WO1991004298A1

WO1991004298A1 - Process for producing reinforced isocyanate reaction injection molding product

Info

Publication number: WO1991004298A1
Application number: PCT/JP1989/000963
Authority: WO
Inventors: Akira Shimoda; Yoshio Ota; Kazuo Shoji
Original assignee: Dow Chemical Japan Limited; Yabashi Industries Co., Ltd.; Md Kasei Limited
Priority date: 1988-04-01
Filing date: 1989-09-21
Publication date: 1991-04-04
Also published as: JPH01253414A

Abstract

The invention relates to a process for producing a reinforced isocyanate reaction injection molding product from a composition comprising a hydroxyl- and/or amino-terminated polyether and/or a hydroxyl-terminated polyester, a chain extender, a polyisocyanate and a filler, wherein a calcium carbonate whiskers are used as said filler.

Description

Specification Manufacturing method for reinforced cyanide injection molding technology

The present invention relates to a method for producing an isocarbonate-based reinforced reaction injection molded article, and particularly to a polyolefin and / or a polyurea reinforced reaction injection molded article having a filler, with excellent moldability. TECHNICAL FIELD The present invention relates to a method for producing an isocyanate-based reinforced reaction injection molded article which can be molded into a high-quality molded article. Background technology

Conventionally, in the reaction injection molding method, various materials and shapes were applied and various surface treatments were applied to improve the dimensional stability of the molded product, that is, to reduce the coefficient of linear thermal expansion and the coefficient of water expansion. Fillers have been used.

Conventionally, as a filler used in the reaction injection molding method, there are a fiber glass filler, a calcium titanate and the like.

However, each of the previously proposed fillers has some disadvantages, and it has been difficult to efficiently produce high quality products.

For example, among the fillers conventionally used, a fibrous glass filler has a sufficient reinforcing effect and can provide good dimensional stability. No,

Pita group There is a drawback that the resulting molded article has poor surface smoothness (Japanese Patent Application Laid-Open Nos. 60-159031, 62-68710).

This defect in surface smoothness is caused by the thermal shrinkage of the resin, and is caused by the inclusion of fillers having different shrinkage rates. Therefore, surface clarity after painting is closely related to the surface smoothness of unpainted products. In the past, to improve such problems in painted products, improvements have been made by applying multiple layers of paint or applying low-temperature baking overcoating, but a sufficient improvement effect has not been obtained.

On the other hand, there has been known a molding method using a potassium titanate whisker as a filler to obtain a sufficient reinforcing effect and dimensional stability and at the same time to obtain a good surface smoothness (Japanese Patent Application Laid-Open No. 61-20717). However, in this method, for example, when a filler is mixed on the roll side by urethane reaction injection molding, the viscosity is significantly increased, handling becomes difficult, or when a large molded product is molded, There were drawbacks such as poor filling properties and, in some cases, poor mixing during molding due to the difference in viscosity between the polyol side and the isocyanate side. In addition, when attempting to obtain a sufficient reinforcing effect due to such an increase in viscosity, there is also a disadvantage that the filler cannot be used at a high concentration and the reinforcing effect cannot be sufficiently improved. there were. Attempts have been made to lower the viscosity by improving the surface treatment method of the filler. However, a sufficient improvement effect has not been obtained.

In addition, when fillers are generally used, the fillers are mixed and used, for example, on the polyol side in polyurethane reaction injection molding.

New paper In this case, if the filler settles quickly, the tank and the filling device, etc., where the mixture is filled are not constantly stirred and circulated, the liquid will be non-uniform. Etc. occur.

In addition to the above-mentioned fillers, various fillers such as glass flakes, my strength, and wallacetonite are commercially available, but the balance of the formability, the surface smoothness and the physical properties of the molded product is balanced. It is difficult to satisfy well, and at present, these fillers are rarely used (Japanese Patent Laid-Open No. 62-54755). Disclosure of the invention

The present invention solves the above-mentioned conventional problems, and provides an reinforced reaction injection mold capable of producing a polyurethane and Z or polyurea reinforced reaction injection molded article with excellent moldability and quality characteristics. An object of the present invention is to provide a method for producing a molded product.

The process for producing an isocarbonate-based reinforced reaction injection molded article of the present invention comprises a polyether having a hydroxyl group and a Z or amino group at the terminal and a polyester having a Z or hydroxyl group at the terminal, a chain extender, and a polyether. In a method for producing an reinforced reaction injection molded product of an isocyanate type by subjecting a composition containing an isocyanate and a filler to reaction injection molding, a whisker of carbonated calcium carbonate is used as a filler. It is characterized by. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

New paper Examples of the polyether and polyester having a hydroxyl group at the terminal used in the present invention include, for example, relatively high hydroxyl groups disclosed in JP-A-60-500418 and JP-A-61-501575. Equivalent amounts of polyetherpolyol and polyesterpolyol are included. The number of hydroxyl functional groups in such a polyol is preferably 2 to 3 on average, and the hydroxyl equivalent is preferably 1500 to 2500 on average.

Relatively high hydroxyl equivalent polyester polyols suitable in the present invention include, for example, alkylene oxides, halogen-substituted or aromatic-substituted alkylenoxides or mixtures thereof and an active hydrogen-containing initiator compound. Can be produced by reacting In addition, a suitable polyester terpolyol in the present invention can be produced, for example, by reacting a polycarboxylic acid or an acid anhydride thereof with a polyhydric alcohol.

Other polyols having relatively high hydroxy equivalent weight include, for example, US Patents RE29,118 (Stamberger), RE28,715 (Stamberger), RE29,014 (Picchini et al.), And US Patent 3,869,413 (Brankenship ), U.S. Pat. No. 4,394,491 (Hoffman et al.) And U.S. Pat. No. 4,390,645 (Hoffman et al.).

On the other hand, the amino group terminal polyether used in the present invention (hereinafter sometimes referred to as “amino polyether”) has at least two amino groups as terminal groups. Po

New tear paper PT JP 9 00963

A polyester having an average molecular weight of about 1800 to 12000, preferably about 2000 to 8000 is suitable. This aminopolyether can be prepared by known methods, for example, polyhydroxypolyether.

(Specifically, polypropylene glycol ether) can be produced (for example, Belgian Patent No. 634, 741, US Patent No. 3,654, 370, West Germany) No. 1,193,671, U.S. Pat. No. 3,155,728, U.S. Pat. No. 3,236,895, French Patent No. 1,551,605, and French Patent No.

(See Nos. 1, 466, 708)

In the present invention, examples of the chain extender include an aromatic amino group-containing chain extender, an aliphatic amino group-containing chain extender, a hydroxyl group-containing chain extender, and a mixture of two or more thereof. Among them, examples of the chain extender containing an aromatic amino group include 2,4-bis (p-amino benzyl) aniline and 2,4 diamido. Notoruene, 2, 6—Diaminotriene, 1,3 1-Diphenylamine, 1,4—Diphenylamine, 2,4'-Diaminodiphenyl 1, 4,4'-diaminodiphenylmethane, naphthalene 1> 5 -diamin, triphenylmethane 4,4 ', 4 "triamine, 4, 4'-G (methylamino) diphenyl methane, 1 methyl 1 2 — methylamino 4 — amino benzene, poly Phenylpolymethylenepolyamine, 1,3—Jethyl2,4—Diaminobenzene, 2,4—Diaminomecitylene, 1—Methyl3,5- Getyl 1, 2, 4 — diaminobenzene, 1 methyl 1, 3, 5

New paper Jechiru one 2, 6 - di § Mi Roh benzene, 1, 3, 5 - Application Benefits Echiru 2, 6 - Jiami Bruno benzene, 3, 5, 3 ^r, 5 'one te preparative La Echiru 4, 4' Jia Mi Bruno Divinylmethane, 4,4'-methylenebis (2,6-diisopropylamine), a mixture thereof and the like can be used.

Examples of the aliphatic amino group-containing chain extender include aliphatic amines disclosed in JP-B-61-36843.

Examples of the hydroxyl group-containing chain extender include, for example, ethylene glycol, propylene glycol, ′ ′ silicone resin, and trimethyl alcohol. Rono. 1,4-butanediol, diethylene glycol, zippered pyrene glycol, bisphenols, nitrodroquinone, catechol, reso'J resinine, triethylene Low molecular weight ethylenoxy, such as glycole, tetraethylene glycol, dicyclopentagen gentanol, glycerin, glycerin or ethylene diamine or ethylene triamine And Z or propylene oxide derivatives, mixtures thereof, and the like.

Examples of the polyisocyanate used in the present invention include an aromatic polyisocyanate, an aliphatic polyisocyanate and a mixture thereof. Specifically, 2,4—toluene engine, 2,6—toluene engine, P, P 'diphenylmethanine engine, p—finenji engine Polyesters having two or more NC0 groups per molecule, such as polymethyl propylene polyisocyanates and mixtures thereof.

New paper Lysocyanate, or a prepolymer obtained from such a polyisocyanate and a compound having two or more active hydrogen atoms, and a uretonimine bond or a carbodiimide bond Such polyisocyanates and Z or prepolymers thereof modified to include: hydrogenated derivatives of the above-mentioned aromatic polysocyanates; 1,6-hexamethylene diisocynate; 1 O, 4-cyclohexyldiisocyanate, 1,4-bis-iso-methoxymethylcyclohexane, etc.

In the present invention, a calcium carbonate whisker is used as a filler used together with each of the above components.

The carbonated calcium filler used in the present invention is a single crystal, usually fibrous particles having a major axis of 5 to 100 and a minor axis of 0.2 to 5, and is therefore referred to as a carbonated calcium carbonate.

The method for producing the calcium carbonate whiskers used in the present invention includes:

① Quick lime (CaO) and slaked lime by the so-called “liquid-gas method”

A method of producing a carbonated calcium whisker by reacting an aqueous solution of hydroxylated calcium obtained from (Ca (0H) ₂ ) or the like with a gas containing carbon dioxide (Japanese Patent Application Laid-Open No. 62-278123).

(2) A method of obtaining an aqueous solution of calcium bicarbonate from limestone or the like and a gaseous substance containing carbon dioxide to generate a whisker (JP-A-62-27325).

However, the method (1) is far more advantageous from the viewpoint of industrial economics.

In the present invention, the carbonic acid

¾ ； ¾ The whisker may be used without any surface treatment, or may be used with various surface treatments such as aminosilane. The amount of addition is not particularly limited, but is preferably in an amount such that the amount is 5 to 30% by weight based on the total resin weight.

As the catalyst for the reaction injection molding of the present invention, an organotin compound or a tertiary amine catalyst is usually used.

In the present invention, in addition to the components described above, Japanese Patent Publication Nos. 60-500418, 61-501575, 61-83215, 60-245622, and 62-97808, etc. An internal mold release composition using a metal salt, or a silicon-based internal mold release agent disclosed in Japanese Patent Publication No. 54-8513, Japanese Patent Publication No. 55-1176, Japanese Patent Publication No. 62-44763, etc. You may. Further, a surfactant, a coloring agent, a flame retardant, and other additives can be added.

The production method of the present invention can be easily carried out by carrying out reaction injection molding in the usual manner using predetermined amounts of the above-mentioned various raw materials.

The method for producing an isocarbonate-based reinforced reaction injection molded article of the present invention uses a whisker of calcium carbonate as a filler.

(1) The problem of the conventional wiper filler has been solved. For example, the viscosity of the mixed solution does not rise to the extreme even when mixing with polycarbonate.

(2) The problem of glass fiber filler is solved, and it is possible to obtain molded products with excellent surface smoothness.

New paper ③ The settling of the filler is small, and the problems caused by the settling are not solved or reduced.

Thus, excellent effects that could not be satisfied at the same time have been achieved, and high-quality molded products can be efficiently manufactured based on good moldability and workability. Industrial applicability

INDUSTRIAL APPLICABILITY The present invention can be advantageously used for the production of a strengthening agent-containing isocarbonate-based molded article having excellent properties.

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples, and Reference Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. In the following

“Parts” means “parts by weight”.

Example 1

Po Li O carboxymethyl ethylene pro propylene ether Po Li ol (Dow Ke Mi Cal Nippon Co., hydroxyl value 28ni _g - KOHZ _g) 80 parts, Jechi Le emissions preparative Rue Njiami down mixture (manufactured by E chill Corporation Leh sucrose emissions Co.) 19 parts, 0.8 parts of surfactant (manufactured by Nippon Tunicer, SZ-1907), 0.1 part of tin catalyst (manufactured by Witco, UL-28) and 0.1 part of amine catalyst (manufactured by Nippon Emulsifier, DABCO 33LV) 0.1 part of the mixture was used as solution B, and calcium carbonate I-scar (manufactured by Yabashi Kogyo Co., Ltd., minor axis 0.5-4 jm, major axis 10-60 (untreated surface)) 16.5 parts were mixed. Stir well. To this, 48.2 parts of liquid diphenylmethane solution (Amm-D Chemical Co., Ltd., NC0 23% by weight) was used as liquid A, and the reaction injection molding machine MC-104 manufactured by Polyurethane Engineering was used. hand

Ceremony The raw material was injected into a flat mold (500 mm x 700 mm x 3 mm) to obtain a molded product.

Table 1 shows the surface smoothness and physical properties of the obtained molded article.

Example 2

As a filler, 1 kg of the whisker used in Example 1 was soaked in 4 pounds of a 2% by weight aqueous solution of an aminosilane (A1100, manufactured by Nippon Riki Co., Ltd.) for 15 minutes, and the water was filtered off. Molding was carried out in the same manner as in Example 1 except that the dried product was dried for 10 hours and used.

Comparative Example 1

Molding was performed in the same manner as in Example 1 using 100 parts of the liquid B of Example 1 and 48.2 parts of the liquid A of Example 1.

Table 1 shows the surface smoothness and physical properties of the obtained molded article. Comparative Example 2

16.5 parts of glass fiber (FESS-005.0413, fiber diameter 10 / πη, fiber length 100 lord) was mixed with 100 parts of the solution B of Example 1 and stirred well. Molding was performed in the same manner as in Example 1 using this mixture and 48.2 parts of the solution.

Table 1 shows the surface smoothness and physical properties of the obtained molded article. As is apparent from Table 1, according to the method of the present invention, a molded article having extremely high physical properties, particularly dimensional stability, can be obtained by blending the filler. Moreover, the obtained molded article has the same excellent surface smoothness as when no filler is blended (Comparative Example 1).

New paper Table 1

* All samples were post-cured at 120 for 1 hour, and then the physical properties were measured.

II: Liquid flow direction

丄: Direction perpendicular to the liquid flow

Reference example 1

The fillers shown in Table 2 were mixed with the solution B of Example 1 (without adding α1), and the viscosity was measured at 25 ° C with a Tokyo Keiki Β type viscometer.

· · — O

Also, 200 cc of the mixed solution was placed in a bottle, allowed to stand at room temperature for 5 days, and the rate of sedimentation was determined by determining the ratio of the thickness of the supernatant liquid layer to the total thickness when the filler settled. Was examined.

The results are shown in Table 2.

As is evident from Table 2, the carbonated calcium whisker used in the present invention has both an increase in the viscosity of the mixed solution and a small sedimentation rate of the whisker due to the compounding, and is extremely advantageous in terms of molding workability. O)

New paper P8900963

13 Table 2

* L: Whisker used in Example 1

*? : The whisker used in Example 2

* 3: Glass fiber used in Comparative Example 2

* 4: "Chismo D105" manufactured by Otsuka Chemical Co., Ltd.

* 5: "HT-200A" manufactured by Titan Kogyo

* 6: “MO S Heidi A j” manufactured by Ube Industries, Ltd.

* 7: "M〇S Heidi B" manufactured by Ube Industries, Ltd.

* 8: Franklin Fiber A-30 manufactured by GYPSUM, USA

Claims

The scope of the claims

1. Reaction of a composition containing a hydroxyl- and Z- or amino-terminated polyester and a Z- or hydroxyl-terminated polyester, a chain extender, a polysocyanate and a filler. A method for producing an isocarbonate-based reinforced reaction injection molded article by injection molding, wherein a carbonated whisker whisker is used as a filler. The method of manufacturing the product.

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