JPS60181115A - Production of polyurethane - Google Patents

Abstract

PURPOSE:To obtain a polyurethane having high reactivity, and excellent self mold-releasability and initial strength, by using a specific polyoxyalkylene polyol as a high-molecular polyol, and reacting the polyol with an organic polyisocyanate. CONSTITUTION:The objective polyurethane is produced by reacting (A) a high- molecular polyol wherein a blocked polyoxyalkylene polyol containing terminal polyoxyethylene chain and having a functionality of >=5 and an equivalent of >=1,450 accounts for >=20wt% of the whole high-molecular polyol with (B) a polyisocyanate, if necessary in the presence of a foaming agent. The component B is preferably diphenylmethane diisocyanate, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyurethane, specifically a method for producing polyurethane having self-molding properties (highly reactive), particularly -11,I
Molded using Myl (reaction injection molding method) / High reactivity superior to ζ field, self = ++-
This invention relates to a method for producing polyurethane that provides moldability.

BACKGROUND ART The RIM method has been put into practical use as a means of manufacturing urethane molded products for applications such as exterior and interior parts of automobiles, such as handlebars, instrument panels, and control handles. Urethane raw materials for RIM are required to have high reactivity and be able to be cured and removed from the mold in a short period of time, as well as to have self-releasing properties so that there is no need to apply a mold release agent to the mold each time. However, it is desired that the mold release is easy.

The present inventors investigated to find a raw material polyol and a method for producing polyurethane that satisfy these requirements. 1. By using a specific polyoxyalkylene polyol, a polyurethane molded product with high reactivity and self-releasing property was created. The present invention was achieved by discovering that the following can be obtained.

That is, the present invention provides a method for producing polyurethane by reacting an organic polyisocyanate and a polymeric polyol in the presence of a blowing agent if necessary, in which a terminal polyurethane having a functional group number of 5 or more and an equivalent weight of 1450 or more is used as at least a part of the polyol. A method for producing a polyurethane having self-releasing properties (first invention), characterized in that oxyethylene chain-containing bropolyoxyalkylene polyol (5) is used in an amount of 20% or more based on the weight of the polymeric polyol (first invention), and the above-mentioned method. This is a method for manufacturing a polyurethane molded article (second invention), characterized in that molding is performed by the RIM method in the polyurethane manufacturing method.

The block polyoxyalkylene polyol 4 used in the present invention is a compound having at least 5 (preferably 6 to 12) active hydrogen atoms (for example, polyhydric alcohol, polyhydric phenol, amines) and ethylene. Compounds having a block addition structure of oxide and other alkylene oxides to form the above-mentioned terminal oxyethylene'dLt, and mixtures thereof are included.

Examples of the above-mentioned polyhydric alcohols include sugar alcohols such as pentitol, sorbitol, mannitol, quinlitol, etc.
Nohexyl, such as talitol, dulcitol;
Sugars Tatoehaglucose, mannose, fructose,
Monosaccharides such as sorbose.

Low sugar content such as levalose, lactose, laninose, etc., glycols such as polyols (tc toj?-14) Glycols such as ethylene glycol and propylene glycol, glycerin, trimethylolpropane, hegisan I and lyol , pentaerythri 1 hale lc which alkane polyol) group: I
/i; poly(alkanopolyols) such as polyglycerols such as triglycerin and teri-laglycerin, polypentaerythrol such as dipentaerythrol and tripene erythrol; and cyclo , alkane polyols such as tetrakis(hydroxymethyl)cyclohexano. Examples of the above-mentioned polyhydric phenol include novolac, for example, U.S. et al.
Polyphenols described in No. 65641; and examples of amines include polyalkylene polyamines such as diethylenetriamine and triethylenetetramine. Two or more of these active hydrogen atom-containing compounds may be used in combination. In addition, one or more of these compounds and two to
Compounds having 4 active hydrogen atoms [for example, (B
) Listed as raw materials for polyether polyol]
The average number of functional groups (number of active hydrogen atoms) is 5 in the mixture with
Those having the following number (preferably 6 to 12) can also be used. Preferred among these are polyhydric alcohols, especially sorbitol and sucrose.

”2 Active hydrogen atom-containing compound with ethylene oxide (
Propylene oxide (hereinafter abbreviated as PO) is normally used as another 1-alkylene oxide (hereinafter abbreviated as AO) to be added together with EO (hereinafter abbreviated as AO), but PO
Add a small amount (for example, 5% or less) of other alkylene oxides (butylene oxide, styrene oxide, etc.) to
They can also be used together.

The above-mentioned block polyoxyalkylene polyol (A) used in the present invention includes those obtained by adding EO and AO to the above-mentioned active hydrogen atom-containing compound in the order of (1) AO-EO (chipped), (II) AO -E
Added in the order of O-AO-EO (balanced).

Examples include (n+) E(J -AO'-B□ in which i is added). Among these, (i) and (II) are preferable.

13 Self-locking polyoxyalkylene polyol (A
) has an equivalent weight il (molecular weight per OL) of 1450 or more, preferably 1500 to 3200, particularly preferably 160
0 to aooo. If the Jn is lower than 1450, the resulting polyurethane will have poor physical properties such as temperature characteristics and elongation. If the equivalent weight exceeds 8,200, the viscosity increases, flowability deteriorates, and reactivity decreases, which is not preferable.

Terminal polyoxyethylene chain content (hereinafter referred to as terminal EO) of (A)
Amount and abbreviation) are usually 10% (weight%, same as below, 9 or more,
Preferably 12-30%, more preferably 15-28%
%. If the amount of terminal EO is less than 10%, it is not possible to mold a polyurethane that has low reactivity, low curing properties and low initial physical properties, and has self-releasing properties, and particularly when molding is performed by the IM method, satisfactory effects cannot be obtained. I can't do it. Aida terminal 1
If the bow content exceeds 30%, the curing properties will improve, but the viscosity will increase and it will become cloudy at a temperature slightly lower than room temperature, resulting in poor workability.In terms of physical properties, temperature characteristics and water absorption properties will deteriorate, so it is preferable. do not have. In addition, even if the terminal EO amount is less than 10%, it may be combined with a terminal EO amount of 10 or more, or if the terminal EJ exceeds 30%, it may be combined with a terminal EJ of 30% or less, and the (average) terminal They can be used in combination so that the amount of E 2 O falls within the above range.

Still, (N total polyoxyethylene silver gold # (hereinafter referred to as total EO
(abbreviated as 凰) is usually 10 chi or more, preferably 12 to 30 chi.

In carrying out the method for producing polyurethane of unexploded H11, the block polyoxyalkylene polyol (Al is used alone or in combination with another polymeric polyol (B) or/and a low-molecular active hydrogen-containing compound (Cl) It can be carried out by reacting with organic polyisocyanate.In some cases, other components, ipolyol (
As 13), polyether polyols, polyester polyols, and polymer polyols other than (A) can be used. Examples of polyether polyols other than (A) include compounds having 2 to 4 active hydrogen atoms (low-functional polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl, Dihydric alcohols such as glycol, 1,6-hexanediol, trihydric alcohols such as glycerin, trimethylolpropane, hexane 1-liol,!-liethanolamine, and tetrahydric alcohols such as pentaerythri I-luamethylglucoside; Tsukuda I phenol) - hydroquinone, bisphenol A; alkylene oxide (J'0) of amines such as ethylenediamine, aminoethylpiperazine, etc.
and/or PO nato (D A O ) (1 addition,
Low-functionality polyether polyol such as polytetramethylene ether glycol; polyether polyol with a functional group number of 5 or more, with terminal polyoxyethylene chains and internal random poly(oxyethylene/oxopropylene)
(less than 10%) mono (PO publication, I) o/E with no terminal polyoxyethylene chains.

Examples include random additives, PO/EO blocky additives having a polyoxy/ethylene chain only inside) 1, or those having an equivalent weight of less than 1450. As polyester polyols, "2 low functional polyhydric alcohols (
Mixtures of dihydric alcohols such as ethylene glycol and diethylene glycol with trihydric alcohols such as glycerin and trimethylolpropane) and/or polycarboxylic acids (such as ampic acid and maleic acid) and/or the above-mentioned low-functionality polyether polyols. , phthalic acid, etc.).

or its anhydride and alkylene oxide (Eo
Examples of polymer polyols include those obtained by reacting (condensing) lactones (such as A polyol obtained by polymerizing an ethylenically unsaturated monomer (acrylonitrile, 1-styrene, etc.) with an ethylenically unsaturated monomer (such as ether polyol and/or polyester polyol) (for example,
4-101899 and the one described in JP-A-54-122896). Among (B), preferred are polyether polyols [especially low-functionality polyether polyols having terminal polyoxyethylene chains (diol and /-!, ta 1, I-liol, terminal EOj, i: 10 ~30%)] and its polymer polyol.

The amount of (A) in the total amount of polymer polyol [(A) and optionally (B)]:11i is usually 20
more than 30%, preferably 30% or more, more preferably 40%
That's all.

If (A) is less than 20%, a polyurethane with good tightness, initial physical properties and self-releasing properties cannot be obtained.

In addition, the terminal Eo amount of the entire polymer polyol is usually 10 or more, preferably 12 to 30, more preferably 15 to 30.
It is 28 chi.

The average weight of the entire polymer polyol is usually 1450~
3000 preferably 1600-2800. Optionally used low-molecular active hydrogen-containing compounds (q can be chain extenders such as low-molecular diols, diamines, amino alcohols, etc. Low-molecular diols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene Glycol, butanediol, neopentyl glycol, hexanediol, polyethylene glycol and polypropylene f')col with a molecular weight of 200 to 400, low-molecular-weight diols having a cyclic group (for example, those described in Japanese Patent Publication No. 1474/1974; propylene of bisphenol A) Oxide adducts, etc.), 3rd
or quaternary nitrogen atom-containing low-molecular diols (for example, those described in JP-A-54-180699; alkyl dialkanolamines and their quaternized products),
Examples include thiodiethylene glycol. The diamine is toluenediamine.

Dicylylene diamine, diethyl diamine toluene.

Aromatic diamines such as aminodiphenylmethane, methylenebis-〇-chloroaniline, diaminophenylsulfone, dichlorobenzidine, dianisidine, and 0-nitro-p-phenylenediamine; alicyclic diamines such as inphoronediamine, dicyclohexylmethanediamine, and cyclohexylenodiamine Formula 9 Formula % Aliphatic diamines such as n, hexanediamine, 2,2,4-trimethylhexanediamine 1-piperazine! Examples include heterocyclic diamines such as. Examples of the amino alcohol include ethanolamine, propatoolamine, ethylethanolamine, phenylethanolamine, and 3-amino-2-methyl-1-soropanol. Among these, -C is preferable for low-molecular diols (especially ethylene glycol, 1,4-butanediol, neopenz-・1-1.h-+・I
L+-57kin・+tshi/? γl-+1. Yang diamine, diethyl diamine toluene).

By using a chain extender in combination, the amount of heat generated during the reaction with incyanate becomes larger, so that curing properties are improved.

In addition to the flexibility possessed by the polyether, the hardness increases due to the increased concentration of urethane bonds (or urea bonds) in the molded product, resulting in a high physical property with a good balance of rigidity and flexibility. A molded product is obtained. The amount of chain extender used can be varied depending on the required performance (rigidity, etc.).

In the case of low-molecular-weight diols, the amount used is usually 80% or less, preferably 4 to 25% of the total polyol. When a diamine is used, it is added in a smaller amount than the above, for example, in a total amount of 10% or less, preferably 1 to 8% of the polyol and amine. If the number of chain extender claws is greater than the above, the urethane becomes too rigid, resulting in a decrease in initial strength, elongation, and impact properties. The molar ratio of polymer polyol and chain extender is usually 1:
The ratio is 20 to 160, preferably 1:25 to 140.

Chain extenders are preferred as (C), but alternatively or in addition thereto are crosslinking agents such as glycerin.

It is also possible to use trivalent or higher trivalent lower ivoriol such as diethyldiaminotoluene. The use of crosslinking agents increases the viscosity of the reaction system, reduces the flowability during mold injection, reduces the elongation of the physical properties of the molded product, and increases the hardness, so it is better not to use them, and if used, use a small amount to prevent chain elongation. It is preferable that the amount is 20 or less of the amount of the agent.

Total active hydrogen components [(A) and optionally II) (B)
The average equivalent of (C)] is usually 120-1
000, preferably 140-900.

As the organic polyisocyanate used in the present invention, those conventionally used in the production of polyurethane can be used. For example, aliphatic polyisone-1-(hexamethylene diisocyanate).

lysine diisocyanate, etc.), alicyclic polyisocyanates (hydrogenated diphenylmethane diisocyanate, etc.), inphorone diisocyanate, hydrogenated tolylene diisocyanate, etc.
1-, etc.), aromatic polyisocyanates [toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, xylylene diisocyanate, etc.], and mixtures thereof.

Among these, preferred are aromatic diisocyanates, and particularly preferred are TDr, n, and ni. These polyisocyanates are crude polyisocyanates, such as crude TL)1. Crude Ml) i , [crude diaminophenylmethane (mixture of diaminodiphenylmethane, a condensation product of formaldehyde and an aromatic amine or a mixture thereof, and a small amount (for example, 5 to 20% by weight) of a trifunctional or higher functional polyamine) phosgenates: polyallylpolyisocyanate (PA1'I)), or modified polyisocyanes-1--for example, liquid MDI (carposiimide modification, trihydrocarbyl phosphate modification, etc.) or excess polyisocyanate (Tp, MD).
It can also be used as a free isone-containing prepolymer obtained by reacting a polyisocyanate (I, etc.) with a polyol, or they can be used in combination (for example, a modified polyisocyanate and a prepolymer are used together). The polyol used for producing the above prepolymer has an equivalent weight of 30 to
200 polyols such as glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol; triols such as trimethylolpropane and glycerin; high functional polyols such as pentaerythritol and nrubitol; and their alkylene oxides (ethylene oxide and/or 4k is propylene oxide). Among these, those having 2 to 3 functional groups are preferred. The free incyanate group content of the above-mentioned modified polyincyanates and prepolymers is usually from 10 to 33 inches, preferably from 15 to 30 inches, and particularly preferably from 20 to 29 inches.

In producing polyurethane using the block polyoxyalkylene polyol (A) according to the present invention, 1
Polyurethane foam can be manufactured by foaming, but polyurethane resin (enstoma, top, sheet) can be produced without foaming.
may be manufactured. In the former case, the total density of the resulting polyurethane (foam) is usually 0.89 g/crd or higher, preferably 0.5 i/c++ or higher, particularly preferably 0.8 g/crd or higher.
It is preferable to carry out the foaming so that the thickness is equal to or greater than m. If the total density is lower than o,89/crd, a polyurethane resin with excellent self-releasing properties cannot be produced.

Foaming is usually carried out using a foaming agent, but foaming can also be carried out by introducing a gas such as air during molding (air loading).

As the blowing agent, water and/or a halogen-substituted aliphatic hydrocarbon blowing agent (fluorocarbons such as trichloromonofluoromethane) can be used. The amount of water used in the polymer polyol (polyether polyol) is usually 0.4% or less, preferably 0.2% or less.

If the amount of water used exceeds 0.4% kg, the carbon dioxide scum generated by the reaction will be exposed to the surface as bubbles, damaging the appearance of the molded product.

In terms of the physical properties of the casing, the hardness increases due to the increase in urea bonds.The amount of gunpowder used is usually 80% based on the weight of the resin raw material (total of organic polyisocyanate, polymeric polyol, chain extender, and crosslinking agent) when water is not used. % or less (preferably 2 to 20
When 0.4% water is used together with the polymer polyol, the resin raw material type Jj'l is tied to the resin raw material type Jj'l (usually less than 20% (especially 0 to 15%)). stomach.

The ratio of polyisocyanate and active hydrogen atom-containing compound (polymer polyol, chain extender, crosslinking agent, water) may be the same as that of ordinary polyurethane (resin, foam) (NC
For example, the O index is 95 to 120 t<d 100 to 11
0). It is also possible to form a polyisocyanate (resin, foam) using an excess of isomerate (for example, as an index of 120 to 1000, especially 150 to 500).

If necessary, the reaction may be carried out in the presence of catalysts (tertiary amines, organotin compounds, organic complex compounds, etc.), surfactants (silicone surfactants, etc.), and other auxiliaries. can be done. If necessary, a filler, a flame retardant, a solvent, an internal mold release agent, a thixotropic agent, etc. may be added.

The polyurethane manufacturing method may be the same as conventional methods, and either one-shot method or prepolymer method (quasi-prepolymer method) can be applied.

The polyurethane production method of the present invention is particularly applicable to the J(, If14 method).

In the present invention (second invention), a method for producing a polyurethane molded article by molding by the xtiM method can be carried out by a conventional method. For example, a chain extender, a crosslinking agent, a polyol,
Catalyst, blowing agent (water and/or fluorocarbons) if necessary
, a pigment, and a foam stabilizer were added and mixed uniformly as A 7&, and as B liquid, Ison Ane-1 was prepared in advance and filled into tanks A and B of a high-pressure foaming machine. The injection nozzle of the high-pressure foaming machine is connected to the injection port of the mold in advance, and liquids A and 13 are mixed using a mixing head, and the mixture is injected into a sealed mold and removed from the mold after hardening.

According to the present invention, by reacting with an organic polyisocyanate using a block polyoxyalkylene polyol (~) containing a terminal polyoxyethylene chain having a functional group number of 5 or more and an equivalent weight of 1450 or more as at least a part of the polyol, the curing property can be quickly improved. In addition, the polyether polyol has excellent self-releasing properties and greatly improves the strength of the resin, resulting in a polyurethane with excellent initial strength.In addition, the polyether polyol has excellent curing properties and requires less catalyst usage. This avoids deterioration of the physical properties and heat resistance of polyurethane caused by molding.In addition, when polyurethane molded products are used for painting, the paint color changes over time if the molded product uses a large amount of catalyst to speed up curing. However, according to the present invention, such a problem does not occur.Furthermore, in the present invention, by using a chain extender in combination with the polyol (A), the veraretane bond concentration becomes higher than when it is not used in combination. The exothermic ffi is further increased, the initial strength is increased, and the curing properties can be further improved.Also, the curing properties can be improved while maintaining the viscosity of the urethane reactant low, and the balance between elongation and hardness of the physical properties of the molded product can be improved. Good points and excellent effects.

The present invention, in which the polyol (A) and organic polyisocyanate are reacted and molded by the lum method, is superior to conventional methods in the following points.

1) Since it has excellent curing properties, it is extremely effective in shortening the cycle time from injection to demolding, which is the original purpose of the 14IM method. 11) Excellent curing properties even with a small amount of catalyst. Because of this, the increase in viscosity when reacted with polyisocyanate is moderate, and it is possible to avoid insufficient filling and the formation of voids caused by poor flowability in molded products.

111) Conventional methods for increasing curing properties require a large amount of catalyst, and the physical properties of the molded product are greatly deteriorated by oral administration, but the RIM method of the present invention uses catalyst J11. Since the amount of water required is small, problems such as deterioration of the physical properties of molded products due to catalysts and discoloration of coated molded products do not occur.

lv) It has excellent curing properties even with a small amount of catalyst, so the viscosity increase is mild when reacted with polyisocyanate-1, but it quickly reaches the cream state, which is the state before reaction curing. When flowing in the mold) it penetrates into the uneven surfaces of the mold surface and hardens.
In addition, the method of the present invention can be applied to various polyurethane manufacturing methods (foam, elastomer, sea 1) other than the iM method. , etc.), it exhibits excellent effects particularly in polyurethane production methods that conventionally required relatively large amounts of catalysts and polyurethane production methods that use chain extenders.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. (The parts shown in the Examples are the heavy-duty parts.) The components used in the Examples and Comparative Examples are as follows.

Polyol ■: A polyether polyol with a valence of 011 and 28 obtained by adding 9418 parts of propylene oxide and then 2400 parts of ethylene oxide to 182 parts of sorbitol.

Polyol ■: OI (polyether polyol with a valence of 21) obtained by adding 9738 parts of propylene oxide to 182 parts of sorbitol, then 2080 parts of ethylene oxide, 1600 parts of propylene oxide, and then 2400 parts of ethylene oxide.

Polyol ■: A polyether polyol with an OH value of 34 obtained by mixing 92 parts of glycerin and 228 parts of sucrose to give an average functional group number of 5 and adding 6115 parts of propylene oxide and 1815 parts of ethylene oxide.

Polyol ■: 0I- obtained by adding 842 parts of sucrose, 184'00 parts of propylene madeide, 2054 parts of a mixture of propylene oxide and ethylene oxide, and then 2154 parts of ethylene oxide. Polyether polyol with a monovalent value of 25.

Polyol ■: Polyether polyol with an ON value of 28 obtained by adding 12Q8 parts of propylene oxide and 3200 parts of ethylene oxide to 842 parts of sucrose.

Polyol W, a polyether polyol with an OIL value of 25 obtained from 180 parts of glucos, 8220 parts of propylene oxide, and 2800 parts of ethylene oxide.

Polyol vn: Novolac 622 with an average functional group number of 6
OHHBO2 polyether polyol obtained by adding 7800 parts of propylene oxide and 2800 parts of ethylene oxide to 1 part of OHHBO2.

Polyol till: triethylenetetramine 14
A polyether polyol with an OH value of 24 was obtained by adding 9841 parts of propylene oxide to 6 parts, then 2333 parts of a 7711 (weight ratio) mixture of propylene oxide and ethylene oxide, and further 1680 parts of ethylene oxide.

Polyol Ix: 21,000 parts of a polyether polyol obtained by adding 182 parts of sorbitol, 18,726 parts of propylene oxide, and then 21,000 parts of ethylene oxide were reacted with 1 to 774 parts of anhydrous trimeri, and then 2,400 parts of ethylene oxide. 12 functionals obtained by reacting. A polyol with an OfI value of 28.

Polyol A: A polyether polyol with an OH value of 24 obtained by adding 4,908 parts of propylene oxide and then 2,000 parts of ethylene oxide to 92 parts of glycerin.

Polyol B, 136 parts of pentaerythritol, 4,660 parts of propylene oxide, 11,200 parts of a mixture of propylene oxide and ethylene oxide at a ratio of 1:1 (weight ratio), and O obtained by adding xs6omle4''J of ethylene oxide.
HHBO2 polyether polyol.

Polyol C: A polyether polyol having an OH value of 35 obtained by adding 5,060 parts of propylene oxide to 60 parts of ethylene diamine and then 1,280 parts of ethylene oxide.

Polyol D = polyether polyol with an OH value of 28 obtained by adding 8124 parts of propylene oxide to 76 parts of propylene glycol and then adding 800 parts of ethylene oxide in step (a).

Guiflon-11u: 70"-11 black toner manufactured by Daikin Industries, Ltd. Carbon black, anti-aging agent (mixture of ultraviolet absorber, antioxidant, heat resistance improver, etc.) dispersed in polyether polyol.

DABCOsa, t, v: Amine catalyst manufactured by Sankyo Air Products.

DABCODO-2 Catalyst manufactured by Nisankyo Air Products.

DBTDL: Dibutyl tin dilaurate omelette, UL-28: Chemical upgrade ■ Handling tin catalyst.

Sumidur p, c: Modified MI) I manufactured by Sumitomo Bayer Urethane Co., Ltd. Solubility agent B-511 + External mold release agent manufactured by Chukyo Yushi Co., Ltd. (Table 2)
The appearance and analytical values of the above polyols are shown in Table 1. ◎ Examples and Comparative Examples Using polyols 1 to IX and polyols A and D,
A high density polyurethane was formed under the following conditions.

That is, a polyol component (A7ffl) containing a polyol, a chain extender, and a catalyst as main components, an incyane-1 component ("
lj't) and l';:April were respectively charged into the raw material tanks of the foaming machine, and after mixing liquids A and B with the high-pressure foaming machine,
The molded products No. 2 to 5 are flat plate type closed molds (hereinafter abbreviated as flat plate molds) with a thickness of 2.5 mm, a width of 400 inches, and a length of 1000 mm (hereinafter abbreviated as flat plate type), and Tables 6 to 7 show the molds of the above-mentioned molds. High-density and medium-density polyurethane molded products were created by injecting into a flat plate mold with a molded product thickness of 5 mm. CIC9'/ctdG):
160/150 injection time: Approximately 15 to 22 seconds Raw material temperature (both A and B liquids): Approximately 40°C Mold temperature: Approximately 70°C Isocyanate index = 105 The molding recipe and the physical properties of the obtained heavy density polyurecne are shown in Table- 2 to 7.

The molded polyurethane was left to stand under the following conditions and then measured. The molded products in Tables 8 and 5 were annealed at 120" O for 30 minutes after being released from the mold, and then taken up and left for 3 days at 25°C x 60" R11.The molded products in Table 7 were measured at 25°C after being released from the mold. CX60
Measurement was carried out after leaving it for one week or more at Chi-11.

The mold release time and physical properties are as follows.

Mold release time: The time from the start of injection of the reaction solution to the time it is removed from the mold.

Initial strength -■ = Time (in seconds) from the start of injection until the end of the molded product is bent 180° and no cracks appear immediately after the molded product is removed from the mold.

Initial strength - 2 Immediately after removing the molded product from the mold 1
Create a sample for tensile strength measurement by punching it out with a No. 1 dumbbell. Next, the tensile strength of this sample was measured 60 seconds after release from the mold, and the tensile strength was determined as the initial strength.

Self-side molding number: After applying an external mold release agent to the mold once, the number of times continuous molding is performed to obtain the same mold release properties as when applied. The molds are flat plate type and projecting type (Table 2 and Table 4 are molds for producing passenger car bumpers).

Table 5 shows the type for producing passenger car handles) It was used.

Tear strength: Dumbbell type B, crosshead speed 50m
m1 minute bending modulus: sample 25 x 125 x 2
．． 5mm span 40mm Loading nose 51'L Crosshead speed 10mm/min Chart speed M100mm/min Heat sag: Sample 25 x 125'X 2.5
After leaving the sample above at 120°C x 1br with an overhang of 100 mm, the distance traveled was measured after cooling at room temperature for 30 minutes.

Brittle temperature: According to JIS K-6801.

Table-2 Molding recipe, mold release time and initial strength Table-3 Physical properties of molded products

Claims (1)

[Claims] l A method for producing polyurethane by reacting an organic polyisocyanate and a polymeric polyol in the presence of a blowing agent if necessary, in which at least a part of the polyol has a functional group number of 5 or more and an equivalent weight of 1450. The above terminal polyoxyethylene chain-containing block polyoxyalgylene polyol (A) is 20% based on the weight of the polymer polyol.
1. A method for producing polyurethane having self-releasing properties, characterized by using all of the above. The terminal polyoxyethylene chain content of 2(A) is 10% by weight
The manufacturing method according to claim 1, wherein: :3. Borioxyethylene chain content of (A): 10 to 3
The manufacturing method according to claim 1 or 2, wherein the weight Jit% is 0 weight Jit%. 4(A) and other sieve molecular polyols (uniform or/and low-molecular active water-free non-compounds (q. The production method according to claim 4, wherein (C) is an ethylene chain-containing diol and/or triol. 6. The production method according to claim 4 or 5, wherein (C) is a low molecular diol. A) t (B) + (q (D total li, it d iii
8. The manufacturing method according to any one of claims 4 to 6, using 4 to 25% (7) (C). The manufacturing method according to any one of claims 1 to 7 to be used. 9. In the method of manufacturing borine by reacting an organic polyincyanate and a polymeric polyol in the presence of a blowing agent if necessary) As part of the process, a block polyoxyalkylene polyol having a terminal polyoxyethylene chain having a functional group number of 5 or more and f and k of 1450 or more is used in an amount of 20i or more based on the weight of the polymer polyol, and the RIM method is used. 10. A method for producing a polyurethane molded article, characterized in that the organic polyisocyanate and polyol are introduced into the mold without applying a mold release agent each time.