JP3611932B2 - Process for producing active hydrogen component and polyurethane resin - Google Patents

Description

【００５０】
【発明の効果】
本発明の活性水素成分を用いて、本発明の方法で得られるポリエステル系ポリウレタン樹脂は、従来のものに比べて耐加水分解性に優れ、さらに撥水性、耐汚染性にも優れた性能を有する。
上記効果を奏することから、本発明の方法により得られるポリウレタン樹脂は合成皮革、塗料、インキ、接着剤、エラストマー、フォーム、繊維処理剤用などの原料として広く利用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel polyester-based active hydrogen component for producing a polyurethane resin and a method for producing a polyester-based polyurethane resin using the same. More specifically, the present invention relates to an active hydrogen component for producing a polyurethane resin having performances excellent in hydrolysis resistance and water repellency, and a method for producing a polyurethane resin using the active hydrogen component.
[0002]
[Prior art]
Conventionally, polyester polyurethane resins are known to be obtained by reacting polymer polyester polyols, organic polyisocyanates and, if necessary, chain extenders and / or crosslinking agents. Examples of the polymer polyester polyols include glycols. A polyester polyol obtained by condensation reaction of a component (ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexamethylene glycol, etc.) and a polyvalent carboxylic acid (adipic acid, phthalic acid, etc.), or Polylactone diols (poly-ε-caprolactone diol, etc.) obtained by ring-opening polymerization of lactones using the above glycols as initiators are used. Polyester polyurethane resins using these are resistant to hydrolysis. The problem of inferiority The had. For the purpose of improving hydrolysis resistance, a method of using a high-molecular polyester polyol using 3-methyl-1,5-pentanediol as a glycol component has been proposed (for example, Japanese Patent Publication No. 4-58803). .
[0003]
[Problems to be solved by the invention]
However, even in these, the hydrolysis resistance of the polyurethane resin is still insufficient.
[0004]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have intensively studied a method for producing a polyester-based polyurethane resin excellent in hydrolysis resistance, and as a result, use a polyester-based polyol having a specific structure as an active hydrogen component. As a result, the present invention has achieved the object of excellent hydrolysis resistance, and has also been found to be excellent in water repellency and oil resistance, and has reached the present invention.
[0005]
That is, the present invention provides a diol component consisting of one or more diols selected from the group consisting of the following (a1), (a2), (a3), (a11) and (a13), and dicarboxylic acids (c). The lactone monomer (d) is added to a polyester diol (A1) and a diol component comprising at least one diol selected from the group consisting of the following _ (a2), (a3), (a11), (a12) and (a13) Is composed of one or more polyester diols (A) selected from polylactone diols (A2) to which is added, contains 5 to 80 wt% of aliphatic hydrocarbon side chains having 3 to 40 carbon atoms, and has a number average molecular weight Is a polyester-based active hydrogen component for producing a polyurethane resin, characterized by being from 500 to 10,000.
(A1) 1,2-alkanediol having 5 to 42 carbon atoms.
(A2) Glycerin monoalkyl ether having 6 to 43 carbon atoms.
(A3) Glycerin fatty acid monoester having 7 to 44 carbon atoms.
(A11) A diol obtained by adding an alkylene oxide (b) having 2 to 4 carbon atoms to (a1), (a2) or (a3).
(A12) A diol obtained by adding 2 moles or more of an alkylene oxide (b) having 2 to 4 carbon atoms to an alkylamine (a4) having 3 to 40 carbon atoms.
(A13) A diol obtained by adding an alkylene oxide composed of an α-olefin oxide (a5) having 5 to 42 carbon atoms to two active hydrogen atom-containing compounds.
And a method for producing a polyester-based polyurethane resin in which an organic polyisocyanate (B) is reacted with the active hydrogen component and, if necessary, a chain extender (C), a crosslinking agent (D), and a terminator (E).
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the aliphatic hydrocarbon side chain having 3 to 40 carbon atoms in the active hydrogen component include linear, branched or alicyclic, saturated or unsaturated hydrocarbon side chains. A straight-chain or branched saturated hydrocarbon side chain.
The carbon number of the aliphatic hydrocarbon side chain is usually 3 to 40, preferably 5 to 30, and more preferably 8 to 20. When the number of carbon atoms is less than 3, the hydrolysis resistance of the polyurethane resin is inferior, and when it exceeds 40, the esterification reactivity during the production of the polyester polyol is lowered.
[0007]
The content of the aliphatic hydrocarbon side chain having 3 to 40 carbon atoms in the active hydrogen component of the present invention is usually 5 to 80% by weight, preferably 10 to 70% by weight, particularly 15 to 60% by weight. If it is less than 5% by weight, the resulting polyurethane resin has poor hydrolysis resistance, and if it exceeds 80% by weight, the esterification reactivity during the production of the polyester polyol is lowered.
[0008]
The number average molecular weight of the active hydrogen component of the present invention is usually 500 to 10,000, preferably 700 to 6,000. If it is less than 500, the resulting polyurethane resin is hard and brittle, and if it exceeds 10,000, the resin becomes soft and the strength decreases.
[0009]
The following (a1)-(a5) is mentioned as an example of the compound which gives an aliphatic hydrocarbon side chain in a polyol for obtaining polyester diol (A).
(A1) 1,2-alkanediol having 5 to 42 carbon atoms: 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-octadecanediol Such
(A2) C6-C43 glycerol monoalkyl ether: glycerol monohexyl ether, glycerol monooctyl ether, glycerol mono-2-ethylhexyl ether, glycerol monodecyl ether, glycerol monododecyl ether, glycerol monooctadecyl ether, etc.
(A3) Glycerin fatty acid monoester having 7 to 44 carbon atoms: glycerin hexanoic acid monoester, glycerin octanoic acid monoester, glycerin-2-ethylhexanoic acid monoester, glycerin decanoic acid monoester, glycerin dodecanoic acid monoester, glycerin octadecane Acid monoester etc.
(A4) C3-C40 alkylamine: butylamine, hexylamine, 2-ethylhexylamine, octylamine, dodecylamine, stearylamine, etc.
(A5) α-olefin oxide having 5 to 42 carbon atoms: α-decene oxide, α-dodecene oxide, α-octadecene oxide, etc.
[0010]
The 1,2-alkanediol (a1) and the α-olefin oxide (a5) can be produced by a known method such as a method of reacting acetic acid with hydrogen peroxide in the presence of an acid catalyst.
The glycerin alkanol monoether (a2) can be produced by, for example, (1) a method in which a long-chain alkyl alcohol is reacted with epichlorohydrin and then hydrolyzing; and (2) a method in which glycerin is reacted with an alkyl halide.
The glycerin fatty acid monoester (a3) can be produced by a method of esterifying glycerin and a fatty acid in the presence of an alkali catalyst.
[0011]
By using the above (a1) to (a5), the following (a11) to (a13) may be mentioned as the diol that is a structural unit of (A) obtained.
(A11) 1,2-alkanediol (a1) having 5 to 42 carbon atoms, glycerol monoalkyl ether (a2) having 6 to 43 carbon atoms or glycerol fatty acid monoester (a3) having 7 to 44 carbon atoms, Diol obtained by adding 2-4 alkylene oxide (b).
(A12) A diol obtained by adding 2 moles or more of an alkylene oxide (b) having 2 to 4 carbon atoms to an alkylamine (a4) having 3 to 40 carbon atoms
(A13) A diol obtained by adding an alkylene oxide composed of an α-olefin oxide (a5) having 5 to 42 carbon atoms to two active hydrogen atom-containing compounds.
[0012]
Examples of the alkylene oxide (b) having 2 to 4 carbon atoms used in (a11) and (a12) include ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), butylene oxide, or a combination thereof. It is done. (A11) and (a12) can be produced by a conventionally known alkylene oxide addition reaction. When two or more kinds of alkylene oxide are used, the addition form may be either block or random.
[0013]
(A13) can be obtained by adding α-olefin oxide (a5) alone to two active hydrogen atom-containing compounds or by adding (a5) and the alkylene oxide (b) in combination.
Examples of the two active hydrogen atom-containing compounds include lower diols having 9 or less carbon atoms (ethylene glycol, propylene glycol, neopentyl glycol, etc.), monoamines having 10 or less carbon atoms (methylamine, ethylamine, butylamine, 2-ethylhexyl). Liquids such as amines can be suitably used.
A method of adding (a5) alone or (a5) and (b) to these may be a known method, and the addition format when adding two or more types may be either block or random.
[0014]
The polyester diol (A1) comprises a diol component composed of one or more diols selected from the group consisting of (a1), (a2), (a3), (a11), and (a13), and dicarboxylic acids ( obtained by reacting with c).
[0015]
Other diols may be used as the diol component in (A1). Other diols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol having a number average molecular weight of less than 500, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,5- Pentanediol, 1,6-hexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1, 6-hexanediol, 3,3,5-trimethyl-1,6-hexanediol, 1,9-nonanediol, cyclohexyldimethanol, bis (hydroxyethoxy) benzene, low molar adduct of EO or PO of bisphenols , Number average molecular weight less than 500 and these 2 It is mentioned or in combination.
[0016]
When other diols are used, the ratio of one or more diols selected from the group consisting of (a1), (a2), (a3), (a11), and (a13) to other diols is the result. As described above, the content of the aliphatic hydrocarbon side chain having 3 to 40 carbon atoms in the active hydrogen component of the present invention is usually 5 to 80% by weight, preferably 10 to 70%, particularly 15 to 60% as described above. Any ratio may be used.
[0017]
Examples of the dicarboxylic acids (c) in (A1) include the following (c1) and (c2) and combinations of two or more thereof.
(C1) C4-C10 aliphatic dicarboxylic acids (adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid, etc.) or ester-forming derivatives thereof (anhydrides, lower alkyl esters, etc.)
(C2) Aromatic dicarboxylic acids (phthalic acid, terephthalic acid, isophthalic acid, etc.) or ester-forming derivatives thereof
Among these, preferred are aliphatic or aromatic dicarboxylic acids having 6 to 10 carbon atoms, particularly adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, and ester-forming derivatives thereof.
(A1) can be produced by a conventionally known method. For example, it can be obtained by a method of dehydrating polycondensation or transesterification from an excess molar amount of the diol component and the dicarboxylic acid (c) to obtain a terminal hydroxyl group polyester. It is done.
[0018]
The polylactone diol (A2) is a lactone monomer in addition to a diol component consisting of one or more diols selected from the group consisting of the above-mentioned _ (a2), (a3), (a11), (a12) and (a13). It is obtained by adding (d).
[0019]
Examples of the lactone monomer (d) used in (A2) include ε-caprolactone and δ-valerolactone. (A2) can be produced by a conventionally known method of adding a lactone monomer to a diol component.
[0020]
In the process for producing the polyurethane resin of the present invention, the content of the aliphatic hydrocarbon side chain having 3 to 40 carbon atoms in the active hydrogen component of the present invention is usually 5 as described above in addition to (A) as the active hydrogen component. Other polyester polyols can be used alone or in combination of two or more, if necessary, within a range of -80% by weight, preferably 10-70%, particularly 15-60%.
Other polyester polyols include known polyester polyols (polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyneopentyl adipate diol, poly-3-methylpentylene adipate diol, polycaprolactone diol, polyvalerolactone diol, Polyhexamethylene carbonate diol).
[0021]
Examples of the organic polyisocyanate (B) in the production method of the present invention include the following (B1) to (B5) and a mixture of two or more thereof.
(B1) C6-C16 aromatic diisocyanate [2,4- and / or 2,6-tolylene diisocyanate (TDI), 4,4 ′ -Diphenylmethane diisocyanate (MDI) and the like];
(B2) C6-C10 aliphatic diisocyanate [hexamethylene diisocyanate (HDI), lysine diisocyanate, etc.];
(B3) C6-C16 alicyclic diisocyanate [isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), norbornane diisocyanate, etc.];
(B4) an araliphatic diisocyanate having 8 to 12 carbon atoms [xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), etc.];
(B5) Modified products of these organic diisocyanates (for example, modified products of isocyanurate, burette, carbodiimide, etc.)
[0022]
In the process for producing the polyurethane resin of the present invention, one or more of chain extender (C), crosslinking agent (D) and terminator (E) can be used as an optional component.
Examples of (C) include the following (C1) to (C3) and combinations of two or more thereof.
(C1) Low molecular polyol having an average molecular weight of less than 500: compounds exemplified as other diols constituting the above (A1), alkylene oxide adducts of bisphenols, dimethylolpropionic acid, etc.
(C2) Polyamine compound: aliphatic diamine (ethylenediamine, hexamethylenediamine, etc.), alicyclic diamine (isophoronediamine, 4,4′-dicyclohexylmethanediamine, norbornanediamine, etc.), aromatic diamine (4,4′- Diaminodiphenylmethane), araliphatic diamines (xylylenediamine, etc.), hydrazine or its derivatives, etc.
(C3) Alkanoldiamine: hydroxylethylethylenediamine, N, N′-dihydroxyethylethylenediamine, etc.
[0023]
As (D),
(D1) Alkanolamine: triethanolamine, diethanolamine, etc.
(D2) Polyhydric alcohol having an average molecular weight of less than 500: trimethylolpropane, glycerin, pentaerythritol, sorbitol, shoelace, etc.
Is mentioned.
[0024]
Examples of (E) include monoalcohol (such as methanol and butanol), monoamine (such as butylamine and dibutylamine), and alkanolamine (such as monoethanolamine and diethanolamine).
[0025]
The amounts of the chain extender (C), the crosslinking agent (D) and the terminator (E) used in the production method of the present invention are as follows.
(C) is usually 0 to 30 parts by weight, preferably 2 to 25 parts by weight, per 100 parts by weight of the active hydrogen component of the present invention.
(D) is usually 0 to 30 parts by weight, preferably 0 to 20 parts by weight, per 100 parts by weight of the active hydrogen component of the present invention.
(E) is usually 0 to 20 parts by weight, preferably 0 to 15 parts by weight, per 100 parts by weight of the active hydrogen component of the present invention.
[0026]
The process for producing the polyurethane resin of the present invention is a urethanation reaction between the active hydrogen component and the organic polyisocyanate (B) by a known method except that an active hydrogen component comprising the polyester polyol (A) is used. You just have to do.
For example,
(1) One-shot method in which organic polyisocyanate (B) is added to the polyester-based active hydrogen component and optional components (C), (D), and (E) and reacted at once.
(2) A multi-stage method in which the active hydrogen component, a part of the active hydrogen compound as an optional component, and (B) are reacted to form an NCO-terminated prepolymer, and then the remaining active hydrogen compound is reacted.
Etc.
In addition, the polyurethane resin to be produced can be obtained either thermoplastic or thermosetting depending on the active hydrogen component and (B) to (E).
[0027]
The total of the isocyanate group of (B) and the active hydrogen component of the present invention and the active hydrogen groups of (C), (D) and (E) in the production of the polyurethane resin (water in the case of water foaming, moisture curing, etc.) The equivalent ratio is usually 1: (0.70 to 2.0), preferably 1: (0.80 to 1.3).
[0028]
In the production of the polyurethane resin, the urethanization reaction temperature is usually 30 to 200 ° C, preferably 60 to 160 ° C. (However, when an amine compound is reacted as the chain extender (C) or the like, the reaction is usually performed at a temperature of 0 to 150 ° C., preferably 30 to 100 ° C.)
[0029]
In addition, in order to accelerate the urethanation reaction as necessary, catalysts used in ordinary urethane reactions [amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), tin-based catalysts (dibutyltin dilaurate, dioctyltin dilaurate, octylic acid) Tin, etc.), titanium-based catalysts (tetrabutyl titanate, etc.)] and the like may be used.
[0030]
If necessary, the urethanization reaction may be carried out with organic solvents [ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, ethyl cellosolve acetate, etc.), ethers (dioxane, tetrahydrofuran, ethyl cellosolve, etc.) , Butyl cellosolve, propylene glycol monomethyl ether, etc.), hydrocarbons (n-hexane, n-heptane, cyclohexane, tetralin, toluene, xylene, etc.), alcohols (methanol, ethanol, isopropyl alcohol, isobutanol, tert-butanol, etc.) Amides (dimethylformamide, dimethylacetamide, etc.), N-methylpyrrolidone, etc.], and the organic solvent may be added during or after the reaction.
[0031]
In the process for producing the polyurethane resin of the present invention, an auxiliary compounding agent may be blended in advance with the raw material, if necessary, or may be blended after the urethanization reaction. Examples of the auxiliary compounding agents include colorants (dyes, pigments, etc.), inorganic fillers (fine powder silica, etc.), organic modifiers (silicon oil, etc.), stabilizers (weather resistance stabilizers, antioxidants, etc.). And plasticizers (phthalic acid esters, fatty acid esters, etc.).
[0032]
An example is shown below about the usage method of the polyester-type polyurethane resin obtained by the method of this invention using the active hydrogen component of this invention. For example, (1) a method of synthesizing a substantially linear high molecular weight thermoplastic polyurethane resin, and heat-melting the pelletized product, followed by injection molding and processing; (2) this thermoplastic polyurethane A method in which a resin is dissolved in a solvent to form a resin solution, which is used as a coating agent, an impregnating agent, etc. for raw materials for elastic fibers, synthetic leather and fibers, etc .; (3) Functional groups (OH, NH, NH2, COOH, etc.) ) Is used for paints, inks and the like with or without a curing agent; (4) the terminal from the polyester-based active hydrogen component of the present invention and an excess equivalent amount of organic polyisocyanate; A method of synthesizing a prepolymer having an isocyanate group and using it as a moisture curable coating material, an adhesive, a sealing agent, etc .; (5) a curing agent (polymer) is added to this terminal isocyanate group prepolymer. Lyol, aromatic polyamine, etc.) to form a thermosetting cast elastomer product; (6) the polyester active hydrogen component of the present invention, an organic polyisocyanate and a foaming agent; For example, a method for forming a foam product.
[0033]
Specific applications of the polyurethane resin obtained by using the method of the present invention include sheets, films, rolls, hoses, tires, belts, vibration-proof materials, automotive parts, packing materials, elastic fibers, synthetic leather, artificial leather , Shoe soles, fiber treatment agents, cushioning materials, paints, adhesives, ink binders, sealing agents, potting agents, waterproofing agents, flooring materials and the like.
[0034]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. In the following, “parts” represents parts by weight, and “%” represents% by weight.
[0035]
[Synthesis of Polyester Diol (A)]
Synthesis example 1
In a four-necked flask equipped with a reflux, thermometer, nitrogen inlet tube, and stirrer, “Linearene 12” (molecular weight 168, 1-dodecene; manufactured by Idemitsu Petrochemical Co., Ltd.) 254 parts, acetic acid 159 parts, sulfuric acid 3 60% hydrogen peroxide solution was gradually dropped and reacted while maintaining the temperature at 85 ° C.
Thereafter, 271 parts of toluene, 90 parts of sodium hydroxide and 200 parts of water were added, neutralized and hydrolyzed, and further 11 parts of hydrochloric acid was added, followed by separation in a separatory funnel, and 520 parts of a supernatant toluene solution. Got. This was transferred to another four-necked flask and toluene was removed, followed by purification by distillation under reduced pressure to obtain 220 parts of 1,2-dodecanediol.
In another four-necked flask, 200 parts of 1,2-dodecanediol and 140 parts of adipic acid were charged, and esterification was carried out while distilling off water at 190 to 210 ° C. through nitrogen gas under normal pressure.
When the acid value of the produced polyester became 1 or less, the degree of vacuum was increased to complete the reaction. The obtained polyester [hereinafter referred to as polyester diol [1]] had a hydroxyl value of 55.2, an acid value of 0.3, and a molecular weight of 2020.
[0036]
Synthesis example 2
In a four-necked flask equipped with a reflux condenser, thermometer, nitrogen inlet tube, and stirrer, 381 parts of “Linearene 18” (molecular weight 252, 1-octadecene; manufactured by Idemitsu Petrochemical Co., Ltd.), 159 parts of acetic acid, 3 sulfuric acid 60% hydrogen peroxide solution was gradually dropped and reacted while maintaining the temperature at 85 ° C.
Thereafter, 271 parts of toluene, 90 parts of sodium hydroxide and 200 parts of water were added for neutralization and hydrolysis, and after 11 parts of hydrochloric acid was further added, the mixture was separated in a separatory funnel, and 520 parts of the supernatant toluene solution was added. Obtained. This was transferred to another four-necked flask and toluene was removed, followed by purification by distillation under reduced pressure to obtain 340 parts of 1,2-octadecanediol.
In another four-necked flask, 200 parts of 1,2-octadecanediol and 94 parts of adipic acid were charged, and esterification was performed while distilling off water at 190 to 210 ° C. through nitrogen gas under normal pressure.
When the acid value of the produced polyester became 1 or less, the degree of vacuum was increased to complete the reaction. The obtained polyester [hereinafter referred to as polyester diol [2]] had a hydroxyl value of 56.5, an acid value of 0.3, and a molecular weight of 1975.
[0037]
Synthesis example 3
A four-necked flask equipped with a reflux, thermometer, nitrogen inlet tube, and stirrer was charged with 186 parts of 1-dodecanol, 138 parts of epichlorohydrin and 200 parts of toluene, and while maintaining the temperature at 35 ° C., sodium hydroxide 60 was gradually added. Part was added and reacted.
Then, 200 parts of water was added and liquid separation was performed with a separatory funnel to obtain a supernatant toluene solution.
This was transferred to another four-necked flask, 1 part of sulfuric acid was added, and the mixture was hydrated at a temperature of 85 ° C. for 5 hours. After cooling to 40 ° C., 1 part of sodium hydroxide was added for neutralization, followed by liquid separation using a separatory funnel to obtain 500 parts of a supernatant toluene solution.
This was transferred to another four-necked flask and toluene was removed, followed by purification by distillation under reduced pressure to obtain 220 parts of glycerin dodecanol monoether.
In a separate four-necked flask, 200 parts of the glycerin dodecanol monoether and 92 parts of adipic acid were charged, and esterification was performed while distilling off water at 190 to 210 ° C. through nitrogen gas under normal pressure.
When the acid value of the produced polyester became 1 or less, the degree of vacuum was increased to complete the reaction. The obtained polyester (hereinafter referred to as polyester diol [3]) had a hydroxyl value of 57.0, an acid value of 0.2, and a molecular weight of 1970.
[0038]
Synthesis example 4
In another four-necked flask, 286 parts of 1,2-octadecanediol obtained in Synthesis Example 2, 714 parts of ε-caprolactone monomer and 0.02 part of tetrabutyl titanate were charged, and nitrogen gas was passed under normal pressure to react the reaction temperature. It was made to react at 160-180 degreeC for 6 hours. The obtained polylactone diol [hereinafter referred to as polylactone diol [4]] had a hydroxyl value of 112.0, an acid value of 0.1, and a molecular weight of 1002.
[0039]
Synthesis example 5
In an autoclave, 269 parts of octadecylamine was charged, and 88 parts of EO was injected and reacted at a temperature of 110 ° C., followed by aging at 130 ° C. to obtain N-octadecyl-diethanolamine.
This was charged with 643 parts of ε-caprolactone monomer and 0.02 part of tetrabutyl titanate, and allowed to react at a reaction temperature of 160 to 180 ° C. for 6 hours by passing nitrogen gas under normal pressure. The obtained polylactone diol [hereinafter referred to as polylactone diol [5]] had a hydroxyl value of 112.0, an acid value of 0.1, and a molecular weight of 1002.
[0040]
[Manufacture of polyurethane resin]
Example 1
In a four-necked flask, 200 parts of the polyester diol [1] obtained in Synthesis Example 1, 36 parts of 1,4-butanediol, 125 parts of MDI and 842 parts of DMF were charged and dissolved to obtain a 30% concentration solution. The solution was allowed to react until the solution viscosity reached 100 poise (25 ° C.). The number average molecular weight of the obtained polyurethane resin was 45,000.
[0041]
Example 2
Into a four-necked flask, 200 parts of the polyester diol [2] obtained in Synthesis Example 2, 36 parts of 1,4-butanediol, 125 parts of MDI and 842 parts of DMF were charged and dissolved to obtain a 30% concentration solution. The solution was allowed to react until the solution viscosity became 70 poise (25 ° C.). The number average molecular weight of the obtained polyurethane resin was 35,000.
[0042]
Example 3
In a four-necked flask, 200 parts of the polyester diol [3] obtained in Synthesis Example 3, 36 parts of 1,4-butanediol, 125 parts of MDI, and 842 parts of DMF were charged and dissolved to obtain a 30% concentration solution. The solution was allowed to react until the solution viscosity reached 80 poise (25 ° C.). The number average molecular weight of the obtained polyurethane resin was 40,000.
[0044]
Example 5
In a four-necked flask, 200 parts of the polylactone diol [5] obtained in Synthesis Example 5, 25 parts of 1,4-butanediol, 120 parts of MDI and 805 parts of DMF were charged and dissolved to obtain a 30% concentration solution. The reaction was continued until the solution viscosity was 300 poise (25 ° C.). The number average molecular weight of the obtained polyurethane resin was 42,000.
[0045]
Comparative Example 1
In a four-necked flask, 200 parts of poly (3-methylpentylene adipate) diol (“Kurapol P-2010”; manufactured by Kuraray Co., Ltd.) 200 parts, 36 parts of 1,4-butanediol, 125 parts of MDI and 842 parts of DMF Was dissolved to give a 30% concentration solution, and the reaction was carried out at a reaction temperature of 70 ° C. until the solution viscosity became 500 poise (25 ° C.). The number average molecular weight of the obtained polyurethane resin was 42,000.
[0046]
Comparative Example 2
In a four-necked flask, 200 parts of polyneopentyl adipate diol having a molecular weight of 2000, 36 parts of 1,4-butanediol, 125 parts of MDI and 842 parts of DMF were dissolved to form a 30% concentration solution. The reaction was allowed to reach 800 poise (25 ° C). The number average molecular weight of the obtained polyurethane resin was 40,000.
[0047]
[Resin performance evaluation]
Test example
Polyurethanes obtained by applying the polyurethane resin solutions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 onto a glass plate so that the film thickness after drying was 100 μm and drying at 80 ° C. for 60 minutes. Performance evaluation was performed by the following test method using the film.
The evaluation results are shown in Table 1.
[0048]
<Test method and evaluation>
(1) Hydrolysis resistance test
After the test piece was immersed in hot water at 100 ° C. for 1 week, the strength retention (%) after the test with respect to the tensile strength before the test was measured.
Tensile strength measurement conditions
JIS K6301 (No. 3 dumbbell used, tensile speed: 500 mm / min)
(2) Pollution resistance
0.1 ml of office blue ink was dropped on the surface of the test piece with a dropper, left for 4 hours, wiped off with a household detergent, and the surface was observed.
Evaluation criteria ○: No dirt △: Some dirt remains ×: Some dirt remains
(3) Water repellency test
The test piece was fixed on a 45 ° inclined plate, sprayed with water from above for 30 seconds, and then the wet state of the surface was observed.
Evaluation criteria
○: No adhesion on the surface △: Wet in the form of water drops ×: Wet on the whole
(4) Contact angle measurement
The contact angle (°) between the surface of the test piece and water was measured using a contact angle meter manufactured by Kyowa Interface Science Co., Ltd.
[0049]
[Table 1]

[0050]
【The invention's effect】
The polyester-based polyurethane resin obtained by the method of the present invention using the active hydrogen component of the present invention is superior in hydrolysis resistance compared to conventional ones, and further has excellent performance in water repellency and stain resistance. .
Due to the above effects, the polyurethane resin obtained by the method of the present invention can be widely used as a raw material for synthetic leather, paints, inks, adhesives, elastomers, foams, fiber treatment agents and the like.

Claims (2)

Polyester diol (A1) from a diol component consisting of one or more diols selected from the group consisting of the following (a1), (a2), (a3), (a11) and (a13), and dicarboxylic acids (c) And a lactone monomer (d) is added to a diol component consisting of one or more diols selected from the group consisting of the following _ (a2), (a3), (a11), (a12) and (a13) It consists of one or more polyester diols (A) selected from polylactone diol (A2), contains 5 to 80% by weight of aliphatic hydrocarbon side chains having 3 to 40 carbon atoms, and has a number average molecular weight of 500 to 10, A polyester-based active hydrogen component for producing a polyurethane resin, characterized in that it is 000.
(A1) 1,2-alkanediol having 5 to 42 carbon atoms.
(A2) Glycerin monoalkyl ether having 6 to 43 carbon atoms.
(A3) Glycerin fatty acid monoester having 7 to 44 carbon atoms.
(A11) A diol obtained by adding an alkylene oxide (b) having 2 to 4 carbon atoms to (a1), (a2) or (a3).
(A12) A diol obtained by adding 2 moles or more of an alkylene oxide (b) having 2 to 4 carbon atoms to an alkylamine (a4) having 3 to 40 carbon atoms.
(A13) A diol obtained by adding an alkylene oxide composed of an α-olefin oxide (a5) having 5 to 42 carbon atoms to two active hydrogen atom-containing compounds. A process for producing a polyester-based polyurethane resin comprising reacting an organic polyisocyanate (B) with the active hydrogen component according to claim 1 and, if necessary, a chain extender (C), a crosslinking agent (D), and a terminator (E).