JPS63176102A - Manufacture of flameproof flitch - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to flame retardant plywood mainly used for stages, exhibitions, etc., by mixing a flame retardant into the adhesive without changing the manufacturing process of the plywood. Accordingly, the present invention relates to a method for producing flame-resistant plywood that is excellent in flame-retardant properties, adhesive properties, and economical efficiency, and that does not adversely affect secondary processing of plywood (processing such as printing, painting, adhesion, etc.).

[Prior art] Conventionally, in order to make wood and plywood flameproof, ammonium phosphate, niummonium phosphate, guanidine phosphate,
Fireproof wood and plywood by impregnating or coating them with agents such as methylol or methoxymethylol guanidine phosphate, guanylurea phosphate, methylol or methoxymethylol guanylurea phosphate, ammonium sulfamate, ammonium bromide, borax, or boric acid. A method of giving sex is being used. In these methods, the chemicals are attached to the surface of the wood and plywood, or the chemicals impregnated inside the wood and plywood come out to the surface, so secondary processing of the wood and plywood (printing, painting, gluing, etc.) is not possible. ) had the disadvantage of inhibiting

In order to improve these drawbacks, a method of mixing flame retardants into plywood adhesives has been used. However, although the adhesive layer of the top board contains a flame retardant, there is no flame retardant on the surface, so the flame retardant properties vary widely, making it difficult to obtain sufficient flame retardant properties. , effective flame retardants are needed.

[Problems to be Solved by the Invention] Ammonium polyphosphate [cum], melamine phosphate, borax, borax, carbamate polyphosphate, etc. are used as flame retardants for adhering plywood. Ammonium, melamine phosphate, borax, and boric acid are water insoluble or have very low solubility in water, and are also poorly compatible with formaldehyde condensation resins, making it difficult to dissolve and disperse them uniformly. In order to obtain this, a large amount must be incorporated, thus resulting in a decrease in adhesion. especially,
Since ammonium polyphosphate promotes gelation of formaldehyde condensation resin, it must be processed within a short time and has poor workability.

In addition, regarding polyphosphoric acid carbamate, adhesive properties are described in "Mok + J Kogyo J Vol. 28-6. Pages 241 to 246 f About flame-retardant plywood", which describes the manufacturing method of flame-retardant plywood with excellent adhesive properties. Although it has excellent flame retardant properties, it has the disadvantage that it contains a lot of polyphosphoric acid carbamate W and is poor in economic efficiency.

The present invention was made in order to solve the above-mentioned conventional problems, and an object of the present invention is to provide a method for manufacturing flame-resistant plywood that is excellent in flame-proofing, adhesion, and workability.

[Means for Solving the Problems] The present invention has a solid content weight ratio of (1) formaldehyde condensation resin, (2) condensation reaction product consisting of condensed phosphoric acid ester ammonium salt, formaldehyde and dicyandiamide, and guanidine sulfamate of 40: 60-70
: 30% to 70% of the solid content of the formaldehyde condensation resin as a solid content of the flame retardant, and 10 to 60% of the polysaccharide filler based on the solid content of the formaldehyde condensation resin. This is a method for producing flame-resistant plywood, characterized in that adhesion is performed using a plywood adhesive.

Examples of the formaldehyde condensation resin used in the present invention include urea-formaldehyde condensate, melamine-formaldehyde condensate,
Formaldehyde condensates, urea-melamine-formaldehyde co-condensates, co-condensed resins thereof, etc.
Two or more of these may be used.

The condensation reaction product consisting of condensed phosphate ester ammonium cum salt, formaldehyde, and dicyandiamide used in component (1) of the present invention is, for example, 1-El phosphorus pentoxide and 1.8 to 2.2 moles of lower alcohol. (for example, lower alcohols having 1 to 4 carbon atoms) at 80°C or less) is neutralized with ammonia, and 0.6 to 2.0 mol of the mixture is neutralized with ammonia. Formaldehyde, 0.6 to 2.0 moles of dicyandiamide to 70
A 50% aqueous solution obtained by condensation reaction at °C is rejected.

Further, as the guanidine sulfamate, a commercially available product manufactured by Sansho Chemical Co., Ltd. or Hontowax Co., Ltd. can be used.

Furthermore, the solid content weight ratio of the condensation reaction product consisting of condensed phosphoric acid ester ammonium salt, formaldehyde, and dicyandiamide in the component (■) and guanidine sulfamate is 40.
: 60-70 : 30, more preferably 50 :
50-70: A synergistic flame retardant effect is exhibited within the range of 30. If the ratio is outside the range of 40:60 to 70:30, the flame retardance will be significantly reduced. In addition, the solid content of a flame retardant consisting of a condensation reaction product consisting of a condensed phosphoric acid ester ammonium salt, formaldehyde, and dicyandiamide, which is necessary for the component (■), and guanidine sulfamate in a solid content ratio of 40:60 to 70:30, is combined with the formaldehyde that is the component (■). 30 to 70% based on the solid content of the condensed resin, more preferably 4
It is necessary to mix 0 to 70%.

When it is less than 30%, the flame resistance is insufficient, and 70%
Even if the amount is larger, no improvement in flame retardancy is observed and the adhesion and water resistance of the plywood are reduced, which is not preferable.

The condensation reaction product consisting of condensed phosphoric acid ester ammonium salt, formaldehyde, and dicyandiamide and guanidine sulfamate may be uniformly dissolved in advance so that the solid content ratio is within the above range, or the above They may be separately mixed into the formaldehyde condensation resin so as to fall within the range of .

The thickening agent used in the present invention may be wheat flour, rice flour, starch, etc. as long as it is generally used as a thickening agent for plywood adhesives, and the solid content of the formaldehyde condensation resin is It is necessary in 10 to 60%.

The flame retardant adhesive used in the present invention consists of: ■ formaldehyde condensation resin, ■ condensation reaction product consisting of condensed phosphoric acid ester ammonium salt, formaldehyde, and dicyandiamide, and guanidine sulfamate, ■ polysaccharide-based filler, and other general adhesives. additives, such as multi-bait alcohol (
It may contain carbonization accelerator during combustion), melamine (adhesion improver), other flame retardants, etc.

[Function] The condensation reaction product consisting of a condensed phosphoric acid ester ammonium salt, formaldehyde, and dicyandiamide and guanidine sulfonomimate used as a flame retardant in the present invention are uniformly dissolved in the formaldehyde condensation resin,
It promotes the gelation phenomenon and has a strong effect, and also exhibits a synergistic effect on flame retardant properties with a solid content weight ratio of 40:60 to 70:30, so it can be mixed in a smaller amount than conventional flame retardants. Provides excellent flame resistance.

Moreover, the cheapest urea-formaldehyde condensate among formaldehyde synthetic resins can be used, and a flame-retardant plywood can be produced with excellent adhesion, workability, and economy.

Next, the present invention will be explained by examples. In the following, "1 part" and "%" are all based on weight unless otherwise specified.

Example 1 142 parts (1 mol) of phosphorus pentoxide and 64 parts of methyl alcohol
The condensed phosphoric acid methyl ester mixture obtained by reacting 136 parts (2 mol) of 2596 aqueous ammonia for 3 hours at 80'C or lower, and further 162 parts (2 mol) of 37% formalin mol), 168 parts of dicyandiamide (
2 mol) was reacted at 70°C for 3 hours to achieve a solid content of 50%.
An aqueous solution (A-1) was obtained.

Urea-formaldehyde condensate (Dainippon Ink & Chemicals ITl "AN Primamine TD-2712, solid content 50% aqueous solution) 400 parts of the above condensed methylnisderammonium phosphate, formaldehyde, dicyandiamide condensation reaction product (A-1) 80 parts and 40 parts of sulfuric acid/herring (B), 80 parts of wheat flour,
Thoroughly stir 2 parts of ammonium chloride and apply the dissolved plywood adhesive to the core board (1.4# thickness) at a rate of 30 g/2 pieces (15 g/2 pieces on each side), and then apply the veneer to this. Compete with (0,8 thickness)! There will be 3 layers. Cold pressure is 10kg at room temperature
/cffl pressure for 30 minutes, heat pressure was 120'C and 10K (1 part cm pressure for 1 minute).

The flame retardancy was determined by the plywood flame retardant test method specified in Section 4-3 of the Fire Service Act Construction Regulations (45° Metschel burner method, flame contact time 2 minutes,
The acceptance criteria were charred area of 5 oc or less, afterflame of 10 seconds or less, and residual flame of 30 seconds or less). Adhesion was determined in accordance with the JAS flameproof plywood agriculture and forestry standard adhesion test (warm and cold water immersion test). The results are shown in Table-1.

Examples 2-4. Comparative Examples 1 to 4 Condensed phosphoric acid methyl ester ammonium salt of Example 1,
Formaldehyde, dicyandiamide condensation reaction product (
The solid content ratio of A-1) and guanidine sulfamate (B) was set to 0:100 to 100:O as shown in Table 1, and the solid content of these flame retardants was calculated based on the solid content of the urea-formaldehyde condensation resin. ()40% bob. Otherwise, plywood production, flame retardancy test, and adhesion test were conducted in the same manner as in Example 1.

The results are shown in Table-1.

(Left below) Examples 5 to 8. Comparative Examples 5-6 Condensed phosphoric acid methyl ester ammonium salt of Example 1,
Formaldehyde, dicyandiamide condensation reaction product (
The solid content ratio of A-1) and guanidine sulfamate (B) was set to 50:50, and the solid content was mixed in an amount of 20 to 80% based on the solid content of the urea-formaldehyde condensate, and plywood was produced in the same manner as in Example 1. , flame retardancy and adhesion tests were conducted. The results are shown in Table-2.

Example 9 Plywood was manufactured in the same manner as in Example 1 using a plywood adhesive obtained by adding 50 parts of aluminum hydroxide to the plywood adhesive of Example 1, and flame retardant and adhesive tests were conducted. The results are shown in Table-2.

Example 10 Using a plywood adhesive prepared by adding 30 parts of pentaerythritol to the plywood adhesive of Example 1, plywood was manufactured in the same manner as in Example 1, and flame retardant and adhesive tests were conducted. The results are shown in Table-2.

Example 11 142 parts of phosphorus pentoxide (1-El) and 9 parts of ethyl alcohol
The condensed phosphoric acid ethyl ester mixture obtained by reacting 2 parts (2 moles) at 80°C or less for 3 hours was neutralized with 136 parts (2 moles) of 25% aqueous ammonia, and further 9 parts of 37% formalin.
4.6 parts (1.5 mol), dicyandiamide 126 parts (
1.5 mol) was subjected to a condensation reaction at 70°C for 3 hours to reduce the solid content to 5.
A 0% aqueous solution (A-2) was obtained.

To 400 parts of urea-formaldehyde condensate (manufactured by Dainippon Ink & Chemicals, Priamine TD-2712, 50% solids aqueous solution) was added the above condensed ethyl phosphoric acid ester, formaldehyde, and dicyandiamide condensation reaction product (A-2).
) Plywood was manufactured in the same manner as in Example 1 using a plywood adhesive consisting of 80 parts of guanidine sulfamate, 40 parts of guanidine sulfamate, 80 parts of wheat, and 2 parts of ammonium chloride, and flame retardant and adhesive tests were conducted. The results are shown in Table-2.

Example 12 Instead of the urea-formaldehyde condensate of Example 1, a urea-melamine-formalin cocondensate (Dainippon Ink Chemical Industry Co., Ltd. (wooden, Primamine TD-2940, solid content 54
% aqueous solution> and the same plywood adhesive as in Example 1, plywood was manufactured and subjected to flame retardant and adhesive tests.

The results are shown in Table-2.

(Left below) Comparative Examples 7 to 11 Condensed phosphoric acid methyl ester ammonium salt of Example 1,
Plywood was prepared in the same manner as in Example 1, using ammonium phosphate, ammonium sulfamate, ammonium bromide, guanylurea phosphate, and ammonium polyphosphate instead of the formaldehyde and dicyandiamide condensation reaction product.
U^, flame retardant properties, adhesion tests, and gel time measurements of plywood adhesive were conducted. The results are shown in Table-3.

(The following is a blank space) [Effects of the invention] In the present invention, condensed phosphoric acid ester ammonium salt,
Solid content ratio of formaldehyde, dicyandiamide condensation reaction product and guanidine sulfamate: 40:60~
A flame retardant having a ratio of 70:30 exhibits a significant synergistic effect on flame retardancy, as shown in the examples.

In addition, the flame retardant solid content of the above combination with respect to the formaldehyde condensation resin solid content that passes the main standards for flame retardant plywood is 40 to 70%, and is shown in the comparative example in Table 3. Provides sufficient flame retardant properties with a very small amount of incorporation compared to conventional flame retardant solid content.

Furthermore, it has advantages such as excellent adhesiveness, uniform dissolution in formaldehyde condensation resin, and excellent workability because it does not promote gelation.

Claims (1)

[Claims] (1) The solid content weight ratio of [1] formaldehyde condensation resin, [2] condensation reaction product consisting of condensed phosphoric acid ester ammonium salt, formaldehyde, and dicyandiamide, and guanidine sulfamate is 40:60 to 7
[3] A flame retardant with a solid content of 0:30 is 30 to 70% based on the solid content of the formaldehyde condensation resin, and [3] a polysaccharide filler is 10 to 60% based on the solid content of the formaldehyde condensation resin. 1. A method for producing flame-resistant plywood, which comprises bonding using a plywood adhesive containing: