JPS5852378A - Lamination molding of porous material - Google Patents

Abstract

PURPOSE:To effect high speed bonding operation and increase productivity by using an adhesive consisting mainly of a water soluble urethane prepolymer and containing a hardener consisting mainly of water, in the lamination molding of adherends one or both of which are made of a porous material. CONSTITUTION:In the lamination molding of two adherends at least one of which is a porous material (e.g., wood, slate, paper or plastic foam) (the other maybe a porous material or non-porous material such as metal or plastic sheet), a chief component consisting mainly of water-soluble urethane prepolymer (e.g., a reaction product of ethylene oxide-contg. polyalkylene ether polyol and an excess amount of polyisocyanate) and a hardener consisting mainly of water, are coated or sprayed separately or sprayed simultaneously for mixing in the air, on the adhesive surface of one or both adherends. The coated adherends are laid one on top of the other and lamination molded under pressure. The method speeds up bonding operation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for laminating and processing adherends, at least one of which is a porous material.

Currently, various adhesives are used for laminating and forming porous materials such as wood, slate, paper, cloth, felt, and plastic foam, or for laminating and molding such porous materials and non-porous materials such as metal and plastic sheets. is used, but
In recent years, especially on factory production lines, thermosetting adhesives and dual-reactive adhesives have been introduced to improve safety and health, prevent environmental pollution, and save resources and energy for heat use by removing solvents, as well as to save energy and streamline equipment. Instead of adhesives, thermoplastic resin hot melt adhesives, and solvent volatilization adhesives,
Water-based adhesives have come into use.

However, water-based adhesives generally have a drawback in adhesion speed, and cannot be said to be sufficient for improving productivity, as well as ensuring product quality and improving reliability.

Therefore, the present inventors have conducted extensive research in order to provide a laminated molding processing method that meets the above social demands, and have found that when laminating an adherend in which at least one side is a porous material, conventional adhesive bonding He discovered that by using a water-based curing agent based on a water-soluble urethane prepolymer, which had not been used as an agent, the adhesive work speed is extremely high and can contribute to improved productivity, and the present invention was completed. reached.

That is, in laminating and molding an adherend in which at least one of the adherends is a porous material, the present invention provides a base material made of a water-soluble urethane prepolymer and a curing agent mainly composed of water on one or both bonding surfaces of the adherend. The object of the present invention is to provide a method for laminated molding of porous materials, which is characterized by applying or spraying them separately, or simultaneously spraying them by mixing in the air, and then stacking them and joining them under pressure.

The porous material may be any material having pores such as wood, slate, paper, cloth, felt, or plastic foam. The other adherend may be a porous material, but may also be a non-porous material such as metal or plastic sheet.

The water-soluble urethane prepolymer used in the present invention has the advantages of being easily designed to have hard and soft properties, being heat resistant and durable, and being easily made solvent-free, similar to urethane adhesives commonly used as adhesives. However, it is distinguished from conventional urethane adhesives in that it has excellent water core compatibility and exhibits excellent adhesion speed using a water-based curing agent. Therefore, unlike the two-component curing type that normally uses polyols, amines, etc. as curing agents, there are no problems with mixing the two-component, curing speed, toxicity, etc. There are no problems with curing speed, temperature/humidity dependence, storage stability, etc. as in the case of a one-component curing type that utilizes curing. Although the polyalkylene ether polyol is produced by reaction, the molar ratio of ethylene oxide in the polyalkylene ether polyol is preferably 30 to 90.

Such polyalkylene ether polyols are usually produced by adding ethylene oxide to a compound containing two or more hydroxyl groups in a molar ratio of 30 to 90%. For example, compounds containing two or more active hydrogens include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythol,
It is produced by addition reaction or co-addition reaction of ethylene oxide or other alkylene oxides such as propylene oxide and butylene oxide using sorbitol, sucrose, etc. by a known method.

Considering hydrophilicity and workability, the molecular weight of polyalkylene ether polyol is 1000 to 20,000, especially 100.
Those in the range of 0 to 5000 are preferred, and among polyalkylene ether polyols, polyalkylene ether diols are preferred. As the polyisocyanate, those used in the production of ordinary urethane prepolymers can be used, such as purified products and crude products of toluene diisocyanate and diphenylmethane-4,4I-diincyanate. In particular, diphenylmethane-4,4'-diincyanate is suitable from the viewpoint of physical properties such as odor, workability, curability, adhesiveness, and toxicity, and cost.

The ratio of polyalkylene ether polyol to polyisocyanate is NC010H==3.0-6.
The resulting urethane prepolymer has between 4 and 13% of residual active incyanate groups.
, those with a viscosity of 3,000 to 10,000 cps are reactive;
Preferable in terms of workability, performance, etc.

Of course, fillers, anti-aging agents, coloring pigments, reaction catalysts, adhesion agents, solvents, and plasticizers may be added to the urethane prepolymer as necessary.

The water-based curing agent used in the present invention is a water-based curing agent that contains water as a main component and has an active hydroxyl group that reacts with the active incyanate group of the urethane prepolymer, and is in the form of an aqueous solution that can be sprayed by adding various reaction catalysts. It is preferable to This catalyst includes organic amines such as triethylenediamine, triethylamine, dimethylethanolamine, tetramethylpropylenediamine, and tetramethylenetriamine, as well as inorganic basic compounds such as borax and sodium hydroxide, urea, thiourea, and amino acids. Many substances such as salts or basic amino acids can be used, but from the viewpoint of toxicity, odor, water solubility, economic efficiency, etc., inorganic basic compounds, urea, thiourea, amino acid salts, and one type of basic amino acid are particularly recommended. Alternatively, it is preferable to use a mixture of two or more types. Adhesion promoters, dyes and pigments, fillers, surfactants, etc. may be added to the curing agent as necessary. In particular, the addition of a surfactant improves the compatibility with the urethane prepolymer, and the addition of dyes and pigments makes it possible to mix the spray surface and check the amount of coating. Furthermore, by adding a filler, it is possible to prevent penetration into porous materials and reduce costs.

Hereinafter, the present invention will be explained in more detail based on specific examples.
(Production of urethane prebolimano) Diphenylmethane-4,4'-diisocyanate to 200 parts by weight of polyalkylene ether diol with an average molecular weight of 3000 (product name Adeka Polyether PR3007, manufactured by Kadenka ■, ethylene oxide 70% molar ratio) 100 parts by weight (NCO1
0H Ratio 6.0) was added to a stirrable container with a heat-insulating jacket, mixed, and reacted for 3 hours at elevated temperature, resulting in a residual active incyanate group of 9.33% and a viscosity of 4000. A cps water-soluble urethane prepolymer is obtained.

Production Examples 2 to 8 (Production of urethane prepolymer) 1st below
The water-soluble urethane prepolymers shown in Table 1 below were obtained in the same manner as in Production Example 1 using the polyalkylene ether polyols shown in Table 1 and the diisocyanates shown in Table 1 below.

Production Examples 9 to 14 (hardening agent mainly composed of water) 2nd below
The components shown in the table are dissolved in water at predetermined ratios to obtain a curing agent used as a reaction catalyst for urethane prepolymers.

Table 2 Example 1 Urethane foam (dimensions: 300 x 300 At the same time, spray and mix and apply, and attach the other urethane foam to this, and 0.2 Km-
A laminated molded material is obtained by pressing with a pressing pressure of j. The 180 degree peel strength of this laminated material when left at room temperature [25°C] for 60 seconds after pressing was 0.5 KP/in, and 90
After a few seconds, the urethane foam broke through at 1 Kp/in.

Example 2 The method of Example 1 was repeated except that 70 g/cd of the base material was applied using a roll coater, then the hardening agent 35 was applied to the back using an airless spray, and after being left for 20 seconds, it was bonded to the other urethane foam. A laminated molded material is obtained in the same manner. Room temperature (25°C) after pressing this laminated material
180 degree peel strength after leaving for 60 seconds at 0.5Kf/i
After n0.90 seconds, it is 1Kfx n.

Urethane foam broke through.

Example 3 A laminated molded material was obtained in the same manner as in Example 1 except that the other urethane foam was replaced with a nonwoven fabric.

180° peel strength 60 seconds after pressing 05KVin.

After 90 seconds, the urethane foam was broken down.Example 4 A laminated material was obtained in the same manner as in Example 2, except that the other urethane foam was replaced with a nonwoven fabric.

The test results were similar to Example 3.

Example 5 The same procedure as Example 2 was carried out except that the other urethane foam was replaced with a nonwoven fabric, the curing agent was replaced with the main agent application side of the urethane foam, and the hardening agent was applied to the nonwoven fabric bonding surface and bonded without leaving it. Obtain laminated molded material.

180 degree peel strength 90 seconds after pressing 0.8KV/in
.

After 120 seconds, the urethane foam was broken at I Kf/in.Example 6 A slate (dimensions: 300 x 300 x 3) was coated with 70.17 d of the water-soluble urethane prepolymer obtained in Production Example 2 and 35 fI/lyl of the curing agent obtained in Production Example 10. ' at the same time and apply by mixing in the air, leave for 20 seconds, paste decorative paper and press with a roller, then press with a press with a clamping pressure of 2 Kli + / cI to obtain a laminated molded material. . 180 degree peel strength after 30 seconds after pressing is Q, 5Kp
/in, after 60 seconds it is 1.0 to 9/in, and 90
After a few seconds, the decorative paper was broken at 1.5~z, oKv'in.

Example 7 Same as Example 6, except that the main agent was applied to the slate using a roll coater, then the hardening agent was applied using an airless sprayer, and after leaving it in the air for 30 seconds, decorative paper was attached. to obtain a laminated molded material.

The 180 degree peel strength of this laminated material was 0.5K11l/in after 30 seconds at room temperature after pressing, and 1.1K after 60 seconds. O1'f
/in, and after 90 seconds it is 1. s ~ z, (1+/i
Breaking power of decorative paper (observed) at n.

Example 8 150 Vd of the water-soluble urethane prepolymer obtained in Production Example 3 and 75 g/rrl of the hardening agent obtained in Production Example 10 were applied to plywood (dimensions: 300 x 300 x 5 g) by simultaneous spray mixing, and the mixture was applied in air. After standing for 20 seconds, slates (dimensions 300 x 300 x 3 wm) are bonded together and pressed with a pressing force of 2 Kf/d from a press to obtain a laminated molded material.

The tensile shear force after 60 seconds at room temperature after pressing is 5 ridges.
After 90 seconds, the adhesive strength at which the slate breaks is ・
Obtained.

Example 9 The same procedure was followed as in Example 8, except that the water-soluble urethane prepolymer was applied using a roll coater, the hardening agent was applied using an airless sprayer, the material was left in the air for 30 seconds, and the slate was bonded. to obtain a laminated molded material.

The tensile shear force after 60 seconds at room temperature after compression is 5
It was an instant failure, and after 90 seconds, the adhesive strength was such that the slate was broken.

Example 10 One of the wooden boards (dimensions: 300 x 300 x 9 m) was sprayed and mixed at the same time, and after being left in the air for 20 seconds, this was pasted with another wood board and pressed with a press at 21 to form a laminate. Obtain processed material.

The tensile shear force after 60 seconds at room temperature after pressing is 5~/a#,
After 90 seconds, the strength was 10 KV'cd, and after 3 minutes, the strength was 25, which is close to the final strength.

Example 11 In Example 10, instead of simultaneous spray mixing, o-/
L/: After applying the water-soluble urethane prepolymer at 1-9-, apply the curing agent using an airless sprayer, and apply the hardener in the air for 3
A laminated molded material is obtained in the same manner except that the materials are bonded after being left for 0 seconds.

The tensile shear force after pressing was the same as in Example 10.

Example 12 Water-soluble urethane prepolymer 100 obtained in Production Example 2 was applied to urethane foam (dimensions 300x300xlOm)
P/Go and the hardening agent Kan7/Bo obtained in Production Example 10 were simultaneously spray mixed and applied, and immediately bonded to the coated surface of a back coated steel plate (dimensions: 300 x 300 x O, 8 tone), and rolled with a roller. Press under 1 KvaI to obtain a laminated molded material.

The 180 degree peel strength after 60 seconds at room temperature after pressing was 0.8 Kp/in, and after 90 seconds, Ureta 77
, i-m had an adhesive strength that caused the material to break.

Example 13 A laminate molded material is obtained in the same manner as in Example 12, except that the water-soluble urethane prepolymer obtained in Production Example 1 and the curing agent obtained in Production Example 1O are used.

The results of the 180 degree peel test after pressing were the same as in Example 12.

Example 14 Water-soluble urethane prepolymer 709/d obtained in Production Example 2 and curing agent 35 y/rd obtained in Production Example 10 were simultaneously spray-mixed and applied to plywood (dimensions 300 x 300 x 5 m), and the mixture was coated in air for 20 m. Leave it for a second, then apply PVc'
Z sheets (dimensions: 300 x 300 x 2 mm) are pasted together, pressed with a roller, and then pressed with a press at a pressure of 2 degrees to obtain a laminated molded material.

The 180 degree peel strength is 0.5 to 1.0 Kg/in after 60 seconds at room temperature after pressing, and 1.0 to 1.0 after 120 seconds.
l, 5Kg/in, and the final strength after moisture drying is 2.
It was 5Kg/in.

Example 15 Water-soluble urethane prepolymer 100 F obtained in Production Example 3 was applied to a painted steel plate (dimensions 300 x 300 x 0.8 mm).
/d and curing agent obtained in Production Example 10 50 t/rd
A honeycomb board (dimensions: 300 x 300 x 30+++ m) is immediately attached to this and pressed with a pressing pressure of 0.51'l/c+# to obtain a laminated molded material.

After 60 seconds at room temperature after pressing, the adhesive is almost cured and the laminated molded material can be carried. After 5 minutes, the honeycomb board broke in a manual tear test.

Examples 16-29 According to the method described in Example 1, the adherends shown in Table 1 were laminated using various water-soluble urethane prepolymers (base ingredients) and curing agents. The results are also listed in Table 1.

Claims (4)

[Claims] (1) When laminating an adherend in which at least one side is a porous material, a main agent made of a water-soluble urethane prepolymer and a curing agent mainly composed of water are separately applied to one or both joint surfaces of the adherend. A method for laminated forming of porous materials, which is characterized by coating or spraying on or simultaneously spraying them in the air, and then overlapping and compressing the two. (2) The laminate molding method according to item (1), wherein the porous material is wood, slate, paper, cloth, felt, or plastic foam. (3) No. (1) in which the water-soluble urethane prepolymer is a reaction product of a polyalkylene ether polyol containing ethylsin oxide and an excess of polyisocyanate;
Laminated molding processing method described in section. (4) A curing agent containing water as a main component contains one or more selected from the group consisting of organic amines, inorganic basic compounds, urea, thiourea amino acid salts, and basic amino acids. Laminated molding method described in section 1).