JPH01261412A - Soft polyurethane foam resin composition for composite molding at high temperature - Google Patents

Abstract

PURPOSE:To obtain the title compsn. providing a uniform molded item even if it is poured and exposed in a mold having the same temp. as the molding temp. of a material to be compounded, by incorporating a specified amt. of a specified mixed catalyst together with other components. CONSTITUTION:The title compsn. is obtd. by compounding a polyol (A), a crosslinking agent (B) (including a chain extender), water (C), a polyisocyanate (D) and a catalyst (E) in such a way that the catalyst (D) consists of a combination of an amine catalyst (a) and an organometallic catalyst (b) and the ratio is in the range of a/b of 100/5-100/20 and the amt. of the catalyst E to be added is in the range of 0.5-5 pts.wt. based on 100 pts.wt. of the sum of the components A, B, C and D. When this compsn. is used in a process where a polyurethane resin is poured in a mold a part or the whole of the inner face of which is kept at 110 deg.C or higher and expanded therein to obtain a molded item, even if the resin is exposed to a high temp. on pouring into the mold, poor flow and nonuniformity of quality such as shrinkage and breakage of cells hardly occur and a uniform molded item can be obtd. thereby. It is therefore unnecessary to bring the mold temp. to 80 deg.C or lower as in the conventional process and it is thus possible to improve drastically the molding cycle.

Description

Detailed Description of the Invention "Industrial Application Field" The present invention is a high-temperature composite material used in a method for obtaining a molded product by injecting and foaming a polyurethane resin into a mold whose inner surface is partially or completely set at 110'C or higher. This article relates to flexible polyurethane foam resin compositions for use in high-temperature composites. The present invention relates to a polyurethane foam resin composition.

"Prior Art" Conventionally, when a molded article is obtained by injecting a flexible polyurethane foam resin composition into a mold and foaming it, the temperature at which the polyurethane resin comes into contact with the composition at the time of injection is 80° C. or lower. This principle [1] is that when polyurethane resin comes into contact with high temperature at the time of injection, the formation of hoids increases, gelation, etc. is partially promoted by heat, and uneven Ii! This is due to the fact that it was possible to obtain only high quality products, and there was no need to heat it to a particularly high temperature.

``Problem to be solved by the invention'' However, in recent years, polyurethane molded products
There is a need for further improvements in design, productivity, and performance, and in particular there is a method to obtain composite molded products by installing inserts and skin materials in the mold, injecting resin into the mold, and foaming it. It is being said. Among these methods, as in the method disclosed in JP-A-59-190826 and JP-A-62-56109, the material to be composited with the flexible polyurethane foam resin composition is first molded, and then , when the mold is opened and a flexible polyurethane foam resin composition is injected and foamed to obtain a composite molded article, the initially molded material immediately after molding (due to its required molding temperature) is at the l temperature of the mold. is 110'C or more, and if left as is, it will become impossible to obtain a uniform foam of polyurethane that will be injected later. Therefore, in such a case, it was necessary to cool the mold temperature to 80° C. or lower after opening the mold.

For this reason, productivity decreases in the production of conventional soft polyurethane foam composite molded products, and -
Since the adhesion on the surfaces also deteriorates, it was necessary to perform brimer treatment on the 1υ mating surfaces of the pre-molded material before injecting the flexible polyurethane foam resin composition.

The present invention has been made in view of the above circumstances, and consists of a flexible polyurethane foam resin composition that allows a uniform molded product to be obtained even when the composite material is injected into a mold at substantially the same temperature and foamed. The challenge is to provide goods.

"Means for Solving the Problems" In order to solve the above problems, the present inventors have conducted extensive research,
After repeated experiments, we came to the following findings.

In other words, if the flexible polyurethane foam resin composition is adjusted to satisfy the following conditions (1) and (2), a uniform molded product can be obtained even if it is injected and foamed into a mold at substantially the same temperature as the molding temperature of the composite material. It has been found that a flexible polyurethane foam resin composition can be obtained.

■ The following ingredients must be essential.

A. Polyol, Crosslinking agent (including chain extender), C. Water (blowing agent), B. Polyisocyanate, E. Catalyst, ■ Of the above essential components, the catalyst (E) is an amine catalyst. It is composed of a combination with an organometallic catalyst, and
The ratio of these catalysts is amine catalyst/propyrometal catalyst-1
0015 to 100/20, and furthermore, the total amount of these catalysts added to the other essential component polyol (
A), crosslinking agent (B), water (C), and polyisocyanate (
Total amount of (d) I should be set in the range of 0.5 to 5 parts by weight for the OO heavy base part.

The present invention has been made based on the above findings.

That is, in the present invention, a part or all of the inner surface is heated to 110°C.
A flexible polyurethane foam resin for high-temperature composites used in the method of injecting and foaming a polyurethane resin into the mold described above to obtain a molded product ♀ ■ An acid compound, a) a polyol, a crosslinking agent (including a chain extender) , C. water, 2. polyisocyanate, and Catalyst/organometallic catalyst-10
015 to 100/20, and the total amount of these catalysts added is about 100 parts per total amount of the polyol (a), crosslinking agent (b), water (c), and polyisonoanate (d). It is characterized by a range of 0.05 to 5 small parts.

As mentioned above, in the present invention, the ratio of catalysts contained, that is, amine catalyst/organometallic catalyst, is 100%.
Used in the range of 15 to 100/20, preferably 10
It is in the range of 0/7 to 100/15. The limitation on the mixing ratio of this catalyst is that an organometallic catalyst is mixed with an amine catalyst lOO streetcar! If the amount of 11 is less than 5 parts by weight, voids will occur in the molded product, resulting in poor molding. If the amount of the organometallic catalyst is more than 20 parts by weight, the fluidity of the raw material will become unstable and it will not fit into the mold. This setting was based on the knowledge that filling becomes difficult and unevenness occurs on the surface of the molded product.

In addition, in the present invention, polyol (a), crosslinking agent (
The preferred blending amounts of polyol (b) and water (c) are
b) 0.5 to 2 of the crosslinking agent (b) per 100 parts by weight
0 parts by weight, and 0.1 to 5 parts by weight of water (c).

Furthermore, in the present invention, an NGO component consisting of polyson atom (d), and an O H (NH
The equivalent ratio with the component (including NGO10) is preferably
H=0.8-1.10, particularly preferably 0.90-1.
It is 05. This is because if NGOloH is larger than 1.10, the surface of the molded product will become rough if the demolding time is short, and if it is smaller than 08, wrinkles will occur on the surface, air voids will increase, and the molding will be difficult. This is because it causes a decrease in the strength of the object.

As described above, in the present invention, the total amount of catalyst added is 0.5 to 1100 parts by weight of the total of polyol (a), crosslinking agent (b), water (c), and polyisocyanate (d). Although the amount is in the range of 5 parts by weight, it is preferably 1 to 2 parts by weight, especially when molding is performed in a high temperature mold of 150° C. or higher. This is because if it is less than 0.5 parts by weight, the molded product will have many voids, surface shrinkage will occur, and the skin will turn up. If it is more than 5 parts by weight, the surface of the molded product will become uneven. This is because the fluidity of the composition deteriorates, resulting in insufficient filling.

+ The polyol of iii (a) has a molecular weight of 500
As mentioned above, polyether polyols, polymer polyols, urea fraction polyether polyols, polyester polyol diols, acrylic polyols, polybutadiene polyols, terminal -NH of polyether polyols, preferably having a talkative hydrogen at the terminals of 1000 to 8000, One or more selected from polyether polyamines and polyols used in conventional polyurethane resins can be used.

Examples of the crosslinking agent mentioned above include ethylene glycol, diethylene glycol, I,4-buta/diol, bishydroethoxyhensen, trimethylolpropane, glycerin, sorbitol, and alkylenes thereof, which have an active hydrogen at the end with a molecular weight of less than 500. Polyhydric alcohols such as oxide adducts, propylene oxide adducts of ethylenediamine, -class and secondary polyamines, aliphatic. One or more crosslinking agents selected from alicyclic polyamines, aromatic amines such as diphenylmethanediamine, m-phenylenediamine, diethyltoluenediamine, and 4,4'-methylenebischloroaniline are used. be able to.

The water in (c) above is used as a blowing agent, and in the present invention, it is possible to use a physical blowing agent such as a chlorofluorocarbon blowing agent together with this water as necessary, and water is essential. It is a component of

The polyisocyanate (2) has 1N at the end.
Toluene diisocyanate, diphenylmethane diisocyanate having GO group, 1. 5-naphthalene diisocyanate, 3.3'-dimethyldiphenyl4.
4°-diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, paraphenylene diisocyanate, trans-1,4-7 chlorohexyl diiso/anate,
Hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diiso/anate, ricinodiisocyanate.

Tetramethylquinone diison atomite, 2,2゜4
(2,4,4) Diiso/anates such as trimethylhexamethylene diisonanate, triisocyanates, trimethylolpropane, toluene diisocyanate, l,6-hexamethylene diiso/anate, isophorone/iso/anate, etc. diiso/anates, triphenylmethanetriisonanate, tris(incyanate phenyl)thiophosphate, 1.6.1
Triisocyanates such as 1-undecane triisocyanate and 1,3.6-hexamethylene triisocyanate, trimethylolprobantotoluene/isocyanate, hexamethylene diiso/anate, isophorone/
Select from adducts such as iso/anate, dimers, tripers, carbodiimides, allo/percentate, biuret, urea modified products, modified polyisomers such as urea polymers, derivatives, etc. One or more of these can be used. The catalyst in (e) above is a combination of an amine catalyst and a metal catalyst in m combinations U (
Use Φ.

On the other hand, triethylamine, N,
Monoamines such as N-dimethylcyclohekifluamine,
N, N, N', N''-tetramethylethylenediamine,
N, N, N", No-tetramethylhexane-1,6-
Diamines such as diamine, N, N, N', N", N"
- Triamines such as bentalmethyldiethylenetriamine and tetramethylguanidine, cyclic amines such as triethylenediamine and N-methylmorpholine, alcohol amines such as dimethylamine/ethanol, and N,N,N'-1-limethylaminoethylethanolamine. At least one compound selected from the group consisting of ether amines such as, bis(2-dimethylaminoethyl) ether, and ethylene glycol bis(3-dimethyl)-amino/propyl ether can be used.

Examples of the other organometallic catalyst include stannath octoate, dibutyltin diacetate, dibutyl dilaurate, dibutyl tin merbutide, dibutyl tin thiocarboxylate, dibutyl dilaurate, dioctyl tin mercbutide, and no octyl tin thiocarboxylate. /rate,
One or more compounds selected from compounds such as phenylmercury propionate and lead octenoate can be used.

In the present invention, other additives that may be used as necessary include CF, Cf! , CCf1!3F foaming agents, flame retardants such as chloroalkyl phosphates, polymeric phosphites, dibromopropanol, brominated polyethers, fillers such as silica, glass, carbon black, asphalt, and hydrated carposis and fatty acid amides. Anti-decomposition agent, bistarchybutylnohydrooxytoluene, lrga no x 1
010 (Phenolic antioxidant manufactured by Ciba Geigy)
Antioxidants such as Tinuvin 327 (benzotriazole ultraviolet absorber manufactured by Ciba Geigy), anti-mildew agents such as pentachlorophenol and thiabendazole, boronoxane-polyoxyalkylene block polymer, sulfonated silane 1 selected from foam stabilizers such as sodium salts of acids, etc.
More than one species is used as appropriate.

In addition, in the present invention, the density of the flexible polyurethane foam obtained in 1) after thermoforming is practically 0.05 to
1.0 g/cm3 is preferred. Furthermore, according to the present invention, a flexible polyurethane foam having a low density of 0.05 to 0.5 g/cm3 can be obtained.

"Function" According to the flexible polyurethane foam resin set 1 with the above structure, when performing integral molding using polyurethane resin, there is no need to keep the mold temperature below 80'C, and the mold can be molded in advance in the mold. Temperature inside the mold (110'c)
Even in 2), a composite molded product with a beautiful surface can be obtained, and the molding cycle can be greatly improved. Additionally, the higher the t-temperature of the composite surface, the better the adhesiveness of the polyurethane resin, eliminating the need for brimer treatment and significantly streamlining the process. Furthermore, since it is possible to heat the mold to a high temperature, the fluidity of the polyurethane resin is improved, and it is also possible to mold a film-shaped mold or a thin-walled mold with a large surface area. Furthermore, a thin molded product of about 2 to 3 mm usually has a density of 0.5 g/cm3 or more, but if the flexible polyurethane foam resin composition of the present invention is used, it is possible to achieve a density of 0.5 g/cm3 or less. .

In addition, when using the flexible polyurethane foam resin composition for high-temperature composite molding of the present invention to obtain a synthetic sculpture, the molding material that is molded in advance in a mold is a fiber-reinforced thermosetting resin composition (FRP). For example, it is obtained from unsaturated polyester resin, vinyl ester resin, epoxy resin, phenol resin, etc. as a matrix resin and reinforcing material such as glass fiber, carbon fiber, etc. /-Tomolding compound, Examples include bulk molding compounds.

"Examples" Examples of the present invention will be shown below to specifically explain the present invention, but the present invention is not limited to these Examples.

(Example 1) - Efsenol 820 (polyether polyol manufactured by Asahi Glass Co., Ltd., Mw = 4900) ......100 parts, - Ethylene glycol ......2 .5ff
iffi club,・Wednesday・・・・・・・・・・・・・・・・
......1.6 parts by weight, Polycat 12
(Tertiary amine catalyst manufactured by Sun Abbott Co., Ltd.) ...1.57 parts by weight, ・UL-1 (Mday Kasei Co., Ltd. plaster tin catalyst) ......0.08 parts by weight, Above Add 42.5 fflffl of polyol compound Niisonate 143L (liquid modified diphenylmethanediyne/ananate, manufactured by M-D Kasei Co., Ltd.) mixed with the ingredients, stir rapidly for 10 seconds to mix, and immediately press into an electric press. The mixture was poured into a mold, the mold was closed by a press, and held for 2 minutes, and then the molded product was taken out from the mold to obtain a foam. The size of the mold at this time is 300 x 2
It is made of 50 x 2 mm furanone 2+M construction, and gas vents are provided in the center of the left and right short sides in a V-shape at a depth of about 1 mm. In addition, the mold temperature was changed to 40°C, 160°C, 580°C, 100°C,
+10℃5130℃1150'C, 170℃, 190℃
It was molded in the same way.

The results are shown in Table 1. As is clear from this table,
A uniform foam was obtained at a mold temperature in the range of 110°C to 150°C.

(Example 2) A molded article was obtained in the same manner as in Example 1, except that Polycat 12 and tJL-1 were changed to 1 part by weight and 0.15 parts by weight, respectively. The results are also shown in Table 1. A uniform foam was obtained at mold temperatures ranging from 100°C to 1700°C.

(Example 3) Polychara) 12 of Example 1 was added to 1.375 parts by weight, and U
Molded articles were obtained in the same manner as in Example 1, except that L-1 was changed to 0.275 parts by weight. The results were the same (shown in Table 1). Uniform foams were obtained at mold temperatures ranging from 80°C to 130°C.

(Comparative Examples 1 to 7) The total amount of Polycat 12 and tJL-1 added was <1.65 parts by weight, the same as in Examples 1 to 3, and the blending ratio was changed from Comparative Examples 1 to 7 in order: toolo, +00/1 ．． too/4
0, +00/70.100/100.0/loo,
A molded article was obtained in the same manner as in Example 1 above. The results are in Table 1
It was shown to.

As is clear from the table, if the mold temperature is 110° C. or higher, a uniform foam cannot be obtained in any case.

As is clear from Table 1 showing the results of Examples 1 to 3 and Comparative Examples 1 to 7, Polycat 12 (
Both catalysts (amine catalyst) and UL-1 (organometallic catalyst) are required, and the mixing ratio of (amine catalyst)/(organometallic catalyst) is 10015 to 100.
It can be seen that setting the temperature within the range of /20 is necessary to obtain a uniform foam even at a mold temperature of 110° C. or higher.

(Examples 4 to 7) The ratio of (Polycat 12)/(UL-1) is too
/10, and the total addition amount was changed from Example 4 to Example 7 to 0.
73 ffl parts, 1.47 parts by weight, 2.93 parts by weight, 7
．． A -C molded product was obtained in the same manner as in Example 1 using 33 layers (4 parts).

The results are shown in Table 2. As you can see from this table, mold temperature 1
A uniform foam was obtained even at temperatures above 00°C.

(Comparative Examples 8 to 10) The amounts added in Examples 4 to 7 were changed from Comparative Examples 8 to 10:
, o, ts parts by weight, 0.25 parts by weight, and 147 parts by weight A molded article was obtained in the same manner as in the same example except for the modified eta. The binding is shown in Table 2. As can be seen from the table, a uniform foam could not be obtained at temperatures above 100°C.

Table 2 showing the results of Examples 4 to 7 and Comparative Examples 8 to 1O
As is clear from the figure, the total amount of Polycat 12 (amine catalyst) and UL-1 (organometallic catalyst) is the same as that of Efcenol 820 (polyol), ethylene glycol (crosslinking agent), and water (blowing agent). When the total amount of 31m with isonate (polyisocyanate) is 100 parts by weight,
It can be seen that setting the mold temperature to 085-5 is necessary to obtain a uniform foam even with a single mold at 110°C or higher.

(Hereinafter, blank space) "Effects of the Invention" As explained above, according to the flexible polyurethane foam resin composition for high-temperature abdominal composite molding according to the present invention, when performing integral composite molding using polyurethane resin, the mold is
There is no need to lower the temperature below 0°C, and the molding cycle is significantly improved.

Furthermore, the higher the temperature of the composite surface for boat fishing, the better the adhesion of the polyurethane resin, eliminating the need for brimer treatment and significantly streamlining the process. Furthermore, since it is possible to heat the mold to a high temperature, the fluidity of the polyurethane resin is improved, making it possible to mold molds with complex shapes, thin walls, and large surface areas. Furthermore, a thin molded product of about 2 to 3 mm usually has a density of 0.5 gJcm3 or more, but if the flexible polyurethane foam resin composition of the present invention is used, it is possible to achieve a density of 0.5 g/crr+3 or less. .

Applicant Dainippon Ink & Chemicals Co., Ltd. Aisin Seiki Co., Ltd.

Claims (3)

[Claims] (1) A flexible polyurethane foam resin composition for high-temperature composite use used in a method for obtaining a molded product by injecting and foaming a polyurethane resin into a mold whose inner surface is partially or completely heated to 110° C. or higher, comprising: (a) a polyol; (b) , a crosslinking agent (including a chain extender), iii) water, d) a polyisocyanate, and iii) a catalyst as at least essential components, and the catalyst (e) is composed of a combination of an amine catalyst and an organometallic catalyst. , the ratio of these catalysts is amine catalyst/organometallic catalyst=10
The range is from 0/5 to 100/20, and the total amount of these catalysts added is based on 100 parts by weight of the total amount of the polyol (a), crosslinking agent (b), water (c), and polyisocyanate (d). A flexible polyurethane foam resin composition for high-temperature composite molding, characterized in that the amount of polyurethane foam is in the range of 0.5 to 5 parts by weight. (2) Claim 1 wherein the amine catalyst is a tertiary amine compound.
The flexible polyurethane foam resin composition for high temperature composite molding described above. (3) The flexible polyurethane foam resin composition for high-temperature composite molding according to claim 1 or 2, wherein the organometallic catalyst is an organotin compound.