JP3400985B2 - Method for removing aldehydes from synthetic wood building materials and synthetic wood building materials with reduced aldehydes release - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a synthetic wood building material capable of releasing aldehydes such as formaldehyde,
The present invention relates to a method for removing aldehydes that can remove the aldehydes more efficiently, and a synthetic wood building material that has been subjected to a process for reducing the release of aldehydes.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Various plywood such as plywood, decorative plywood, and printed plywood, synthetic wood building materials such as laminated wood, strand board, particle board, fiber board, etc. are known, but unlike natural wood, glue wood materials with adhesive Together,
Alternatively, it is an artificial wooden building material that is manufactured by adding an adhesive and crimping, and the wooden material and the adhesive are essential elements. As such an adhesive, those suitable for wood adhesion, for example, a phenol adhesive, a melamine adhesive, a urea adhesive, etc. are known, but since all of these have formaldehyde as an essential component, after production, a synthetic wood building material. There is a problem that formaldehyde is emitted from the.

As a means for adsorbing and removing such formaldehyde, it has been conventionally known to treat synthetic wood building materials with deodorants such as hydrazides, azoles and azines, but the removal effect is not yet sufficient. There is a need for means that can more efficiently remove formaldehyde and the like emitted from synthetic wood building materials.

An object of the present invention is to reduce the amount of aldehydes such as formaldehyde released from synthetic wood building materials.

[0005]

Means for treating the plywood with the deodorant is, for example, Japanese Patent Laid-Open No. 11-487.
No. 9 publication. That is, it is described that at least one selected from an azole compound, an azine compound and a 1-aminopyrrolidine compound is treated on plywood. However, the means described in such publication is
Although attention is paid to the components of the deodorant itself, plywood for treating this is not particularly considered.

The inventors of the present invention repeated trial and error with respect to the removal of aldehydes for treating deodorants such as hydrazides and azoles on plywood, and found that specific plywood was treated with deodorants such as hydrazides. In the case of doing, we obtained the finding that the amount of formaldehyde released was reduced compared to the case of treating other plywood, and further, based on such findings, we conducted intensive research and found that the ammonium compound contained in the specific plywood Has been found to act as an auxiliary agent of the above deodorant, and has completed the present invention.

That is, according to the present invention, among synthetic wood building materials capable of releasing aldehydes, a synthetic wood building material containing an ammonium compound is treated with at least one selected from hydrazides, azoles and azines. This relates to a method for removing aldehydes from wooden building materials. Further, the present invention is, among synthetic wood building materials capable of releasing aldehydes,
The present invention relates to a method for removing aldehydes from a synthetic wooden building material, which comprises treating an ammonium compound-containing synthetic wooden building material with at least one selected from hydrazides. Further, the present invention is a synthetic wood building material manufactured using an adhesive containing formaldehyde and ammonium compounds, coated or impregnated with at least one selected from hydrazides, azoles and azines coated or impregnated. Related to synthetic wood building materials with low aldehydes release.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, at least one selected from hydrazides, azoles and azines.
A seed (hereinafter, this compound (mixture) may be referred to as "deodorant composition") is used. As hydrazides,
Examples thereof include monohydrazide compounds having one hydrazide group in the molecule, dihydrazide compounds having two hydrazide groups in the molecule, and polyhydrazide compounds having three or more hydrazide groups in the molecule.

Specific examples of the monohydrazide compound include:
For example, in the general formula _{R-CO-NHNH 2 (1} ) [wherein, R represents an aryl group which may have a hydrogen atom, an alkyl group or a substituent. ] The monohydrazide compound represented by these can be mentioned.

In the general formula (1), the alkyl group represented by R is, for example, a methyl group, an ethyl group or n.
-Propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, etc.
There may be mentioned 12 linear alkyl groups. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group and the like, and among these, the phenyl group is preferable. As the substituent of the aryl group, for example, a hydroxyl group, a halogen atom such as fluorine, chlorine and bromine,
Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group and an iso-butyl group. be able to.

Specific examples of the hydrazide compound represented by the general formula (1) include lauric acid hydrazide, salicylic acid hydrazide, form hydrazide, acetohydrazide, propionic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, and 3 -Hydroxy-
2-naphthoic acid hydrazide etc. can be illustrated.

Specific examples of the dihydrazide compound include, for example, the general formula H ₂ NHN-X-NHNH ₂ (2) [wherein X represents a group -CO- or a group -CO-A-CO-. A represents an alkylene group or an arylene group. ] The dihydrazide compound represented by these can be mentioned.

In the general formula (2), examples of the alkylene group represented by A include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group. , A linear alkylene group having 1 to 12 carbon atoms such as a nonamethylene group, a decamethylene group, and an undecamethylene group. As the substituent of the alkylene group,
For example, a hydroxyl group etc. can be mentioned. Examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a phenanthrylene group. Among these, a phenylene group and a naphthylene group are preferable. As the substituent of the arylene group,
The same as the above-mentioned substituent of the aryl group can be mentioned.

Specific examples of the dihydrazide compound represented by the above general formula (2) include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecane-2 acid dihydrazide. , Maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, dimer acid dihydrazide, dibasic acid dihydrazide such as 2,6-naphthoic acid dihydrazide, and the like. . Furthermore, various dibasic acid dihydrazide compounds described in JP-B-2-4607 and 2,4-dihydrazino-6-
Methylamino-sym-triazine and the like can also be used as the dihydrazide of the present invention.

Specific examples of the polyhydrazide compound include polyacrylic acid hydrazide. Among these, dihydrazide compounds are preferable, dibasic acid dihydrazides are particularly preferable, and adipic acid dihydrazide is even more preferable. The above hydrazide compounds may be used alone or in combination of two or more.

As the azoles and azines, well-known 5-membered to 6-membered heterocyclic compounds having two or three nitrogen atoms as hetero atoms can be widely used.
These heterocyclic compounds include a linear or branched alkyl group having about 1 to 4 carbon atoms, an aryl group which may have 1 or 2 or more substituents, a hydroxyl group, an amino group, an alkylamino group. A dialkylamino group, an arylamino group, a diarylamino group, a mercapto group, an ester group, a carboxyl group, a benzotriazolyl group, or a 1-hydroxybenzotriazolyl group, which is substituted with one or more substituents. May be. Here, as the linear or branched alkyl group having about 1 to 4 carbon atoms, for example, methyl, ethyl,
n-propyl, iso-propyl, n-butyl, iso
-Butyl, tert-butyl and the like can be mentioned. Examples of the aryl group include a phenyl group, a biphenyl group,
Naphthyl groups are mentioned, and even if these groups are substituted with 1 or 2 or more substituents such as a hydroxyl group, a halogen atom, a sulfonic acid group, and a linear or branched alkyl group having 1 to 4 carbon atoms. Good. When the compound has a carboxyl group as a substituent, its ester is also included in the active ingredient of the present invention.

Examples of azoles include diazole compounds, triazole compounds and thiadiazole compounds, and diazole compounds and triazole compounds can be preferably used.

Specific examples of the diazole compound include 3-methyl-5-pyrazolone and 1,3-dimethyl-5.
-Pyrazolone, 3-methyl-1-phenyl-5-pyrazolone, 3-phenyl-6-pyrazolone, 3-methyl-1
Pyrazolone compounds such as-(3-sulfophenyl) -5-pyrazolone, pyrazole, 3-methylpyrazole, 1,
4-dimethylpyrazole, 3,5-dimethylpyrazole, 3,5-dimethyl-1-phenylpyrazole, 3-
Aminopyrazole, 5-amino-3-methylpyrazole, 3-methylpyrazole-5-carboxylic acid, 3-methylpyrazole-5-carboxylic acid methyl ester, 3-methylpyrazole-5-carboxylic acid ethyl ester, 3,
Examples thereof include pyrazole compounds such as 5-methylpyrazole dicarboxylic acid.

Specific examples of the triazole compound include 1,2,3-triazole, 1,2,4-triazole, 3-n-butyl-1,2,4-triazole,
3,5-dimethyl-1,2,4-triazole, 3,5
-Di-n-butyl-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-amino-
1,2,4-triazole, 4-amino-1,2,4-
Triazole, 3,5-diamino-1,2,4-triazole, 5-amino-3-mercapto-1,2,4-triazole, 3-amino-5-phenyl-1,2,4-
Triazole, 3,5-diphenyl-1,2,4-triazole, 1,2,4-triazol-3-one, urazole (3,5-dioxy-1,2,4-triazole), 1,2,4 -Triazole-3-carboxylic acid, 1
-Hydroxybenzotriazole, 5-hydroxy-7
-Methyl-1,3,8-triazaindolizine, 1H-
Examples thereof include benzotriazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole and the like.

Examples of the azines include diazine compounds, triazine compounds, pyridazine compounds and the like. Of these, pyridazine compounds are preferably used. Specific examples of the pyridazine compound include 6-methyl-8-hydroxytriazolopyridazine, 4,5-dichloro-3-pyridazine, maleic hydrazide, and 6-methyl-3-pyridazone. Among these, azoles are preferable,
Triazole compounds such as 1,2,4-triazole and 1,2,3-triazole, pyrazole compounds such as 3,5-dimethylpyrazole, and pyrazolone compounds such as 3-methyl-5-pyrazolone are particularly preferable.

In the present invention, the azoles and azines may be used alone or in combination of two or more.

In the above deodorant composition, if necessary, a surfactant or another known deodorant (for example, perlite,
Zeolite, silica gel, activated carbon, etc.) can be added to make a deodorant.

The deodorant comprising the above components is usually powder,
Used in the form of solution or emulsion. The form of this solution can be obtained by dissolving one or more powders selected from hydrazides, azoles and azines in a suitable organic solvent or a solvent such as water. Here, known organic solvents can be used, for example,
Linear or branched aliphatic saturated alcohols having about 1 to 8 carbon atoms, alicyclic alcohols such as cyclopentanol and cyclohexanol, polyhydric alcohols such as ethylene glycol, and about 1 to 8 carbon atoms Chain-like or branched chain-like or cyclic aliphatic hydrocarbons, alkyl moiety having 1 to 8 carbon atoms
Linear or branched alkyl dialkyl ethers, diaryl ethers, tetrahydrofuran,
Examples thereof include cyclic ethers such as dioxane, ketones, esters, nitriles such as acetonitrile, polar solvents such as dimethylformamide and dimethylsulfoxide, phosphoric acid esters, and mixed solvents of two or more of these. Further, such an organic solvent may contain a proper amount of water. The concentration of the active ingredient at the time of preparation in the form of an organic solvent solution is not particularly limited and can be appropriately selected from a wide range depending on the application of the obtained solution, etc. Usually, the deodorant composition is added to the solution in an amount of 0. It may be about 1 to 80% by weight, preferably about 0.5 to 60% by weight.

The form of the emulsion is also known, for example, one or more powders selected from hydrazides, azoles and azines are mixed with water and a suitable amount of a surfactant. Can be manufactured by Further, by mixing this emulsion with a synthetic resin emulsion, it can be used in the form of an emulsion.
Examples of the synthetic resin emulsion include vinyl acetate polymer emulsion, ethylene-vinyl acetate polymer emulsion, vinyl acetate-versatate copolymer emulsion, ethylene-vinyl acetate-vinyl chloride copolymer emulsion, ethylene-vinyl acetate-acryl. Acid ester copolymer emulsion, acrylic acid ester polymer emulsion, acrylic acid ester-styrene copolymer emulsion, vinyl chloride polymer emulsion, urethane polymer emulsion, silicone polymer emulsion,
Examples thereof include synthetic resin emulsions produced by emulsion polymerization of epoxy polymer emulsions, solution polymerization and the like, and aqueous starch solutions. The amount of the active ingredient used in producing the emulsion is not particularly limited and can be appropriately selected from a wide range. Usually, the deodorant composition is added in an amount of 0.1 to 30 with respect to 100 parts by weight of the solid content of the synthetic resin emulsion. Parts by weight,
It may be appropriately adjusted so that it is preferably about 0.5 to 20 parts by weight.

The deodorants prepared in various forms such as powders, solutions or emulsions are synthetic wood building materials that release aldehydes such as formaldehyde, and are applied to synthetic wood building materials containing ammonium compounds. By performing a treatment such as impregnation, a synthetic wood building material coated or impregnated with at least one selected from hydrazides, azoles and azines can be obtained, and release of formaldehyde and the like can be extremely suppressed. Incidentally, in consideration of workability at the time of processing into a synthetic wood building material and permeability of the deodorant into the inside of the building material, the deodorant is in the form of a solution or an emulsion,
It is particularly preferable to use it in the form of a solution.

The synthetic wood building material to be treated by the method of the present invention is one that releases aldehydes such as formaldehyde and contains an ammonium compound.
An example is one produced by an adhesive containing formaldehyde as an adhesive component and an ammonium compound mixed as a curing agent. Examples of the adhesive include a phenol adhesive, a modified phenol adhesive, a melamine adhesive and a urea adhesive. The ammonium compound to be mixed is not particularly limited as long as it is at least one selected from compounds having ammonium (—NH ₄ ), and examples thereof include ammonium salts of inorganic acids and ammonium salts of organic acids. As ammonium salts of inorganic acids, ammonium chloride, ammonium sulfate, ammonium sulfite, ammonium nitrate, ammonium bromide,
Examples include ammonium fluoride, ammonium sulfide, ammonium phosphate, ammonium tripolyphosphate, ammonium carbonate and the like. Further, as the ammonium salt of an organic acid, an ammonium salt of a carboxylic acid, specifically, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pentanoic acid, hexanoic acid, heptanoic acid, octane. Saturated monocarboxylic acids such as acids, decanoic acid, lauric acid, stearic acid, oxalic acid, malonic acid, succinic acid,
Saturated dicarboxylic acids such as glutaric acid, adipic acid, suberic acid, sebacic acid, and saturated tricarboxylic acids such as citric acid, acrylic acid, methacrylic acid, propiolic acid, crotonic acid, isocrotonic acid, oleic acid, maleic acid,
Unsaturated fatty acids such as fumaric acid, benzoic acid, phthalic acid,
Aromatic carboxylic acids such as isophthalic acid, terephthalic acid, 1-naphthoic acid, toluic acid, atropic acid, and cinnamic acid, and various carboxylic acids such as nicotinic acid, isonicotinic acid, furoic acid, and heterocyclic carboxylic acids such as tenoic acid. The ammonium salts of acids are exemplified. The above-mentioned ammonium salts of inorganic acids and ammonium salts of organic acids may be contained in the synthetic wood building material individually or in combination of two or more kinds. Among them, ammonium chloride, ammonium sulfate, triammonium citrate, In particular, it is most effective to treat synthetic wooden building materials containing ammonium chloride and triammonium citrate.

The type of synthetic wood building material is not particularly limited as long as it is a synthetic wood building material as described above. For example, plywood, decorative plywood,
The present invention can be applied to various kinds of plywood such as printed plywood, laminated wood, strand board, particle board, fiber board, etc. Among them, plywood and boards, especially thin plywood (synthetic wood building materials) It is effective to process it. The deodorant treatment method for synthetic wooden building materials is in accordance with normal usage, such as applying with a brush or spray, or impregnating it by passing the building material through a dipping layer filled with the deodorant, and various treatments. The method can be applied. Further, the entire surface of the synthetic wood building material may be treated with a deodorant, or a part of the surface may be treated with a deodorant.

[0028]

[Examples] Examples, comparative examples, and test examples are given below.
The invention will be described in more detail.Preparation of test deodorant Adipic acid dihydrazide (Otsuka Chemical Co., Ltd.) in 95 parts of distilled water
(Manufactured by the company), add 5 parts and stir well to add a test deodorant
Prepared.Plywood production ・ Ammonium salt-containing plywood (plywood containing ammonium chloride)
ProductionPlywood 1 (3mm thick plywood containing ammonium chloride) Adhesive (Melamine / Uria resin (Oshika Shinko Co., Ltd.,
Product name: Oshika Resin PWP-39) 300 parts by weight, small
Wheat flour (manufactured by Nisshin Seifun Co., Ltd., trade name: Akana) 50 weight
Parts, water 62 parts by weight, ammonium chloride (reagent) 3 parts by weight
Part) on both sides of the veneer, 16g / 900cm per side
²Both sides of the veneer coated on the front and back sides
, Stack other veneers so that the fiber directions are orthogonal,
Immediately about 0.98 MPa (10 kg / cm²) Pressure
Temporary clamping for 20 minutes, then heat kept at a temperature of 120 ° C
Inserted in a plate tube, about 0.78MPa (8kg / cm²)of
It is hot pressed for 60 seconds under pressure, and F2 plywood with a thickness of 3 mm (vertical
A width of 30 mm × 30 mm) was produced.Plywood 2 (12mm thick ammonium chloride containing plywood) The same adhesive as that of the plywood 1 was applied to the front and back surfaces of the single plate on one side.
18g / 900cm ²Apply at the ratio of
Make sure that the fiber directions are orthogonal to each other on both sides of the coated veneer.
Stack the veneers in the same manner and polymerize a total of 5 veneers in the same manner.
And immediately about 0.98 MPa (10 kg / cm²) Pressure
Temporarily tighten with force for 20 minutes, then keep at a temperature of 120 ° C
Inserted into the hot plate tube, and then about 0.78MPa (8kg / c
m²) The heat is applied for 200 seconds at a pressure of
F2 plywood (30 mm x 30 mm) was produced. ・ Salt-free plywood (plywood that does not contain ammonium chloride)Plywood 3 (3mm thick unsalted plywood) Adhesive (300 parts by weight of melamine-urea resin, flour 5
Plywood 1 except that 0 parts by weight and 62 parts by weight of water were used
F2 plywood with a thickness of 3 mm (length and width 30 mm x
30 mm) was produced.Plywood 4 (12mm thick salt-free plywood) Adhesive (300 parts by weight of melamine-urea resin, flour 5
Plywood 2 except that 0 parts by weight and 62 parts by weight of water were used
F2 plywood with a thickness of 12 mm (length and width 30 mm)
× 30 mm) was produced.

Example 1 A test deodorant was added to both sides of plywood 1 and plywood 2 at 22.2 g /
Each m ² was uniformly applied, dried at room temperature, and then cured for 24 hours. Comparative Example 1 A test deodorant was applied to both surfaces of plywood 3 and plywood 2 at 22.2 g /
Each m ² was uniformly applied, dried at room temperature, and then cured for 24 hours. Comparative Example 2 Plywood 1 and Plywood 2 were left untreated at room temperature for 24 hours.
Left for hours. Comparative Example 3 The plywood 3 and the plywood 4 were not treated and left at room temperature for 24 hours.
Left for hours.

Test Example Each of the plywoods obtained in Examples and Comparative Examples 1 to 3 was used in the length and width direction of 15c.
The test piece was cut into a size of m × 5 cm, divided into 10 test pieces, and its deodorizing performance was evaluated according to the following method according to the measuring method of “JAS ordinary plywood formaldehyde emission amount”.
Desiccator (size 2 specified in JIS R3503
Crystal dish (diameter 120 mm, height 60 m) with 300 ml distilled water at the bottom of 40 mm internal volume of about 10 l)
m) was placed, a porcelain plate was laid on the m), the 10 test pieces were placed, the mixture was left at 20 to 25 ° C. for 24 hours, and the released formaldehyde was absorbed in distilled water to prepare a sample solution. The formaldehyde concentration in the sample solution was colorimetrically determined by the acetylacetone method using a photoelectric colorimeter.

The results are shown in Table 1. Deodorant% in the table
Indicates the weight% of adipic acid dihydrazide. In addition, the removal rate in the table is a rate (%) of the release rate (division of the removal rate from the formaldehyde release rate of Comparative Example 3 (formaldehyde release rate from untreated untreated plywood)). Is.

[0032]

[Table 1]

As is clear from the comparison between Example 1 and Comparative Example 1, it was found that the removal of formaldehyde was markedly improved by treating the plywoods 1 and 2 containing ammonium chloride with a deodorant. Also, the plywood to be processed is
It turns out that the thin one is effective immediately. It is speculated that this is because the deodorant penetrates into the inside of the plywood earlier and the ammonium chloride acts.

[0034]

As described above, according to the method for removing aldehydes from a synthetic wooden building material according to the present invention, it is possible to further suppress the release of aldehydes to a specific synthetic wooden building material. Further, the synthetic wooden building material according to the present invention releases less aldehydes such as formaldehyde, and is preferable as an environmental building material.

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Claims (3)

(57) [Claims] 1. Among synthetic wood building materials capable of releasing aldehydes, a synthetic wood building material containing an ammonium compound is treated with at least one selected from hydrazides, azoles and azines. Method for removing aldehydes from synthetic wood building materials. 2. Among the synthetic wood building materials capable of releasing aldehydes include, with respect to the synthetic wood building materials containing ammonium compounds, synthetic wood building materials aldehyde, which comprises treating at least one selected from hydrazides Removal method. 3. A synthetic wood building material manufactured using an adhesive containing formaldehyde and an ammonium compound, wherein at least one selected from hydrazides, azoles and azines is applied or impregnated. Synthetic wood building materials with low aldehyde release.