JP2006206794A - Manufacturing method of polyurethane foam and polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a polyurethane foam having a narrow cell size distribution width and fine cells, and the polyurethane foam. <P>SOLUTION: The manufacturing method of the polyurethane foam comprises a step for feeding a first raw material composition comprised of a polyol, gas-loaded with a gas that has lower solubility in a polypropylene glycol of a molecular weight of 2,000 than a nitrogen gas at a ratio of 1-20 vol% based on the first raw material composition and a second raw material composition comprised of a polyisocyanate into a mixer, and a step for injecting the mixed raw material compositions into a mold from the mixer. The polyurethane foam has closed cells, where the standard deviation of the cell size distribution is at most 8 μm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a production method for producing a polyurethane foam using a gas-loaded raw material composition and a polyurethane foam.

  Conventionally, polyurethane foam is manufactured by various methods. For example, (1) a foaming process with an easily vaporizable substance (liquid at room temperature) that is added to a raw material in advance, vaporizes the liquid by heating or heat generation during the polymerization reaction, and foams in the curing process of the polyurethane; (2) Foaming process (gas loading foaming) by dissolving and precipitating gas, which is foamed in the polyurethane curing process by mixing gas with the raw material in advance by pressurization and stirring, etc. (3) Gas (bubbles) in the polyurethane curing process Foaming by foaming by mixing and stirring to foam, (4) Chemical foaming process by foaming with carbon dioxide gas (CO2) generated by the reaction of water and isocyanate added to polyol in the curing process of polyurethane , Etc. are known.

Carbon dioxide gas, nitrogen gas, and dry air (atmospheric pressure dew point temperature of −50 to −30 ° C.) are used as the loading gas in the gas loading foaming of (2) (Patent Document 1). However, when nitrogen gas is previously loaded into the raw material composition, there is a problem that the bubble size distribution is wide.
Japanese Patent Laid-Open No. 11-293027

  Accordingly, an object of the present invention is to provide a method for producing a polyurethane foam having a narrow cell diameter distribution and having fine cells, and a polyurethane foam.

(1) A first raw material composition obtained by gas-loading a gas having a solubility in polypropylene glycol having a molecular weight of 2000 lower than that of nitrogen gas at a rate of 1 to 20% by volume with respect to a raw material composition comprising a polyol, and a polyisocyanate. A process for producing a polyurethane foam, comprising: a step of supplying a second raw material composition to a mixer; and a step of injecting the mixed raw material composition into a mold from the mixer.
(2) A polyurethane foam having closed cells, wherein the polyurethane foam has a standard deviation of the cell diameter distribution of 8 μm or less.

  According to the method for producing a polyurethane foam of the present invention, it is possible to produce a foam having a narrow cell diameter distribution width and having fine cells. Moreover, this polyurethane foam can be used for an application as a polishing member.

  The gas loading in the present invention refers to a process of forcibly embracing (loading) gas from the outside to the first raw material composition made of polyol. The gas loading method is not particularly limited, but a method in which gas is directly blown into the raw material composition (bubbling), a raw material composition is injected into a container such as a tank, and then pressurized with gas from the top of the tank (gas back pressure is applied) ) A method of dissolving a gas from the surface of the raw material composition, a method of applying a gas back pressure and stirring the raw material composition to dissolve the gas, and the like. Among these, since the gas can be dissolved in a short time, a method of applying a gas back pressure and stirring the raw material composition is preferably used.

The gas loading amount in the present invention is the percentage v / V × 100 of the gas volume v released from the raw material composition with respect to the raw material composition volume V when the gas loaded raw material composition is left at 0.098 MPa (atmospheric pressure). Say the value. If the volume V ₀ of the raw material composition loaded with gas is 0.098 MPa and the total volume of the raw material composition and the gas is V ₁ , then if the vapor pressure of the raw material composition is negligibly small, v = Since V ₁ −V ₀ , the gas loading amount L is obtained by L = v / V × 100 = (V ₁ −V ₀ ) / V ₀ × 100. In the case of pressurized gas loading, the gas volume v released from the raw material composition when the pressure p changes to p ′ is expressed as v = vp−vp ′, where vp is the amount of gas dissolved at the pressure p. Therefore, the gas loading amount L (%) can be expressed as L = v / V × 100 = (vp−vp ′) / V × 100. Here, p ′ = 0.098 MPa.

As a method for measuring the gas loading amount, the gas loaded raw material composition is sampled in a volume V ₀ , and then the pressure is kept at 0.098 MPa and the volume V ₁ at that time is measured. Since the difference v in the amount of dissolved gas accompanying the change in pressure is v = V ₁ −V ₀ , the gas loading amount L (%) can be calculated from L = (V ₁ −V ₀ ) / V ₀ × 100. . As a gas loading amount with respect to a 1st raw material composition, 1-20 volume% is required. When the gas loading amount is less than 1% by volume, foaming due to gas loading is insufficient and a foam containing a specific amount of desired fine bubbles cannot be obtained. On the other hand, when the gas loading amount exceeds 20% by volume, the gas cannot be dissolved in the raw material composition, and some of the gas is present as bubbles with a diameter on the order of mm, so that it is mixed with fine bubbles in the foam. A foam having extremely large bubbles is formed.

In the present invention, the gas solubility means the gas loading amount L at 40 ° C. at p = 0.392 MPa (4.0 kg / cm ² ).
L (%) = (vp−vp ′) / V × 100
Say. Here, p = 0.392 MPa, and p ′ = 0.098 MPa. The solubility of the gas in the raw material composition is defined by the difference in the saturated dissolution amount between 0.098 MPa and 0.392 MPa with respect to the dissolution amount of the gas in the raw material composition at 40 ° C. The high gas solubility means that the value of the gas loading amount L (%) obtained from the difference in the gas dissolution amount at each pressure is large.

The gas solubility is measured by selecting polypropylene glycol (molecular weight 2000) as the polyol. Specifically, PP-2000 (manufactured by Sanyo Chemical Co., Ltd.) or Uniol D-2000 (manufactured by NOF Corporation) can be mentioned. Polypropylene glycol (molecular weight 2000) is temperature-controlled at 40 ° C., a gas back pressure of 0.392 MPa is applied, the raw material composition is stirred, and a saturated amount of gas is loaded. After gas loading, make sure that there is no foam bite in the raw material storage tank and that it is completely dissolved. A volume V _{0 of} gas loaded polypropylene glycol is taken at 0.392 MPa, and then the volume V ₁ is measured while maintaining the pressure at 0.098 MPa. Since the difference v in the gas dissolution amount accompanying the pressure change is v = V ₁ −V ₀ , the gas loading amount L (%), which is a value indicating the gas solubility, is L = (V ₁ −V ₀ ) / V _0. It can be calculated from

  The gas loaded into the first raw material composition is collided with the second raw material composition in a mixer and injected into a mold. From the moment of mixing, the curing reaction with the polyol and polyisocyanate proceeds. Moreover, at the time of injection | pouring, many fine bubbles are expressed by changing from a pressurization state to an atmospheric pressure state at a stretch, and a bubble is fixed and a foam | form is formed with hardening of a polyurethane. In the present invention, the gas solubility was defined by focusing on the difference in the amount of gas dissolved between 0.392 MPa and 0.098 MPa at 40 ° C. However, even if the pressure applied is changed, the gas solubility is 0.098 to 1.0 MPa. If it is within the range, the order of the difference in the amount of gas dissolved by the gas species (that is, the amount of gas contributing to the generation of bubbles in the polyurethane foam) does not change. The gas loading pressure for the raw material composition needs to be 0.098 to 1.0 MPa, and more preferably 0.5 to 1.0 MPa. If the pressure exceeds 1.0 MPa, the pressurization equipment necessary for maintaining the dissolved state becomes excessive, so that it is not suitable for actual use.

  The amount of gas dissolved in polypropylene glycol (molecular weight 2000) is usually in the order of helium, neon, nitrogen, oxygen, and argon. The loading gas in the present invention is not particularly limited as long as the amount of gas dissolved in the raw material composition is smaller than that of nitrogen, but inert gases such as helium and neon are preferably used. The second raw material composition may be gas loaded in the same manner as the first raw material composition.

  The mixer of this invention says the apparatus which mixes at least a 1st raw material composition and a 2nd raw material composition, and starts a urethanation reaction. It is necessary that the raw material composition can be sufficiently and uniformly stirred in the mixer, and the inflow and outflow amounts of the raw material composition must be accurately controlled. Examples of the stirring method include a method using a stirring blade, a method in which a raw material composition is ejected from an opposed nozzle and collides, a method in which a substance (gas) having stirring energy is mixed, and the like. A self-cleaning mixer is preferred so that the resinized polyurethane does not become a foreign substance and remains in the mixer.

  The mold of the present invention refers to an apparatus for injecting and curing a raw material composition to define part or all of the shape of a polyurethane foam. The material of the mold is preferably a metal, but a part thereof may be a resin or may be coated with a resin. In the production of the polyurethane foam of the present invention, a first raw material storage tank for storing a first raw material composition capable of gas loading, a pump for feeding the raw material from the first storage tank to the mixer, and a second raw material composition A second raw material storage tank for storing the raw material, a pump for feeding the raw material composition from the second raw material storage tank to the mixer, a mixer, and a mold are required. Moreover, it is preferable that the temperature of the storage tank and the mold can be controlled in the range of room temperature to 150 ° C. Although there is no limitation in particular about the pump which supplies a raw material to a mixer, It is preferable that a raw material composition can be sent out to a mixer at the high pressure of 10 Mpa or more.

  The bubble diameter of the polyurethane foam of the present invention can be observed with a laser microscope or a scanning electron microscope, and the image can be processed to determine the bubble diameter, the number of bubbles, and the bubble diameter distribution for all the bubbles in the image. From this data, the average bubble diameter, its standard deviation, and the number of bubbles per unit area were calculated. The standard deviation of the bubble diameter needs to be 8 μm or less. The shape of the bubbles is not necessarily a perfect circle, but the major axis and minor axis were measured, and the average value was used as the bubble diameter for image processing. The sample was obtained by observing the surface obtained by slicing the central portion in the thickness direction of the foam.

  In the present invention, the reason why the width of the bubble diameter distribution is narrow by using a specific loading gas with controlled solubility in the raw material composition is not necessarily clear, but since the amount of dissolution is originally small, the bubbles accompanying the pressure change This is presumed to be due to the uniform timing of nucleation.

The following can be mentioned as a particularly preferable embodiment. The average density of the polyurethane foam is 0.5 to 1.0 g / cm ³ , the C-type hardness of the polyurethane foam is 50 to 90 degrees, the average cell diameter of the polyurethane foam is 10 to 50 μm, polyurethane It is preferred that the foam be used as a polishing member or a raw material for the polishing member. The density can be measured according to the method of Japanese Industrial Standard JIS K 7112. The C-type hardness can be measured by “Asker C-type altimeter (manufactured by Kobunshi Keiki Co., Ltd.)”.

  In the present invention, the polyol means a compound having two or more hydroxyl groups. Examples thereof include one or a mixture of two or more selected from polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, ethylene glycol, propylene glycol, glycerin and the like.

  In the present invention, the first raw material composition includes a crosslinking agent, a chain extender, a foam stabilizer, a foaming agent, a resinification catalyst, a foaming catalyst, an antioxidant, and an anti-aging agent in addition to the main component polyol. , Fillers, plasticizers, colorants, antifungal agents, antibacterial agents, flame retardants, and ultraviolet absorbers.

  In the first raw material composition, the polyol is contained at least 50% by weight, preferably 70% by weight or more. In addition, a compound having an active hydrogen such as a carboxyl group or an amino group instead of a hydroxyl group can be used in combination with the polyol.

  As the crosslinking agent, ethylene glycol, propylene glycol, butanediol, glycerin, trimethylolpropane, pentaerythritol, polyhydric alcohols such as sorbitol, amines such as hexamethylenediamine, hydrazine, diethyltoluenediamine, diethylenetriamine, monoethanolamine, Examples thereof include amino alcohols such as diethanolamine and triethanolamine.

  Examples of the catalyst include triethylamine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane-1,3-diamine, N, N, N ', N'-tetramethylhexane-1,6-diamine, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, N ', N ", N" -pentamethyl Dipropylenetriamine, tetramethylguanidine, triethylenediamine, N, N′-dimethylpiperazine, N-methyl-N ′-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N ′, N′-dimethylamino Ethylmorpholine, 1,2-dimethylimidazole, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N ′ Trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxyethyl) -piperazine, N- (2-hydroxyethyl) morpholine, bis (2-dimethylaminoethyl) ether, ethylene glycol bis (3-dimethyl) Amine compounds such as aminopropyl ether, tin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin marker butylide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin marker butylate, dioctyltin thiocarboxylate, acetylacetone metal salt, etc. Metal complexes, 2,4,6-tris (dimethylaminomethyl) phenol, 1,3,5-tris (dimethylaminopropyl) hexahydro-s-triazine, triazines, 2,4-bis (di Such as aziridines such as (tilaminomethyl) phenol, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium acetate, sodium acetate, 2-ethylaziridine, and tertiary amine carboxylates. Examples include quaternary ammonium compounds, diazabicycloundecene, lead compounds such as lead naphthenate and lead octylate, alcoholate compounds such as sodium methoxide, phenolate compounds such as potassium phenoxide, and the like. These catalysts can be used alone or in combination of two or more.

  As the foam stabilizer, compounds usually used in the production of foams can be used. For example, foam stabilizers such as dimethylsiloxane, polyether dimethylsiloxane, and phenylmethylsiloxane can be used.

  Examples of the blowing agent include water, halogenated hydrocarbons such as HCFC-141b, HFC-116a, HFC-305fa, and HFC-365mfc, hydrocarbons such as cyclopentane, isopentane, and normal pentane, nonafluorobutyl methyl ether, and nonafluoro Hydol fluorocarbons such as isobutyl methyl ether, nonafluorobutyl ethyl ether, nonafluoroisobutyl ether, pentafluoroethyl methyl ether and heptafluoroisopropyl methyl ether can be mentioned. Of these foaming agents, water is preferably used from the viewpoint of versatility.

  As the isocyanate in the present invention, aromatic diisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, and naphthalene diisocyanate, aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate, isophorone diisocyanate, hydrogen Examples thereof include alicyclic diisocyanates such as added TDI and hydrogenated MDI. One or a mixture of two or more selected from these polyisocyanates can be used.

  The second raw material composition in the present invention contains, in addition to the above polyisocyanate, a prepolymer having some residual isocyanate groups or no isocyanate groups by previously mixing and reacting these polyisocyanates with polyols. May be. Secondly, in the raw material composition, the compound having an isocyanate group is the main component and contains at least 50% by weight or more.

  Polymeric MDI can be obtained by phosgenating polyphenylmethane polyamine obtained by the condensation reaction of aniline and formalin. Therefore, the composition of the polymeric MDI is basically determined by the raw material composition and reaction conditions during the condensation, and is composed of a binuclear body having two benzene rings and a polynuclear body having three or more benzene rings. There are three types of isomers in the polymeric MDI, 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI. The isomer composition ratio of the binuclear compound is not particularly limited, but the content of 4,4'-MDI is preferably 50% by weight or more.

  The polyurethane foam of the present invention is produced by a high-pressure injection machine in which raw materials collide with each other in the mixing head and a so-called low-pressure injection machine in which each raw material supplied to the mixing head is mechanically mixed by a stirring blade or the like. It can be used for molding, slab molding and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, these do not limit this invention. The evaluation method was performed as follows.
[Average bubble diameter] The surface or sliced surface of the polishing pad was observed at a magnification of 200 times with a scanning electron microscope “SEM2400” (Hitachi, Ltd.), and the image was analyzed with an image processing device. The bubble diameter was measured, and the average value was taken as the average bubble diameter.

(Comparative Example 1)
Polypropylene glycol having a molecular weight of 2000 was charged into the first raw material storage tank of the RIM molding machine. A high-purity nitrogen (purity 99.9%) cylinder was connected to the first raw material storage tank, and nitrogen gas loading was performed by applying a back pressure of 0.392 MPa while rotating the stirring blade in the tank. The operation of nitrogen gas loading and releasing to normal pressure was repeated three times to replace the raw material composition with nitrogen gas and to load nitrogen gas. Then, about the 1st raw material storage tank, after back loading 0.392MPa and carrying out gas loading of the saturated amount of nitrogen gas, when the gas solubility was investigated, it was 9.5%.

  Next, the following raw material compositions were weighed and mixed into the first raw material storage tank and the second raw material storage tank of the RIM molding machine, respectively. High purity nitrogen (purity 99.9%) cylinders were connected to the first and second raw material storage tanks, and nitrogen gas loading was performed by applying a back pressure of 0.392 MPa while rotating the stirring blades in the tank. The operation of nitrogen gas loading and releasing to normal pressure was repeated three times to replace the raw material composition with nitrogen gas and to load nitrogen gas.

Next, nitrogen gas was loaded with a back pressure (0.49 MPa) so that a gas loading amount of 6.9% was obtained with a stirring blade.
<First raw material storage tank>
Glycerin tetrahydrofuran adduct 90 parts by weight 1,4-butanediol 10 parts by weight Triethylenediamine 1.5 parts by weight Tin octoate 0.5 part by weight Dimethylpolysiloxane / poly (ethylene oxide / propylene oxide) copolymer 3 parts by weight purification 0.2 parts by weight of water <second raw material storage tank>
Diphenylmethane diisocyanate (MDI)
50 parts by weight Polymeric MD 30 parts by weight Raw material storage tank temperature (40 ° C.), discharge pressure (15 MPa), discharge speed (500 g / sec), mold temperature (70 ° C.) are set and molding is performed with a gap of 1.5 mm A polyurethane foam having a thickness of 15 mm and a length of 700 mm was obtained using a mold having a film gate. The obtained foam with a thickness of 15 mm, excluding the front and back sides of 0.5 mm, was sliced into 7 pieces with a thickness of 14 mm, and the bubble diameter was measured using the sheet 4 at the center in the thickness direction. The diameter distribution was determined. The evaluation results are summarized in Table 1. The bubble diameter distribution is shown in FIG.

Example 1
Except that the loading gas was changed from nitrogen gas to helium gas, a gas was loaded with a saturated amount of helium gas in the same manner as in Comparative Example 1, and the gas solubility was examined. As a result, the gas loading amount was 6.9%. The bubbles did not disappear from the raw material storage tank. From this, it was found that the solubility could not be quantified by this method, and the solubility of helium gas was very low as compared with the solubility of 9.5% in the nitrogen gas of Comparative Example 1. Next, a polyurethane foam was prepared and the bubble diameter distribution was measured in the same manner as in Comparative Example 1 except that the loading gas was changed from nitrogen gas to helium gas. The evaluation results are summarized in Table 2. The bubble diameter distribution is shown in FIG.

(Example 2)
Various characteristics of the sheet 4 (thickness center) of the molded product obtained in Example 2 were measured. The density was 0.838 g / cm ³ , the C-type hardness was 82 degrees, and the average bubble diameter was 34 μm.

This foamed polyurethane sheet was immersed in methyl methacrylate to which 0.15 parts by weight of azobisisobutyronitrile was added for 15 hours, and then the swollen foamed polyurethane sheet was sandwiched between glass plates and held at 70 ° C. for 24 hours. After removing the glass plate, vacuum drying was performed. Both surfaces of the obtained rigid foamed sheet were ground to produce a polishing pad having a thickness of 1.25 mm. When polishing was performed using silica-based slurry, the polishing rate of the SiO ₂ film was 2100 Å / min.

  As described above, according to the method for producing a polyurethane foam of the present invention, a polyurethane foam having a narrow cell diameter distribution and having fine cells can be obtained. Moreover, this polyurethane foam can be used for an application as a polishing member.

Bubble size distribution of Comparative Example 1 Bubble diameter distribution of Example 1

Claims (10)

  A first raw material composition in which a gas having a solubility in polypropylene glycol having a molecular weight of 2000 is lower than nitrogen gas at a rate of 1 to 20% by volume with respect to the raw material composition made of polyol, and a second raw material made of polyisocyanate A method for producing a polyurethane foam, comprising: a step of supplying a raw material composition to a mixer; and a step of injecting the mixed raw material composition into the mold from the mixer.   2. The method for producing a polyurethane foam according to claim 1, wherein a gas having a lower solubility than nitrogen gas is gas loaded into the first raw material composition under a pressure of 0.5 to 1.0 MPa.   The method for producing a polyurethane foam according to claim 1 or 2, wherein the first raw material composition and the second raw material composition are independently pressurized to 10 MPa or more and supplied to the mixer.   The method for producing a polyurethane foam according to any one of claims 1 to 3, wherein the gas having lower solubility than nitrogen gas is helium gas.   The method for producing a polyurethane foam according to any one of claims 1 to 4, wherein the first raw material composition contains water.   A polyurethane foam having closed cells, wherein the polyurethane foam has a standard deviation of the cell diameter distribution of 8 μm or less. The polyurethane foam according to claim 6, wherein the density of the polyurethane foam is 0.5 to 1.0 g / cm ³ .   The polyurethane foam according to claim 6 or 7, wherein the polyurethane foam has a C-type hardness of 50 to 90 degrees.   The polyurethane foam according to any one of claims 6 to 8, wherein the polyurethane foam has an average cell diameter of 10 to 50 µm. The polyurethane foam according to any one of claims 6 to 9, wherein the polyurethane foam is used as a polishing member or a raw material of the polishing member.

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