C) 5 - (2,5 dioxotetrahydro 2 3 - 咬 基 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) a heterogeneous resin having a carboxyl group at the molecular terminal at the end of the reaction. [Comparative Example 2] <No use of a carboxylic acid anhydride (〇> In a reactor with a nitrogen introduction tube, a thermometer, a stirrer, or a rectification column, a carboxy group is placed. Acidic component (B) of dimethyl naphthalate dicarboxylate _ 〇 ^) 234.9 parts (〇96 Mocha dimethyl vinegar (DMT) 31.3 parts (〇. 16 mol) and 5_ mineral acid steel benzene Diacid dihydrate (SIPM) 47.8g (G.16 mole), and added bisphenoxyethanol (BPfF) 424.5 parts (0.97 mol) and ethylene glycol) 13多元2 parts (2 1 〇 Mo Er diethylene glycol (DEG) 51.4 parts (G.48 Moer), and added reminders The agent dibutyltin oxide (of DBTO) 0.2 parts of zinc acetate and 0.2 parts by 7〇~24 warmed to hoot, the alcohol or water 15201209073 A GU to 'the reaction for 8 hours while the produced polyester resin. [Comparative Example 3] <Addition of carboxylic anhydride (〇> using dicarboxylic acid naphthalate of carboxylic acid component (B) _CM) 289 1 part (118 mol) and dinonyl terephthalate (〇 ΜΤ) 28·8 parts (〇.15 moles) and 5 (2 5 2 gas tetrahydro- 3 - fluorenyl)-3-methyl-3-cyclohexene-u-dicarboxylic acid (DIC Co., Ltd., EPICLONB-4400) 39.1 parts (0.15 mol), and using phenoxyphene (PE) of 510 (parts of phenoxyethanol) and 31.4 parts of diethylene glycol (DEG) _ g Comparative Example 2 is the same to make a vinegar tree,) Month in: 匕二-cyclohexene dianhydride and other ships into a husband: 3 - methyl -3 should be, so in the group I a human carboxyl group, and the ingredients for the ingredients used in the counter-reagents and their use

S 16 201209073 [Table 1] Example 1 Example 2 Carboxylic acid component (8) NDCM 229.2 parts (0.94 mol) Polyester polyol raw material BPEF 658.3 parts (1.50 mol) Polyol component (A) BPEF 743.3 parts (1.70 Mo Ear) DEG 31.3 parts (0.30 mol) Carboxylation starting material carboxylic anhydride (C) PMAn 112.6 parts B-4400 77.9 parts

SuAn 147, 5 parts (1.48 moles) Comparative Example 1 Comparative Example 2 Comparative Example 3 fA NDCM 113·5 parts ΐδ12# _ Moer) (0_66 Mo 1 --- SuAn 286, 9 parts (2.87 mol) NDCM 234.9 parts (0.96 moles) NDCM 289.1 parts (U8 moles) DMT 31.3 parts (0.16 moles) DMT 28.8 parts (0.15 moles) SIPM 47.8 parts (0.16 moles) B-4400 39.1 parts (0.15 moles) BPEF BPEF 748.8 parts 720.8 parts Moore) BPEF 440.0 # Cl.00 Moer) BPEF 424.5 parts (0.97 mol) BPEF 519.6 parts (1.18 mol) DEG deg 3.6 parts 2.8 parts DEG 121.7 parts (1.15 mol) EG 130.2 parts (2.10 mol) EG 91.9 parts (M8 Moore) DEG 51.4 parts (0.48 mol) DEG 31.4 parts _ Moer) 115.2 Parts 52 Molar) 1 (0.30 <carboxylic acid component (9)> NDCM · Cai Didi Dimethicone SuAn: succinic anhydride IPA: isononanoic acid DMT - terephthalic acid dimethyl g SIPM: 5-sulfonic acid sodium bismuth diacetate - oxotetrahydro-3 - thiol thiol 3--- B-4400 : 5-(2,5-cyclohexene-1,2-dicarboxylic anhydride 134.1 parts (061 ^ 151.5 parts (0.57 mol) &lt;polyol component (A)&gt; BPEF : double ethoxyethanol DEG: diethylene glycol eg: ethylene glycol &lt;carboxyl Anhydride (C)&gt; PMAn: pyromellitic acid diterpene·4400: the same as the left-anhydride blended with two moles of the second molar =. Further, the raw materials of the respective components used, [Measurement of the physical properties of the polyester polyol] 1) The number average molecular weight of the polyester polyol is determined according to the above-described measurement method. 2) The base value of the polyester polyol is determined by JIS_7G to obtain the base value of the __ol. 17 201209073 [The physical properties of the polyester resin Measurement] 1) The number average molecular weight of the polyester resin was measured in accordance with the above-described measurement method. 2) Acid value of polyester resin The acid value of the polyester tree wax measured according to JIS K0070. 3) Glass transition temperature (Tg) of polyester resin 1. The test piece is heated and cooled by room temperature at a ratio of 1 (TC/min, and the heat is measured by a differential scanning calorimeter, and the heat absorption curve or the heat release curve is drawn. 2 extension cords, set the temperature of the 1⁄2 wire touch curve or the intersection point of the exothermic parent between the extension lines as the glass transition temperature (Tg). [Preparation of Polyester Resin Aqueous Solution] The resin is used to prepare a water-based liquid of a vinegar-based resin as follows. First, 800 parts of water is added to a reaction H towel with a nitrogen introduction tube, a thermometer, a win, and a cold part. Resin ls. parts and 50 parts of butyl 赛路苏. After the input, the internal temperature was raised to 7 (rc, adding 114% of 28% ammonia water, dissolved in the internal temperature 2 2 hours, prepared as shown in Table 2 Polyester-based resin aqueous liquid (water dispersion) having a solid content (% by weight). The polyester-based resin aqueous liquid obtained as described above was evaluated by the following method (water solubility, aqueous solution stability, Moisture resistance, refractive index (D-line Abbe number, birefringence). The results are shown below. 2. [Water Solubility] / When the polyester resin aqueous solution (aqueous dispersion) of the example and the comparative example is used for 5 weeks, the polyfluorene t-based resin is sufficiently dissolved or dispersed in the aqueous solvent, and is aggregated. The ester tree is not sufficiently dissolved or dispersed in the aqueous solvent, and the polyester resin is not prepared. The water content of the polyester resin is (X aqueous dispersion). X. [Aqueous solution stability] The solid content shown in Table 2 below is used. The concentration (% by weight) of the polyester resin aqueous solution (aqueous dispersion) is 60% when stored in a thermostatic bath for 1 month, and the case where the phase is not separated and maintained in a uniform state is 〇, and the phase separation is X. [Heat and Heat Resistance] 201209073 Preparation of polyethylene terephthalate composed of the aqueous polyester resin (aqueous dispersion) obtained in the examples and the comparative examples and dried (film thickness: 1 μηι) pET) film (_Easy-adhesive PET film) (thickness of PET film ΙΟΟμηη). Next, an ultraviolet curable resin composition composed of the following blended components is prepared, and a film forming surface of the easy-adhesive PET film is formed. The ultraviolet curable resin is coated using a coating rod The product was uniformly coated, and the film thickness after hardening was 1 μm ηη. After coating, it was dried at 8 〇. 〇 dried for 3 minutes, using i2〇w/cm set at 2 〇cm higher than the coated surface. The south pressure mercury lamp of the irradiation intensity is irradiated with ultraviolet rays of 4 〇〇 mJ/cm 2 to cure the ultraviolet curable resin composition to form a hard coat layer. The sample prepared as described above is placed at 75. After 300 hours in a thermo-hygrostat having a humidity of 9%, the adhesion evaluation shown below was carried out. In detail, one piece was formed by cross-cutting on the sample, and Cellotape (Cellotape, manufactured by C., Ltd.) was used. The trademark is attached to the surface of the adhesive PET film. After the force is applied by the fingers, the film is quickly peeled off in the direction of 9°°, and the three-stage evaluation shown below is performed according to the number of residues. Then, the following evaluations were determined to have good adhesion. 〇: 100/100 (number of residues / number of measurements) △ : 80/100 or more, not up to ι〇〇/1〇〇X: less than 80/100 <UV-curable resin composition> Hard coating amine Urethane acrylate (Nippon Synthetic Chemical Industry Co., Ltd., Violet UV-7600B)...25 parts ^ , , methyl ethyl ketone / methyl isobutyl mixture weight ratio)].....75 parts photopolymerization start (Irgacure 184, manufactured by Changyun Industrial Co., Ltd.). 3 parts [Measurement evaluation of refractive index, Abbe number, and birefringence], using a coating bar, the water of the polyester resin obtained in the examples and the comparative examples was water-based. The liquid (aqueous dispersion) was applied to a 1 μm of a biaxially stretched polyethylene terephthalate (PET) film, and dried at 1 〇〇c for 2 minutes to prepare a measurement sample (coated). The dry film thickness is about Ιμπι). Then, an optical film (refractive index (D line), Abbe number, and birefringence) of the measurement sample was measured using an optical film measuring device (Scientific Computing International, optical film measuring device FnmTek3). 19 201209073 [Table 2 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Polyester polyol raw material: carboxylic acid component (B) (% by mole) NDCM 33 - 23 - 35 34 SuAn — 39 — A 51 — — IPA One One 23 One One One — DMT One — — One 4 4 SIPM — — — 一 一 5 — B-4400 — — — — 一 一 6 Polyester polyol Raw material: Polyol Ingredient (A) (% by mole) BPEF 50 45 56 57 18 35 45 EG — — — One 16 8 DEG A 8 1 1 21 5 3 Carboxylic anhydride (C) (% by mole) PMAn 17 — 20 19 One by one A B-4400 — 8 — a 10 _ polyester polyol physical quantity number average molecular fl(Mn) 428 1,626 836 457 976 acid value (mgKOH / R) 1.9 1.0 1.2 1.3 1.0 hydroxyl value (mgKOH / g) 260 68 133 244 114 Physical properties of polyester resin with carboxyl group Number average molecular β(Μη) 499 1,935 978 528 1,275 11,222 Gelation acid value (mgKOH/g) Hydroxyl value (mgKOH/g) 32 28 66 40 58 5 193 30 48.7 173 30 5 TgfC) 173 100 141 143 68 170 Solvent (parts) Water 800 800 800 800 800 800 Butyl Cyrus 50 50 50 50 50 50 15 15 15 15 15 15 Water solubility 0 〇0 0 〇Water solution stability 0 〇0 〇0 Heat and humidity resistance 〇〇0 〇X Refractive index (D line) 1.65180 1.62749 1.68592 1.64603 1.59041 -— Abe sin birefringence ^ - -------- 15.1 0.172 24.8 0.187 16.4 0.191 16.3 0.196 32.3 0.184 —~二__ —=___ Compared with the specific example of the specific range of the material composition of the 'multi-o-alcohol component (A), The water-based property is a good problem, but the silk resistance is poor, the refractive index (D line) is low, and the high-quality compound 2 of the non-carboxylic acid liver is not obtained, and the polyester resin water is prepared, and is soluble in water. Since the solvent is used, the poly-I-preservation liquid cannot be obtained.

S 20 201209073 Perform other measurement evaluations. Moreover, it is used in the preparation of polyacetal polyols and incorporates a secret in the main chain of the polyester resin =' fat. (4), the invention is not limited to the specific form of the present invention, but the embodiment is not limited to the scope of the present invention. The change is all in the gamma of _. #状申_围的均上的用系系树树解光光_稜鏡层等, optical material #剂' The film-type film is used for the magnetic card f $ to form the film light material with the aqueous liquid . Disc, printed material, image material, salt [Simplified description of the drawing] J&. 0 [Key component symbol description] Benefit. &lt;,*, 21

Claims (1)

201209073 VII. Patent application range: 1. A polyester resin containing a polyol component (a) containing 50 mol% or more of a fluorene compound (Al) represented by the following formula (1) and a tickic acid The polyester-based resin composed of the component (b) is characterized in that it is bonded to a slow-acting group derived from a slow acid acid (C) at a molecular end, [Chemical Formula 1] [In the formula (1), R1 is a stretching group having a carbon number of 1 to 4, and R2, horse, and R5 are hydrogen or a carbon group having 1 to 4 carbon atoms, an aryl group or an aryl group, and the same may be the same. Can be different. 2. The polyester resin according to the first aspect of the patent application is a polyol component (A) and a carboxylic acid component containing 50 mol% or more of the first compound (Al) represented by the following formula Q). The polyester polyol 1 (B) is produced by an addition reaction with a carboxylic acid anhydride (c), and has a carboxyl group derived from the carboxylic anhydride (C) at the molecular terminal. 3. The polyester resin according to claim 1 or 2, wherein the number average molecular weight is from 300 to 10,000. 4. The poly-resin resin according to claim 1 or 2, wherein the acid value is 1 〇 1 〇〇 mg KOH / g ° 5. The polyester resin according to claim 2, wherein the poly The number of vinegar polyol (1). The average molecular weight is 300~8000, and the base value is 2〇~5〇〇. 6. If the dance resin of the second item is applied for, the amount of the towel anhydride (c) used is 1 to 50 mol% relative to the polyester polyol (I). 7. A method for producing a poly-Sf-based resin, which is a method for producing a polyacetic resin according to any one of the claims of the invention, which is characterized in that it contains a first compound represented by the following formula (A1) 5 〇 mol% or more of the polyol component (A) and the carboxylic acid component (8): 22 S 201209073, and as the polylactic acid polyol (1), by adding the slow anhydride (c) addition reaction In the di-octanol (1), the carboxylic anhydride (c) is bonded to the molecular end of the polyester polyol (I) [Chemical 2] *(1) Carboniferous number (in the formula (1), 'Rl is a carbon number of 1 to 4, and H.p.> 1~4 fluorenyl, aryl or a group of 3 is a gas or a second liquid. If the towel is different, the patents are different. 〕 Comes to the Japanese resin dissolved or dispersed in an aqueous solvent ^ made in the first to sixth items - Item: None. twenty three