JPS6016983B2 - Molding composition based on thermosetting condensation resin for molding processing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a molding composition based on a thermosetting condensation resin for molding, which contains a reaction product of an amino-substituted aromatic compound and an epoxyalkane and/or a carboxylic acid.

Thermosetting molding compositions contain as an essential component a binder which can be crosslinked by polycondensation under the action of heat and pressure.

Phenol, cresol,
Precondensates of resol type or novolac type phenolic resins obtained by condensing xylenol, naphthol or polyphenols with formaldehyde, polymerized formaldehyde or other aldehydes, or urea, guanidine, substituted ureas, melamine, substituted melamine or aniline with formaldehyde There are precondensates of aminoplast resins obtained by condensation with , polymerized formaldehyde, furfural or other aldehydes. The molding composition may also contain other binders such as phenolic/borac type resins, melamine formaldehyde resins. In addition to the above-mentioned characteristic binder, the curable composition for molding may additionally contain a crosslinking agent such as hexamethylenetetramine,
Contains hardening accelerators such as magnesium oxide, fillers such as chalk, asbestos, cellulose or wood flour, pigments, plasticizers, stabilizers and boar agents.

Zero lubricant has an important meaning on the moldability (workability) of the thermosetting composition for molding. In order to ensure uniform mold filling in compression molding, transfer molding or injection molding, the fluidity of the composition must be improved by the boar agent. Furthermore, the lubricant has the role of facilitating release of the cured product, and when an external template agent is used, complicated molding processes are unnecessary. The improved fluidity and internal mold release function work together to make the surface of manufactured parts steel-tight and smooth. For the purpose of uniform distribution as well as to prevent adhesion and premature hardening of the composition in rolling mills, jaw extruders or tablet presses, the lubricant is preferably added to the molding composition at the latest during the manufacture of the resin. It is added when manufacturing powder, chips, tablets or tablets.

As lubricants, conventionally, first of all stearic acid and other fatty acids, metallic soaps of fatty acids of various basicities such as calcium stearate, zinc stearate, magnesium stearate, aluminum stearate, and also natural waxes such as beeswax and carnauba wax are used. Synthetic waxes such as ester, montanate, cetyl palmitate, stearyl stearate, ethylene diamine distearate, paraffin waxes made from various raw materials, mineral oils or tar oils have been used.

The lubricants conventionally added or proposed are not fully satisfactory and are particularly problematic when considering the entire process of resin production, molding composition production and molding processing.

In the case of the above-mentioned thickeners, it is thus difficult to completely distribute them in the molding composition, especially when the precondensed resin is produced in the form of an aqueous solution or dispersion. The hydrophobic nature of the lubricants mentioned above inhibits uniform distribution. For example, the more a hydrophilic lubricant such as an alkylene oxide adduct of a monofunctional or polyfunctional aliphatic alcohol or its carboxylic acid ester is added, the better the distribution in the molding composition becomes. When used in addition, the lubricant tends to leach out from the molded product during the curing reaction. Attempts have been made to reduce the disadvantages of leaching during molding operations by using small amounts of lubricants; The effect of the thickener on the fluidity of the curable composition for molding is no longer sufficient. Another disadvantage of conventionally added lubricants is that in order to achieve a sufficient mold release effect, the lubricant must be enriched and present in large quantities on the surface of the molded product, which is caused by the pressure during molding. It can be achieved.

This provides better mold releasability, but the lubricant that is present in a high concentration near the surface does not separate together with the molded product.
On the contrary, large amounts of residue remain on the mold surface over several successive molding operations, resulting in a change in the dimensions of the molded article according to the dimensions of the mold. Furthermore, since the residual lubricant is thermally decomposed in the mold, there is a disadvantage in that discoloration occurs even when attempting to produce light-colored molded products. Conventionally, it has been impossible to satisfy all processing technology requirements with a single type of boar agent. For example, fatty acid metal soaps exhibit extremely good mold release properties, but their effect on melt viscosity is particularly poor in injection molding. The plasticizing effect is extremely small.

Furthermore, attempts have been made to combine multiple lubricants, such as metal soap and mineral oil, to achieve a variety of functions, but due to their mutually exclusive effects, they are less compatible than a single lubricant. becomes even worse. As mentioned above, various attempts have been made to overcome the difficulties encountered during the molding process of thermosetting condensation resin compositions for molding, but despite all efforts, no method has been found sufficient to solve this problem. I haven't seen it yet and it hasn't been released yet.

The present inventors have determined that the formula <・) [where RI and R2 are hydrogen, methyl group, methoxy group,
and may be the same or different, R3 means a methyl group, phenyl group or ZfO-CHX-CH2am, x is hydrogen and/or an alkyl group having 1 to 2 carbon atoms, and Y and Z is hydrogen or R°C01 (here, R4 represents a hydrocarbon residue having 12 to 26 carbon atoms).

), and the sum of n and m is a value from 0 to 10bo≧,
However, when n is less than 10 or 10, and X is hydrogen or an alkyl group having 1 to 9 carbon atoms, at least one of Y and Z is R4CO-, and the compound of formula 1 is at least provided that it has one unsubstituted ortho or para position. It has been found that the above-mentioned disadvantages can be avoided by incorporating the compound] into a molding composition based on phenol or melamine resin. For the production of compounds of formula 1 used in the molding compositions of the invention, aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine, p-anisidine, o-phenylenediamine, m-phenylenediamine, Nylenediamine, p-phenylenediamine, symmetrical triaminobenzene, methylaniline, diphenylamine,
Aromatic compounds substituted with amino groups containing free hydrogen atoms are used, such as benzidine, 4,4'-diami/diphenylmethane or asymmetric-dimethyl-p-phenylenediamine.

In addition to ethylene oxide and propylene oxide, examples of epoxy alkanes include 1,2-epoxybutane, 1,
2-epoxydecane, 1,2-epoxydodecane, 1,
1,2-epoxyalkanes having 4 to 2 carbon atoms such as 2-epoxybentadecane, 1,2-epoxyoctadecane and 1,2-epoxytetracosane may also be used. It is also possible to use 1,2-epoxyalkane mixtures prepared from commercially available olefin mixtures by methods known per se. Such olefin mixtures have been obtained, for example, in a process following the chemistry of alumino compounds according to Ziegler.

Examples of brewing ingredients used in the production of the compound of formula 1 of the present invention include fatty acids obtained from natural fats and oils such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid, stearic acid-palmitic acid mixtures, Fatty acid mixtures such as beef tallow fatty acid mixtures, coconut oil fatty acid mixtures, as well as branched carboxylic acids such as isopalmitic acid or isostearic acid, substituted fatty acids such as phenylstearic acid, hydroxystearic acid or ricinoleic acid may be mentioned.

Examples of the compound of formula 1 of the present invention include aniline.
(Ethylene oxide), Aniline・Group 0・1Group 0 (Propylene oxide), Aniline・32E○, Aniline・40P○, Aniline・6Group 0, Aniline・33E0・
Group 3 0, Aniline 3 is ○-monostaric acid ester, aniline 1,2-epoxydodecane, phenylstearisoyl anilide, o-toluidine 100P○, p-toluidine isostearic acid anilide, p-phenylene Diamine・7group0, p-phenylenediamine・30E○
・40P○, o-phenylenediamine ・2PO-monolauric acid ester, asymmetrical dimethyl-p-phenylenediamine linoleic acid anilide, benzidine 15○・solution○-distearic acid ester, benzidine-tetracosanoic acid anilide, 4,4 -diaminodiphenylmethane-monostearic acid anilide, 4,4-diaminodiphenylmethane diisopalmitic acid anilide, and 4,4'-diaminodiphenylmethane 6-shaped.

Among the compounds of formula 1, particularly preferred compounds in the present invention are those obtained by adding 11 to 100 moles, especially 40 to 70 moles of ethylene oxide and/or propylene oxide to an amino-substituted aromatic compound, especially aniline. addition reaction products, amide/substituted aromatic compounds, especially anilides obtained by reacting 4, diamino diphenylmethane or asymmetric-dimethyl-p-phenylenediamine with 1 to 2 moles of a solid carboxylic acid having 14 to 2 carbon atoms. It is. The compound of formula 1 according to the invention is added to the molding composition or resin dispersion to be processed in an amount of from 0.1 to 1% by weight, preferably from 0.2 to 1% by weight, based on the total amount of condensed resin.
It is added in an amount of 3% by weight.

This compound achieves good fluidity and moldability even when added in a very small amount, such as 0.1% by weight, and more preferably, unlike known processing aids, it can be used in relatively high amounts added. Even if the product is used, it will not have a detrimental effect on the properties of the molded product.
A decisive advantage of the compounds of formula 1 according to the invention is that they can react with components of the resin mixture under the curing conditions of the thermoset and become themselves an ingredient of the thermoset at the end of the curing process. For this reason, the compound of formula 1 of the present invention is
Even at relatively high loadings, there is no leaching (sweating) phenomenon during the molding process and during use of the product.

Moreover, the properties of the compounds of formula 1 of the present invention as detergents are maintained until the final curing. The compound of formula 1 can be added during the preparation of the binder, i.e. novolak type phenolic resin, resol type phenolic resin, urea-formaldehyde condensate or melamine-formaldehyde condensate, and partially participates in the condensation reaction, The compounds of formula 1, either combined with precondensates or by themselves, form reactive methylol compounds.

This reaction makes the compound of formula 1 extremely compatible with the resin component. Good homogenization is also obtained when the resin condensation is carried out in aqueous solution, as is customary in the case of molding urea-formaldehyde compositions or melamine-formaldehyde compositions. The compounds of formula 1 of the present invention can also be used in any processing step after the production of the resin, such as the step of combining cellulose with an aqueous urea-formaldehyde resin solution or an aqueous melamine-formaldehyde resin solution, or in powdering the aminoplast composition for molding in a ball mill. The aminoplast molding composition is added to the molding composition in the process of rolling the molding aminoplast composition or mixing it with the powder-forming novolak-type phenolic filler and other additives before jaw granulation in a double screw. You can also do that.

The above mixing process is made very easy because the compound of formula 1 includes liquid substances and various solid substances with different melting points, so that for each process a compound of formula 1 with optimal properties is selected. This is because it can be done.

The addition of this compound of formula 1 in the processing process of a thermosetting composition for molding based on a condensation resin makes the processing process extremely easy.
) or mixed rolls (Mishwalze
This prevents the composition from sticking to the filler (n) and at the same time prevents the composition from sticking to the filler (n).
This allows for easy incorporation of additives) and, furthermore, its non-stick properties eliminate premature hardening of parts of the molding material that have been subjected to excessive heat.

This new ability to incorporate the compounds of formula 1 of the present invention is due to the fact that the compound of formula 1 reacts with formaldehyde to form a water-dispersible reaction product, and in this form the compound of formula 1 reacts with formaldehyde to form a water-dispersible reaction product. This is because the compound is fixed.

The compound of formula 1 is in this case precondensed to a methylol compound. Since this reaction is carried out in the aqueous phase, an aqueous dispersion of the compound of formula 1 according to the invention is obtained as an initial product in the form of a methylol compound, which aqueous dispersion is likewise an aqueous dispersion or It is very easily mixed with resins in solution, such as melamine-formaldehyde precondensates. During the molding process, the compounds of formula 1 according to the invention exhibit an excellent internal lubrication effect, since they reduce the melt viscosity, resulting in good mold filling and precise dimensional stability. Furthermore, internal stress was significantly alleviated. In addition to this, the compound of formula 1 of the present invention does not have tackiness due to external lubricating action, so
The removed molded product is prevented from adhering to the mold surface, and as a result, the molded product can be easily modeled without any hindrance. The following examples are intended to explain the present invention in more detail, but the present invention is not limited to these examples.

MANUFACTURING EXAMPLES Example 1 Add 93.1 molar (1 mol) of aniline and 20 molar of 30% sodium methylate solution into an autoclave with a Takahiro mechanism, and after filling the autoclave with nitrogen about 7 molar
Evacuate for 10 minutes at 0qo.

Next, heat to 150 oooh and at this temperature, 2904 yen (66
mol) of ethylene oxide. Flaking using a flaking roll (Schuppen skin) gave a light colored solid product A. The melting point of this product A is 5900, and the cloud point of a 5% solution (NaCI) is about 9.
7q0, OH value was 31. The following products were prepared in a similar manner.

(EC stands for ethylene oxide, PO stands for propylene oxite.

)0 Example 2 Addition reaction product 150 in which 32 moles of ethylene oxide was added to 1 mole of aniline in a three-necked flask with a concentrated side.
1 mole (1 mol) and stearic acid 284 mole (1 mol) and p
and 18 liters of toluenesulfonic acid and heated to 180 to 19,000 ℃ until a total of about 18 liters of water separates.

On cooling, a solid waxy product E having a melting point of 5500 and an OH number of 34 is separated. Example 3 In a three-necked flask with a rope mechanism, 4,4'-di○aminodiphenylmethane (1 mol) and stearic acid 284 mol (1 mol) were added to the reaction water at a temperature of 200 to 250°C. The reaction was allowed to proceed until separation was completed.

The product F obtained has a melting point of 143-15,000. Further products were prepared in the same manner. Application Examples Example 4 A phenolic resin composition for molding having the following composition is powdered using a high speed mixer.

Thread sardine 1: Phenol-formalde 45.5 parts by weight Human resin hexamethylenetetramine 4.5
〃Wood powder 50.0 〃Magnesium oxide 10″ Thin strip 2: Thread 1 101.0″
Stearic acid workshop 1.0 〃Itozougobofumumu 3: System sagogo antikanbutsu 1 101-0 〃
Product A (1 mole of aniline and 66 moles of ethylene oxide)
1.0 〃 Reaction product of Kiside) Ito Hayabusa Hifubutu 4: Ito Hayabusa Hanfu 1 1
01-0 〃Product F (1 mole of 4,4'-Mamamones ≧ Hands-on worries.--.

〃reaction of beef waste) The shaping composition is pulverized.

Threaded sardine 5: Melamine stiff muscle end 60 parts by weight Gofun 40 minutes Composition 6: Boxed sardine 5
100″Stekawa Oribyo Shrine 1
〃Fabric: Fine 5 100'' Product A (reaction of 1 mol of Ani IJZO and 66 mol of Ethylene 1'' oxide) Plump 8
: Textile 100 Product E (reaction product of 1 mol of Zantane, 32 mol of ethylene oxide and 1 mol of stearic acid) of the total composition in a Brabender plastograph. Fluidity was measured.

The measurement conditions are as follows. Volume of crosstalk room
30 Mantle temperature 12000 Sample addition amount 28 Evening blade rotation speed (Schaufeldrehzahl)
From the kneading diagram of FIG. 1 at 30 revolutions per minute, it is clear that the use of the products of the invention reduces the level of kneading resistance of the composition due to the lubricating effect.

Example 5 In order to test the compatibility of products A and F in a phenolic resin composition, molding composition no. Molded plates were made at curing temperatures of 1-4 to 170 qo.

No deposits were formed on the boards obtained using Composition 1 (no adhesive added) and Compositions 3 and 4 (added with the compound of formula 1 of the present invention), whereas no deposits were formed using Composition 2. In the obtained molded plates, deposits were significantly formed due to leaching of zinc stearate.Example 6 The fluidity of compositions 5 to 8 was measured in a melamine resin molded lavender blastograph having the following composition using a high-speed operation mixer. .

The measurement conditions are as follows. Kneading room capacity
30 Flow mantle temperature: 13500 Sample addition amount: 32 Rotating blade speed: 20 revolutions/min It is clear from the enrichment diagram in FIG. 2 that the product of the present invention reduces the dispersion resistance due to its lubricating action.

Example 7 In order to test the compatibility of products A and E in melamine resin compositions, four molding compositions No. 16 using 5-8
A molded plate was produced at a curing temperature of 0qo.

No deposits were formed on the boards produced using Composition 5 (no lubricant added), Compositions 7 and 8 (addition of the compound of formula 1 of the present invention), whereas no deposits were formed using Composition 6. In the produced molded plates, significant deposits were formed due to leaching of zinc stearate.

[Brief explanation of drawings]

FIG. 1 shows the kneading curve of Example 4, and FIG. 2 shows the kneading curve of Example 6. Figure 1 Figure 2

Claims (1)

[Claims] 1 Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Here, R^1 and R^2 are hydrogen atoms, methyl groups, methoxy groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc.▼, which may be the same or different, and R^3 is a methyl group, phenyl group, or Z-[O-CHX-CH_2]
_m- group, where X is a hydrogen atom and/or has 1 to 1 carbon atoms
26 alkyl group, Y and Z are hydrogen atoms or R^
4CO- (here, R^4 indicates a hydrocarbon residue having 12 to 26 carbon atoms), and the sum of n and m is a value from 0 to 100, provided that n is less than 10 or 10. Arikatsu X
is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, at least one of Y and Z is R^4CO-, and the compound of formula I has at least one unsubstituted ortho or para position. The condition is that it has. ], characterized by containing a compound represented by
A molding composition based on a phenol or melamine resin for molding. 2. A molding composition according to claim 1, wherein the aniline contains a compound of formula I obtained by adding 11 to 100 mol of ethylene oxide and/or propylene oxide. 3. The molding material according to claim 1, which contains a compound of formula I obtained by reacting 4,4'-diaminodiphenylmethane with 1 to 2 moles of a carboxylic acid having 14 to 20 carbon atoms. Composition. 4. The molding composition according to claim 1, which contains a compound of formula I obtained by reacting asymmetric dimethyl-p-phenylenediamine with 1 mole of a carboxylic acid having 14 to 20 carbon atoms. 5. A molding composition according to claim 1, containing the compound of formula I in an amount of 0.1 to 10% by weight, based on the total amount of resin. 6. A molding composition according to claim 1, which contains a compound of formula I in the form of a water-dispersed reaction product obtained by reaction with formaldehyde.