JPH11130848A - Polyol and urethane resin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyol good in workability and curability, and capable of giving a cured product of high crosslink density and excellent solvent resistance, chemical resistance and coating film properties, by reaction of a specific triol with a specific lactone or cyclic ether. SOLUTION: This polyol is obtained by reaction of (A) a triol of formula I (R<1> to R<3> are each an alkyl or the like) (e.g. 3-hydroxymethyl-1,6-hexanediol) with (B) a lactone of formula II (R<4> is a cycloalkyl or the like; (n) is 1-6) (e.g. ε-caprolactone) or (C) a cyclic ether of formula III (R<5> is an alkyl or the like; (n) is 0-7) (e.g. ethylene oxide). The other objective polyurethane resin is obtained by reaction of the above polyol with a polyisocyanate compound pref. at 10-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyol, specifically, a ring-opening polymerization type polyol and a polyurethane resin using the same. More specifically, the present invention relates to a lactone-based polyester polyol and a polyether-based polyol which are easy to handle during production and have a short reaction time, and have excellent curing properties, and a polyurethane resin using the same.

[0002]

2. Description of the Related Art Conventionally, lactone-based and ether-based polyols (ring-opening polymerization-based polyols) obtained by ring-opening polymerization have easy control of hydroxyl value and molecular weight during production, and have flexibility and water resistance. Because of its excellent properties, low-temperature properties, and weather resistance, it is used as a raw material for producing polyurethane in many fields such as foams, adhesives, elastomers, and various paints. In addition, such ring-opening polymerization-based polyols, in addition to the polyurethane raw material, its hydroxyl group, various curing agents having reactivity, such as melamine resin, epoxy resin and the like in combination with adhesives, coating agents and the like. It is also used as a raw material.

In general, ring-opening polymerization polyols are obtained by subjecting a dihydric or trihydric alcohol as a raw material to a ring-opening polymerization of a lactone such as caprolactone or ethylene oxide or a cyclic ether with a terminal. It is known as a polyol having a hydroxyl group. For example, as a raw material alcohol, trifunctional alcohols such as glycerin and trimethylolpropane are mainly used in order to increase the crosslink density and improve the physical properties of the coating film. However, when glycerin is used, the reactivity with lactones is low due to the secondary hydroxyl group, and (1) the reaction requires time, so that depolymerization and thermal decomposition occur, so that the acid value increases.
(2) Depending on the number of moles of lactone added, 2
Grade hydroxyl groups remain. (3) The molecular weight distribution is widened.
(4) secondary hydroxyl groups of glycerin remain unreacted,
The number of lactones added to the two hydroxyl groups is different from the number of lactones added to the primary hydroxyl groups, causing problems such as a difference in reactivity. These problems adversely affect the properties of the coating film, such as poor cross-linking, coating film strength, and solvent resistance, when a cured coating film is obtained using a curing agent that reacts with a hydroxyl group.

[0004] Trimethylolpropane and the like all having a primary hydroxyl group are solid and are inconvenient to handle in production. Furthermore, Japanese Patent Publication No. 58-61119 describes the synthesis of a polyol of trimethylolpropane and caprolactone.
At 6 ° C., a reaction time of 6 hours is required. In addition, when two hydroxyl groups react from the structure of trimethylolpropane, it is expected that the reactivity of one hydroxyl group is reduced from the three-dimensional structure. Therefore, the same problem as that of glycerin occurs.
To a lesser extent, it remains. In addition, due to the same problem, it also exists in the case of ring-opening polymerization of cyclic ethers.

When a conventional ring-opening polymerization type polyol is used as a urethane raw material, the ratio of the molecular terminal functional groups of the urethane is (isocyanate group / active hydrogen group (hydroxyl group))>
In the case of 1, the reactivity with the isocyanate group hardly progresses due to the presence of a hydroxyl group having low reactivity. Therefore, there is a problem that a considerable time is required to complete the reaction, and the molecular weight distribution of the obtained polyisocyanate compound is widened.

Also, (isocyanate group / active hydrogen group)
<1, For example, when a polyhydric hydroxyl compound such as a ring-opening polymerization polyol is added in excess to an organic isocyanate, for example, if the alcohol is a trihydric alcohol, one of the three hydroxyl groups has low reactivity. Therefore, there is a problem that a hydroxyl group having low reactivity easily remains at the molecular terminal, and it is difficult to obtain a polyurethane polyol having a high molecular weight.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a trifunctional ring-opening polymerization polyol which has good workability and can shorten the reaction time, has good curability, and has a high crosslink density of the cured product. Highly solvent-resistant, ring-opening polymerization-based polyols with excellent chemical resistance and coating film properties, and paints using the same,
It is intended to provide a polyurethane resin suitable for use in the fields of coatings, adhesives, films, elastomers and the like.

[0008]

Means for Solving the Problems The present inventors have investigated the ease of handling during production, the reactivity with a polyisocyanate compound, the strength of a paint or adhesive film using the same,
As a result of intensive research and study to improve adhesiveness, etc.,
The present inventors have found that improvement can be achieved by using the triol represented by the general formula (A), and have reached the present invention.

That is, the gist of the present invention is to provide a triol represented by the general formula (A) and a triol represented by the general formula (B) or (C)
And a ring-opening polymerization type polyol characterized by being reacted with a lactone or a cyclic ether represented by the formula:

[0010]

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[0011]

Embedded image R ⁴ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or a monocyclic aromatic hydrocarbon group. However, n + 2 R ⁴ are hydrogen atoms.

[0012]

Embedded image

R ⁵ is each independently a hydrogen atom, an alkyl group,
Represents a cycloalkyl group or a monocyclic aromatic hydrocarbon group. However, n + 2 R ⁵ are hydrogen atoms. Another gist of the present invention resides in a polyurethane resin obtained by reacting the above-mentioned polyol with a polyisocyanate compound, and a paint and an adhesive using the same.

Hereinafter, the present invention will be described in detail. The triols used in the present invention are represented by the general formula (A),
Having a structure branched from a secondary carbon, wherein all three hydroxyl groups are 1
Class.

[0015]

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In the general formula (A), R ¹ , R ² , R ³
Each independently represents an alkyl group, an alkenyl group or an alkynyl group, and among them, an alkyl group; R ¹ , R ² , R ³
Preferably have different carbon numbers. Particularly preferred is 3-hydroxymethyl-1,6-hexanediol in which R ¹ = methyl group, R ² = ethyl group, and R ³ = propyl group.

In the present invention, other initiators such as the above-mentioned triol, that is, a bifunctional initiator may be used in combination as long as the effect of the trifunctional initiator is not impaired. Specifically, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-
Butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2
-Methyl-2-propyl-1,3-propanediol,
2-butyl-2-ethyl-1,3-propanediol,
1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, neopentyl glycol , 1,3,
5-trimethyl-1,3-pentanediol, 2,2
4-trimethyl-1,3-pentanediol, 1,8-
Aliphatic glycols such as octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol,
Examples include alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, and aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene. Glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,3
Examples include 2,4-butanetriol, erythritol, sorbitol, pentaerythritol, dipentaerythritol and the like.

The reaction rate between the initiator and the lactone in synthesizing the ring-opening polymerization-based polyol of the present invention is appropriately selected depending on the grade of the target polylactone polyester. As one of the cyclic monomers used in the present invention, lactones represented by the general formula (B) can be mentioned.

[0019]

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In the general formula (B), n is 1 to 6. R ⁴ each independently represents hydrogen, an alkyl group, a cycloalkyl group or a monocyclic aromatic hydrocarbon group. However, n + 2 R ⁴ are hydrogen atoms. Examples of unsubstituted lactones wherein R ⁴ is all hydrogen include γ-butyrolactone, δ-valerolactone,
ε-caprolactone, ζ-enantholactone, η-caprylolactone and the like. Examples of the substituted lactones include alkylcaprolactones having a substituent ranging from a methyl group, an ethyl group, an (iso) propyl group, and the like to a dodecyl group of the lactones, and substituted with two alkyl groups at the same or different carbon atoms. Or trialkylcaprolactones in which two or three carbon atoms in the lactone ring are substituted, or alkoxylactones such as methoxy- and ethoxy-, or Examples thereof include cycloalkyl-, aryl-, aralkyl-caprolactones such as cyclohexyl-, phenyl- and benzyl-. These are preferably those in which the carbon atom adjacent to C = O of the lactone is unsubstituted.

Among these lactones, preferred are substituted or unsubstituted ε-caprolactones. These various lactones may be used alone or in plural at an arbitrary ratio according to the purpose. Ring-opening polymerization of lactones can be performed by a known method. In general, it is preferable to use a ring-opening reaction catalyst and to pass an inert gas such as nitrogen gas into the reaction system in order to prevent coloring of the obtained polyester polyol.

Examples of the ring opening reaction catalyst include organic titanium compounds such as tetrabutyl titanate, tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate; organic tin compounds such as dibutyl tin dilaurate, tin octylate, dibutyl tin oxide and dibutyl tin acetate; Stannous halide compounds such as stannous chloride, stannous bromide and stannous iodide are exemplified. Among them, organic titanium compounds are preferable because they exhibit sufficient catalytic activity. Furthermore, acetylacetonate compounds of various metals and metal salts of organic carboxylic acids can also be used.

The catalyst is added in an amount of 0.1 to the whole reaction system.
0.1-1000 ppm, preferably 0.1-10
It is 0 ppm. If the added amount of the catalyst exceeds 1000 ppm, the product may be colored or the product obtained from the product as a raw material may contain a large amount of metal, which may deteriorate the storage stability and durability of the product. May have adverse effects.

On the other hand, if the amount of the catalyst is less than 0.01 ppm, the reaction rate becomes extremely slow, which is not preferable. The ring-opening polymerization of the initiator, a triol represented by the general formula (A), with a lactone is generally performed at 50 to 250 ° C, preferably 130 to 220 ° C at normal pressure. If the reaction temperature is not lower than 50 ° C., the reaction rate is low. If the reaction temperature is higher than 250 ° C., depolymerization or thermal decomposition occurs and the acid value becomes high.

The cyclic ethers represented by the general formula (C) include, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and the like.
Propylene oxide is preferred. Ring-opening polymerization of alkylene oxides can be performed by a known method. Usually, a ring opening reaction catalyst is used, and an acid catalyst or an alkali catalyst is used as the ring opening reaction catalyst.

The ring-opening polymerization-based polyol of the present invention is suitable as a raw material for producing a urethane paint, an adhesive, a urethane foam, a spandex fiber, etc. by reacting with a polyisocyanate compound. Also, melamine resin,
It also has reactivity with epoxy resins, and can be applied to adhesives, coating agents and the like in combination with these resins. A method for producing a polyisocyanate compound using the ring-opening polymerization-based polyol of the present invention will be described below.

(1) Polyisocyanate Compound Introducing Ring-Opening Polymeric Polyol Containing Triol Represented by General Formula (A) Reaction with Ring-Opening Polymeric Polyol Containing Triol Represented by General Formula (A) Any organic isocyanate compound that can be used can be used, and conventionally known organic isocyanate compounds can be used. As such an organic isocyanate compound, a diisocyanate or more is usually used, and specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-
Diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-
Diisocyanate, m-phenylene diisocyanate,
p-phenylene diisocyanate, naphthylene-1,4
-Diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-
Diisocyanate, tetramethyl xylylene diisocyanate, polyphenylene polymethylene polyisocyanate, aromatic diisocyanate such as carbodiimide modified product of 4,4'-diphenylmethane diisocyanate, modified uretonimine, tetramethylene diisocyanate,
Alicyclics such as aliphatic diisocyanates such as hexamethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, and lysine diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Group diisocyanates.
Further, modified isocyanurate, modified buret, modified uretonimine, modified carbodiimide, and the like are also included. These organic isocyanate compounds may be used alone or in combination of two or more. Further, if necessary, a tri- or more functional triisocyanate compound may be used.

In the production of a polyisocyanate compound into which a ring-opening polymerization polyol containing a triol represented by the general formula (A) is introduced, the ring-opening polymerization polyol of the present invention is an essential component. A hydroxyl group compound may be used in combination. Polyhydric hydroxyl compounds include monomeric glycols such as ethylene glycol,
Diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2
-Butanediol, 1,3-butanediol, 1,4-
Butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,
3-propanediol, 2-methyl-2-propyl-
1,3-propanediol, 2-butyl-2-ethyl-
1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 2-ethyl-1,3 -Hexanediol, neopentyl glycol, 1,3,5-trimethyl-1,3-
Pentanediol, 2,2,4-trimethyl-1,3-
Pentanediol, 1,8-octanediol, 1,9
Aliphatic glycols such as -nonanediol and 2-methyl-1,8-octanediol; alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; xylylene glycol; bis Aromatic glycols such as hydroxyethoxybenzene, and trihydric or higher polyhydric alcohols include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, erythritol, and sorbitol Pentaerythritol, dipentaerythritol, etc., and other high molecular weight polyols such as glycols such as ethylene oxide or propylene oxide adducts of bisphenol A, polyester polyols, polyetherester polyols, polycarbonates Sulfonates polyols, and polyols polyacrylic polyols, polyether polyols other than the present invention, polycaprolactone polyols.

Examples of the polyether polyol include glycols such as ethylene glycol, propylene glycol and diethylene glycol; polyols having three or more functional groups such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol; and polyamines such as ethylenediamine and toluenediamine. And a polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran, and the like, and a hydroxyl group-containing polyether polyol obtained by addition polymerization of an alkylene oxide such as ethylene oxide and propylene oxide.

Examples of the polyester polyol include dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, and phthalic acid; tri- and tetracarboxylic acids such as trimellitic acid and pyromellitic acid; ethylene glycol;
Propylene glycol, 1,4-butanediol, 1,
5-pentanediol, 3-methyl-1,5 pentanediol, 2,2-diethylpropanediol, 2-ethyl2-butylpropanediol, 1,6-hexanediol, neobentyl glycol, diethylene glycol, 1,4 -Cyclohexanediol, diols such as 1,4-cyclohexanedimethanol, or triols such as trimethylolpropane and glycerin, or those obtained by a polycondensation reaction with bisphenol A, bisphenol F and the like. .

Polyetherester polyols obtained by reacting a mixture with ether-containing diols or other glycols with the above-mentioned dicarboxylic acids or anhydrides thereof, or by reacting polyester glycols with alkylene oxides, For example, poly (polytetramethylene ether) adipate and the like can be mentioned.

Examples of the polycarbonate polyol include a dealcoholization condensation reaction of a polyhydric alcohol with a dialkyl carbonate such as dimethyl carbonate and diethyl carbonate, a phenol condensation reaction of a polyhydric alcohol with a diphenyl carbonate, and a de-ethylene glycol of a polyhydric alcohol with ethylene carbonate. Obtained by a condensation reaction or the like. Examples of the polyhydric alcohol include 1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2-
Aliphatic diols such as diethylpropanediol, 2-ethyl 2-butylpropanediol, neopentyl glycol, or 1,4-cyclohexanediol,
Polycarbonate polyol using an alicyclic diol such as 1,4-cyclohexanedimethanol and the like.

It is also possible to use diamines, amino alcohols and the like. Examples of diamines include hexamethylenediamine, xylenediamine, isophoronediamine, N, N-dimethylethylenediamine, and the like.
Examples of the amino alcohol include monoethanolamine and diethanolamine. The preferred molecular weight of these polyol components is 500-5000. If a polyol having a molecular weight of more than 5000 is used, the crosslinking density is lowered, and the strength of the coating film is sometimes lowered.

The temperature of the urethanization reaction of the polyisocyanate compound into which the ring-opening polymerization type polyol containing a triol represented by the general formula (A) is introduced is usually from 10 to 10.
It is selected from the range of 0 ° C. Although a catalyst for this purpose is not particularly necessary, in some cases, an organotin catalyst such as dibutyltin dilaurate or dibutyltin dioctaate, an organic lead catalyst such as lead octanoate, or triethylamine, dimethyloctylamine, diazabicycloun It is also effective to use a catalyst of a tertiary amine compound such as decene. The progress of the urethanization reaction can be monitored by measuring the NCO content at an intermediate stage of the reaction. The reaction is stopped when the target NCO content is reached.

These reactions are possible even in a solvent.
Examples of the solvent used include inert solvents commonly used in polyurethane production, for example, aromatic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and esters such as ethyl acetate, butyl acetate, and isobutyl acetate. Solvents, glycol ether ester solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, and ether solvents such as tetrahydrofuran and dioxane Can be used alone or in combination of two or more. By selecting the type and amount of the solvent to be used and the resin concentration, the viscosity can be adjusted according to the use conditions.

The molecular weight of the polyisocyanate compound introduced with the ring-opening polymerization type polyol containing a triol represented by the general formula (A) is from 350 to 100 in terms of weight average molecular weight.
000, preferably 650 to 20,000. If the weight average molecular weight is more than 100,000, the molecular weight between crosslinks becomes longer and the strength of the coating film decreases, and the viscosity becomes too high and the workability deteriorates, which is not preferable.

(2) Polyurethane polyol into which ring-opening polymerization polyol containing triol represented by general formula (A) is introduced Ring-opening polymerization polyol containing triol represented by general formula (A) is introduced In producing the polyurethane polyol, the organic diisocyanate compound is not particularly limited, and the above-mentioned organic diisocyanate and the like which have been conventionally used for producing a polyurethane resin can be used. In producing a polyurethane polyol into which a ring-opening polymerization polyol containing a triol represented by the general formula (A) is introduced, other polyols other than the ring-opening polymerization polyol of the present invention may be used as the polyol to be used. Good. This polyol is not particularly limited, and any of the above-mentioned polyols conventionally used for producing a polyurethane resin can be used.

As a chain extender used for producing a polyurethane polyol into which a ring-opening polymerization type polyol containing a triol represented by the general formula (A) is introduced,
Examples of low molecular weight diols having a number average molecular weight of less than 500 include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, and 1,3.
-Butanediol, 1,4-butanediol, 2,3-
Butanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2
-Methyl-2-propyl-1,3-propanediol,
2-butyl-2-ethyl-1,3-propanediol,
1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-
Hexanediol, neopentyl glycol, 1,3
5-trimethyl-1,3-pentanediol, 2,2
4-trimethyl-1,3-pentanediol, 1,8-
Aliphatic glycols such as octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol,
Examples include alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, and aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene. Examples of low molecular weight diamines include 2,4-tolylenediamine 4,4'-diphenylmethanediamine and 2,6-tolylenediamine 4,
Aromatic diamines such as 4'-diphenylmethanediamine,
Ethylenediamine, 1,2-propylenediamine, 1,
Aliphatic diamines such as 6-hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and fats such as 1-amino-3-aminomethyl-3,3,5-trimethylcyclohexane and 4,4-dicyclohexanediamine Cyclic diamines, N-methyldiethanolamine and the like are also included.

In addition, if necessary, as a terminal terminator, dialkylamines such as di-n-butylamine, monoalkylamines such as butylamine, monoalcohols such as ethanol, isopropyl alcohol and butanol, and monoaminoamines such as monoethanolamine and diethanolamine. Alcohol or the like may be used. These reactions may be carried out in the presence of a solvent. As the solvent to be used, one or more inert solvents commonly used in the production of polyurethane described above can be used. By selecting the type and amount of the solvent to be used and the resin concentration, the viscosity can be adjusted according to the use conditions.

The weight average molecular weight of the polyurethane resin of the present invention is 5,000 to 300,000, preferably 15
000 to 200,000. Weight average molecular weight 5000
If it is less than 3,000, the strength of the coating film is low. The polyurethane polyol of the present invention may be used by mixing the above-described polyisocyanate compound of the present invention or an existing polyisocyanate compound as necessary.
Examples of the mixture include adducts of diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate with trimethylolpropane, trimers of these diisocyanates, and modified burettes obtained by reaction with water. Is mentioned.

In the paint and adhesive of the present invention, the mixing ratio (molar ratio) of the polyisocyanate compound to the polyvalent hydroxyl compound having an active hydrogen group such as a hydroxyl group is isocyanate group / active hydrogen group = 0.1 to 20. Is more preferable, and more preferably, it is in the range of 0.5 to 15. If the ratio of isocyanate group / active hydrogen group is less than 0.1, the crosslinked cured product is insufficient and the coating film strength is low, and the physical properties such as chemical resistance and solvent resistance deteriorate. If it exceeds 20, the cured product becomes brittle,
Impact resistance may deteriorate.

In the paint and adhesive of the present invention, various additives and pigments, such as a curing accelerator, a retarder, an ultraviolet absorber, an antioxidant, a plasticizer and a leveling agent, which are generally used, if necessary. May be included. The paint containing the isocyanate curing agent for paint of the present invention can be applied by a usual coating method, for example, an airless spray machine, an air spray machine, an electrostatic coating, an immersion, a roll coating machine, a brush, a collision mixing type. Spraying machine, and a coating speed of a paper injection cure (VIC) method.

According to the present invention, it is possible to provide a polyisocyanate curing agent excellent in reactivity, coating film properties and the like. And, the polyurethane coating composition of the present invention comprising the curing agent and the polyhydric hydroxyl compound, the polyurethane adhesive composition has better coating performance than conventional coatings and adhesives, or has excellent adhesiveness. I have. for that reason,
Paints for metals, plastics, concrete, wood,
It can be applied to a wide range of fields, such as magnetic recording media such as audio tapes, video tapes and floppy disks, inks, synthetic leathers, adhesives, adhesives, and fibers, and can contribute to a wide range of industries.

[0044]

Next, the present invention will be described more specifically with reference to examples and comparative examples. “Parts” and “%” in Examples and Comparative Examples are unless otherwise specified.
Means "parts by weight" and "% by weight". Further, the present invention is not limited to the following examples. In synthesizing the lactone-based polyester polyol, the refractive index of the reaction system was measured, and the point where the refractive index showed a constant value was defined as the end point of the lactone ring-opening reaction. The hydroxyl value and acid value of the obtained lactone-based polyester polyol were measured by the following methods.

(1) Refractive index The refractive index at 25 ° C. was measured by using a refractometer (Abago refractometer type 1 manufactured by Atago Co., Ltd.). (2) Hydroxyl value (KOHmg / g) Measured by the phthalic anhydride-pyridine method according to JIS K1557 (Section 6.4). (3) Acid value (KOHmg / g) According to JIS K1557 (Section 6.6), 1 / 50N
-Measured by an indicator titration method using a KOH methanol solution.

[0046]

Example 1 ε-caprolactone 82 was placed in a four-necked flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube.
8.3 parts, 171.7 parts of 3-hydroxymethyl-1,6-hexanediol and tetrabutyl titanate
While charging 0.01 part, while flowing nitrogen into the reaction system, 180 parts
C. and heated until the refractive index became a constant value to obtain a polyester polyol. The refractive index showed a constant value in 2 hours, and the numerical value was 1.4732. In addition, the measurement result of the obtained lactone-based polyester polyol was a hydroxyl value of 190.0 KOHmg /
g, acid value 0.4 KOHmg / g.

[0047]

Example 2 A four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen inlet tube was charged with propylene oxide 6
92.3 parts, 3-hydroxymethyl-1,6-hexanediol 277.7 parts and potassium hydroxide 30.0
Then, the mixture was heated at 60 ° C. for 1 hour and further at 110 ° C. for 8 hours. After the completion of the reaction, dry nitrogen gas was blown in to remove some remaining unreacted propylene oxide and moisture. Subsequently, potassium hydroxide was neutralized by adding phosphoric acid, and the mixture was filtered to completely remove the alkali component, thereby obtaining a polyether polyol. The measurement results of the obtained polyether polyol are as follows.
It was 7.0 KOHmg / g and the acid value was 0.3 KOHmg / g.

[0048]

Comparative Example 1 Trimethylolpropane 160.1 instead of 3-hydroxymethyl-1,6-hexanediol
And the synthesis was carried out in the same manner as in Example 1 except that 839.9 parts of ε-caprolactone was used to obtain a polyester polyol. The refractive index showed a constant value for 6 hours, and the numerical value was 1.4729. The measurement results of the obtained lactone-based polyester polyol were as follows: hydroxyl value 197.3 KOH mg / g, acid value 1.7 KOHm
g / g.

[0049]

Comparative Example 2 Trimethylolpropane 261.3 in place of 3-hydroxymethyl-1,6-hexanediol
The synthesis was carried out in the same manner as in Example 2 except that 708.7 parts of propylene oxide was used to obtain a polyether polyol. The measurement result of the obtained polyether polyol was a hydroxyl value of 330.0 KOHm
g / g, acid value 0.1 KOHmg / g.

[0050]

Example 3 A polyisocyanate compound (GP105A manufactured by Mitsubishi Chemical Corporation) was added to 100 parts of the lactone-based polyester polyol obtained in Example 1 with an equivalent ratio of hydroxyl group / isocyanate group of 1 / 1.1. The resulting resin solution was coated on release paper, heated at 80 ° C. for 24 hours, cured and cured to a film thickness of 100
A μm coating film was obtained. The obtained coating film was subjected to JIS K 63
01 and a relative humidity of 6 using Tensilon UTM-III-100 (manufactured by Toyo Baldwin Co., Ltd.).
It was measured under the condition of 5%. The results are shown in Table 1.

[0051]

Example 4 A polyisocyanate compound (NY710A, manufactured by Mitsubishi Chemical Corporation) was added to 100 parts of the lactone-based polyester polyol obtained in Example 1 with an equivalent ratio of hydroxyl group / isocyanate group of 1 / 1.1. Evaluation was performed in the same manner as in Example 2 by adding the number of parts shown in Table 1 so that the results were shown in Table 1.

[0052]

Comparative Example 3 A polyisocyanate compound (GP105A, manufactured by Mitsubishi Chemical Corporation) and a hydroxyl group / isocyanate group equivalent ratio of 1 / 1.1 to 100 parts of the lactone-based polyester polyol obtained in Comparative Example 1 were used. Evaluation was performed in the same manner as in Example 2 by adding the number of parts shown in Table 1 so that the results were shown in Table 1.

[0053]

Comparative Example 4 A polyisocyanate compound (NY710A, manufactured by Mitsubishi Chemical Corporation) was added to 100 parts of the lactone-based polyester polyol obtained in Comparative Example 1 with an equivalent ratio of hydroxyl group / isocyanate group of 1 / 1.1. Evaluation was performed in the same manner as in Example 2 by adding the number of parts shown in Table 1 so that the results were shown in Table 1.

[0054]

[Table 1] * 1: GP105A (manufactured by Mitsubishi Chemical Corporation, trimethylolpropane adduct of tolylene diisocyanate, ethyl acetate solution, resin solid content 75%, NCO content 13.3 wt%) * 2: NY710A (Mitsubishi Chemical Corporation ), Trimethylolpropane adduct of hexamethylene diisocyanate, ethyl acetate solution, resin solid content 75%, NCO content 13.0 wt%)

From the above examples and comparative examples, the following becomes clear. (1) 3-hydroxymethyl-1,5 used in Example 1
-Hexanediol is a liquid at room temperature, is easy to handle at the time of charging, and the lactone-based polyester polyol obtained in Example 1 is obtained in 2 hours, while Comparative Example 1 is obtained.
The trimethylolpropane used in (1) is a solid at room temperature and is slightly inferior in handling, and it takes as long as 6 hours to complete the reaction of the lactone-based polyester polyol. (2) In Example 3 and Comparative Example 3, the elongation at break was almost the same, whereas the elongation at break was higher in Example 3 and the physical properties of the coating film were good.

[0056]

The ring-opening polymerization type polyol of the present invention comprises:
(1) The handling during manufacture is simple, (2) the manufacturing time can be shortened, and (3) chemical resistance and weather resistance can be obtained by combining with various curing agents such as polyisocyanate, melamine resin and epoxy resin. It is possible to form an excellent coating film. Thus, it is possible to provide a ring-opening polymerization-based polyol having a wide range of applications and to provide a resin suitable for use in the fields of paints, coatings, adhesives, films, elastomers and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 175/04 C09D 175/04 C09J 175/04 C09J 175/04

Claims (7)

[Claims] 1. A polyol obtained by reacting a triol represented by the general formula (A) with a lactone or a cyclic ether represented by the general formula (B) or (C). Embedded image Embedded image R ⁴ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or a monocyclic aromatic hydrocarbon group. However, n + 2 R ⁴ are hydrogen atoms. Embedded image R ⁵ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or a monocyclic aromatic hydrocarbon group. However, n + 2 R ⁵ are hydrogen atoms. 2. The polyol according to claim 1, wherein R ^{1 to} R ³ in the general formula (A) are an alkyl group. 3. In the general formula (A), R ¹ = methyl group,
^3. The polyol according to claim 2, wherein R ² = ethyl group and R ³ = propyl group. 4. In the general formula (B), n = 4 and R ⁴ = H
The polyol according to any one of claims 1 to 3, wherein 5. A polyurethane resin obtained by reacting the polyol according to claim 1 with a polyisocyanate compound. 6. A paint containing the polyurethane resin according to claim 5. 7. An adhesive containing the polyurethane resin according to claim 5.