JPS58198580A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide an adhesive compsn. which has improved bonding strength and water resistance, reduces evaporation of free formaldehyde and can be produced at a low cost, prepared by adding microbial bacteria as filler to an amino resin-containing adhesive. CONSTITUTION:The adhesive compsn. is prepared by adding microbial bacteria as filler to an adhesive consisting mainly of amino resin obtained by condensation reaction of amino compd. and formaldehyde, such as urea/formaldehyde or melamine/formaldehyde resin. The bacteria is added in an amount of 5-120pts. wt. as waste or dry bacteria per 100pts.wt. solids to the amino resin. The bacteria include bacillus (e.g. those of genus Pseudomonas), yeast (e.g. those of genus Saccharomyces) and preferred are those remaining after extraction of lipid-soluble effective ingredients with solvent.

Description

[Detailed description of the invention] The present invention relates to adhesive compositions, and more particularly to adhesive compositions.

The present invention relates to an adhesive composition suitable for bonding wood, which contains an amine resin having improved properties as a resin component.

These amino resins are used as adhesives and 1. In particular, it is widely used as a wood adhesive in the production of plywood, particle board, laminated wood, etc.

In addition, we have improved the characteristics of wood adhesives, in particular, improved workability in the adhesive application process, prevented penetration into objects to be adhered, improved adhesive strength, and reduced adhesive raw material costs. Generally used for flour.

Cereals and starches such as soybean flour, barley flour, rice flour, and potato starch are used as fillers, and air amino type #l [
C is added and blended. These @type flours and rice flours are valuable both as food and as livestock feed, and their prices are also affected by the crop, making them unsuitable as industrial raw materials. be. If the I11 adhesive has a particularly high moisture content or is made of a material with a high tl content, it is generally used more often. A filler whose main ingredient is protein is used in combination to increase adhesion, but it has the drawback that the price of the filler is too high compared to its beneficial effects. In the wood industry, which is represented by plywood and per-vehicle board, it is difficult to obtain good quality wood due to the depletion of high-quality wood resources in Southeast Asia and the rise of resource obsessiveism in Southeast Asian countries.
The aim is to use hard-to-adhesive woods such as shochu and Kabul wood, or northern woods, mainly coniferous trees, which are becoming more dense. There is an increasing demand for strong bonding of bulky materials with a moisture content of 4.

In recent years, large amounts of microorganisms have been used as raw materials for antibiotics, fat-soluble vitamins, and coenzyme Q.

After extracting these fat-soluble active ingredients with a solvent, the abandoned garden body contains only a very small amount of these fat-soluble active ingredients, and contains a large amount of protein. Regardless of the book, the current situation is that Jin's abandoned garden bodies are not being used effectively and are being discarded.

As a result of intensive research into photonic agents for amino-based resin adhesives that can replace fillers, we have found that not only can microbial cells whose cell walls are not substantially destroyed be used as photonic agents for amino-based resin adhesives, Furthermore, they discovered that it is effective in improving the water resistance of adhesives and reducing the amount of formaldehyde volatilized from adhesives, which is a drawback of amino resin adhesives, by 1%, and completed the present invention.

That is, the present invention is an adhesive composition containing an amino resin and a filler, which is characterized by containing microorganism cells as the filler.

The amino resin 7 used in the present invention may be any resin commonly used in adhesives, such as urea+l-, 7L
A7 Ruthehyde resin, urea-melamine-phor 1,
It is a resin produced by a condensation reaction between an amino compound and formaldehyde, such as a ruthehyde resin, a melamine-polmaldehyde resin, and a pe/zoguanamine-urea-formaldehyde resin.

For example, phenols and amine compounds can be used together, such as phenol-urea-formaldehyde resin, phenol-melamine-formalbutyl resin, or co-condensed resins with formaldehyde can be used. These can be used alone or in combination. Furthermore, water-based resins such as beer acetate resin emulsion and acrylic resin resin can be used in combination with these 7-mino resins.

The microbial cells used in the present invention are not particularly limited, but include bacteria, yeast, filamentous fungi, and fungal cells. Among these, bacteria are most preferred. Otakowara's microbial cells are usually found in methanol, ethanol, other alcohols, methane, ethane, propane, n-paraffin, and other hydrocarbons, vinegar, other organic acids, blackstrap molasses, or valves. The main channel is the Cape of Waste Water, and L.
This is a bacterial cell obtained by culturing in a tube. Among these carbon sources, methanol, ethanol and n-)! Microbial cells cultured using rough-in [11]7 are preferred.

In addition, the waste after extracting the microbial cells, i-Teke, and the fat-soluble active ingredients with a solvent such as acetone, n-hexanes, and ethanol is preferably used. Although the cells of this waste material were not substantially destroyed, it is presumed that the cell wall was denatured by the extracting medium and the formaldehyde passed through the cell wall. It is also possible to use each dried bacterial cell in its own form.The dried bacterial cells can be prepared by heat sterilizing the microbial culture solution at 70 to 100°C, and then sterilizing it by conventional methods such as centrifugation. It is obtained by collecting microorganisms and drying the wet rigid body at 1°r using a dryer, dryer, spray dryer, etc. in a conventional manner.＼Representatives of suitable microorganisms used in the present invention Examples are as follows: Bacteria include - 7m-negative bacteria such as Tomonas spp., Methanomonas spp., Rosaconococcus spp., Methylococcus spp., Methylomonas spp.; Durham-positive yeasts such as Mycobacterium, Mycobacterium, Cardiac, etc. can be used, but Durham-negative yeasts are particularly preferred from the viewpoint of reducing the amount of aldehyde volatilization.As yeasts, Vithia,
...genus Nsenu, genus Kya/Dida, genus Satucharomyces,
It is a yeast that belongs to the true Toru r1bugis. In addition, fungi belonging to the genus Aspergillus are included as filamentous fungi.
・0 There is no particular limit to the amount of microbial cells to be used, but for practical purposes, it is usually 120 parts by weight or more as waste or dried microbial cells per 100 parts by weight of anno-based resin solid content [, preferably 5 to 100 parts by weight].
The proportion is 120 parts by weight, particularly preferably 10 to 80 parts by weight.

In the present invention, the entire amount of the filler can be made of microbial cells, but a portion of it can be replaced with a filler derived from cultivated crops such as wheat flour and soybean flour. There is no limit to the percentage of the filler derived from the flower crops, but for practical purposes, it is usually at least 10 times the weight of the Fi fungal cells.

The adhesive composition of the present invention is relatively inexpensive, has high adhesive strength and water resistance, and has a significantly reduced amount of volatile dehyde. Furthermore, since the microbial cells of the present invention are used as they are without actively destroying the cell tubes by grinding or the like, it is possible to save energy during production.

The adhesive composition of the present invention is used for adhering wood (.

Although it is preferably used for bonding other materials, it can also be used for bonding other materials.

Next, the present invention will be further illustrated by reference examples and examples. Explain in detail.

In the following Examples, the microbial cell rA) refers to the cultivation of Cichudomonas mei (Noris BNK-84 (micro: L Research Reference #42247), which is a methanol-assimilating microorganism, using methanol as a carbon source. The culture medium obtained from 7mer was heated at 70°C.
This is a powdered microbial cell obtained by heat sterilization at ~80°C for 3 hours, followed by Takushin-bunjo and drying. Microbial cells [B
) is a powdered microbial waste after extracting the fat-soluble components from the microorganism [A'1] using A7T (25°C x 24 hours) and removing the solvent.

The present invention is not limited to these.

Reference fI11 Urea-formaldehyde resin: Use the urea-formaldehyde resin synthesized according to the procedure in F.1. That is, 37% formali/1. OQ Og',
Urea 390"r, Ojhihekit Min-104r
, polyvinyl alcohol (PV A-217 manufactured by Kuraray)
>7, 5grt preparation/vf 10% oW property 71
＼ Add each to adjust the pH of the reaction system to 7.5-8.0.
It was knotted. After raising the temperature to 80°C to 5°C over about 60 minutes while stirring, the reaction was continued for 30 minutes at 80°C to 85°C. Next, 10% acetic acid was added to adjust the pH of the reaction system to 5°C.
．． After adjusting the temperature to 0 and continuing heating at 80° C. to 85° C. for another 30 minutes, heating was stopped. The pH of the reactant was neutralized to 7.0-7.5 by adding 10% caustic soda, and 45 g of urea was added thereto, followed by cooling with stirring to give a viscosity of t, s''.

of unconcentrated urea-formaldehyde resin (solid content 51wt
%) was obtained.

Reference Example 2 Urea-/lamin-formaldehyde resin @: urea-melamine-formaldehyde resin 1j% JJ, A four-sol fluff equipped with a reflux condenser, a stirrer, and a thermometer using a resin synthesized in the following order: JJ, F 7 to 37% formalin 900
gr% urea 335g', -quidamine 0.9g' and polyvinyl alcohol (PVA-217 manufactured by Kuraray)
After about 60 minutes, the temperature was raised to 80°C. When the reaction system reached 80°C, 10% acetic acid was added to adjust the pH of the reaction system to 5.0, and after reacting at 80°C to 85°C for 30 minutes, 10% caustic soda was added to react. The pH of the system was adjusted to 7.5. then 3
7% Ho A? 1J 7580gr, / 5 myy40
React at 85℃ for 60 minutes,
After that, 10% caustic soda was added again to adjust the pH of the reactant to 8.5! ,Ta. The reaction product was cooled to room temperature to obtain unconcentrated urea-melamine-formaldehyde (solid content: 55 wt%) with a viscosity of 1.5 degrees.

Example 1 Using the urea-formaldehyde resin shown in Example 1,
An adhesive composition having the size liquid composition shown in Table 1 was prepared by pi a t,
? c. Using the adhesive composition of adhesive liquid l11 & 11 to Nl Adhesive strength, adhesive strength after immersion in cold water, percentage of wood breakage, and Japanese Agricultural Standards (Notification-No. 1320)
The amount of aldehyde emitted from the plywood was measured using the method specified in the following article (using the desiccator method), and the results shown in Table 3 were obtained.

Compared to the adhesive M α-, which uses only wheat flour as a filler, the adhesive composition that uses a microbial enclosure as a filler is superior in terms of adhesive strength, wood breakage rate, and formaldehyde release. . In the case of the adhesive composition using % Trapei Niu Mengtai ('B), the amount of formaldehyde emitted from plywood can be significantly reduced, which improves the shortcomings of amine-based resin adhesives and has practicality. It was 6t, which can be considered expensive. Comparison with commercially available Dai-Q Protein Shiroitokoten agent 1. Example 2, which is also excellent.Using the urea-melamine-polmaldehyde 41I411Fi' shown in Reference Example 2, an adhesive composition having the size liquid composition shown in Table 1-4 was prepared. 17. Prototype ho'noid lauan 3-ply plywood was made using adhesive compositions of size liquid N15 to floor 8 under the plywood production conditions shown in Table 2. to evaluate the adhesive strength. The results are shown in Table 5, using only wheat flour as a filler! , compared to the adhesive composition 1. However, the adhesive composition using eubiotic bacteria showed good adhesive strength after repeated boiling tests, showing excellent adhesive performance.

Example 3 Nine plywood sheets were trial-produced under the conditions shown in Table 2 of Example 1, using Kabul wood veneer as a core material and using the adhesive of N13 and the size liquid ml shown in Table IK of Example 1. The evaluation results of adhesive performance are shown in Table 6. An adhesive composition using microbial cells in combination (Size liquid Nn3) is an adhesive composition using only wheat flour as a filler (
It exhibits higher adhesive strength than adhesive paste 1) and also has higher strength after immersion in hot and cold water. It also has an excellent wood breakage rate.

Table-6 Performance of prototype plywood (Kabul material) (adhesion% + It
Using the adhesive composition No. 1, plywood was made from white lauan veneer with a moisture content higher than that of veneers used in normal plywood production (6 to 10%) □ The prototype plywood was veneer Run 1 in row 1 under the conditions shown in Table 2 of Example 10, except that the water content was 16 to 18%. The evaluation results of adhesive performance are shown in Table-7.

9 Adhesive composition using microbial cells (Glue #3) d Adhesive composition using only wheat flour as a filler (Glue #lm4)
It exhibits higher adhesive strength compared to , and is also superior in terms of strength after immersion in hot and cold water and wood breakage rate.

Claims (1)

[Claims] An adhesive composition containing an amine resin and a filler, which contains microorganism cells as a filler.