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WO1982003629A1 - Procede de fabrication de mousse de resine d'uree - Google Patents

Procede de fabrication de mousse de resine d'uree Download PDF

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Publication number
WO1982003629A1
WO1982003629A1 PCT/JP1981/000083 JP8100083W WO8203629A1 WO 1982003629 A1 WO1982003629 A1 WO 1982003629A1 JP 8100083 W JP8100083 W JP 8100083W WO 8203629 A1 WO8203629 A1 WO 8203629A1
Authority
WO
WIPO (PCT)
Prior art keywords
urea resin
resin
foam
foaming
urea
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1981/000083
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English (en)
Japanese (ja)
Inventor
Electric Works Ltd Matsushita
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Electric Works Co Ltd
Original Assignee
Matsushita Electric Works Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Works Ltd filed Critical Matsushita Electric Works Ltd
Priority to PCT/JP1981/000083 priority Critical patent/WO1982003629A1/fr
Publication of WO1982003629A1 publication Critical patent/WO1982003629A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20

Definitions

  • the present invention belongs to the technical field of manufacturing plastic foams, specifically, urea resin foams. Therefore, basically, the production of the resin used as the raw material of the foam, specifically, the technical field of production of urea resin, and more generally, the production of thermosetting resin Belongs to the technical field.
  • Urea resin foam (hereafter, “uriaform”) is used in various fields, such as heat insulating materials, sound absorbing materials, anti-condensation agents, packaging buffer materials, and plant cultivation beds. Yes.
  • Uriforms are manufactured depends on the force with which the resulting form is turned to the intended use. For example, when filling a building wall and using it as a heat insulator, at the construction site, foam the urea resin liquid into the voids of the wall and inject it. Then, a method of hardening with a force that fills the voids is adopted. Also,
  • ⁇ For example, when producing plate-shaped or block-shaped Uriform, it is possible to use a casting method or any other type of mold. A method of obtaining a lump-shaped form and cutting out a form having a predetermined shape is employed.
  • the method of producing a urform it is possible to foam a hardener solution with a surfactant or the like and mix it with a urea resin solution.
  • the method can be classified into a method in which the foam is fixed by hardening the urea resin in the first place, and a method in which a foaming agent and a curing agent are added to the urea resin liquid to cause foaming and hardening.
  • the former is used for the construction method that fills voids in the wall.
  • the strength is low.
  • the surface is chipped in powder form only by playing with the lump in the hand, and the surface becomes thinner as soon as possible. It explains the drawback that the form as a form is difficult to maintain during handling. In particular, when the expansion ratio was set to a high value, the above-mentioned drawbacks were remarkably exhibited, and the strength was significantly reduced.
  • One of the manufacturing problems is that the stability of the resin is poor. In other words, if the adjusted urea resin is stored, the crystals of methyl urea will precipitate out or the whole resin will be solidified. Not only the problem of resin stability, but also the problem of not being able to secure the appropriate resin viscosity required during foaming is also linked to S '. This made it difficult to achieve stable high-ratio expansion.
  • Another problem with the production method is that, in the latter method, in which urea resin is directly foamed, the resin foaming speed and curing speed are controlled by a balance. It is very difficult to control well, and it is important to mention that it is difficult to perform stable foaming. It was thought that this was the cause of the inability to obtain a uniform form.
  • the present invention provides a method for improving the stability of urea resin or a foamed state in the production of a urethane foam, and improving the stability of the foam itself.
  • the purpose was to improve the performance of the.
  • the present invention is more preferable by blending the urea resin with a substance, which is also referred to as a foam fixing agent, to foam the urea resin.
  • the above object has been achieved by blending a foaming fixative with a specially modified urea resin and foaming.
  • the present invention will be described in detail.
  • the main constituent of the urform is a urea resin.
  • a urea resin is a resin obtained by reacting urea with honolean aldehyde in the presence of an acid or alkaline catalyst (often an alkaline catalyst). However, usually, what is called an initial condensate is used.
  • the source of formaldehyde for reacting with urea is a mixture of honolemarin and honolem T-nordealdehyde dissolved in organic solvents at a high concentration. , Or No, 0 La Honorem is used.
  • c it is preferable to use a highly concentrated formaldehyde source, such as Lahosolem O
  • the reaction system can be kept in a preferable PH range without any catalyst.
  • caustic soda, caustic soda, sodium carbonate, carbonated carbonate, magnesium hydroxide which is a well-known Al catalyst
  • No known anolyte catalysts such as aluminum, magnesium oxide, zinc hydroxide, ammonium, and amines; formic acid, phosphoric acid, or Weakly acidic catalysts such as the salts of these or pH control in the weakly acidic range
  • a buffer or other buffer is used to remove oil
  • the pH of the reaction is preferably about 5.5.80, and more preferably about 6.0.
  • honolealdehyde is used in an amount of 1.3 to 3.9 moles, preferably 1 mole, per mole of urea, as used in the present invention. Based on the method of condensation reaction under weak acidity or alkalinity using mono-ole, e-strike program or polyvalent The alcohol modifies the urea resin.
  • Polyhydric alcohols used as denaturing agents include, for example, ethylene glycol, polyethylene glycol, propylene, and the like. These include Lenco-core, Glycerin, and Pentaerythrill. Among them, polyethylene glycol is preferred. These multi-functional cameras can be used in conjunction with £ -force programs, or they can use either of the two. . When used in combination, the stability of the resin solution is further enhanced. The amount used is 0.1 to 2.0, preferably 0.5 to 1.0, mol per mol of e-force s' urea. On the other hand, the polyhydric alcohol mixes 3 to 20% by weight (hereinafter simply referred to as%), preferably 5 to 10% with respect to the resin solution.
  • the time for adding the denaturing agent may be after the reaction, but it is preferable to add it during the reaction. More preferably, the method is This is done by previously reacting or mixing the urea with a part of the urea and then adding the remaining or all of the urine later.
  • the reaction system becomes solid, so e-force pro- gram or multivalent It is convenient to dissolve the oleoresin at the beginning of the reaction or before dissolving it in the raw material of the formaldehyde source and then subjecting it to the reaction with urea.
  • the reaction temperature is 40 ° C or the reflux temperature.
  • the reaction time is between 30 minutes and 4 hours. These reaction conditions are not intended to be limiting. .
  • the amount of solid content when the resin solution obtained as described above is used is preferably 75 or more, more preferably 85% or more. If the solids content of the resin solution after the reaction is not sufficiently high, shrink by dehydration under reduced pressure or a thin film evaporation method. In consideration of these points, it is better to use a high-permeability home-aldehyde source from the beginning. Therefore, paraformaldehyde is most preferred.
  • a resin solution with a high concentration as described above has a high viscosity, so that the stability of the foam at the time of foaming is better, and the foaming state is better and a uniform foam is obtained. can get . From a certain viewpoint, it is possible to find a preferable range of the viscosity of the resin.
  • Sunawa Chi tree moon effect the viscosity of Nami 1 0, 0 0 0 ⁇ 4 0 0, 0 0 0 c P s 2 0 ° C, and rather are preferred, 1 0, 0 0 0-5 0 0 0 0 cps / 20 ° C.
  • This viscosity range does not always coincide with the above-mentioned range of the resin concentration. The point is that either the resin concentration or the resin viscosity should be within the above range.
  • the resulting resin solution has a pH of 7.5 to 8.5.
  • a curing agent, a foaming agent, a foaming agent, etc. are uniformly mixed in the resin solution, and then the mixture is not heated to room temperature. Keep under heating. This makes it easier to get the form.
  • foaming agents are used. For example, substances that can be decomposed by acids or nausea to generate gas are used. Belong charcoal acid Na door Li cormorant-time, Jusumi Hayao Na door Li cormorant-time, to the substance of Nono 0 La door Norre et emissions scan le ho twenty-one Norre human de. La-di-head soil force it. It is also possible to use low-point substances such as butane, pentane, and tricyclone monophenolic ethane. Low boiling materials are more preferred.
  • foaming agents can be used, but those having a strong foaming power and a good total holding power are preferred.
  • This includes high-alcohol sodium phosphate sodium salt, high-grade alcohol sodium salt amine salt, high-grade alcohol salt.
  • Ano-core sodium salt, sodium salt of high-grade alcohol, high-grade alcohol salt, amin salt, high-grade alcohol salt Benzene sulphonate, dodecinoleben benzene sulphonate, phenol olenosulphate ester, alkyl naphthalene sulphonate Power is used.
  • the curing agent a known curing agent that is usually used as a curing agent for a urea resin is used.
  • phosphoric acid for example, phosphoric acid.
  • Acidic substances such as rat enormous olenoic acid are used.
  • the amount of the curing agent used depends on the properties of the resin and the temperature at which the resin is foamed. In the end, the appropriate amount will be determined concretely in consideration of various circumstances.
  • the polyoxylated fatty acid ester, the sorbitan fatty acid ester, and the silicone resin be used.
  • An activator such as a filler can be blended in an amount of 1 to 3% based on the resin solution.
  • a foam fixing agent for keeping the foamed resin in a foamed state until the foamed resin is completely cured is compounded. They try to get more form.
  • the conventional method it is very difficult to control the foaming of the resin during the production of the polyurethane foam and the speed of the curing of the resin accompanying the foaming.
  • the curing speed is too fast, the foaming is sufficiently performed and the foam is cured, and a foaming force with a low expansion ratio can be formed.
  • the foam becomes hardened and a foam with a high expansion ratio cannot be obtained. That is, the foaming stability was bad.
  • foam fixatives It may be added to the resin solution in advance, or may be added just before foaming.
  • resorcinol which is a solid
  • a foam fixative as an aqueous solution with a concentration of 60 to 80% and mix it with the resin solution. Is easy.
  • advance amount of the resin solution and blended with our Ku c foam fixing agent but it may also be added as an aqueous solution even if is against the resin liquid 0.1:! 330%, preferably 5-15%.
  • phenolic furyl alcohol Even in the case of phenolic furyl alcohol, the smaller the amount, the smaller the shrinkage after foaming, and a favorable result can be obtained.
  • the present invention has a feature in that resorcin or phenolic free alcohol is used as a foam fixing agent, and the above-mentioned modified urea resin is used. Or by using the above-mentioned foaming agent or by using the above-mentioned foaming agent. Or the combination of the use of the above-mentioned activators to obtain even better results.
  • a foam fixative Without using a foam fixative, add a foaming agent and a foaming agent to the resin solution modified with e-force and multi-alcohol. Then, a foaming agent is added to the mixture to form a foam, which is not sufficient in terms of water resistance as compared with the case where the foam fixing agent is used. When you can get an effect
  • Another effect of the use of the foaming agent is that the smoothness of the cut surface when the foam is cut is greatly reduced.
  • parts ⁇ -30 parts by weight of force pro- gram (abbreviated as “parts” hereinafter), 40 parts of polyethylene glycol, 40 parts of para-holon rubber (80% pure) Then, 100 parts were charged into a reaction vessel, heated and dissolved, and 4 parts of a 40% aqueous sodium hydroxide solution was added thereto, and the mixture was maintained at reflux for 30 minutes. Then, while maintaining the reaction system at 95 ° C, 200 parts of paraformaldehyde and 260 parts of urea were each divided into four parts and added alternately to the reaction system. Was. After charging all of them, the mixture was reacted at 90 to 95 for 60 minutes. The PH 5. temperature of 6 to 5.
  • Example 1 With respect to 100 parts of the resin liquid obtained in Example 1, the distribution shown in Table 1 was applied. A resin solution for foaming was produced in this way, and foamed at 30 ° C. in a foaming mold to obtain a foam. The quality of the foam was examined and also shown in Table 1.
  • T — 40 means polyoxyethylene sorbitan monomitrate.
  • the compound containing phenolic resin and resin containing phenolic resin and resin containing resin are more effective in improving the uniformity of foaming, the expansion ratio (low density), and the strength as compared with the non-compounded product. Admitted.
  • the foam obtained by blending the foaming agent was smooth when cut with a blade, and the foam was not pulverized by friction.
  • the foam shrank slightly after foaming, but the shrinkage was smallest for ⁇ 15.
  • the odor of formaldehyde compared to the case of Example 4, the odor of formaldehyde is generated at the time of foaming and from the foam.
  • the number of samples with the combination of resorcin was the lowest.
  • the adhesiveness was excellent for all samples. ⁇ '

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Les procedes conventionnels de fabrication de mousses de resine d'uree ne permettent pas d'obtenir un moussage uniforme, et les mousses resultantes sont fragiles et subissent facilement un retrait. Ce procede consiste a former un compose de resine d'uree de preference modifie avec du (Alpha)-caprolactame, de l'alcool polyhydrique, ou analogue, avec du resorsinol et/ou de l'alcool phurphuryle, et a faire dilater le melange resultant. Ce procede produit une expansion uniforme et permet d'obtenir des mousses de resine d'uree possedant une resistance elevee, un faible taux de retrait et des cellules uniformes. Les mousses resultantes sont utiles en tant que materiaux d'isolation thermique et materiaux d'emballage.
PCT/JP1981/000083 1981-04-09 1981-04-09 Procede de fabrication de mousse de resine d'uree Ceased WO1982003629A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP1981/000083 WO1982003629A1 (fr) 1981-04-09 1981-04-09 Procede de fabrication de mousse de resine d'uree

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
WOJP81/00083810409 1981-04-09
PCT/JP1981/000083 WO1982003629A1 (fr) 1981-04-09 1981-04-09 Procede de fabrication de mousse de resine d'uree

Publications (1)

Publication Number Publication Date
WO1982003629A1 true WO1982003629A1 (fr) 1982-10-28

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Application Number Title Priority Date Filing Date
PCT/JP1981/000083 Ceased WO1982003629A1 (fr) 1981-04-09 1981-04-09 Procede de fabrication de mousse de resine d'uree

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3414526A (en) * 1964-03-13 1968-12-03 Allied Chem Flame-retardant, nonshrinking ureaformaldehyde foams
US3554936A (en) * 1968-03-26 1971-01-12 Grace W R & Co Stable high expansion foam composition and process of foaming
US4026980A (en) * 1973-08-06 1977-05-31 Imperial Chemical Industries Limited Process for producing moulded expanded urea formaldehyde products
JPS5273970A (en) * 1975-12-18 1977-06-21 Booden Purodakutsu Ltd Foaming system
JPS5580444A (en) * 1978-12-14 1980-06-17 Mitsui Toatsu Chem Inc Production of urea resin foam

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3414526A (en) * 1964-03-13 1968-12-03 Allied Chem Flame-retardant, nonshrinking ureaformaldehyde foams
US3554936A (en) * 1968-03-26 1971-01-12 Grace W R & Co Stable high expansion foam composition and process of foaming
US4026980A (en) * 1973-08-06 1977-05-31 Imperial Chemical Industries Limited Process for producing moulded expanded urea formaldehyde products
JPS5273970A (en) * 1975-12-18 1977-06-21 Booden Purodakutsu Ltd Foaming system
JPS5580444A (en) * 1978-12-14 1980-06-17 Mitsui Toatsu Chem Inc Production of urea resin foam

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