TW201037015A - Polyol compound and thermocurable composition containing the same - Google Patents

Abstract

Provided is a novel polyol useful as a starting material of a polyurethane which provides a cured coating having excellent flexibility, chemical resistance, heat resistance, and rapid curability, and capable of being regenerated from waste plastics, and also provided is a thermally curable composition containing the same. A polyol compound obtained by depolymerizing a polyester with a polyol having a plurality of hydroxy groups per molecule is provided. Also, a thermally curable composition containing the polyol compound and an isocyanate compound or a block isocyanate compound or an amino resin is provided. Preferably, the polyol compound is obtained by heating and melting the polyester without using a solvent and depolymerizing the polyester by adding the polyol thereto, and is a semi-solid or flowable liquid. The polyester is preferably regenerated PET.

Description

201037015 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a coating, an ink, a coating agent, an adhesive, an urethane for use as a substrate for paper, wood, metal, plastic, glass, ceramics, and the like. A polyol compound useful in a vinegar foam raw material, and a thermosetting composition containing the polyol compound. [Prior Art] The polyurethane has been used as an adhesive component and a bismuth coating component. However, when the polyurethane has poor heat resistance and adhesion as compared with an epoxy resin or the like, its use is limited. The polyamino phthalate is composed of a polyol component and an isocyanate component. Further, since the polyol component has an alcohol terminal ', the density of the aromatic ring does not rise as compared with the epoxy resin which uses a phenol resin as a starting material. Therefore, it is considered that this is a cause of a decrease in heat resistance of the polyurethane. Further, there is also a method of adding an isocyanate in an excess amount to the alcohol to increase the crosslinking density to obtain heat resistance. However, in this case, there is a problem that "softness is lowered, adhesion is poor, and coating performance is lowered". 〇 On the other hand, PET bottles made of polyester vinegar have been used in recent years because of their light weight, excellent transparency, gas barrier properties, and high strength. Along with this, the method of disposal has become a social problem. Therefore, PET bottles are generally collected separately and recycled. However, in the recovery process, the molecular weight of PET is reduced due to hydrolysis of the ester bond, and there is a problem that the melt viscosity and mechanical strength of the so-called ΕΤρΕΤ are reduced. Therefore, such quality degradation has become a major cause of hindering the recycling of PET bottles. Therefore, the regeneration of ΕΤ ΕΤ resin is currently mainly used in the field of fibers and industrial materials. However, with the increase in the amount of PET bottles discarded, the new and effective use of recycled resin is being explored. As for the example of the new method, it has been reviewed that the alkyd resin for coatings is produced by the depolymerization reaction of 3 201037015 caused by glycols (refer to the polyester resin for coatings produced by the patented recycled polyester) (see Patent Document 2, for use in Recycled polyester is used as a photocurable amino phthalate resin, and it is disclosed in the literature 4), etc. (refer to the poly-alcohols which are represented by the polyester in the patent documents disclosed in these patent documents) The alcohol oxime which is synthesized as a raw material is obtained by depolymerization of a polyester or after depolymerization, and is directly condensed with bis-succinic acid, from the viewpoint of "recycling resin". 7 The use rate of the fat is low. Further, the exemplified polyol has a hydroxyl group value of KOH/g, and it is difficult to improve the heat resistance of the crosslinked 宓^ mg by using the composition of the polyol. [Patent Document 1] Patent Document 1 [Patent Document 1] Japanese Patent No. 3,310,661 (Patent Application) [Patent Document 2] Japanese Patent No. 3443409 (Application Patent Specification [Patent Document 3] Patent No. 3256537 (Application for Special Purpose) Scope [11] [Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-307779 (Applied to vol. Providing a novel polyol which can be used as a material for softening, chemical properties, heat and quick-curing properties of a hardened coating, which can be regenerated from plastic waste, and heat containing the polyol A hardening composition. [Means for Solving the Problem] In order to achieve the above object, according to the present invention, there is provided a polyol compound 201037015 (A) which is a polyol having two or more hydroxyl groups in one molecule (b) Further, according to the present invention, there is also provided a thermosetting composition comprising (A) the above polyol compound and (B) an isocyanate compound or a blocked isocyanate (block isocyanate). a compound or (C) an amine-based resin. In a preferred aspect, when the (A) polyol compound is 100 parts by mass, the (B) isocyanate vinegar compound or the isocyanuric acid vinegar The compounding amount of the compound is 20 to 3 parts by mass.

In a preferred embodiment, the polyol compound (A) has a hydroxyl group value of from 200 to 800 mg ΚΟΗ / g. In a preferred embodiment, the above polyol compound (A) is obtained by using the solvent in an unused solvent. (a) Heating and melting, and the above polyol (b) is added thereto to carry out depolymerization. In this case, the above polyester is preferably a regenerated PET, and a polyol having two or more hydroxyl groups in a fraction f (in the component of 'inclusive of at least di-methylpropane or polycarbonate diol) Further, the obtained polyol compound (A) is in the form of a non-volatile fraction of 〇〇%, and is an amorphous semi-solid or liquid having a fluidity, preferably having solvent solubility. According to the present invention, there is further provided a method for producing the aforementioned polyol compound, which comprises: providing a polyester (a); and depolymerizing the polyester using a polyhydric alcohol (b) having two or more hydroxyl groups in one molecule In order to obtain a polyhydric alcohol compound. [Effect of the Invention] The novel polyol compound of the present invention and the chemical composition containing the same are in particular having two or more hydroxyl groups in one molecule (8) When the polyacetate (a) is depolymerized to obtain a polyhydric alcohol compound (4), the polyamine II, the raw material and the material which are excellent in chemical resistance, moisture resistance, flexibility, and the like can be obtained. Use (A) the above polyol compound with [, Ssl Sa Sa & A thermosetting composition of a mixture of isocyanuric acid (bi〇ck is〇Cyanate) or (C) an amine tree. It can be used in 201037015 to form heat resistance, chemical resistance, and flexibility. Such an excellent hardening film. ^, the above polyol compound (A) is in a non-volatile fraction of 1% by weight and is semi-solid = suitable for an adhesive, a sealant, and further, by adding a solvent, reacting and diluting the body It can also be used in various coating agents and coatings. Further, when the above-mentioned polycondensation is recovered from waste, it can be synthesized by depolymerization in a solvent without using a high-concentration regenerated tree, and environmental protection砚In other words, it can be applied as a product which contributes to the reduction of c〇2. [Embodiment] The polyol compound (8) of the solvent is characterized in that it has no more than one solution and has two or more base polyols (8). Polyacetate (4) and; Li: Regeneration of ρετ, etc. as the above-mentioned polyester (8), a semi-solid polyol compound which does not form a ruthenium. The main one is the study of the present, and it is known that there are 2 compounds in the molecule. , ^ (4) (4) depolymerized to obtain a novel polyol Polyol with more than 2 groups of bases (8) When it is a diol or a trifunctional polyol, the Umi people's 'features are best characterized. If according to this or the season, tetraacid-le" propanol a bifunctional alcohol such as neopentyl glycol, which is used alone or in a tetrafunctional or higher alcohol such as an alcohol, and which does not form a compound; f. (10), after a few days of standing, it must be insoluble in the crystal. Solvent, in addition, if you want to use the repeating unit with PET (4), when the molecular weight Mn7G () ~ _, not m propylene, can be precipitated so that after 3 months The crystal is not transparent. In addition, the solubility in the solvent is extremely high, and it is in the state of 201037015. Further, it has been found that the substance can be used even in a state of being diluted with a solvent or a reactive diluent. This phenomenon is unexpected and surprising. The above-mentioned poly (a) depolymerization reaction is carried out by a polyol (b) having two or more hydroxyl groups in one molecule, without using a solvent, and the polyester (a) is heated and melted, and a liquid is added ( When it is solid, the polyol (b) which is heated and melted into a liquid state is preferably about 2 Torr to 3 (8) in the presence of a catalyst. Hey. A polyester (8) used in the synthesis of the above polyol compound (A), wherein all of the conventionally known polyesters can be used. Among them, polyethylene terephthalate (PET), polytrimethylene terephthalate (ptt), polybutylene terephthalate (pBT), polyethylene naphthalate (PEN) And polybutylene naphthalate (pBN). Further, it may be a pulverizer of a ρΕτ bottle, a PEI film, or a PET product, or a regenerated ΡΕτ which is washed away from waste. Preferred is recycled pet. However, it can be purchased from the market if it is washed and granulated. In the above-mentioned hall, there are more than two hydroxyl groups in the above-mentioned molecule.

^^ Isoprene - fine diol _, 14 4 and an elastomer such as a compound). 'Quality compound, co-carbonate diol of ethylene bromide and propylene bromide, polyester diol, diamond diol, hydrazine, hydroxy terminal polydiene diol (for example, 1 > 4 _ 1, 4- and 1,2-polybutanol and the 氲7 of these materials 2010 20101515 For commercial products, for example, the above-mentioned hydroxy-terminated polydiene diols are commercially available, 'Epol (E-light) Manufactured by the company, hydrogenated polyisoprene diol, molecular 罝i, 860, average degree of polymerization 26), PIP (manufactured by Idemitsu Kosan Co., Ltd., polyisoprene diol) molecular weight 2,200, average degree of polymerization 34), PolytelHA (manufactured by Mitsubishi Chemical Corporation, hydrogenated polybutadiene diol, molecular weight 2,200, average polymerization degree 39), R-45PIT (manufactured by Idemitsu Kosan Co., Ltd., polytetramethylene glycol, molecular weight 2,270, average degree of polymerization) 42) Etc. 3 g can be used in the glycerol, diglycerin triglyceride, carbamazepine - 11⁄2 mercaptopropene, sorbitol, pentaerythritol, two (three meridian f *, two seasons fine Alcohol, tridecyl alcohol, gintriol, etc. In addition, it can also be modified with such epoxy bake or epoxy bromide. The oxypropane modified product of the above-mentioned compound, and the polyol having a heterocyclic ring may be Theic, etc., which is manufactured by Siguo Chemical Industry Co., Ltd. The mono-alcohol may be used alone or in combination of two or more groups of S acid vinegar diol. In the case of long-chain diol or tri-methyl propyl 4, θ: 蜀, decyl sterol, it is possible to obtain a turbid, solid-shaped semi-solid shape and high solubility when forming a depolymerized polymer.鲂祛 盅 盅 π π Γ Γ Γ 又 又 对 对 对 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的A, therefore, the above-mentioned serotonol contains such a polyol; compared; "4, and yuan r: special, base propyl coffee, etc., "dibutyl phthalate, dibutyl laurate; Tin oxide, zinc 2-ethylhexanoate, manganese acetate, cobalt acetate 7 vinegar; 2, stannous oxide, tin acetate, vinegar undercobalt plaque calcium, lead acetate, antimony trioxide, titanium 201037015 tetrabutyl phthalate, titanium Tetraisopropyl acid, etc. The amount of the depolymerization catalyst used is 1 part by mass based on the total amount of the polyester (a) and the polyol (b). It is preferably 0.005 to 5 parts by mass, and more preferably in the range of 5 to 3 parts by mass. Further, although the polymer is not depolymerized, the compound which promotes depolymerization has water. In the case of recycled PET, since it is a cause of a decrease in the molecular weight of ρΕτ, it is usually necessary to remove it by a very energy-consuming step of "drying". However, in the use of the present invention, it is not necessary. The regenerated PET pellets obtained by adding water and being melted by a pelletizing machine such as an extruder can reduce the reaction temperature at the time of depolymerization because the molecular weight of the regenerated pet is low. Further, in this case, the viscosity at the time of blooming becomes low, so that it is preferable from the viewpoint of being able to react at a high concentration. 〇〇About the mixing ratio of the above polyester 0) to the polyol (b), the ratio of the molar number (al) of the repeating unit of the polyester to the molar number (bl) of the polyol, to (al)/(bl ) - 0.5 to 3 is preferably 'in the range of 〇. 8 to 2 is preferred. When the ratio is less than 0.5, the amount of the polyol contained is excessive, and the ratio of the aromatic ring derived from the polyester is decreased. The effect of improving heat resistance and chemical resistance is small, which is not preferable. On the other hand, if the above ratio is more than 3, the depolymerized polymer is almost uniformly crystallized, which is insoluble in a solvent, and thus is not preferable.热 The thermosetting composition of the present invention can be obtained by blending the polyol compound (A) 'obtained in the above manner with an isocyanate compound (B) or a blocked isocyanate compound or an amine-based resin (c) . These components ((B) and may be used singly or in combination of two or more kinds. The total amount of each of the above (B) and (C) is 20% by mass relative to 100 parts by mass of the polyol compound (A). The range of 300 parts by mass is preferably. For the above isocyanate compound (B), for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate may be used. Specific examples of the aromatic polyisocyanate may be used. It is 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene diisocyanate, meta-xylene diiso Cyanide 201037015 acid ester, 2,4-extended phenyl diisocyanate dimer, etc. Specific examples of the aliphatic polyisocyanate may be tetradecyl diisocyanate, hexamethylene diisocyanate, fluorenylene diisocyanate, three Mercaptohexamethylene diisocyanate, 4,4-mercaptopurine (cyclohexyl isocyanate), isophorone diisocyanate, etc. Specific examples of the alicyclic polyisocyanate may be bicycloheptane triisocyanate or the like. Can be listed above An adduct of a sulphuric acid vinegar compound, a biuret body, and an isocyanurate. The isocyanate compound (B) may also be a commercially available one, for example, Duranate (for example) Registered trademark) 24A-100, Duranate 22A-75PX, Duranate ΤΡΑ-100, Duranate THA-100, Duranate P-301-75E, Duranate 21S-75E, Duranate 18H-70B, Duranate MFA-90X (above is Asahi Kasei Chemicals) Company, trade name), Basonat HB-175, Basonat HI-100, Basonat HI-190B, Basonat HI-290, Basonat HB-275B, Basonat HI-168, Basonat HI-268, Basonat HW-180PC, Basonat HW- 100, Laromer LR9000 (above, manufactured by BASF Corporation, trade name), etc. The blocked isocyanate group contained in the blocked isocyanate compound (B) is based on an isocyanate group and a blocking agent. The reaction is protected and temporarily becomes an inactive group. When the temperature is raised to a predetermined temperature, the blocking agent dissociates to form an isocyanate group. In terms of the blocked isocyanate g compound (B), An addition reaction of an isocyanate compound with an isocyanate blocker can be used to form The isocyanate compound which can react with the blocking agent may be an iso-cyanate type, a biuret type, an adduct type or the like. As the isocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanurate, and the alicyclic polyisocyanate may be the compounds exemplified above. The isocyanate-based blocking agent may, for example, be a phenolic blocking agent such as a test, a bismuth, a bismuth, a chlorine test or an ethyl phenol; ε-caprolactam, δ-valeroinamide , 201037015 γ-butyrolactam and β-propionalamine and other internal amide-blocking agents; active methylene-based blocking agents such as ethyl acetate and ethyl acetoxyacetone; methanol, ethanol, and C Alcohol, butanol, pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl hydrazine, propylene glycol monomethyl ether, benzyl mystery, decyl glycolate Alcohol-based blocking agents such as butyl glycolate, diacetone alcohol, decyl lactate and ethyl lactate; formaldehyde oxime, acetaldoxime, acetoxime, mercaptoethyl ketone Terpene blockers such as hydrazine, diethyl hydrazino, cyclohexane, etc.; thiols such as butyl mercaptan, hexyl mercaptan, tributyl thiol, thiophenol, methyl thiophenol and ethyl thiophenol Blocking agent; guanamine, benzoguanamine and other amide-based blocking agents; amber succinimide and maleimide and other flavonoid blocking agents; diphenylaniline, aniline, butylamine, two Amidine and other amine seals Agents; m [deg.] Ride, 2-ethyl-η m laugh laugh like taste based blocking agent; Yue alkylene imine group, propyl extending imine imine blocking agents. Xinshangqi acid vinegar compound (Β) can also be commercially available, such as Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS- 2117, Desmotherm 2170, Desmotherm 2265 (above, manufactured by Bayer Aminophthalate Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (The above is manufactured by 曰 聚 polyamine phthalate industrial company, product Ο Name), B-830, B_815, B-846, B-870, B-874, B-882 (above is manufactured by Mitsui Chemicals, Inc., trade name), TPA-B80E, 17B-60PX, E402_B80T (Asahi Kasei Chemicals) Stock company system, product name), etc. Further, Sumidur BL-3175 and BL-4265 were obtained by using methyl ethyl ketone oxime as a blocking agent. The above-mentioned isocyanate compound having two or more isocyanate groups or a blocked isocyanate compound having a blocked isocyanate group may be used singly or in combination of two or more kinds. The amine resin (C) may, for example, be a hydroxydecyl melamine compound, a sulfhydryl basic amide compound, a methyi 〇i giycoluril compound or a hydroxy thiourea compound. Further, the alkoxymethylated melamine 11 201037015 amine compound, the alkoxylated phenyl decylamine compound, the alkoxymethylated glycoluril compound, and the alkoxylated urea compound are respectively It is obtained by converting a hydroxy group of a hydroxymethyl melamine compound, a hydroxymethyl phenyl guanamine compound, a hydroxymethyl glycoluril compound, and a methylol urea compound into an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and examples thereof include an anthracenyloxy group, an ethoxylated fluorenyl group, a propoxymethyl group, and a butoxy fluorenyl group. In particular, it is particularly preferable to use a melamine derivative which is harmless to the human body or the environment and has a furfural concentration of 0.2% or less. As a commercial item of the amine-based resin (C), for example, Cymel 300,

Cymel 301, Cymel 303, Cymel 370, Cymel 325, Cymel 327,

Cymel 701, Cymel 266, Cymel 267, Cymel 238, Cymel 1141

Cymel 272, Cymel 202, Cymel 1156, Cymel 1158, Cymel 1123, Cymel 1170, Cymel 1174, Cymel UFR65, Cymel 300 (above, manufactured by Cytec Industries, Japan), Nikalac Mx-750, Nikalac Mx-032, Nikalac Mx-270, Nikalac Μχ·280, Nikalac Mx-290, Nikalac Mx_706, Nikalac Mx-708, Nikalac Mx-40, Nikalac Mx-31, Nikalac Ms-11, Nikalac Mw-30, Nikalac Mw-30HM, Nikalac Mw-390, Nikalac Mw -IOOLM, Nikalac Mw_75〇LM (above, manufactured by Sanwa Chemical Co., Ltd.), and the like. As the above-mentioned amine-based resin (C), one type may be used alone or two types may be used in combination. In the thermosetting composition of the present invention, it is necessary to further add a coloring agent such as a catalyst, a pigment, a dye, or the like, an antioxidant, a stabilizer, a UV absorber, a flame retardant, and a mechanical strength required for thermal curing. An inorganic filler, an organic solvent used for reducing the viscosity, a decane coupling agent, an antifoaming agent, a leveling agent, and the like, or other additives. Further, a conductive material such as a metal such as silver or copper or carbon may be added to form a conductive composition. [Examples] 12 201037015 Hereinafter, the examples and comparative examples are exemplified in more detail, but the present invention is not limited by the following examples. In addition, the field description of the present invention and the "❶/〇" are as long as the "parts" of the following are not specifically stated. Synthesis Example 1 In a mixer equipped with a stirrer, a nitrogen gas introduction tube, and a cold-filled four-port round bottom separable flask, 192 pieces of 500 ml pieces of ιν value 〇/ were added, and the inside of the flask was made into a nitrogen atmosphere, and then immersed in the mold. Recycling. ΡΕΤ In the salt bath. Stirring was started when the PET was dissolved, and it was raised to 300 parts by weight of 300 lt. Then, 134 parts of the 7-state were added in a small amount in the case where the PET was not cured and the dibutyltin ruthenium oxide was previously heated to 13 G ° C to melt the trimethyl group. During the period of viscosity reduction, the stirring speed is increased. This is the same as changing from the salt bath to the oil bath which is previously heated to WC. Soft: ΐ slightly = it is called ab] resin. The W tree spectrum is not in the first picture. Synthesis Example 2 In a 500 ml four-neck round bottom separable flask equipped with a scrambler, a nitrogen introduction tube, and a cooling tube, 192 parts of the recovered ρΕτ piece of iv^〇6~〇7 were added to form a flask. In a nitrogen atmosphere, the temperature was raised to a salt bath of 3 dynasties. Stirring was started while the PET was dissolved, and 0.65 parts of dibutyltin oxide was added. Then, Attention was paid to the solidification of the pET, and 694 parts of the tris-propyl propyl group which was previously heated to 130 C and dissolved was added in small portions. During this time, the agitation speed was increased to 15 rpm during the stage of viscosity reduction. Then, change from salt Luo Qiao. The oil bath was previously heated to 24 ° C to maintain the internal temperature of the flask at 220 C ± 10 C and react for 5 hours. The reactant is yellow transparent and hard viscous at normal temperature. This is called ab_2 resin. The IR spectrum of the ab_2 resin is shown in the second figure. 13 201037015 Synthesis Example 3 In a separable flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooled four-neck round bottom, 192 parts of IV/it = fine house liters were added to form a nitrogen atmosphere in the flask, and then immersed in 7 fields. In the salt bath. When the PET is dissolved, the mixing is started, and the temperature of the third to the fine C is preheated to 130 ° C, and the melted trimethylol propyl p and the lining are added to the stage of decreasing the viscosity to increase the rotation speed to the portion = this ^' The bath is changed to the oil bath that has been warmed up to the front of the boot, and the & insider 2 half 20 solid C is opened: will, time. The reactants were ‘lower’ white turbid, = medium resin. IR spectrum of a'-3 resin is shown in Synthesis Example 4. In a four-neck round bottom separable flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooling tube, a recovery pET having an IV value of 0.6 to 〇7 was added. For 39 parts, a nitrogen atmosphere was formed in the flask, and the temperature was immersed to 3 Torr. 〇之 salt bath. The scrambling was started when the PET was dissolved, and 0.65 parts of dibutyltin oxide was added. Then, 161 parts of Duranol T5650J (manufactured by Asahi Kasei Chemicals Co., Ltd.) which had been previously heated to 130 ° C were added in small amounts with a small amount of attention. During this time, the mixing speed was increased to 150 rpm during the stage of viscosity reduction. Then, the salt bath was changed to an oil bath which was previously heated to 24 ° C, and the inner temperature of the flask was maintained at 220 ° C ± 1 (TC, and reacted for 5 hours. The reactant was yellow transparent and liquid at normal temperature. This is called ab-4 resin. The IR spectrum of the _4 resin is shown in the fourth figure. Synthesis Example 5 In a 500 ml four-port round bottom separable flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube Adding 39 parts of recycled PET sheets with an IV value of 0.6 to 0.7, forming a nitrogen atmosphere in the flask, immersing them in a temperature of 30 (rc 14 201037015 2, 4 PET dissolution), adding dibutyltin oxide first to cure the PET Next, add 80.5 wounds of pre-ano1 T5650J (made by Asahi Kasei Chemicals Co., Ltd.) in a small amount. During this period, the viscosity is lowered to (9). Then, change from salt bath to pre-heating to 24〇=degree by ^ (2) The mouth = trc ± io °c, and reacted for 5 hours. The reactants were yellow, slightly turbid, and liquid under the two servings. The IR spectrum of the resin, which is called ab resin, is shown in the fifth figure. (4) ab ab-5 Ο Ο Synthesis Example 6 Is there a 5〇〇2 type with a stirrer, a nitrogen inlet pipe, and a cooling pipe? In the 'add 1v value 〇.6~〇.7 recycling pet d ΐ 时 时 开始 ' ' ' ' ' ' ' nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor nor 22〇〇c± UTC liter:: 油2?0 oil bath to keep the inner temperature of the flask in a fibrate shape. When J: AL, the reactant is yellow white turbidity = medium resin at normal temperature. The IR spectrum of -6 resin is shown in Synthesis Example 7. The ampoule has a stirrer, a nitrogen gas guiding tube, and a cooling tube. The _ = round bottom separable flask is filled with 1¥ value G6~q ^ 192 parts to make the flask After the formation of nitrogen, = medium: * PET begins to mix when dissolved, while adding force = two = • 65 injuries. Then, pay attention to ^ ^ ^ ^ Tuxi 130 ^ ^ ^ ^ 1? 3. Τ. / 9 〇 In the stage of viscosity reduction, the speed is increased to Pm. n趟15 201037015 The bath is changed to pre-heated to 2403⁄4, from the bath, 220 bauxite 1 (rc ' and reacted for 5 hours. The reactants are soft and sticky in the reaction. It is called ab_7 resin dish and it is shown in the seventh figure. The IR light synthesis example 8 of the ab-7 resin is equipped with a scrambler and a nitrogen inlet tube. In the bottle, add W? 500 liters of the house; 9) After forming a nitrogen atmosphere in the flask, start to disturb when immersing the two solutions, and add m ίίί 0.65 injury. Then, pay attention to not emulsification of butyl butyl tin. The glycerin 92 which is heated to 130 ° C and melted is added in small amounts one by one.

In the lowering stage, the stirring speed is increased to 15 =====, until the temperature is raised to 24 (TC oil bath, by twisting, and then, the salt is changed and exchanged, and reacted for 5 hours. The reactant is in ^; The tile is inside == Temple is called (four) resin in the boot soil. IR synthesis example 9 of ab_8 resin

In a flask equipped with a swimming machine, a nitrogen gas, and a cold-bottom separable flask, an IV value of 二P 2: 2: 192 parts was added to form a nitrogen atmosphere in the T salt bath. At the beginning of the dissolution of PET, and at the same time, the quaternary 丄 = eight-solidification, a small amount of ft is added from the salt bath to the pre-heating to the boot. The yellow solid half-solid shape at room temperature. |反反;;=Tree Synthesis Example 10 16 201037015 Four in the women's clothing machine, nitrogen inlet tube, cooling tube 500 - round bottom separable flask, add ^^ value 06~07 back ί η ' 5 After nitrogen (4) was formed in the flask, the person was immersed in a vessel of 3 °C. Stirring was started while the PET was dissolved, and 65 parts of dithizone was added. Then, taking care not to cure the PET, the second quarter: alcohol 254 # is added successively. During this period, the mixing speed was increased to 15 rpm during the stage of viscosity reduction. Then, change from the salt bath to the pre-wave | 240 ° C oil bath, the internal temperature of the flask is maintained at 22 (rc ± 1 〇 t:, and = Ο Ο = the reactant is yellow transparent solid shape at room temperature. This is called a synthesis example. In a five-neck round bottom separable flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooling tube, 192 parts of an IV value of 0 6 to 0 7 were added to form a nitrogen gas in the flask. After the atmosphere, immerse in the temperature to 3 (8) salt * PET starts to stir, dissolve at the same time, add dibutyltin oxide ^ \ then = in the case of not to cure, add a small amount of 戍 二 酵 酵 127 127 127 67 67 67 67 67 67 67 67 67 In this stage of lowering, the stirring speed was increased to 150 rpm. Then, from the bath to the m 〇 m4 (rc * bath, the flask was held at C ± l 〇 C, and reacted for 2 hours. The reactants were at room temperature. The yellow solid shape is referred to as ab-li resin. Only Babian month synthesis example 12 In a four-neck round bottom separable flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube Add 250 parts of the recovered pET sheet with an IV value of 〇6 to 〇7, and then immerse the temperature in the flask to form a nitrogen atmosphere. In the salt bath of 〇t>c. Stirring is started when the PET is dissolved, and dibutyltin oxide is added at the same time. Then, 'Be careful not to make the PET solidify, add a small amount of pre-heating to 13 (TC Duranol T5650J (Asahi Kasei) Chemicals shares 17 201037015 system) 104 parts, trimethylolpropane 157 parts. In this low J stage, the stirring speed is increased to 15 rpm. Then J = to 2, the oil bath 'will burn the internal temperature (10) Synthesis Example 13 ❹ In a separable flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooling tube, 'addition! v value 〇6 to 〇7 was recovered. L was injured to form a nitrogen atmosphere in the flask. After that, the person is heated to 3 〇 (rc 纟 纟 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 , , , 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解- 醢1 person added SaPa ^ U in the evening, Ding Yizhi 45 wounds, pentaerythritol 68 parts. Here in the stage of severe reduction (four) mixing speed increased to coffee pm. Then, Sottfn changed to pre-heating to 2 Fu oil bath Keep the inner temperature of the flask at night and react for 5 hours. The reactants are at normal temperature. It is a transparent yellow liquid. It is called ab-13 resin. Production of varnish: € Use heating melting kettle (7) Chauzhou "(10) copies of the trademark (10)) (Toyo Textiles) One part of PMA as a solvent was added to the company, and the mixture was heated to 6 (rc, and stirred until completely dissolved. This was called varnish A. The polyol obtained in the above Synthesis Examples 1 to 8 was used. The peak utilization rate, appearance, base price, molecular weight, and solvent II =, and the fruit are not shown in Table 1 and Table 2. The evaluation method of solubility is as follows. 〇: Dissolved Δ: dissolved by heating to 80 ° C x: insoluble 18 201037015 ο ο [I! ' ab-6 yellow white turbid waxy 〇 64.0 ι 379 1048/719 f XXXXXX 〇 XXX ab-5 yellow white turbid| Liquid | 〇32.8 4171/1789 1 〇〇〇〇〇〇〇〇〇〇ab-4 Yellow transparent liquid 〇T—^ 19.5 1____ . (N r-Η 3377/1543 1 〇〇〇〇〇〇〇〇 〇〇ab-3 I yellow white turbid semi-solid 〇 310 2557/1048 1 <<1<] 0 0 〇<1 < ab-2 yellow transparent liquid 〇Τ·"Η 67.1 422 2254/ 939 1 〇〇〇〇〇〇〇〇〇〇丨ab_l yellow transparent liquid | ο τ1 Η 60.1 CT) inch 1639/805 6400/4900 〇〇〇〇〇〇〇〇〇〇 appearance shape non-volatile (%) Recycled resin usage rate (%) Base price (mgKOH/g) GPC Solvent: THF (Mw/Mn) GPC Solvent: DMF (Mw/Mn) MBK butyl acetate acetate cellosolve carbitol acetic acid Ethyl propylene glycol monomethyl ether acetate DMS0 methyl lactate ethyl lactate dipropylene glycol monoterpene ether 1 molecular weight 姨冢姨 ± 1 201037015 [3! ab-13 yellow transparent liquid 〇t—Η 63.0 1 XXXXXX 〇XXX ab-12 Yellow transparent liquid Ο 48.9 438 1460/725 t 〇〇〇〇〇〇〇〇〇〇ab-11 Brown transparent solid ο Η 49.7 636 1 16100/9100 XXXXXX 〇 XXX ab-10 brown transparent solid ο τ—Η 43.0 〇〇in 1 85300/15700 XXXXXX 〇XXX ab-9 yellow white turbid wax Ο τ—Η 58.5 1235/713 12000/8000 XXXXXX 〇XXX ab-8 yellow white wax Ο 67.6 (N On 1023/676 1 XXXXXX 〇 XXX ab-7 yellow and white turbid liquid Ο 68.8 oo On m 929/639 4500/3900 XXXXXX 〇XXX Appearance shape non-volatile (%) Recycled resin usage rate (%) Hydroxyl group Price (mgKOH/g) GPC Lysate: THF (Mw/Mn) GPC Lysate: DMF (Mw/Mn) MIBK butyl acetate acetate cellosolve carbitol acetate........ ..........J Propylene glycol monomethyl ether acetate DMS0.1 Methyl lactate ethyl lactate dipropylene glycol monomethyl ether|Molecular weight 1 珑 珑 ti 201037015 Addition examples 1 to 8 The above synthesis example 1 The polyol obtained in 2, 4 is mixed with isocyanate and hydroxydecyl melamine, and the evaluation is performed as The agent, the performance of the coating agent. The mixing ratio is shown in Table 3. [Table 3] Addition Example 1 2 3 4 5 6 7 8 Polyol resin ab-1 30 30 30 30 ab-2 40 40 ab-4 120 120 Polyester resin varnish A 100 100 100 Isocyanate compound 氺 1 30 30 30 30 30 30 氺2 50 Hydroxymethyl melamine methyl ether 氺 3 20 Hardening catalyst 氺 4 1 Photopolymerization initiator 氺 5 10 Remarks * 1 TPA-100 (made by Asahi Kasei Chemicals Co., Ltd.) *2 Laromer LR9000 (Japan BASF shares) *3 Nikalac MW-100LM (manufactured by Sanwa Chemical Co., Ltd.) * 4 Nacure 2500X (manufactured by King Industries, USA) * 5 Irgacure-184 (manufactured by Ciba Japan KK)

Examples 1 to 6 The compositions of Addition Examples 1 to 6 were coated on a glass plate by an applicator to have a film thickness of 30 μm. This was dried by a hot air circulating drying oven at a 1 knives clock' and allowed to harden at 120 C for 30 minutes. Regarding the obtained cured product ^, the following test was carried out. Rubbing test In order to test the hardenability of the cured product obtained in the above manner, the rubbing test.疋仃乂 21 21 201037015 The obtained cured product was wiped 50 times with a crushed yarn containing acetone, and the surface was not dissolved, and it was judged to be sufficiently hardened and evaluated as 〇, and it was evaluated as X when the surface was slightly dissolved. The evaluation results are shown in Table 4. Adhesion test with glass: Each of the compositions (adhesives) of the addition examples 1 to 3 was dropped by a syringe on a glass plate having a thickness of 0.1 mm. The same glass plate was bonded to a glass plate to which an adhesive was added, and it was put into a hot air circulating drying oven, and it was hardened at 12 Torr for 30 minutes. Confirm the adhesion of the glass sheet in this manner. When the glass plate was not peeled off, it was evaluated as 〇, and when the glass plate was peeled off, it was evaluated as x. The evaluation is shown in Table 4. The adhesion test of the mouth coat and the PET film: The test conditions of the addition of the examples 1 to 3: On the PET film of the thickness (2), after applying the crepe cloth, the yttrium injection YET film is bonded to the film coated with the adhesive. A film is now a carboxy-infused layer (6〇.010 minutes X3kgf/cm2德, 120 0^0(4)xl〇kgf/em2) After Q hardening, use a cutter to punch and cut into a poem with a width of lcm. Test piece. Conditions for the preparation of test pieces of Examples 4 to 6 were added. On a PET film having a thickness of 125 μm, 30 μm was applied. After coating, the film thickness is coated by hot air core coating 2

minute. Then, the same ruthenium film was dried on a 1 〇 film, and laminated in two stages (6 〇. The dip agent fPET was cut into a pouch shape having a width of 1 (10), and the film was cut into a knives. The test for the production conditions, the peeling of the pure PET film test piece by the peeling or not evaluation was evaluated as X. The evaluation results are shown in Table 4°, the peeling was evaluated as 〇, and the peeling was 22 201037015 [Table 4] — T. *n rff -W? Γ- Example 1 2 3 4 5 6 Flute test of enamel and glass plate 密 - Adhesion test with PET ----- 〇 〇〇〇〇Example Ο The composition of the above-mentioned addition example 7 was coated on a B〇ndelite steel sheet to a thickness of 500 μm, and was subjected to three kinds of hardening conditions (1〇(Γ(:χ3〇 min, minute ^16(TCx30 minutes) Hardening. Obtained in any of the hardening conditions = The coating film was confirmed to be not peeled off in the wrong pen hardness 3H test, the checkerboard test 1〇〇, and the 2-face test. Example 8 Using an applicator The composition of the above-mentioned addition example 8 was applied to a PET film having a thickness of 125 μm to a film thickness of 3 μm. After coating, the same The ρΕτ film is laminated on the PET film with the adhesive on the adhesive film, and the laminate is carried out in two stages (6 (rCxl〇〇$, x3kgf/cm2, 12〇°Cx20 minutes xl〇kgf/cm2). After hardening, The peeling test of the test was carried out, and it was confirmed that the PET films were strongly adhered to each other. Then, the tape exposure apparatus of the mercury lamp was mounted, and the test piece was irradiated with an exposure amount of u/cm 2 , and the same peeling test was performed to confirm the PET. The films are strongly adhered to each other. As described in detail above, the novel polyol compound of the present invention, since no solvent is used in the synthesis process, and the recycled resin is used efficiently, I reduce the load on the environment, and The polyol compound of the present invention can be used as a thermosetting resin in combination with an isocyanate compound or an amine-based resin, and is particularly suitable for use as a 1C card, which is bonded to a polyester film. Control panel, organic EL display, etc. 23 201037015 film bonding adhesive, coating agent, sealant. [Simplified schematic] The first figure is the infrared of the polyol compound obtained in Synthesis Example 1. The second absorption spectrum is the infrared absorption spectrum of the polyol compound obtained in Synthesis Example 2. The third diagram is the infrared absorption spectrum of the polyol compound obtained in Synthesis Example 3. The fourth figure is a synthesis example. The infrared absorption spectrum of the polyol compound obtained in 4. The fifth chart shows the infrared absorption spectrum of the polyol compound obtained in Synthesis Example 5. The sixth chart shows the infrared absorption spectrum of the polyol compound obtained in Synthesis Example 6. The seventh chart shows the infrared absorption spectrum of the polyol compound obtained in Synthesis Example 7. The eighth graph is the infrared absorption spectrum of the polyol compound obtained in Synthesis Example 8. 1,1 24

Claims (1)

201037015 VII. Patent application scope: Ο Ο Polyol (b) Depolymerization of polyester (a) to obtain ^ 未 未 使用 Γ Γ Γ Γ ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ϊ ϊ ϊ ϊ ϊ It is solvent soluble. =====The compound is a non-volatile brain = the polyol compound of the patent range No. 1, wherein the poly-system is the patent range! The polyol compound, wherein the component of the molecule is more than 2 or more than 2 or more of the conjugated poly-). As described in any one of the claims i to 6 of the patent application, it is used as a raw material for the production of a polyurethane.蛘化口8 The polyol of any one of the claims 1 to 6 is used as a raw material for the production of polyester. The polyhydric alcohol compound of any one of the above items i to 6 is used as a raw material for an adhesive, a coating, an ink, or a coating agent. Fif shouting: its ship is miscellaneous) as in the patent scope of items 1 to 6 of the sylvanic alcohol compound, (9) isocyanate compound. Qing A 11. The composition of claim 10 of the patent scope 'where the (eight) polyolized person counts 100 parts by mass of the (8) isocyanate compound or block isocyanate compound in an amount of 20 to 300 mass Share. 12. The composition of claim </ RTI> wherein the (4) polyhydric acid has a hydroxyl number of from 200 to 800 mg KOH/g. A thermosetting composition comprising (A) a polyol compound according to any one of claims 1 to 6 and (c) an amine-based resin. 2. 3. 4. 5.6. 8. 9. 10. 25 201037015 14. 15. 16. 17. 18. 19. The composition of claim 13 wherein the (A) polyol compound is 100 mass The amount of the (C) amino resin blended is 20 to 300 parts by mass. The composition of claim 13, wherein the (A) polyol compound has a hydroxyl group value of from 200 to 800 mg KOH/g. A method for producing a polyol compound according to claim 1, which comprises: providing a polyester (a); and depolymerizing the polyester (8) using a polyol having two or more hydroxyl groups in one molecule (b) To obtain a polyol compound. The preparation method of claim 16, wherein the polyester (a) is a regenerated glutinous polyester. The preparation method of claim 16, wherein the component of the polyol (b) having more than one of the radicals in the one molecule contains at least trihydromethane propane or polyglycol. Please refer to the preparation method of item 16, wherein the ratio of the number of moles of the polyester (8) to the number of moles of the polyol is 0.5 to 3. 26