JP2007224062A - Polyol composition having fine resin particle dispersed therein - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyol composition containing no vinyl monomers that is caused to react with a polyisocyanate to be used as a raw material of a polyurethane resin such as polyurethane foams, polyurethane elastomers or the like. <P>SOLUTION: The polyol composition having fine polyester particles dispersed therein comprises a polyol (A) and fine polyester particles (B), where (B) is dispersed in (A) and the (B)/(A) mass ratio is 5/95-60/40. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin fine particle-dispersed polyol composition. More specifically, the present invention relates to a polyol composition suitable as a raw material for polyurethane resins such as polyurethane foam and polyurethane elastomer by reacting with polyisocyanate.

Polyol compositions used as raw materials for polyurethane resins such as polyurethane foams and polyurethane elastomers by reacting with polyisocyanates are used for the purpose of improving the physical properties of polyurethane foam, such as increasing the compression hardness and improving the durability. In particular, it is obtained by polymerizing an ethylenically unsaturated monomer in the presence of a polymerization initiator, but it is inevitable that the monomer as a starting material remains in the polymer.
For example, the polyol polymerization dispersion itself is not toxic, but the remaining monomer may be toxic, and the burden on the human body and the environment is a problem. For this reason, the range of use of the vinyl polymer polyol is limited, and if the residual amount is large, it cannot be used depending on the working environment at the production site. Even if the monomer is not toxic, there is a need to reduce the residual monomer as much as possible depending on the application field.

Conventionally, as a method of reducing the residual monomer in the polymer polyol, a method of removing it from the system by normal pressure heating, normal temperature reduced pressure, reduced pressure heating or the like can be mentioned. Usually, reduced pressure heating is adopted in terms of removal efficiency. (For example, the Example of patent document 1).
JP-A-8-109205

  However, it is difficult to completely remove the residual monomer even by the above method. Moreover, since a high temperature and high vacuum facility is required, a radical solution is desired.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention comprises a polyol (A), polyester fine particles (B) and a dispersant (C), wherein (B) is dispersed in (A), and (B) / (A) (mass ratio) is The polyol composition (I) is 5/95 to 60/40, and the dispersant (C) is 2 to 20% by mass based on the total of (A) + (B).

  By using the resin fine particle-dispersed polyol of the present invention, it is possible to reduce the burden on the human body and the environment due to unreacted vinyl monomers while having the same physical properties as conventional products.

In the present invention, as the polyol (A), a known polyol that is usually used for producing a polymer polyol can be used. For example, a compound (A1) having a structure in which an alkylene oxide is added to a compound having at least two (preferably 2 to 8) active hydrogens (polyhydric alcohol, polyhydric phenol, amines, polycarboxylic acid, phosphoric acid, etc.). And mixtures thereof.
Among these, a compound having a structure in which an alkylene oxide is added to a polyhydric alcohol is preferable.

  Examples of polyhydric alcohols include dihydric alcohols having 2 to 20 carbon atoms (aliphatic diols such as ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol. And alicyclic diols such as cyclohexane diol and cycloalkylene glycol such as cyclohexane dimethanol, trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols such as glycerin, trimethylol propane and trimethylol) Alkanetriols such as ethane and hexanetriol); 4 to 8 or more polyhydric alcohols having 5 to 20 carbon atoms (aliphatic polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglyceride) Emissions, intramolecular or intermolecular dehydration products of alkane polyols and their or alkane triol, such as dipentaerythritol; and sucrose, glucose, mannose, fructose, sugars and their derivatives such as methyl glucoside) and the like.

  Examples of the polyhydric phenol include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A, bisphenol F, and bisphenol sulfone; condensates (novolacs) of phenol and formaldehyde.

Examples of amines include ammonia; aliphatic amines, alkanolamines having 2 to 20 carbon atoms (for example, monoethanolamine, diethanolamine, isopropanolamine, and aminoethylethanolamine), and alkylamines having 1 to 20 carbon atoms (for example, n -Butylamine and octylamine), alkylenediamines having 2 to 6 carbon atoms (for example, ethylenediamine, propylenediamine and hexamethylenediamine), polyalkylenepolyamines (dialkylenetriamine having 2 to 6 carbon atoms in the alkylene group) to hexaalkyleneheptamine For example, diethylenetriamine and triethylenetetramine).
C6-C20 aromatic mono- or polyamines (for example, aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline, and diphenyletherdiamine); C4-C20 alicyclic Examples include amines (isophoronediamine, cyclohexylenediamine, and dicyclohexylmethanediamine); heterocyclic amines having 4 to 20 carbon atoms (for example, aminoethylpiperazine) and the like.

  Examples of the polycarboxylic acid include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.), and aromatic polycarboxylic acids having 8 to 18 carbon atoms (terephthalic acid, Isophthalic acid and the like), and a mixture of two or more thereof.

  The alkylene oxide added to the active hydrogen-containing compound is preferably one having 2 to 8 carbon atoms, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-. 1,3-, 1,4- or 2,3-butylene oxide (hereinafter abbreviated as BO), styrene oxide (hereinafter abbreviated as SO), etc., and combinations of two or more thereof (block and And / or random addition). Preferably, PO or a combination of PO and EO (EO content is 25% by mass or less).

Specific examples of the polyol include those obtained by adding PO to the active hydrogen-containing compound and those obtained by adding PO and another alkylene oxide (hereinafter abbreviated as AO), preferably EO in the following manner, Alternatively, an esterified product of these addition compounds and polycarboxylic acid or phosphoric acid can be used.
<1> A block added in the order of PO-AO (chiped)
<2> Blocks added in the order of PO-AO-PO-AO (balanced)
<3> Blocks added in the order of AO-PO-AO <4> Blocks added in the order of PO-AO-PO (active secondary)
<5> Random adduct in which PO and AO are mixed and added <6> Random or block addition in the order described in US Pat. No. 4,226,756

As the polyol (A), another polyol (A2) can be used in combination with the compound (A1) having a structure in which an alkylene oxide is added to the active hydrogen-containing compound. In this case, the use ratio (mass ratio) of (A1) / (A2) is preferably 100/0 to 80/20.
Examples of the other polyol (A2) include polymer polyols such as polyester polyols and diene polyols, and mixtures thereof.

  Examples of the polyester polyol include the above-mentioned polyhydric alcohol and / or polyether polyol [ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. Polyhydric alcohols or mixtures thereof with trihydric or higher polyhydric alcohols such as glycerin and trimethylolpropane, and alkylene oxide low-molar (1 to 10 mol) adducts of these polyhydric alcohols], and the polycarboxylic acid Alternatively, condensation with an anhydride or an ester-forming derivative such as a lower alkyl (carbon number of alkyl group: 1 to 4) ester (for example, adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.) Reactants, or A condensation reaction product of a hydric alcohol and / or a polyether polyol with the carboxylic acid anhydride and alkylene oxide; an addition reaction product of these condensation reaction products with an alkylene (EO, PO, etc.); a polylactone polyol such as Examples thereof include those obtained by ring-opening polymerization of a lactone (e.g., ε-caprolactone) using a monohydric alcohol as an initiator; polycarbonate polyols, for example, a reaction product of the polyhydric alcohol and an alkylene carbonate;

Furthermore, diene polyols such as polybutadiene polyol and hydrogenated products thereof; hydroxyl group-containing vinyl polymers such as acrylic polyols; natural oil polyols such as castor oil; modified products of natural oil polyols, and the like.
These polyols (A2) usually have 2 to 8, preferably 3 to 8, hydroxyl groups and usually have a hydroxyl equivalent of 200 to 4,000, preferably 400 to 3,000.

  The weight average molecular weight of the polyol (A) [by gel permeation chromatography (GPC)] is usually 500 or more, preferably 500 to 20,000, particularly preferably 1,200 to 15,000, most preferably 2,000. ~ 9,000. A weight average molecular weight of 500 or more is preferable from the viewpoint of foamability of the polyurethane foam, and a weight average molecular weight of 20,000 or less is low from the viewpoint of handling properties of the resin fine particle dispersion. The hydroxyl equivalent of (A) is preferably 200 to 4,000, more preferably 400 to 3,000.

Examples of the polyester resin fine particles (B) dispersed in the polyol (A) include fine particles obtained by pulverizing a polyester resin.
As the polyester resin, a dihydric carboxylic acid, acid halide or acid anhydride and a dihydric alcohol are directly polycondensed, and polycondensed by transesterification of a dihydric alcohol with a lower alcohol ester of a divalent carboxylic acid. And those obtained by ring-opening polymerization of lactones.

  Examples of the divalent carboxylic acid include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.), and aromatic polycarboxylic acids having 8 to 18 carbon atoms (terephthalic acid). Acid, isophthalic acid and the like), and a mixture of two or more thereof. Examples of the acid halide include these acid chlorides. Examples of the acid anhydride of the divalent carboxylic acid include maleic anhydride and phthalic anhydride. Examples of the lower alcohol ester of a divalent carboxylic acid include dimethyl terephthalate.

  Examples of the divalent alcohol include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol; cyclohexanediol, cyclohexanedimethanol, etc. Alicyclic diols such as cycloalkylene glycol, and low-molar (1 to 10 mol) adducts of these alkylene oxides (EO, PO, etc.).

  These divalent carboxylic acids, acid halides or acid anhydrides and divalent alcohols are directly polycondensed by a known method under normal pressure or reduced pressure while dehydrating as necessary to obtain a polyester resin. Further, the polyester resin is obtained by polycondensation by transesterification of a dihydric alcohol with a lower alcohol ester of a divalent carboxylic acid.

  Further, the lactone or the monomer (b1) represented by the general formula (1) is used alone or in combination, and polymerized with a ring-opening polymerization catalyst in the presence of an initiator (b2) having an active hydrogen as necessary to obtain a polyester resin. .

R _{1 to} R _{4 in} the general formula (1) are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, n-heptyl. 1-ethylpropyl, isoamyl, n-hexyl and the like.

  Examples of the lactone include ε-caprolactone, 4-methylcaprolactone, 3,5,5-trimethylcaprolactone, various methylated caprolactones such as 3,3,5-trimethylcaprolactone, β-propiolactone, γ-butyrolactone, and δ-valero. Lactones, enanthlactones, and their alkyl and alkoxy derivatives.

  As the ring-opening polymerization initiator (b2), known polyols used for the production of the polymer polyols described above can be used.

  The ring-opening polymerization catalyst is not particularly limited, but is generally known as a ring-opening polymerization catalyst for cyclic esters, such as tin, zinc, lead, titanium, bismuth, zirconium, germanium, antimony, Examples thereof include metals such as aluminum and derivatives thereof. Derivatives are preferably metal alkoxides, carboxylates, carbonates, oxides and halides. Specific examples include tin chloride, tin octylate, zinc chloride, zinc acetate, lead oxide, lead carbonate, titanium chloride, alkoxytitanium, germanium oxide, and zirconium oxide. Among these, a tin compound, particularly tin octylate, is particularly preferable in order to obtain a high molecular weight.

  The weight average molecular weight (by GPC) of the polyester fine particles (B) is usually from 5,000 to 200,000, preferably from 8,000 to 180,000, particularly preferably from 10,000 to 150,000. When polyester fine particles having a weight average molecular weight of less than 5,000 are dispersed, the viscosity becomes high, which causes problems in both handling properties and foam physical properties during foam molding. Further, if the weight average molecular weight exceeds 200,000, there is a problem in terms of dispersion stability.

  As the content of the polyester fine particles (B), the weight ratio (B) / (A) of the polymer (A) to the polyester fine particles (B) is usually 5/95 to 60/40, preferably 10/90 to 55/45. More preferably, it is 15/85 to 50/50. If it is less than 5/95, there is a problem in terms of foam physical properties, and if it exceeds 60/40, there is a problem in terms of dispersion stability.

In order to maintain a stable dispersion state, the polyester fine particle-dispersed polyol composition of the present invention preferably contains a dispersant (C). The amount of (C) is not particularly limited, but is usually 2 to 20% by mass, preferably 3 to 18% by mass, and more preferably 4 to 15% by mass based on the total of (A) + (B).
Further, the composition of the dispersant (C) to be used is not particularly limited as long as the high-concentration polyester fine particles (B) maintain a stable dispersion state in the polyester fine particle-dispersed polyol composition. .

In the polyol composition, the dispersant (C) capable of stably dispersing the polyester fine particles (B) has a solubility parameter (SP value) of 8.0 to 12.0 (cal / cm ³ ) ^{1 /} There are ^two . The lower limit is preferably 9.0, and more preferably 9.5. The upper limit is preferably 11.0, more preferably 10.5. When the SP of (C) is outside the range of 8.0 to 12.0, the fine particles are difficult to disperse and tend to aggregate.

  The SP value is expressed by the square root of the ratio between the cohesive energy density and the molecular volume shown in the following calculation formula (1).

SP value (cal / cm ³ ) ^1/2 = (ΔE / V) ^1/2 (1)

Here, ΔE represents the cohesive energy density.
V represents the molecular volume, and its value is Robert F. Based on calculations by Robert F. Fedors et al., For example, described in Polymer Engineering and Science, Vol. 14, pages 147-154.

  In the present invention, the arithmetic average particle diameter of the polyester fine particles (B) dispersed in the dispersed polyol composition (I) is usually 0.05 to 100 (μm), preferably 0.07 to 20 (μm), More preferably, it is 0.1-10 (micrometer). If it is 50 μm or more, there is a problem in terms of foam physical properties, and if it is 0.05 (μm) or less, there is a problem in both handling properties and foam physical properties when forming a foam because it tends to increase in viscosity.

The arithmetic average particle diameter can be measured with a particle size distribution measuring device (for example, LA-750, He-Ne laser manufactured by Horiba, measurement range: 0.04 μm to 262 μm). In order to measure accurately at that time, it is necessary to further dilute the dispersed polyol composition of the sample with the polyol (A) of the medium so that the transmittance of the laser beam is 70 to 90%.
It is calculated by the following calculation formula (2).

Arithmetic mean particle diameter (μm) = Σ [q (J) × X (J)] / Σ [q (J)] (2)
J: Particle size division number (1 to 85)
q (J): Frequency distribution value (%)
X (J): Particle size division number J-th particle size (μm)

The viscosity at 25 ° C. of the dispersed polyol composition (I) of the present invention is usually 500 to 7,000, preferably 550 to 6,500, and more preferably 600 to 6,500.
If it is less than 500 (mPa · s) or exceeds 7,000 (mPa · s), there is a problem in terms of handleability during foam formation.

  As a method for dispersing the polyester resin in the polyol, there is a method in which the solid polyester resin is pulverized to about 1 to 3 mm, and then the polyol and the pulverized polyester resin are put into a dispersing apparatus and dispersed. Alternatively, the polyol and the molten polyester resin may be separately introduced into the dispersing device, and both may be dispersed in the dispersing device.

  The dispersing apparatus is not particularly limited, and for example, a homomixer, a homogenizer, high-speed rotating system stirring, an ultrasonic disperser, a high-pressure emulsifying disperser, a high-pressure collision disperser, and the like can be used.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. In the following, parts,%, and ratio refer to parts by mass, mass%, and mass ratio, respectively.

<Production Example 1>
In a water-cooled jacket type pressure resistant reactor, 95 parts of glycerin and 3,000 parts of propylene oxide were reacted in the presence of 3 parts of potassium hydroxide catalyst to obtain a polyol (a) having a weight average molecular weight of 3,000.

<Production Example 2>
In a water-cooled jacketed pressure-resistant reaction vessel, 25 parts of glycerin and 5,500 parts of lactide are reacted at a reaction temperature of 150 to 160 ° C. in the presence of 6 parts of tin octylate catalyst to obtain a polyester resin (b )

<Production Example 3>
A four-necked flask equipped with a temperature controller, a vacuum stirring blade, and a dropping funnel is charged with 28 parts of tolylene diisocyanate (TDI) and 0.01 part of tetrabutyl titanate, cooled to 30 ° C., and then 2-hydroxy 9 parts of ethyl methacrylate was added dropwise. Meanwhile, the reaction temperature was kept at 40-50 ° C. The reaction solution was placed in 2,963 parts of polyol (a) previously placed in a four-necked flask equipped with a temperature controller, a stirring blade, and a dropping funnel, and reacted at a reaction temperature of 80 to 90 ° C. After confirming that no unreacted isocyanate group was present in the infrared absorption spectrum, a reactive dispersant (d) was obtained.

<Example 1>
In a water-cooled jacket-type container, 55 parts of polyol (a) and 40 parts of polyester (b) are charged, using a homomixer in a nitrogen atmosphere, at a dispersion temperature of 30 ° C., a rotational speed of 12000 rpm, and a stirring time of 30 minutes. Dispersion was performed to obtain a resin fine particle-dispersed polyol (F-1) of the present invention.

<Example 2>
Dispersion was carried out under the same conditions as in Example 1 except that the stirring time in Example 1 was changed to 60 minutes to obtain a resin fine particle-dispersed polyol (F-2) of the present invention.

<Comparative Example 1>
A four-necked flask equipped with a temperature controller, a vacuum stirring blade, a dropping pump, a pressure reducing device, a Dimroth condenser, a nitrogen inlet and an outlet, 30 parts of polyol (a) prepared in Production Example 1, 7 parts of xylene and reaction 1 part of the ionic dispersant (d) was added, and after replacing with nitrogen, the temperature was raised to 130 ° C. with stirring in a nitrogen atmosphere (until the end of the polymerization). Next, 4 parts of allyl alcohol propylene oxide adduct 4 parts, 15 parts of acrylonitrile, 34 parts of styrene, 13 parts of polyol (a), and raw material previously mixed with 8 parts of polyol (a) and 2,2 ′ -The raw material which mixed 1 part of azobisisobutyronitrile was dripped continuously using the dripping pump simultaneously, respectively, and was superposed | polymerized at 130 degreeC. Further, the unreacted monomer and xylene were stripped under reduced pressure at 20 to 30 torr for 5 hours to obtain a polyol composition (F-3) for comparison.

<Comparative Example 2>
A polyol composition (F-4) for comparison in the same manner as in Comparative Example 1 except that the monomer used was changed to 4 parts of an allyl alcohol propylene oxide 2.2 mol adduct, 34 parts of acrylonitrile, and 15 parts of styrene. Got.

  Table 1 shows the analysis results of the polyol compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2.

Evaluation methods in the examples are as follows.
<Polymer concentration>
The resin fine particle dispersed polyol is diluted with methanol so that the resin fine particle dispersed polyol / methanol = 1/3 (ratio). The resin fine particles are separated by a cooling centrifuge (18000 rpm × 60 min. 20 ° C.), and the supernatant is removed. After repeating this three times, the resin fine particles are dried under reduced pressure (60 ° C. × 1 hr), the mass is measured, and the ratio to the polyol is determined.

<Viscosity>
BL type rotational viscometer (manufactured by TOKIMEC)
Measurement temperature: 25 ° C
Rotor No .: No3 or No4
Rotation speed: 12rpm

<Dispersion stability>
100 ml of a polymer polyol placed in a 140 ml glass sealed container is left in a constant temperature bath at 50 ° C. for 2 days. After standing, the dispersion stability was confirmed visually.
○ There was no sediment and it was in a uniformly dispersed state.
Δ: There was a sediment, and the sample bottle was tilted 5 times and then uniformly redispersed.
X Precipitate was present and the sample bottle was not redispersed after being turned down 5 times.

<Measurement of acrylonitrile and styrene content>
The measurement was performed by gas chromatography using a polyethylene glycol column filler.

  The polyester resin-dispersed polyol composition of the present invention remains in the conventional polymer polyol while having the same dispersion stability, polymer content, viscosity, and arithmetic average particle diameter as compared with the conventional vinyl polymer polyol. It was possible to obtain a polyol composition having a small burden on the human body and the environment, which does not have the vinyl monomer.

The polyester resin-dispersed polyol composition of the present invention is a polyol composition that is excellent in dispersibility without agglomeration / sedimentation in the polyester fine particles in the polyol, and does not contain a residual vinyl monomer, which was unavoidable in the production of conventional vinyl polymer polyols. Can be manufactured. Moreover, when manufacturing polyurethane resins, such as a urethane foam, using the polyester resin dispersion | distribution polyol of this invention, the highly safe polyol composition which does not have a residual vinyl-type monomer can be provided.
Furthermore, it is also possible to provide a polyol composition having a high plant degree, which is an evaluation scale for reducing the environmental load, by using the raw material of the polyester resin of the dispersion as a source of biomass.

Claims (8)

Polyester fine particle dispersion comprising a polyol (A) and polyester fine particles (B), wherein (B) is dispersed in (A) and (B) / (A) (mass ratio) is 5/95 to 60/40 Polyol composition (I). The polyester fine particle-dispersed polyol composition (I) according to claim 1, further comprising 2 to 20% by mass of the dispersant (C) based on the total of (A) + (B). The polyester fine particle-dispersed polyol composition (I) according to claim 1 or 2, wherein (B) is a resin fine particle obtained by polymerizing a lactone or a monomer (b1) represented by the general formula (1) in a ring-opening polymerization catalyst.
The polyol composition according to any one of claims 1 to 3, wherein the arithmetic average particle diameter of (B) in the dispersed polyol composition is 0.05 to 100 µm. The weight average molecular weight of (B) is 5,000-200,000, The polyester fine particle dispersion | distribution polyol composition in any one of Claims 1-4. The polyester fine particle-dispersed polyol composition (I) according to any one of claims 1 to 5, having a viscosity at 25 ° C of 500 to 7,000 mPa · s. The polyester fine particle-dispersed polyol composition (I) according to any one of claims 2 to 6, wherein the solubility parameter (SP value) of (C) is in the range of 8.0 to 12.0 (cal / cm3) 1/2. The polyester fine particle-dispersed polyol composition (I) according to any one of 1 to 7, wherein the weight average molecular weight of (A) is 500 to 20,000.