JP2019123871A - Highly branched polycarbonate polyol composition - Google Patents

Abstract

To provide a polycarbonate polyol that is easily handled and when formed into polyurethane, exhibits high tensile strength and a high elongation percentage and is excellent in durability.SOLUTION: A highly branched polycarbonate polyol composition has a structure derived form an aliphatic diol and a structure derived from a polyhydric alcohol and has a branching factor g' of 0.55 to 0.82.SELECTED DRAWING: None

Description

  The present invention relates to a polyurethane compound useful as a paint, a coating agent, a leveling agent, or a raw material thereof, a composition containing the polyurethane compound, and a novel highly branched polycarbonate polyol composition which gives a cured product thereof.

  Polyurethane compounds are widely used as raw materials for paints, coatings, adhesives and the like, for example, for interior and exterior of aircrafts and automobiles, exterior wall surfaces and floors of houses, parts such as home appliances and electronic materials, and the like. A coating film such as the above-mentioned paint or coating agent not only imparts beauty of the appearance but also serves to protect the substrate, so that durability and the like are required in addition to hardness and strength. As a raw material of polyurethane used for this purpose, polycarbonate polyol is reacted with an isocyanate compound, and polyurethane resin which can be used, for example, for rigid foam, flexible foam, paint, adhesive, artificial leather, ink binder, etc. It is known that it can give. The polyurethane resin using polycarbonate diol gives a material excellent in water resistance, heat resistance, oil resistance, stress relaxation performance, abrasion resistance, weather resistance, etc. by high cohesive strength derived from carbonate group (Non-patent Document 1 and See Non-Patent Document 2). In order to bring about physical properties such as high hardness and high elastic modulus, for example, polycarbonate polyols provided with a branched structure using polyhydric alcohol are used (Patent Document 1).

  On the other hand, hyperbranched polymers having a highly branched three-dimensional structure are attracting attention as novel materials. Hyperbranched polymers, unlike simple branched polymers, are also easily prepared by one-pot synthesis where the molar mass and branching structure can not be controlled. Hyperbranched polymers are believed to be provided by their high degree of branching, such as thermal properties, mechanical properties, solubility, rheological properties etc. (see non-patent documents 3, 4 and patent document 2).

JP 2012-184380 A US Patent Publication 20090093589

Latest Polyurethane material and applied techniques, CMC Publishing, Chapter 2, page 43 Costa, V. and Nohales, A. Enhanced polyurethane based on different polycarbonates, SAGE Publications, Journal of Elastomer & Plastics, 2012, 45 (3), 217-238. ) Voit, B. I. and Lederer, A., ACS, Chemical Reviews, 109, 5924-5973, Hyperbranched and highly branched polymer architectures-synthetic strategies and major characterization aspects Wang, Z. Fu, Y. Guo, P. Ren, L. Wang, H. and Qiang, T., Synthesis, characterization, and properties of PCDL hyperaliphatic branched polyurethane coatings John Wiley & Sons, Inc., Journal of Applied Polymer Science, 2013, 2671-2679

  As described above, although polyurethane resins are required to have physical properties such as good durability, excellent elongation and high tensile strength, polycarbonate diols having a linear structure are often solid at room temperature and It may be inconvenient in terms of handling in preparation. Moreover, in the polyurethane resin which used the polycarbonate polyol known until now, durability was not yet enough regarding physical properties, such as hardness and an elastic modulus, and the improvement was calculated | required.

  Therefore, an object of the present invention is to provide a polycarbonate polyol which is easy to handle, has high tensile strength and elongation when made into polyurethane, and is excellent in durability.

When the present inventors repeatedly studied, a highly branched polycarbonate polyol composition having a structure derived from an aliphatic diol and a structure derived from a polyhydric alcohol and having a branching factor g ′ of 0.55 to 0.82 It has been found that the above problems can be solved by objects, and the present invention has been made.
The specific means for solving the said subject are as follows.
[1] A highly branched polycarbonate polyol composition having a structure derived from an aliphatic diol and a structure derived from a polyhydric alcohol, and having a branching factor g ′ of 0.55 to 0.82.
[2] The highly branched polycarbonate polyol composition according to the above [1], wherein the number average molecular weight (Mn) of the highly branched polycarbonate polyol composition is 200 to 10,000.
[3] The highly branched polycarbonate polyol composition according to any one of the above [1] to [2], which has a hydroxyl value of 50 to 500 mg KOH / g.
[4] The used amount (molar ratio) of the aliphatic diol and the polyhydric alcohol is 0.3 to 4.0 in terms of “total number of moles of hydroxyl groups of polyhydric alcohol / total number of moles of hydroxyl groups of aliphatic diol”. It is a highly branched polycarbonate polyol composition as described in any one of said [1]-[3].
[5] The highly branched polycarbonate polyol composition according to any one of the above [1] to [4], wherein the highly branched polycarbonate polyol composition is obtained by reacting an aliphatic diol, a polyhydric alcohol and a carbonate ester. It is a thing.
[6] The highly branched polycarbonate polyol composition according to any one of the above [1] to [5], which is liquid at room temperature.
[7] A polyurethane composition obtained using the highly branched polycarbonate polyol composition according to any one of the above [1] to [6].
[8] A synthetic leather obtained by using the highly branched polycarbonate polyol composition according to any one of the above [1] to [6].
[9] An aqueous polyurethane resin dispersion obtained by using the highly branched polycarbonate polyol composition according to any one of the above [1] to [6].

  According to the present invention, a polycarbonate polyol is obtained which is easy to handle, has high tensile strength and elongation when made into polyurethane, and is excellent in durability. In addition, although the physical properties of the polymer may change due to the method of preparation, the present invention is particularly problematic in terms of durability by using a hyperbranched polymer in which terminal functional groups are concentrated on the particle surface of the molecule. The state of the reaction point, which is

  Hereinafter, embodiments of the present invention will be described in detail. In addition, the high molecular compound like this invention is a thing from which the product which has many structures is obtained by reaction of several types of raw material compounds. Therefore, a macromolecular compound can be described by a general formula with a large number of structures included, but is not uniquely indicated by the structure. In addition, it is difficult to directly measure and identify the physical properties of the compound by instrumental analysis or the like or to distinguish it from existing compounds. Therefore, in the present invention, a product containing a polymer such as “hyperbranched polycarbonate polyol composition” or “aqueous polyurethane resin dispersion” is specified by the production method as needed.

[Highly Branched Polycarbonate Polyol Composition]
The highly branched polycarbonate polyol composition of the present invention is a polycarbonate polyol composition having a branching factor g 'of 0.55 to 0.82. In the present invention, “highly branched” refers to a state in which the branching factor g ′ calculated by gel permeation chromatography (GPC) is 0.55 to 0.82.
The branching factor g ′ is 0.55 to 0.82, preferably 0.58 to 0.80, more preferably 0.60 to 0.78, and still more preferably 0.60 to 0.75. is there. Hereinafter, the description of the above-mentioned suitable range is applied also to the part explaining that branching degree factor g 'is 0.55-0.82, unless there is particular notice.

(Bifurcation factor (g '))
The degree of branching factor g 'is a value for evaluating how much branching the polymer has. In general, the degree of branching factor g 'takes a smaller value as the number of branches in the polymer increases.
The branching factor (g ') of the hyperbranched polycarbonate polyol composition can be calculated by gel permeation chromatography (GPC).
GPC uses a Tosho HLC-8220GPC equipped with one Shodex KF-G as a column, two KF-805Ls and one KF-800D as a detector and TriSEC302TDA made by Viscotek as a detector, and the eluent is tetrahydrofuran The flow rate is 1.0 mL / min, the concentration is 0.1 wt / vol%, the injection volume is 300 μL, the temperature is 40 ° C., and the Mark-Houwink plot is made using the analysis software OmniSec 4.0. The branching factor g 'is calculated from the molecular weight and the intrinsic viscosity.

  The degree of branching factor g 'indicates the degree of branching of the polymer. The degree of branching factor g 'is correlated with the molecular weight, so that the shape of the polymer, such as whether it is close to a sphere or close to an ellipse, can be represented in more detail. On the other hand, the highly branched polycarbonate polyol composition of the present invention has a structure in which a plurality of hydroxyl groups derived from a polyol are present at the end of a highly branched molecular chain. That is, since the number of hydroxyl groups at the polymer end varies depending on the degree of branching, the branching factor g 'is the average number of terminal hydroxyl groups per molecule of polycarbonate polyol (hereinafter sometimes referred to as "valence") It can also be related. When expressing the highly branched polycarbonate polyol composition of the present invention by the valence, a polycarbonate polyol composition having a valence of 4.0 to 15 is a more preferable embodiment in the present invention. In addition, it is more preferable that the range of the branching factor g 'is satisfied.

  The branching factor g 'of the highly branched polycarbonate polyol composition of the present invention is 0.55 to 0.82. When the degree of branching factor g 'is in this range, it becomes easy to handle as a liquid substance at room temperature, and when it is polyurethane, it is possible to achieve both high strength and high elongation rate.

(Number average molecular weight (Mn))
The number average molecular weight (Mn) of the highly branched polycarbonate polyol composition is 200 to 10000, preferably 350 to 10000, more preferably 400 to 8000, more preferably 450 to 6000, and particularly preferably 500 to 5000.
The number average molecular weight (Mn) is determined from the viscosity detector using the same GPC as described above.

(OH value)
The hydroxyl value of the highly branched polycarbonate polyol composition can be calculated by the following procedure.
0.9 g of the hyperbranched polycarbonate polyol composition and 10 mL of a phthalate agent (a mixture of 160 g of phthalic anhydride, 24 g of imidazole and 1000 mL of pyridine) are reacted at around 100 ° C. for 30 minutes. Next, 4 mL of water and 20 mL of pyridine are added to this reaction solution, and then titrated with a 0.5 mol / L potassium hydroxide ethanol solution.
The phthalizing agent was titrated with a 0.5 mol / L potassium hydroxide-ethanol solution (this is a blank test for determining a blank value).
Based on the obtained titration amount, a hydroxyl value is calculated by the following formula (1).
Hydroxyl value (mg KOH / g) = [B (mL)-A (mL)] x f x 28.05 / S (g) + acid value (mg KOH / g) ... Formula (1)
A: Use amount of 0.5 mol / L potassium hydroxide ethanol solution necessary for titration of sample (mL) B: Use of 0.5 mol / L potassium hydroxide ethanol solution necessary for titration of blank Volume (mL)
f: Potency S of 0.5 mol / L potassium hydroxide ethanol solution: Weight of sample (g)
The acid value can be calculated by the following method.
A 10 g sample dissolved in a 50/50 (w / w) solution of toluene / ethanol was prepared and titrated with 0.1 N KOH ethanol solution. The acid value is expressed by the following formula (2):
5.61 × (C−B ¹ ) × f / s (2)
Determined by
Here, B ¹ is the amount (mL) of 0.1 N KOH ethanol standard solution required to neutralize the blank, and C is 0.1 N KOH ethanol standard solution required to neutralize the sample. Volume (mL), f is a factor of 0.1 N KOH ethanol standard solution, and s is the weight of the sample (g).

(Characteristics at room temperature)
The properties of the hyperbranched polycarbonate polyol at room temperature are visually confirmed after placing the sample heated at 80 ° C. for 3 hours for 24 hours at 25 ° C. The liquid is determined by heating the polycarbonate polyol at 80 ° C. for 3 hours and then leaving it at room temperature, ie 25 ° C. for 24 hours to check if it is clear and fluid. It is judged that the solid is not visible and is not turbid as transparent.

The hyperbranched polycarbonate polyol composition may substantially have a branching factor g 'of 0.55 to 0.82, and a part of terminal hydroxyl groups may be unsaturated bond (for example, terminal ethylene) or ether It may be a bond (eg, terminal methoxy group or terminal phenoxy group).
Here, the proportion of terminal hydroxyl groups in the terminal structure of the hyperbranched polycarbonate polyol composition can be measured by 1 H-NMR, and is preferably 90% or more, more preferably 95% or more. Within this range, for example, the molecular weight of the urethanation reaction using the highly branched polycarbonate polyol composition of the present invention can be increased.
In addition, among the terminal hydroxyl groups, the ratio of the primary terminal hydroxyl group is preferably 95% or more. Within this range, for example, the urethanation reaction using the highly branched polycarbonate polyol composition of the present invention proceeds smoothly.

(Production of Hyperbranched Polycarbonate Polyol Composition)
The method for producing the hyperbranched polycarbonate polyol composition is not particularly limited. For example, a polyhydric alcohol, an aliphatic diol, a carbonate ester and a catalyst are mixed to distill off low boiling point components (for example, by-produced alcohol etc.) The reaction is carried out by methods such as reaction.
In the reaction of the present invention, after obtaining a prepolymer of hyperbranched polycarbonate polyol (lower molecular weight than the desired hyperbranched polycarbonate polyol), a plurality of reactions such as reacting the prepolymer in order to further increase the molecular weight are carried out. It can also be divided into times. Hereinafter, each component which comprises a highly branched polycarbonate polyol composition, and the conditions regarding preparation are demonstrated.

(Aliphatic diol)
Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- A linear aliphatic diol having 2 to 12 carbon atoms, such as octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol;
2-methyl-1,3-propanediol, 2- or 3-methyl-1,5-pentanediol, 2,2,4- or 2,4,4-trimethylhexanediol, 1,5-hexanediol etc. Branched aliphatic diols having 3 to 18 carbon atoms;
C6-C18 cyclic aliphatic diols such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like are used.
These may be used alone or in combination of two or more.

(Polyhydric alcohol)
Examples of polyhydric alcohols include compounds having three or more hydroxyl groups in one molecule, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol.
These may be used alone or in combination of two or more.

(Molar ratio of aliphatic diol and polyhydric alcohol)
The amount (molar ratio) of the aliphatic diol and polyhydric alcohol used is such that the branching factor g ′ of the hyperbranched polycarbonate polyol composition is in the range of 0.55 to 0.82 (molar ratio). For example, it is preferably 0.3 to 4.0 in terms of “total number of moles of hydroxyl groups of polyhydric alcohol / number of moles of total hydroxyl groups of aliphatic diols”, although not particularly limited. As an example, a hyperbranched polycarbonate polyol composition is completely hydrolyzed, and aliphatic diols and polyhydric alcohols are identified and quantified by means of gas chromatography, mass spectrum, NMR measurement, etc. The molar ratio of alcohol can be determined.

(Carbonate ester)
Examples of carbonates include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate; diaryl carbonates such as diphenyl carbonate; ethylene carbonate, propylene carbonate (4-methyl-1,3-dioxolan-2-one), trimethylene Carbonates), butylene carbonate (4-ethyl-1,3-dioxolan-2-one), tetramethylene carbonate, cyclic carbonates such as 5-methyl-1,3-dioxane-2-one, etc., but preferably carbonate Dimethyl, diethyl carbonate, ethylene carbonate are used.
These may be used alone or in combination of two or more.

The amount of the carbonic ester used is preferably 0.25 to 0.65 mol, more preferably 0.30 to 0.60 mol, per 1 mol of "total hydroxyl groups of polyhydric alcohol and aliphatic diol" to be used. It is.
By setting it as this range, the target highly branched polycarbonate polyol composition can be obtained efficiently with sufficient reaction rate.

(catalyst)
As a catalyst used in the reaction for obtaining the hyperbranched polycarbonate polyol composition of the present invention, known transesterification catalysts can be used, for example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, Metals such as zinc, aluminum, titanium, zirconium, cobalt, germanium, tin, cerium and their hydroxides, alkoxides, carboxylates, carbonates, hydrogencarbonates, sulfates, phosphates, nitrates, organometallics And sodium hydride, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, dibutyltin dilaurate, dibutyltin dimethoate. Sid, dibutyl tin oxide is used.
In addition, you may use these catalysts individually or in mixture of 2 or more types.
The amount of the catalyst used is preferably 0.001 to 0.1 millimole, more preferably 0.005 to 0.05 millimole, more preferably 1 mole of “total hydroxyl group of polyhydric alcohol and aliphatic diol”. Is 0.01 to 0.03 millimoles.
By setting it as this range, the target highly branched polycarbonate polyol composition can be obtained efficiently, without making a post-process complicated.
The catalyst may be used all at once at the start of the reaction, or may be used (added) twice or more at the start of the reaction and after the start of the reaction.

(Reaction temperature and reaction pressure)
The reaction temperature in the reaction for obtaining the highly branched polycarbonate polyol composition of the present invention can be appropriately adjusted depending on the type of carbonic ester, but is preferably 50 to 250 ° C., more preferably 70 to 230 ° C.
Further, the reaction pressure in the reaction for obtaining the highly branched polycarbonate polyol composition of the present invention is not particularly limited as long as the pressure is such that the reaction is carried out while removing the low boiling point components, preferably under normal pressure or reduced pressure. It will be.
By setting this range, it is possible to efficiently obtain the target highly branched polycarbonate polyol composition without occurrence of a sequential reaction or a side reaction.

Preferably, the hyperbranched polycarbonate polyol composition of the present invention has the following formula (I):
-(O-C (= O) -O-R) _n- OH (I)
(Wherein, R is a group derived from an aliphatic diol, n is the number of repeating units, and is an integer of 1 or more)
And has a structure bonded to a group derived from a polyhydric alcohol by an amount such that the branching factor g 'is 0.55 to 0.82. For example, when the structure is simplified and a molecule having only one structure derived from pentaerythritol is considered as a polyhydric alcohol, the structure represented by the formula (I) is represented by C (CH _2- ) ₄ Attached to each of the four methylene groups of the structure. In the structure of the formula (I) having a branching factor g ′ of 0.55 to 0.82, each R and n may be different from each other or may be the same. Further, the structures represented by the above-mentioned formula (I) having a branching factor g ′ of 0.55 to 0.82 may be each independently bonded to a group derived from the same or different polyhydric alcohol .

(Highly branched polyurethane composition)
A polyurethane composition can be obtained by reacting the highly branched polycarbonate polyol composition of the present invention obtained as described above with a polyisocyanate (hereinafter sometimes referred to as "polyurethaneation reaction"). The present invention also relates to a hyperbranched polyurethane composition obtained by using the above hyperbranched polycarbonate polyol composition.

(Polyisocyanate)
As said polyisocyanate, although it can select suitably according to the objective or a use, For example, 2, 4- tolylene diisocyanate, 2, 6- tolylene diisocyanate, diphenylmethane 4, 4'- diisocyanate, naphthalene 1 Aroaliphatic diisocyanates such as 5-diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate (XDI), phenylene diisocyanate, etc .; 4,4'-methylene biscyclohexyl Aliphatic diiso, such as diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,3-diyl bis (methylene) diisocyanate, trimethylhexamethylene diisocyanate Cyanate is used.
These polyisocyanates may be used alone or in combination of two or more, and part or all of the structure thereof may be derivatized by isocyanuration, carbodiimide formation, biuretization or the like. .

  The amount of polyisocyanate used can be designed according to the molar ratio (isocyanate group / hydroxyl group (mole)) between the isocyanate group of polyisocyanate and the hydroxyl group of the highly branched polycarbonate polyol composition, and preferably the molar ratio is 0.8 The amount is preferably 1.5 to 1.5, more preferably 0.9 to 1.3.

(Chain extender)
In the polyurethane formation reaction, a chain extender may be used for the purpose of increasing the molecular weight. The chain extender to be used can be appropriately selected according to the purpose and application, for example,
water;
Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl A low molecular weight polyol such as propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane;
Polymer polyols such as polyester polyols, polyester amide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols, etc.
Polyamines such as ethylene diamine, isophorone diamine, 2-methyl-1,5-pentane diamine, aminoethyl ethanolamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine are used.
For chain extenders, reference may be made, for example, to the "latest polyurethane application technology" (CMC Co., Ltd., published in 1985), and for the polymer polyol, for example, "polyurethane foam" (polymer (Publication, 1987).

(Urethanization catalyst)
In the polyurethane formation reaction, known polymerization catalysts can be used to improve the reaction rate, and for example, tertiary amines or organic metal salts such as tin or titanium are used.
As for the polymerization catalyst, reference can be made to pages 23 to 32 of "Polyurethane resin", published by Keiji Yoshida (Nippon Kogyo Shimbun, 1969).

(solvent)
The polyurethane formation reaction can be carried out in the presence of a solvent, for example, esters such as ethyl acetate, butyl acetate, propyl acetate, γ-butyrolactone, δ-valerolactone, ε-caprolactone; dimethylformamide, diethylformamide, dimethylacetamide Amides such as: sulfoxides such as dimethylsulfoxide; ethers such as tetrahydrofuran, dioxane and 2-ethoxyethanol; ketones such as methyl isobutyl ketone and cyclohexanone; and aromatic hydrocarbons such as benzene and toluene.

The polyurethane formation reaction can be carried out with the addition of an endcapping agent to adjust molecular weight.
Further, depending on the purpose, the polyurethane may contain a heat stabilizer, a light stabilizer, a plasticizer, an inorganic filler, a lubricant, a colorant, a silicone oil, a foaming agent, a flame retardant, and the like.

  The obtained polyurethane can be a flexible polyurethane foam, a rigid polyurethane foam, a thermoplastic polyurethane, a solvent-based polyurethane solution, an aqueous polyurethane resin dispersion, and the like. Further, they can be processed into molded articles such as artificial leather and synthetic leather, heat insulating materials, cushioning materials, adhesives, paints, coatings, films and the like.

[Water-based hyperbranched polyurethane resin dispersion]
The present invention also relates to an aqueous hyperbranched polyurethane resin dispersion obtained by using the hyperbranched polycarbonate polyol composition. Specifically, the aqueous hyper-branched polyurethane resin dispersion is, for example, a urethane obtained by reacting the hyper-branched polycarbonate polyol composition of the present invention, polyisocyanate, and acidic group-containing polyol in the presence or absence of a solvent. Preparing a prepolymer, neutralizing acid groups in the prepolymer with a neutralizing agent, dispersing the neutralized prepolymer in an aqueous medium, and dispersing the prepolymer in the aqueous medium with a chain extender It can manufacture by performing the process of making it react sequentially.
In each step, the reaction can be promoted or the amount of by-products can be controlled by using a catalyst as needed.
The aqueous hyperbranched polyurethane resin dispersion derived from the hyperbranched polycarbonate polyol composition of the present invention can be applied particularly to artificial leather and synthetic leather because it gives a film excellent in adhesion, flexibility and touch.
As the hyperbranched polycarbonate polyol composition, the polyisocyanate, the solvent, and the chain extender, those described above can be used.

(Acid-containing polyol)
When producing an aqueous polyurethane resin dispersion, an acidic group-containing polyol can be used for dispersion in an aqueous medium. Therefore, the amount of the polyisocyanate used is the molar ratio (isocyanate) of the isocyanate group of the polyisocyanate to the total hydroxyl groups of the polyol (polycarbonate polyol, acidic group-containing polyol described later, and all polyols such as low molecular weight polyol described later). The ratio can be designed according to the group / hydroxyl group (mole), preferably in an amount such that the molar ratio is 0.8 to 2.0, more preferably 0.9 to 1.8.

Examples of the acidic group-containing polyol include dimethylolalkanoic acids such as 2,2-dimethylol propionic acid and 2,2-dimethylol butanoic acid; N, N-bishydroxyethyl glycine, N, N-bishydroxyethyl Examples include alanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid and the like, preferably dimethylolalkanoic acid, more preferably 4 to 12 carbon atoms containing two methylol groups. Are used.
These acidic group-containing polyols may be used singly or in combination of two or more, and the amount thereof used is not particularly limited as long as the polyurethane resin can be dispersed in the aqueous medium.

(Neutralizer)
Examples of the neutralizing agent include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methyl Organic amines such as morpholine and pyridine; inorganic alkali salts such as sodium hydroxide and potassium hydroxide; and ammonia are preferable, and organic amines are more preferable, and tertiary amines are more preferably used.
In addition, these neutralizing agents may be used individually or in mixture of 2 or more types, and the usage-amount is not restrict | limited especially if it is the quantity which can neutralize the acidic group in a polyurethane resin.

(Water based medium)
Examples of the aqueous medium include water such as fresh water, ion exchange water, distilled water and ultrapure water, and a mixed medium of water and a hydrophilic organic solvent.
Examples of the hydrophilic organic solvent include ketones such as acetone and ethyl methyl ketone; pyrrolidones such as N-methyl pyrrolidone and N-ethyl pyrrolidone; ethers such as diethyl ether and dipropylene glycol dimethyl ether; methanol, ethanol, Alcohols such as n-propanol, isopropanol, ethylene glycol, diethylene glycol; Amides such as β-alkoxypropionamide represented by "Ecamide" manufactured by Idemitsu Kosan Co., Ltd .; 2- (dimethylamino) -2-methyl-1-propanol And hydroxyl group-containing tertiary amines such as (DMAP).
The amount of the hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by mass.

(Low molecular weight polyol)
In the urethanization reaction of the present invention, low molecular weight polyols can be present to adjust the molecular weight. As low molecular weight polyols which can be used, for example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol and the like.
In addition, these low molecular weight polyols may be used individually or in mixture of 2 or more types.

  The highly branched polycarbonate polyol composition of the present invention is excellent in handleability because of its properties, and is useful as a raw material of a polyurethane composition. In addition, since the highly branched polycarbonate polyol composition of the present invention can give a polyurethane composition excellent in tensile strength, elongation rate, and durability, various materials to which polyurethane is applied, such as artificial leather, synthetic leather, heat insulating material It is industrially useful as a raw material which can obtain moldings, such as materials, such as cushioning materials, adhesives, paints, coatings, and films. In artificial leathers where polyurethane is impregnated into non-woven fabrics etc., and in synthetic leathers where polyurethane is applied to natural cloths, the surface is a layer excellent in strength, elongation, and durability, so there are problems with durability. It is more useful than conventional polyurethane-based materials. Moreover, as a coating material or a coating agent, the surface apply | coated and applied becomes what was excellent in various physical properties, and is useful. Furthermore, the polyurethane composition itself using the highly branched polycarbonate polyol composition of the present invention is also useful because it leads to a molded article having excellent durability and the like.

  EXAMPLES The present invention will next be described by way of examples, which should not be construed as limiting the scope of the present invention.

The measurement of the hydroxyl value, the degree of branching factor g ′, the number average molecular weight and the properties at room temperature were performed by the method described above. Moreover, the measurement of an acid value, a viscosity, APHA, glass transition temperature, tensile strength, and elongation at break was performed as follows.
[Acid number]
A 10 g sample dissolved in a 50/50 (w / w) solution of toluene / ethanol was prepared and titrated with 0.1 N KOH ethanol solution. The acid value is determined by the following formula: 5.61 × (C−B ¹ ) × f / s. Here, B ¹ is the amount (mL) of 0.1 N KOH ethanol standard solution required to neutralize the blank, and C is 0.1 N KOH ethanol standard solution required to neutralize the sample. Volume (mL), f is a factor of 0.1 N KOH ethanol standard solution, and s is the weight of the sample (g).
[viscosity]
The viscosity was measured under conditions of melting at 80 ° C. using a LVDV II + Procone and Brookfield plate viscometer in combination with a spindle cone model CPE-41.
[APHA]
It measured according to JIS K 1557. The degree of yellowing is indicated as a unit of APHA.
[Glass-transition temperature]
It measured using a differential scanning calorimeter (DSC). Using a sample of 8 to 10 mg, the temperature rising program was set from 80 ° C. to 250 ° C. at a heating rate of 20 ° C./min. The glass transition temperature was identified by the inflection point of the second scan.

[Tensile strength and elongation at break]
It was carried out according to ISO 527 under an environment of temperature 23 ° C. and humidity 50%. Specifically, the tensile strength and the elongation at break of the test pieces of the polyurethane resin film having a thickness of 0.05 to 0.10 mm were measured at a width of 5 mm, a test length of 20 mm, and a test speed of 100 mm / min.

Example 1 (Synthesis of Hyperbranched Polycarbonate Polyol Composition (1))
In a 500 mL four-neck glass reactor equipped with a distillation column, a stirrer, a thermometer and a nitrogen inlet tube, 60.00 g (0.45 mol) of trimethylolpropane, 126.97 g (1.07) of 1,6-hexanediol Mol), dimethyl carbonate 172.18 g (1.91 mol) and lithium hydroxide 0.0013 g (0.054 mmol) (total hydroxyl group number of trimethylolpropane / total hydroxyl group number of 1,6-hexanediol) The reaction was carried out at 100 to 200 ° C. for 7 hours while distilling off the low boiling point components under normal pressure, while the number = 0.45 * 3 / 1.07 * 2 = 0.63).
The pressure was further lowered to 13.3 kPa over 10 hours, and then cooled to room temperature to obtain a highly branched polycarbonate polyol composition (1) as a viscous liquid.
The physical property values of the obtained highly branched polycarbonate polyol composition (1) were as follows.
Hydroxyl number: 197 mg KOH / g
Acid value: 0.30 mg KOH / g
Viscosity (80 ° C): 460 cP
APHA: 75
Number average molecular weight (Mn): 710
Branching factor g ': 0.7648
Properties at room temperature: liquid

Example 2 (Synthesis of Hyperbranched Polycarbonate Polyol Composition (2))
In a 500 mL four-necked glass reactor equipped with a distillation column, a stirrer, a thermometer and a nitrogen inlet tube, 60.00 g (0.45 mol) of trimethylolpropane, 218.62 g (1,85 g of 1,6-hexanediol) Mol), dimethyl carbonate 266.89 g (2.96 mol) and lithium hydroxide 0.0020 g (0.083 mmol) are mixed (total hydroxyl number of trimethylolpropane / total hydroxyl number of 1,6-hexanediol) The reaction was performed at 100 to 200 ° C. for 7 hours while distilling off the low boiling point components under normal pressure, while the number = 0.45 * 3 / 1.85 * 2 = 0.36).
The pressure was further reduced to 13.3 kPa over 10 hours, and then cooled to room temperature to obtain a highly branched polycarbonate polyol composition (2) as a viscous liquid.
The physical property values of the obtained highly branched polycarbonate polyol composition (2) were as follows.
Hydroxyl number: 121 mg KOH / g
Acid value: 0.21 mg KOH / g
Viscosity (80 ° C): 3800 cP
APHA: 65
Number average molecular weight (Mn): 1640
Branching factor g ': 0.7298
Properties at room temperature: liquid

Comparative Example 1
As Comparative Example 1, polycarbonate diol (manufactured by Ube Industries, Ltd., trade name: ETERACOLL (registered trademark) UH-200) manufactured using 1,6-hexanediol and a carbonate as raw materials was used.
The physical property values of Comparative Example 1 were as follows.
Hydroxyl number: 56 mg KOH / g
Acid value: 0.01 mg KOH / g
Viscosity (80 ° C): 2000 cP
APHA: 15
Bifurcation factor g ': 1
Properties at room temperature: waxy

Comparative example 2
In a 500 mL four-necked glass reactor equipped with a distillation column, a stirrer, a thermometer and a nitrogen inlet tube, 33.5 g (0.25 mol) of trimethylolpropane, 177.0 g (1.50 g of 1,6-hexanediol) Mol), dimethyl carbonate (186.57 g (2.07 mol)) and lithium hydroxide 0.0020 g (0.083 mmol) are mixed (total hydroxyl number of trimethylolpropane / total hydroxyl number of 1,6-hexanediol) The reaction was carried out at 100 to 200 ° C. for 7 hours while distilling off the low-boiling components under normal pressure, with the number = 0.25 * 3 / 1.50 * 2 = 0.25.
The pressure was further reduced to 13.3 kPa over 10 hours, and then cooled to room temperature to obtain a polycarbonate polyol.
The physical property values of the obtained polycarbonate polyol were as follows.
Hydroxyl number: 167 mg KOH / g
Acid value: 0.15 mg KOH / g
Viscosity (80 ° C): 440 cP
APHA: 15
Number average molecular weight (Mn): 926
Degree of branching factor g ': 0.8417
Properties at room temperature: waxy

  From the above, while the hyperbranched polycarbonate polyol compositions (1) to (2) are liquid at room temperature, Comparative Examples 1 to 2 are waxy, and the hyperbranched polycarbonate polyol composition of the present invention is handled It turns out that it is an easy composition.

Example 3 (Synthesis of Hyperbranched Polyurethane Resin (A))
In a 500 mL five-necked reactor equipped with a nitrogen inlet, a thermometer, a condenser and a stirrer, 1.50 g of the hyperbranched polycarbonate polyol composition (1), 28.50 g of the polycarbonate diol of Comparative Example 1, 1,4-butane 2.97 g of diol, 0.05 g of dibutyltin dilaurate, and 92 g of dimethylformamide were mixed and stirred at 70 ° C. Next, 11.74 g of isophorone diisocyanate was added and reacted at 80 ° C. for 5 hours while stirring to obtain a hyper-branched polyurethane resin (A).

Example 4 (Synthesis of Hyperbranched Polyurethane Resin (B))
In a 500 mL five-necked reactor equipped with a nitrogen inlet, a thermometer, a condenser and a stirrer, 1.50 g of the hyperbranched polycarbonate polyol composition (2), 28.50 g of the polycarbonate diol of Comparative Example 1, 1,4-butane 2.89 g of diol, 0.05 g of dibutyltin dilaurate, and 92 g of dimethylformamide were mixed and stirred at 70 ° C. Next, 11.78 g of isophorone diisocyanate was added and reacted at 80 ° C. for 5 hours while stirring to obtain a hyper-branched polyurethane resin (B).

Comparative Example 3 (Synthesis of Polyurethane Resin (C))
In a 500 mL five-necked reactor equipped with a nitrogen inlet, a thermometer, a condenser and a stirrer, 30.00 g of the polycarbonate diol of Comparative Example 1, 3.06 g of 1,4-butanediol, 0.05 g of dibutyltin dilaurate, and dimethyl 92 g of formamide were mixed and stirred at 70 ° C. Next, 11.62 g of isophorone diisocyanate was added and reacted at 80 ° C. for 5 hours while stirring to obtain a polyurethane resin (C).

Comparative Example 4 (Synthesis of Polyurethane Resin (D))
In a 500 mL five-necked reactor equipped with a nitrogen inlet, a thermometer, a condenser and a stirrer, 1.50 g of the polycarbonate polyol of Comparative Example 2, 28.50 g of the polycarbonate diol of Comparative Example 1, and 1,4-butanediol. 91 g, dibutyltin dilaurate 0.05 g, and 92 g of dimethylformamide were mixed and stirred at 70 ° C. Next, 11.84 g of isophorone diisocyanate was added, and the mixture was reacted at 80 ° C. for 5 hours with stirring to obtain a polyurethane resin (D).

Production of Polyurethane Resin Film The polyurethane resins (A) to (D) were each coated on a glass substrate. The size of the substrate mold was 20 cm × 10 cm × 3 mm. This was dried at 70 ° C. for 1 hour and at 120 ° C. for 2 hours to form a polyurethane resin film on a glass substrate.
The tensile strength and the elongation at break of the polyurethane resin film were measured. The measurement results are shown in Table 1 below.

  From the results of Table 1, the polyurethane resin films of Example 3 and Example 4 produced from the highly branched polycarbonate polyol compositions (1) and (2) of the present invention of Example 1 and Example 2 were compared with Comparative Example 1 Compared with the polyurethane resin film of Comparative Example 3 manufactured from the polycarbonate diol of the above, it can be seen that it has high tensile strength while maintaining the elongation at break. The polyurethane resin films of Example 3 and Example 4 have the same or higher tensile strength and higher elongation at break, as compared with the polyurethane resin film of Comparative Example 4 produced from the polycarbonate polyol of Comparative Example 2. It was shown that a film having excellent mechanical properties was obtained.

[Durability test]
Durability tests were conducted using films made from the highly branched polycarbonate polyol compositions of the present invention. The weather resistance and hydrolysis resistance were visually observed for distortion after lapse of time under predetermined conditions, and tensile strength and elongation at break were measured and evaluated based on their retention rates. Heat resistance is evaluated by the degree of yellowing.
Weatherability was assessed by exposing the polyurethane samples to a QUV accelerated weathering tester according to ASTM G154. The samples are automatically switched alternately between the following steps: 1) 0.49 W / m ² / nm, 313 nm UV-B at 60 ° C. for 4 hours; and 2) water at 50 ° C. for 4 hours Exposure for a total of 26 hours. The tensile strength and the retention of elongation at break were measured for tensile strength and elongation at break for the samples after the above-mentioned exposure test, and the film before exposure was evaluated by a percentage as 100. Moreover, the presence or absence of distortion was judged by visual observation.
The heat resistance was evaluated by the degree of yellowing when the yellowness index (YI) was measured according to ASTM E313-05 (C). The sample was heated for 240 hours in an oven at 120 ° C., and the heat resistance was evaluated by the amount of change in YI (ΔYI).
The hydrolysis resistance was evaluated by immersing the sample in a 40 ° C. water bath for 72 hours and calculating the retention of tensile strength and elongation at break. Moreover, the presence or absence of distortion was judged by visual observation.
The results are shown in Table 2 below.

  The polyurethane resin film obtained by using the highly branched polycarbonate polyol composition of the present invention had a high retention ratio of tensile strength and elongation at break, and no distortion was visually observed. Further, it was shown that a polyurethane resin film having a small yellowing and generally excellent durability was obtained.

Claims (9)

  A highly branched polycarbonate polyol composition having a structure derived from an aliphatic diol and a structure derived from a polyhydric alcohol, and having a branching factor g 'of 0.55 to 0.82.   The highly branched polycarbonate polyol composition according to claim 1, wherein the number average molecular weight (Mn) is 200 to 10,000.   The highly branched polycarbonate polyol composition according to any one of claims 1 to 2, wherein the hydroxyl value is 50 to 500 mg KOH / g.   The use amount (molar ratio) of the aliphatic diol and the polyhydric alcohol is 0.3 to 4.0 in terms of “the total number of moles of hydroxyl groups of the polyhydric alcohol / the total number of moles of hydroxyl groups of the aliphatic diol”. Hyperbranched polycarbonate polyol composition of any one of -3.   The highly branched polycarbonate polyol composition according to any one of claims 1 to 4, wherein the highly branched polycarbonate polyol composition is obtained by reacting an aliphatic diol, a polyhydric alcohol and a carbonate ester.   The highly branched polycarbonate polyol composition according to any one of claims 1 to 5, which is liquid at room temperature.   The polyurethane composition obtained using the hyperbranched polycarbonate polyol composition of any one of Claims 1-6.   The synthetic leather obtained using the hyperbranched polycarbonate polyol composition of any one of Claims 1-6.   An aqueous polyurethane resin dispersion obtained by using the highly branched polycarbonate polyol composition according to any one of claims 1 to 6.