JPH0238622B2 - TAISUISEIFUYOZAINOSEIZOHOHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a water resistance imparting agent for a formaldehyde condensation adhesive containing ammonium sulfate as a curing accelerator. At present, formaldehyde condensation adhesives are used as adhesives for organic boards, and paraffin wax emulsion has been used as a water resistance imparting agent. However, since ammonium chloride has low solubility as a curing accelerator for such adhesives, when ammonium chloride is used as a curing accelerator, the resulting adhesive has a low concentration, that is, a low solid content. However, adhesives with a low solid content concentration have drawbacks such as requiring a long time to dry. It is desirable that the adhesive for organic boards has a high solid content concentration. It is conceivable to use highly soluble ammonium sulfate instead of ammonium chloride as a hardening accelerator. However, in formaldehyde condensation adhesives that use ammonium sulfate as a curing accelerator and paraffin wax emulsion as a water resistance imparting agent, the adhesive/ammonium chloride curing accelerator/water resistance imparting agent have poor compatibility and emulsion. The condition is easily destroyed. As a result of research on water resistance imparting agents for formaldehyde condensation adhesives that use ammonium sulfate as a curing accelerator, the present inventors discovered that water-based emulsions produced by a specific manufacturing method were used as water resistance imparting agents. It was discovered that the emulsified state of a formaldehyde condensation adhesive containing ammonium sulfate is not destroyed when used, leading to the present invention. This invention is a by-produced product during naphtha decomposition, from -20°C to
Resin with a softening point of room temperature to 150°C obtained by polymerizing a 250°C fraction by Friedel-Crafts type reaction, an α/β unsaturated polybasic acid adduct of the resin, paraffin wax, oxidized paraffin, micro Crystalline wax, carnauba wax, montan wax,
Water resistance imparted to formaldehyde condensation adhesives containing ammonium sulfate as a curing accelerator, characterized by using 1 to 15 wt% of an emulsifier in at least one wax selected from the group of polyethylene waxes and emulsifying under pressure. The present invention relates to a method for producing a drug. In the present invention, the softening point of the raw material obtained by polymerizing the fraction with a boiling point of -20 to 250°C, which is produced as a by-product during naphtha decomposition, by a Friedel-Crafts type reaction is from room temperature to
A resin having a temperature of 150°C, preferably 40°C to 100°C, or an α/β unsaturated polybasic acid adduct of the resin is used.
(α/β unsaturated polybasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc.) or paraffin wax, oxidized paraffin, microcrystalline wax, carnauba wax, montan wax, polyethylene wax etc. or a mixture thereof may be used. Next, as an emulsifier, phenol, a benzylated product of alkylphenol, or a styryl product, or a formaldehyde or acetaldehyde condensate thereof, or a benzylated product or styryl product of naphthol or phenylphenol, and ethylene oxide, propylene oxide, or is an addition polymerized product of ethylene oxide/propylene oxide in a range of 2 to 40 moles per mole equivalent of -OH group of the above hydrophobic substance, or its sulfonate (K,
Na, NH ₄ , N(CH ₂ CH ₂ OH) ₃ ,

[Formula] etc.) or a salt of a succinic acid derivative is used in an amount of 1.0 to 15 wt%, preferably 2.0 to 10 wt%. Specific examples of emulsifiers are as follows. The general formula below

[Formula] (In the formula, R is an aryl group or alkylaryl group having 2 to 3 benzene rings, R' is an ethylene group or/and a propylene group, n is an integer from 5 to 40, and M is a hydrogen atom, monovalent represents a metal atom or an ammonium group) as an emulsifier. The compound represented by the general formula has 2 to 2 benzene rings.
It is obtained by addition-polymerizing ethylene oxide or/and propylene oxide to an arylphenol or alkylarylphenol having three phenols, followed by esterification with maleic anhydride, and further sulfonation with an acidic sulfite or sulfite. Examples of phenols that can be used as starting materials for producing the compound represented by the general formula include the following. a Ortho, meta, para-phenylphenol,
α・β-Naphthol b Examples of benzylated phenols and alkylphenols

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] c Styryl compound of phenol or alkylphenol (example)

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] d Naphthol, benzylated product of phenylphenol (example)

【formula】

[Formula] e Naphthol, styryl compound of phenylphenol (example)

【formula】

[Formula] Ethylene oxide or/and propylene oxide to be addition-polymerized to the arylphenol or alkylarylphenol is added in an amount of 5 to 40 moles per mole of the phenol. When only propylene oxide is used, there are some performance problems, and the amount of propylene oxide needs to be 50% or less of the amount of ethylene oxide + propylene oxide. A particularly preferable range is a mole number corresponding to 2 to 4 times the amount of ethylene oxide and 0 to 2 times the amount of propylene oxide relative to the weight of the arylphenol or alkylarylphenol. The polyoxyethylene (polyoxypropylene), aryl phenol ether, and polyoxyethylene (polyoxypropylene) alkylaryl phenol ether thus obtained are reacted with maleic anhydride, and the resulting esterified product is treated with acidic sulfite or sulfite. The compounds of the present invention can be obtained by reacting salts, but acidic sulfites, or sulfites are lithium salts,
Sodium salts, potassium salts, or ammonium salts may be used, with the sodium salt being economically preferred. As the rosin and rosin derivatives used in the aqueous emulsion of the present invention, formaldehyde polybasic emulsifiers such as camrosin, tall oil rosin, uddrosin, polymerized rosin, and hydrogenated rosin overcome the drawbacks of conventionally known emulsifiers and have the most excellent effect. I discovered that it can demonstrate the In the present invention, since an aqueous emulsion is produced from rosin and rosin derivatives, potassium hydroxide, sodium hydroxide, alkanolamine, morpholine, etc. can also be used as necessary. Regarding the emulsification method, the above-mentioned resin or wax or mixture thereof is heated at 60°C to 150°C, preferably 70°C to 120°C.
After dissolving the emulsifier in 1.0~15wt% preferably 2.0~
After adding 10wt% and mixing, pre-emulsify by adding warm water under normal pressure or pressurization, and then use a high-pressure emulsifier.
Under pressure of 100Kg/ ^cm2 , preferably 150Kg/ ^cm2 to 300
It is passed once or twice under a pressure of Kg/cm ² and then cooled to obtain an aqueous emulsion with a solids content of 40-60%. The formaldehyde condensation adhesive in the present invention refers to known formaldehyde condensation adhesives such as urea resin adhesives and melamine adhesives. The details will be explained below with reference to examples, but the scope is not limited thereto. Example (1) Boiling point of by-products during naphtha decomposition -20°C to 250°C
96 parts of a resin with a softening point of 63°C obtained by Friedel-Crafts type reaction were charged into a reaction vessel equipped with a stirrer, heated and melted, and then 1.0 part of maleic anhydride was added to 200°C.
The reaction was carried out at ±5°C for 4 hours. After the completion of the reaction, the above reactant was transferred to an emulsification tank equipped with a stirrer and the temperature inside the system was cooled to 90°C, and then 10 parts of sodium polyoxyethylene styrylated phenol ether sulfonate dissolved at 30% as an emulsifier was added. After adding 20 parts of 49% potassium hydroxide and saponifying it, add 80℃ hot water to 73℃.
emulsification was carried out. Thereafter, the mixture was rapidly cooled by passing it twice at a pressure of 250 kg/cm ² using a piston-type high-pressure emulsifier to obtain a white emulsion with a solid content of 50%. Example (2) 95 parts of paraffin wax with a melting point of 25°C was charged into an emulsifying pot with a stirrer, heated and melted, and then 25% was added as an emulsifier.
After adding 20 parts of solid polyoxyethylene/propylene benzylated phenylphenol ether ammonium sulfonate and mixing, 51 parts of 70°C warm water was added to emulsify. After emulsification, the mixture was passed through a piston-type high-pressure emulsifier twice at a pressure of 300 kg/cm ² and then rapidly cooled to obtain a white emulsion with a solid content of 60%. Example (3) 80 parts of paraffin wax with a melting point of 62°C and 10 parts of microcrystalline wax with a melting point of 83°C were placed in an emulsifying pot with a stirrer, heated and melted, and then made into a 30% aqueous solution of polyoxyethylene styrylated phenol ether sulfone. After adding 33 parts of ammonium acid and mixing
Add 58 parts of 90°C warm water to emulsify. Thereafter, the mixture was passed once under a pressure of 300 kg/cm ³ using a piston type high-pressure emulsifying machine and rapidly cooled to obtain a white emulsion with a solid content of 55%. The following tests were conducted on the water resistance imparting agent obtained in the above examples. 4-1 Test method 4-1-1 Adhesive: Urea resin (solid content 66%) 4-1-2 Addition amount of water resistant agent: 2.5 wt% solid to adhesive (visible) 4-1-3 Curing Accelerator addition amount: for adhesive
6wt% (ammonium chloride) 4-1-4 Plate thickness: 150mm 4-2 Test items 4-2-1 Specific gravity 4-2-2 Moisture content (%) 4-2-3 Bending strength [Kg/cm ² ] 4-2-4 Low peeling resistance [Kg/cm ² ] 4-2-5 Wood screw holding force [Kg] 4-2-6 Formaldehyde release amount
[mg/Kg]

[Table] 4-4 Results Using ammonium sulfate as a curing accelerator for adhesives
The test was conducted under the same conditions as above except that 8 wt% was used.

[Table] Commercially available paraffin wax as a control test
The above test was repeated using the emulsion as a water resistance imparting agent, but the adhesive emulsion could not be produced due to poor compatibility with the curing agent.

Claims (1)

[Claims] 1. A resin with a softening point of room temperature to 150°C obtained by polymerizing the -20 to 250°C fraction produced as a by-product during naphtha decomposition using a Friedel-Crafts type reaction, and α and β of the resin.
Using 1 to 15 wt% of an emulsifier in at least one wax selected from the group consisting of an unsaturated polybasic acid adduct, or paraffin wax, oxidized paraffin, microcrystalline wax, carnauba wax, montan wax, and polyethylene wax, A method for producing a water resistance imparting agent for a formaldehyde condensation adhesive containing ammonium sulfate as a curing accelerator, which comprises pre-emulsifying and then emulsifying under pressure using a piston-type high-pressure emulsifier.