JP2016148032A - Method of producing urethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing an urethane resin composition, achieving excellent work efficiency by suppressing an increase in curing rate of the urethane resin composition.SOLUTION: A method of producing an urethane resin composition containing: an urethane resin obtained by reacting an active hydrogen component (A) and an organic isocyanate component (B); and an organic fine particle (C) is provided that includes a step of mixing a dispersion phase composed of a mixture (X1) containing the active hydrogen component (A) and the inorganic fine particle (C) and a continuous phase (F) containing carbon dioxide in a liquid state, subcritical state or supercritical state. A method of producing an urethane resin composition containing: an urethane resin obtained by reacting the active hydrogen component (A) and the organic isocyanate component (B); and the inorganic fine particle (C) is provided that includes a step of mixing a dispersion phase composed of a mixture (X2) containing the organic isocyanate component (B) and the inorganic fine particle (C) and the continuous phase (F) containing carbon dioxide in a liquid state, a subcritical state or a supercritical state.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a urethane resin composition.

  In order to reduce the linear expansion coefficient of the rigid urethane foam, in Patent Document 1, etc., it is necessary to highly fill the urethane resin with a solid inorganic filler or a hollow inorganic filler having a small linear expansion coefficient. In addition, there are many inorganic fillers having a basic surface such as talc, calcium carbonate, and aluminum hydroxide (hereinafter abbreviated as basic inorganic filler) as solid inorganic fillers.

  In addition, since the basic component of the basic inorganic filler serves as a catalyst for the urethane reaction to increase the curing speed and the workability during the production of the urethane resin deteriorates, in Patent Document 2, the urethane reaction is delayed by adding an organic acid bismuth salt. Although attempts have been made to reduce the particle size of the basic inorganic filler, the basic surface area increases, so there is a limit to the applicable particle size.

JP 2009-227993 A JP 2013-189582 A

  The object of the present invention is to solve the above-mentioned problems of the prior art. That is, the present invention is a urethane resin composition that suppresses the curing speed of the urethane resin even when highly filled with a basic inorganic filler having a small particle size, has excellent workability, and has good physical properties of the resulting urethane resin composition. I will provide a.

  As a result of intensive studies to achieve the above object, the present inventor has found the following. The present invention is a method for producing a urethane resin composition comprising a urethane resin obtained by reacting an active hydrogen component (A) and an organic isocyanate component (B) and inorganic fine particles (C), and comprises an active hydrogen component ( A step of mixing a dispersed phase comprising a mixture (X1) comprising A) and inorganic fine particles (C) and a continuous phase (F) containing carbon dioxide in a liquid state, subcritical state or supercritical state. Production method of urethane resin composition; including dispersed phase comprising mixture (X2) comprising organic isocyanate component (B) and inorganic fine particles (C), and carbon dioxide in a liquid state, subcritical state or supercritical state It is a manufacturing method of the urethane resin composition including the process of mixing a continuous phase (F).

  The urethane resin composition obtained by the production method of the present invention can suppress the curing rate of the urethane resin composition even in a high filling with a small particle size basic inorganic filler in the production process, and has excellent workability. And the effect that the physical property of the urethane resin composition obtained is also favorable is produced.

It is a flowchart of the experimental apparatus used for preparation of the surface-modified particle | grain continuous liquid by the mixing method by line blend in this invention.

The present invention is described in detail below.
In the present invention, the urethane resin composition contains a urethane resin obtained by reacting an active hydrogen component (A) and an organic isocyanate component (B) and inorganic fine particles (C). When the inorganic fine particles (C) are not contained, the linear expansion coefficient increases and the dimensional stability of the molded product of the urethane resin composition deteriorates.

  As the active hydrogen component (A) of the present invention, polyol [diol (A-1) and trivalent or higher valent polyol (A-2)], dicarboxylic acid (A-3), trivalent or higher polycarboxylic acid (A -4), polyamine (A-5), polythiol (A-6) and the like} and the like.

Diol (A-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecane. Diol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc .; alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.) ); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol) Knoll S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above bisphenol; other, poly Examples include lactone diols (such as poly ε-caprolactone diol) and polybutadiene diols.
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

  Examples of the trivalent or higher polyol (A-2) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trisphenols (trisphenol) PA, etc.); novolak resins (phenol novolak, cresol novolac, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above novolac resins, acrylic polyols [copolymerization of hydroxyethyl (meth) acrylate with other vinyl monomers Polymer, etc.].

Dicarboxylic acids (A-3) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, dodecenyl succinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid) Branched dialkyl dicarboxylic acids having 8 or more carbon atoms [dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.), alkyl succinic acid (decyl succinic acid, dodecyl succinic acid) And octadecyl succinic acid); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.).
Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

  Examples of the trivalent or higher (3 to 6 or higher) polycarboxylic acid (A-4) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.).

  As the dicarboxylic acid (A-3) or the trivalent or higher polycarboxylic acid (A-4), acid anhydrides or lower alkyl esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used. Good.

The following are mentioned as an example of a polyamine (A-5).
Aliphatic polyamines (C2 to C18):
[1] Aliphatic polyamine {C2-C6 alkylenediamine (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) polyamine [diethylenetriamine, etc.}}
[2] These alkyl (C1-C4) or hydroxyalkyl (C2-C4) substituted products [dialkyl (C1-C3) aminopropylamine, etc.]
[3] Alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc.]
[4] Aromatic ring-containing aliphatic amines (C8 to C15) (such as xylylenediamine, tetrachloro-p-xylylenediamine),
-Alicyclic polyamines (C4 to C15): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.
Aromatic polyamines (C6-C20):
[1] Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine and the like; nucleus-substituted alkyl group [C1-C4 alkyl such as methyl, ethyl, n- and i-propyl, butyl, etc.] Aromatic polyamines such as 2,4- and 2,6-tolylenediamine etc.), and mixtures of various proportions of these isomers [2] nuclear substituted electron withdrawing groups (Cl, Br, I, Aromatic polyamines having halogens such as F; alkoxy groups such as methoxy and ethoxy; nitro groups and the like
[3] Aromatic polyamines having secondary amino groups [partially or all of —NH _{2 in} the aromatic polyamines (4) to (6) above is —NH—R ′ (R ′ is a lower group such as methyl or ethyl) Substituted with an alkyl group] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.],
Heterocyclic polyamines (C4 to C15): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, etc.
Polyamide polyamine: low molecular weight polyamide polyamine obtained by condensation of dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) polyamine (such as alkylene diamine, polyalkylene polyamine, etc.)
-Polyether polyamine: hydride of cyanoethylated polyether polyol (polyalkylene glycol and the like).

  Examples of polythiol (A-6) include ethylenedithiol, 1,4-butanedithiol, and 1,6-hexanedithiol.

The active hydrogen component (A) of the present invention has a weight average molecular weight of preferably 300 to 5000, more preferably 300 to 3000, and particularly preferably 300 to 2500 from the viewpoint of urethane group concentration and linear expansion coefficient.
The weight average molecular weight (Mw) of (A) is measured by gel permeation chromatography (GPC).
(GPC measurement conditions)
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μL
Detection device: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLY STYRENE) manufactured by Tosoh (molecular weight 500, 1050, 2800, 9100, 18100, 37900, 96400, 190000, 355000, 900000, 2890000)

  As the active hydrogen component (A) used in the present invention, the solubility of the continuous phase (F) with respect to the active hydrogen component (A) at 50 ° C. and 15 MPa is 1 to 400% by weight based on the weight of (A). It is preferable. The solubility of the continuous phase (F) with respect to the active hydrogen component (A) is measured by dropping the continuous phase (F) into the active hydrogen component (A) and observing the weight% from the transparent state to the cloudy state. be able to.

  In the organic isocyanate component (B) in the present invention, the following isocyanate (PI) having 2 to 6 or more (preferably 2 to 3, particularly 2) isocyanate groups, and two or more of these Mixtures and the like are included.

  C (excluding carbon in NCO group, the same shall apply hereinafter) 2-18 aliphatic PI (B-1): diisocyanate (hereinafter abbreviated as DI), for example, ethylene DI, tetramethylene DI, hexamethylene DI (HDI), hepta Methylene DI, octamethylene DI, decamethylene DI, dodecamethylene DI, 2,2,4- and / or 2,4,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6 -Diisocyanatoethyl caproate, bis (2-isocyanatoethyl) fumarate and bis (2-isocyanatoethyl) carbonate; trifunctional or higher functional PI (such as triisocyanate), for example 1,6,1 1-undecane triisocyanate 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6 Hexamethylene triisocyanate and lysine ester triisocyanate (phosgenates of reaction products of lysine and alkanol ammonium, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl -2,6-diisocyanatohexanoate, etc.);

  C4-15 alicyclic PI (B-2): DI, for example isophorone DI (IPDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI, bis (2 -Isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- and / or 2,6-norbornane DI; tri- or higher functional PI (such as triisocyanate), such as bicycloheptane triisocyanate;

  C8-15 araliphatic PI (B-3): m- and / or p-xylylene DI (XDI), diethylbenzene DI and α, α, α ', α'-tetramethylxylylene DI (TMXDI);

  C6-20 aromatic PI (B-4): DI, for example 1,3- and / or 1,4-phenylene DI, 2,4- and / or 2,6-tolylene DI (TDI), 4, 4 '-And / or 2,4'-diphenylmethane DI (MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-di Isocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane and 1,5-naphthylene DI; trifunctional or higher functional PI (such as triisocyanate) such as crude TDI, crude MDI (polymethylene polyphenylene poly) Isocyanate);

Modified PI (B-5):
Modified products of the above PI, such as modified products having carbodiimide, urethane, urea, isocyanurate, uretoimine, allophanate, biuret, oxazolidone and / or uretdione groups), such as urethane modified products such as MDI, TDI, HDI and IPDI (polyol and NCO-terminated urethane prepolymer obtained by reacting with excess PI), biuret modified product, isocyanurate modified product, trihydrocarbyl phosphate modified product, and mixtures thereof. The polyol used for urethane modification includes the polyhydric alcohol, PT polyol and / or PS polyol. Preferred are polyols having an OH equivalent of 500 or less, particularly 30 to 200, such as glycols (EG, PG, DEG, DPG, etc.), triols (TMP, GR, etc.), tetrafunctional or higher functional polyols (PE, SO, etc.) ) And their AO (EO and / or PO) (1-40 mol) adducts, especially glycols and triols. The equivalent ratio (NCO / OH ratio) between PI and polyol in urethane modification is usually 1.1 / 1 to 10/1, preferably 1.4 / 1 to 4/1, and particularly 1.4 / 1-2 / 1. The content of free isocyanate groups in the modified PI is preferably 8 to 33%, more preferably 10 to 30%, and particularly preferably 12 to 29%.

When the urethane resin is formed by reacting the active hydrogen component (A) and the organic isocyanate component (B) in the present invention, the ratio of (A) and (B) is represented by the isocyanate index [(equivalent ratio of NCO group / OH group). × 100], the index can be variously changed, but is preferably 80 to 140, more preferably 85 to 120, from the viewpoint of resin strength and ease of cutting of the urethane resin. Especially preferably, it is 90-115.
As a reaction method of (A) and (B), even if it is a one-shot method, after reacting a part of (A) with (B) in advance to form an NCO-terminated prepolymer, the remaining ( A prepolymer method may be used in which a reaction is performed with A), or a part of (A) and (B) are reacted in advance to form an OH-terminated prepolymer, and then the remaining (B) is reacted. .

  As an organic isocyanate component (B) used for this invention, the solubility of the continuous phase (F) with respect to the organic isocyanate component (B) under 50 degreeC and 15 Mpa is 1 to 400 weight% based on the weight of (B). It is preferable. The solubility of the continuous phase (F) in the organic isocyanate component (B) should be measured by dropping the continuous phase (F) into the active hydrogen component (B) and observing the weight percent from the transparent state to the cloudy state. Can do.

The inorganic fine particles (C) in the present invention are preferably basic layered compounds, such as montmorillonite, hydrotalcite, talc, and combinations thereof. Among these, montmorillonite and hydrotalcite are particularly preferable from the viewpoint of the permeability of supercritical carbon dioxide and the aspect ratio of primary particles.
When the inorganic fine particle (C) is a basic layered compound, examples of the interlayer compound include a quaternary amine salt, a tertiary amine salt, a secondary amine salt, a primary amine salt, and an alkyl acid salt. Of these, from the viewpoint of dispersibility of the inorganic fine particles (C), preferred are quaternary amine salts and alkyl acid salts.

The thickness of the inorganic fine particles (C) in the urethane resin composition of the present invention as measured with a transmission electron microscope is preferably 100 nm or less. From the viewpoint of the linear expansion coefficient, it is more preferably 40 nm or less, particularly preferably 30 nm or less, and most preferably 25 nm or less.
As a method of measuring the thickness, the average thickness of 100 particles is measured and calculated by transmission electron microscope measurement (abbreviated as TEM). For example, it can be obtained by analyzing a TEM image. As a measuring device, TEM [model number “H-7100”, manufactured by Hitachi, Ltd.] and image analysis type particle size distribution measurement software [trade name “Mac-View” ", Manufactured by Mountec Co., Ltd.].

The aspect ratio of the inorganic fine particles (C) measured with a transmission electron microscope in the urethane resin composition of the present invention is preferably 100 or more. From the viewpoint of the linear expansion coefficient, it is more preferably 300 or more, particularly preferably 500 or more.
As a method for measuring the aspect ratio, measurement of the ratio of the shortest diameter to the longest diameter of 100 particles by TEM can be mentioned. The measurement method is the same as the measurement of the particle thickness.

  The content of the inorganic fine particles (C) in the urethane resin composition of the present invention is preferably 5 to 50% by weight based on the weight of the urethane resin composition from the viewpoint of viscosity during molding, and more preferably 5 to 5% by weight. 30% by weight, particularly preferably 10 to 30% by weight.

  The method for producing a urethane resin composition of the present invention includes a step of mixing a dispersed phase comprising a mixture (X1) comprising an active hydrogen component (A) and inorganic fine particles (C) and a continuous phase (F). When the continuous phase (F) is not used, workability and resin strength may be deteriorated from the viewpoint of the surface reactivity and aspect ratio of the inorganic fine particles.

Examples of the continuous phase (F) in the present invention include carbon dioxide and nitrogen in a liquid state, a subcritical state, or a supercritical state.
The continuous phase (F) may contain a solvent or the like as long as it is soluble in the continuous phase.
Examples of the solvent include methyl ethyl ketone, ethyl acetate and acetone.

The method for producing a urethane resin composition of the present invention includes a step of mixing a dispersed phase composed of a mixture (X2) comprising an organic isocyanate component (B) and inorganic fine particles (C) and a continuous phase (F). When the continuous phase (F) is not used, workability and resin strength may be deteriorated from the viewpoint of the surface reactivity and aspect ratio of the inorganic fine particles.
Examples of the continuous phase (F) include the same as the continuous phase (F).

  The mixture (X1) containing the active hydrogen component (A) and the inorganic fine particles (C) and the mixture (X2) containing the polyisocyanate (B) and the inorganic fine particles (C) are collectively referred to as the mixture (X). .

  The carbon dioxide and nitrogen used in the production method of the present invention can be used without particular limitation as long as they can be obtained with a known recovery facility or the like, and preferred examples include carbon dioxide and nitrogen having a purity of 90% or more. Examples of a method for obtaining carbon dioxide and nitrogen having a purity of 90% include a chemical adsorption method, a PAS method, a gas cooling recovery method, and the like.

  In the production method of the present invention, the carbon dioxide in the liquid state is a carbon dioxide triple point (temperature = −57 ° C., pressure 0.5 MPa) and carbon dioxide on a phase diagram represented by a temperature axis and a pressure axis of carbon dioxide. Carbon dioxide in the temperature and pressure conditions of the gas-liquid boundary line passing through the critical point of carbon (temperature = 31 ° C, pressure = 7.4 MPa), the isotherm of the critical temperature, and the part surrounded by the solid-liquid boundary line The supercritical carbon dioxide refers to carbon dioxide that is at a temperature and pressure above the critical temperature, and the subcritical carbon dioxide refers to carbon dioxide that is at a temperature slightly lower than the critical temperature. The pressure means the total pressure in the case of a mixed gas of two or more components.

  Carbon dioxide or nitrogen in the liquid state, subcritical state or supercritical state compresses and heats the gas using known pressurizing equipment (such as a blanker pump) and heating equipment (such as an oil temperature controller). Can be obtained.

[Modification and disintegration of inorganic fine particles with supercritical carbon dioxide]
The method for producing a urethane resin composition of the present invention includes an active hydrogen component (A), a mixture (X1) comprising an organic fine particle (C) or an organic isocyanate component (B), and an inorganic fine particle (C). There is no particular limitation as long as it includes a step of mixing the resulting mixture (X2) with carbon dioxide in a liquid state, subcritical state or supercritical state. Carbon dioxide from the dispersion comprising the step of mixing carbon dioxide in a liquid state, subcritical state or supercritical state with mixture (X1) or mixture (X2) and then containing mixture (X1) or mixture (X2) The manufacturing method which performs the process which removes by gas is preferable.

  As the step of removing carbon dioxide from the dispersion as a gas, it is preferable to discharge carbon dioxide from the high-pressure layer simultaneously with the mixture (X1) or the mixture (X2) when taking out the mixture (X1) or the mixture (X2). .

  In the dispersion step of mixing the mixture (X1) or the mixture (X2) and the continuous phase (F), it is possible to produce the mixture by a batch mixing method, a continuous mixing method, or the like. Among these, a line blend (in-line mixing) method that is a continuous mixing method is preferable from the viewpoints of improving productivity, stabilizing quality, and reducing manufacturing space.

Examples of the manufacturing apparatus that performs the dispersion process by a batch mixing method include a pressure-resistant and heat-resistant reaction vessel attached with a mixing apparatus. There is no limitation on the length and pipe diameter of the mixer portion of the mixing apparatus attached to the manufacturing apparatus and the number of mixing apparatuses. It should be noted that the pressure resistance and pressure resistance of the pressure and heat resistant reaction container must be able to withstand the pressure and temperature at which the liquid, subcritical or supercritical state is reached.
It is preferable to provide a nozzle for taking out the urethane resin composition at the outlet of the apparatus used for the batch type mixing method.

Production equipment when the dispersion process is carried out by the line blend method includes static in-line mixers (static mixer, in-line mixer, ramond super mixer, sulzer mixer, etc.) and agitation in-line mixers (vibr mixer, turbo mixer, etc.) Etc. There is no limitation on the length and pipe diameter of the mixer portion of the mixing apparatus attached to the manufacturing apparatus and the number of mixing apparatuses. It should be noted that the pressure resistance and pressure resistance of the pressure and heat resistant reaction container must be able to withstand the pressure and temperature at which the liquid, subcritical or supercritical state is reached.
The outlet of the apparatus used for the line blending method is preferably provided with a nozzle for taking out the urethane resin composition, similar to the pressure vessel.

  In the dispersion step, the volume ratio [(F) :( X1) or (X2)] between the continuous phase (F) and the mixture (X1) or the mixture (X2) is not particularly problematic unless poor solvent precipitation occurs. However, it is preferable that it is 70: 30-0.5: 99.5.

The production method of the present invention includes a step of removing carbon dioxide from the resin composition dispersion as a gas. Examples of the method for turning carbon dioxide into a gas include a method for reducing the pressure in the production apparatus to vaporize carbon dioxide. As for the vaporized carbon dioxide, only carbon dioxide may be discharged from the manufacturing apparatus, or carbon dioxide may be discharged simultaneously with the mixture (X) when taking out the mixture (X) from the manufacturing apparatus.
Among these, it is preferable to discharge the inorganic fine particles in the urethane resin composition at the same time from the viewpoint of high aspect ratio and miniaturization. More preferably, the discharge speed is such that the amount of pressure change within a unit time is small.

In the production method of the present invention, an apparatus used for production by the line blend method will be described with reference to the drawings.
FIG. 1 is a flowchart of an apparatus in the case of carrying out the method for producing hydrophilic resin particles of the present invention by a mixing method using line blending.
As a method for mixing carbon dioxide in a liquid state, subcritical state or supercritical state and the mixture (X), first, in a device for performing line blending of carbon dioxide from a cylinder B1 filled with carbon dioxide through a pump P2 ( It is introduced into the static mixer M1), the pressure and temperature are adjusted so that the carbon dioxide is in a liquid state, subcritical state or supercritical state, and then inside the apparatus through the solution pump P1 from the dissolution tank T1 containing the mixture (X). The dispersion step is carried out by introducing it into carbon dioxide nitrogen.
The temperature at which line blending is performed is the same as in the case of mixing using the above-described pressure vessel. The residence time in the apparatus is not particularly limited as long as mixing is sufficiently performed, but is preferably 0.1 to 1800 seconds.

  The production method of the present invention preferably includes a step of mixing the active hydrogen component (A), the mixture (X1) containing the inorganic fine particles (C) and the organic isocyanate component (B) after the above step. As a method of reacting the mixture (X1) containing the active hydrogen component (A) with the organic isocyanate component (B), a known polymerization method can be used.

  The production method of the present invention preferably includes a step of mixing the organic isocyanate component (B), the mixture (X2) containing the inorganic fine particles (C) and the active hydrogen component (A) after the above step. As a method of reacting the mixture (X2) containing the organic isocyanate component (B) with the active hydrogen component (A), a known polymerization method can be used.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

The composition and symbols of the raw materials used in Examples and Comparative Examples are as follows.
Polyol (A-1): PO adduct of glycerin, polyether polyol with an OH equivalent of 133.3 [trade name “Sanix GP400”, manufactured by Sanyo Chemical Industries, Mw: 440]
Polyol (A-2): PO adduct of glycerin, OH equivalent of 240 [trade name “Sanix GP700”, manufactured by Sanyo Chemical Industries, Mw: 800]
Polyol (A-3): PO adduct of glycerin, polyether polyol having an OH equivalent of 112 [trade name “Sanix GP1500”, manufactured by Sanyo Chemical Industries, Ltd., Mw: 1800]
Polyol (A-4): PO adduct of glycerin, polyether polyol having an OH equivalent of 55 [trade name “Sanix GP4000”, manufactured by Sanyo Chemical Industries, Mw: 4600]
Polyol (A-5): PO adduct of glycerin, polyether polyol having an OH equivalent of 670 [trade name “Sanix GP250”, manufactured by Sanyo Chemical Industries, Mw: 280]
Polyisocyanate (B-1): Polyphenylene polyisocyanate [trade name “MDI-100Be”, manufactured by Nippon Polyurethane Industry Co., Ltd.]
Inorganic fine particles (C-1): Montmorillonite quaternary amine salt [trade name [Kunifil-HY], manufactured by Kunimine Kogyo Co., Ltd.] pH 9-10
Inorganic fine particles (C-2): Talc [trade name “Soapstone C”, manufactured by Nippon Mystron Co., Ltd.] pH 8 to 10 (10 wt% aqueous dispersion)
Inorganic fine particles (C-3): Hydrotalcite [trade name DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.] pH 8-10
Organic acid bismuth salt (D-1): bismuth tris (2-ethylhexanoate) [trade name “Neostan U-600”, manufactured by Nitto Kasei Co., Ltd.]
Curing retarder (E-1): Dilaurylmethylammonium salt of dodecylbenzenesulfonic acid [trade name “Chemistat 3112C-6”, manufactured by Sanyo Chemical Industries, Ltd.]

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

<Production Example 1>
In a pressure-resistant reaction vessel equipped with a stirring bar, a take-out nozzle and a thermometer, 100 parts by weight of polyol (A-1), 57.5 parts by weight of an aggregate of inorganic fine particles (C-1) having a particle size of 10 μm, methyl ethyl ketone 200 parts by weight were charged up to 80% of the volume of the pressure vessel for reaction, sealed, and the inside air was replaced with carbon dioxide, then carbon dioxide was supplied and stirred at 15 MPa and 70 ° C. for 1 hour to infiltrate the organic matter. Thereafter, while maintaining the pressure in the pressure vessel for reaction, the content containing carbon dioxide is taken out from the takeout nozzle, 0.02 part by weight of the organic bismuth salt (D-1) is mixed, and the solvent is distilled off. Thus, a mixture (X-1) was prepared.

<Production Example 2>
In an experimental apparatus using the line blending method shown in FIG. 1 [line blending apparatus (M1): static mixer (manufactured by Noritake Co., Ltd .; inner diameter: 0.5 m, number of elements: 27), length: 2 m], first the melting tank (T1) is placed. Then, 100 parts by weight of polyol (A-1), 57.5 parts by weight of an aggregate of inorganic fine particles (C-1) having a particle size of 10 μm, and 200 parts by weight of methyl ethyl ketone were charged and stirred to prepare a mixture. Next, carbon dioxide in a liquid state is introduced from a carbon dioxide cylinder (B1) into a static mixer whose temperature is adjusted to 120 ° C. at a flow rate of 1 L / h using a carbon dioxide pump (P2), and the valve (V1) is adjusted. Carbon dioxide in a supercritical state was produced by setting the pressure in the static mixer to 15 MPa. While continuously introducing carbon dioxide while maintaining the flow rate, temperature and pressure, the mixture was introduced from the dissolution tank (T1) into the static mixer at a flow rate of 1 L / h using the solution pump (P1). Line blending was performed at M1 while maintaining the pressure. The liquid after line blending is opened in a pressure receiving tank (T2) adjusted to 0.1 MPa from the nozzle at the exit of the static mixer, and the carbon dioxide is vaporized and removed, and the organic bismuth salt (D-1) 0.02 wt. After mixing the parts, the solvent was distilled off to prepare a mixture (X-2).

<Production Example 3>
In an experimental apparatus using the line blending method shown in FIG. 1 [line blending apparatus (M1): static mixer (manufactured by Noritake Co., Ltd .; inner diameter: 0.5 m, number of elements: 27), length: 2 m], first the melting tank (T1) is placed. Then, 100 parts by weight of polyol (A-1), 57.5 parts by weight of an aggregate of inorganic fine particles (C-2) having a particle size of 10 μm, and 200 parts by weight of methyl ethyl ketone were charged and stirred to prepare a mixture. Next, carbon dioxide in a liquid state is introduced from a carbon dioxide cylinder (B1) into a static mixer whose temperature is adjusted to 120 ° C. at a flow rate of 1 L / h using a carbon dioxide pump (P2), and the valve (V1) is adjusted. Carbon dioxide in a supercritical state was produced by setting the pressure in the static mixer to 15 MPa. While continuously introducing carbon dioxide while maintaining the flow rate, temperature and pressure, the mixture was introduced from the dissolution tank (T1) into the static mixer at a flow rate of 1 L / h using the solution pump (P1). Line blending was performed at M1 while maintaining the pressure. The liquid after line blending is opened in a pressure receiving tank (T2) adjusted to 0.1 MPa from the nozzle at the exit of the static mixer, and the carbon dioxide is vaporized and removed, and the organic bismuth salt (D-1) 0.02 wt. After mixing the parts, the solvent was distilled off to prepare a mixture (X-3).

<Production Example 4>
In an experimental apparatus using the line blending method shown in FIG. 1 [line blending apparatus (M1): static mixer (manufactured by Noritake Co., Ltd .; inner diameter: 0.5 m, number of elements: 27), length: 2 m], first the melting tank (T1) is placed. Then, 172.7 parts by weight of polyisocyanate (B-1), 57.5 parts by weight of an aggregate of inorganic fine particles (C-1) having a particle diameter of 10 μm, and 200 parts by weight of methyl ethyl ketone were charged and stirred to prepare a mixture. Next, carbon dioxide in a liquid state is introduced from a carbon dioxide cylinder (B1) into a static mixer whose temperature is adjusted to 120 ° C. at a flow rate of 1 L / h using a carbon dioxide pump (P2), and the valve (V1) is adjusted. Carbon dioxide in a supercritical state was created by setting the pressure in the static mixer to 15 MPa. While continuously introducing carbon dioxide while maintaining the flow rate, temperature and pressure, the mixture was introduced from the dissolution tank (T1) into the static mixer at a flow rate of 1 L / h using the solution pump (P1). Line blending was performed at M1 while maintaining the pressure. The liquid after line blending is opened in a pressure receiving tank (T2) adjusted to 0.1 MPa from the nozzle at the exit of the static mixer, and the carbon dioxide is vaporized and removed, and the organic bismuth salt (D-1) 0.02 wt. After mixing the parts, the solvent was distilled off to prepare a mixture (X-4).

<Production Examples 5-9>
A mixture (X-5) was produced in the same manner as in Production Example 1, except that 57.5 parts by weight of the aggregated laminate of inorganic fine particles (C-1) in Production Example 1 was changed to 16.1 parts by weight.
A mixture (X-6) was produced in the same manner as in Production Example 1 except that 57.5 parts by weight of the aggregated laminate of inorganic fine particles (C-1) in Production Example 1 was changed to 103.5 parts by weight.
A mixture (X-7) was produced in the same manner as in Production Example 1 except that the inorganic fine particles (C-1) in Production Example 1 were changed to (C-3).
A mixture (X-8) was produced in the same manner as in Production Example 1 except that the polyol (A-1) in Production Example 1 was changed to (A-2).
A mixture (X-9) was produced in the same manner as in Production Example 1 except that the polyol (A-1) in Production Example 1 was changed to (A-3).

<Comparative Production Examples 1-4>
In a container equipped with a stirring rod, 100 parts by weight of polyol (A-1), 6.9 parts by weight of an aggregated laminate of inorganic fine particles (C-1) having a particle size of 10 μm, and organic bismuth salt (D-1) 0. A mixture (X′-1) was prepared by mixing 02 parts by weight.
A mixture (X′-2) was produced in the same manner as in Comparative Production Example 1, except that 6.9 parts by weight of the aggregated laminate of inorganic fine particles (C-1) in Comparative Production Example 1 was changed to 340 parts by weight.
Comparative production example 1 except that the polyol (A-1) of comparative production example 1 is changed to (A′-1) and the aggregated laminate 6.9 of inorganic fine particles (C-1) is changed to 36.08 parts by weight. In the same manner, a mixture (X′-3) was produced.
Comparative production example 1 except that the polyol (A-1) of comparative production example 1 is changed to (A'-2) and the aggregated laminate 6.9 of inorganic fine particles (C-1) is changed to 203.9 parts by weight. Similarly, a mixture (X′-4) was prepared.

  The mixtures (X-1) to (X-9) and (X′-1) to (X′-4) are shown in Table 1.

<Examples 1-3 and Comparative Examples 1-4>
Mixtures (X-1) to (X-3), (X-5) to (X-9) and (X′-1) prepared in Production Examples 1 to 3, 5 to 9 and Comparative Production Examples 1 to 4 The density of the molded product is 0.90 g in a mechanical froth foaming step in a two-component mixture containing the total amount of (X′-4) and each part by weight of each polyisocyanate (B-1) listed in Table 2. The mixture was continuously mixed with nitrogen so as to be / cm ³ , and the mixture was discharged.
Liquid feeding ratio of the organic isocyanate component (B) and each of the mixtures (X-1) to (X-3), (X-5) to (X-9) (X′-1) to (X′-4) [NCO / OH equivalent ratio] was 1.7 / 1.0 to 1.0 / 1.0, and the feeding speed was 15 kg / min.
Since the liquid mixed in the mixer unit is continuously supplied from the discharge port, a metal mold is attached to the discharge port in advance and the supplied mixed solution is received. The received liquid mixture was cured in a curing furnace at 110 ° C. for 10 hours to form molded products (Y-1) to (Y-3), (Y-5) to (Y−) made of a urethane resin composition. 9) and (Y′-1) to (Y′-4) were produced. The evaluation results are shown in Table 2.

<Example 4>
With respect to the mixture (X-4) shown in Table 1 created in Production Example 4, a molded product (Y-4) comprising a mechanical floss foaming step and a urethane resin composition was produced by the following method.
The prepared mixture (X-4) and polyol (A-1) as the active hydrogen component (A) are mixed with nitrogen so that the density of the molded product becomes 0.90 g / cm ³ in the mechanical froth foaming step. And continuously mixed, and the mixture was discharged. The composition of the mixture, excluding nitrogen, is as shown in Table 2.
The liquid feeding ratio [NCO / OH equivalent ratio] of the mixture component (X) and the active hydrogen component (A) is 1.7 / 1.0 to 1.0 / 1.0, and the liquid feeding speed is 15 kg / min. I went there.
Since the liquid mixed in the mixer unit is continuously supplied from the discharge port, a metal mold is attached to the discharge port in advance and the supplied mixed solution is received. The received mixed liquid was cured in a curing furnace at 110 ° C. for 10 hours to produce a molded product (Y-4). The evaluation results are shown in Table 2.

<Method for measuring thickness of inorganic fine particles (C)>
The inorganic fine particles (C) contained in the urethane resin composition are TEM [model number “H-7100”, manufactured by Hitachi, Ltd.] and image analysis type particle size distribution measurement software [trade name “Mac-View”, Inc. The average value of the shortest diameter was calculated for 100 particles and used as the thickness.

<Method for measuring aspect ratio of inorganic fine particles (C)>
The inorganic fine particles (C) contained in the urethane resin composition were measured by TEM, the aspect ratio of each particle was determined by the following calculation formula, and an average value of 100 particles was obtained.
Aspect ratio = maximum diameter / shortest diameter of inorganic fine particles (C)

<Curing speed and curing time>
After the mixed solution was supplied from the discharge port, the upper part of the mixed solution was lightly struck with a glass rod or the like, and the time when the mixed solution did not adhere to the glass rod was defined as the curing time. The longer the curing time, the better.

<Density>
The volume and mass of the molded product were measured, and the density was calculated.

<Hardness>
A rectangular parallelepiped molded product was cut into 100 × 100 × 50 mm, and Shore D hardness was measured according to JIS K6253 using a type D durometer.

<Linear expansion coefficient>
After adjusting the test pieces cut at a length × width × thickness = 10 × 4 × 4 mm from the one end and the center of the rectangular parallelepiped-shaped molded product, respectively, at 25 ° C. and 55% RH for 12 hours, It measured according to JISK7197 using the linear expansion coefficient measuring machine [model name "TMA / SS6100", SII Co., Ltd. product]. The dimensional change in 25-80 degreeC was measured, and the average dimensional change rate per 1 degreeC in 30-60 degreeC was calculated among them. This measurement was performed for each of the three test pieces for three end portions and three central portions, and an average value was obtained and used as the linear expansion coefficient of the molded product.

<Heat deformation temperature>
The produced molded product was cut into 127 × 12.7 × 12.7 mm to obtain a test piece, which was measured according to JIS K6911.
The measurement was performed using a load deflection temperature tester [model S3-FH] manufactured by Toyo Seiki Seisakusho.

<Bending strength>
The produced molded product was cut into 80 × 10 × 4 mm to obtain test pieces, which were measured according to JIS K6911.
For the measurement, a precision universal testing machine autograph [model number AG500N / 1kN / 2kNXplus, manufactured by Shimadzu Corporation] was used.

<Impact strength>
The produced molded product was cut into 63 × 12.7 × 12.7 mm to obtain a test piece, which was measured according to JIS K6911.
IZOD impact tester [Model No. 158, manufactured by Yasuda Seiki Seisakusho Co., Ltd.].

  As shown in Table 2, the curing time is long and the workability is excellent as compared with the comparative example. Further, it is apparent that the physical properties of a molded product obtained by reaction curing of the composition are excellent.

  Even if the content of the basic inorganic filler is increased, the urethane resin composition of the present invention maintains the curing time and is excellent in workability, and the physical properties of the obtained urethane resin composition do not deteriorate. For this reason, it is widely used particularly as a model such as a design model and a master model, an inspection jig, a cutting material for a mold such as heat-resistant molding, and the like, and is extremely useful.

T1: Dissolution tank (maximum operating pressure 20 MPa, maximum operating temperature 200 ° C., with stirrer)
T2: pressure tank B1: carbon dioxide cylinder P1: solution pump P2: carbon dioxide pump M1: static mixer (pressure vessel for reaction)
V1: Valve

Claims (4)

  A method for producing a urethane resin composition comprising a urethane resin obtained by reacting an active hydrogen component (A) with an organic isocyanate component (B) and inorganic fine particles (C), the active hydrogen component (A) and an inorganic A urethane resin composition comprising a step of mixing a dispersed phase comprising a mixture (X1) comprising fine particles (C) and a continuous phase (F) containing carbon dioxide in a liquid state, subcritical state or supercritical state. Manufacturing method.   A method for producing a urethane resin composition comprising a urethane resin obtained by reacting an active hydrogen component (A) with an organic isocyanate component (B) and inorganic fine particles (C), wherein the organic isocyanate component (B) and inorganic Urethane resin composition comprising a step of mixing a dispersed phase comprising a mixture (X2) comprising fine particles (C) and a continuous phase (F) containing carbon dioxide in a liquid state, subcritical state or supercritical state Manufacturing method.   The method for producing a urethane resin composition according to claim 1, wherein the solubility of the continuous phase (F) in the active hydrogen component (A) at 50 ° C and 15 MPa is 1 to 400% by weight based on the weight of (A). .   The method for producing a urethane resin composition according to claim 2, wherein the solubility of the continuous phase (F) in the organic isocyanate component (B) at 50 ° C and 15 MPa is 1 to 400% by weight based on the weight of (B). .