Wood and bamboo composite mildew preventive with stable thermal-alkali coupling as well as preparation method and application of wood and bamboo composite mildew preventive

Abstract

The invention discloses a wood and bamboo composite mildew preventive with thermal-alkali coupling stability and a preparation method and application thereof. According to the wood and bamboo composite mildew preventive, the oxidation resistance and thermal stability of the wood and bamboo composite mildew preventive are improved through combined use of an organic phosphoric acid antioxidant and a polymerization inhibition type thermal stabilizer; and the degradation of the wood and bamboo composite mildew preventive under the alkaline environment and high-temperature treatment is inhibited, so that the reduction of the mildew resistance of the wood and bamboo composite material added with the wood and bamboo composite mildew preventive due to a hot pressing process is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of bamboo anti-mildew treatment, and in particular to a wood-bamboo composite mildew preventer with thermal alkali coupling stability, and a preparation method and application thereof. Background Art

[0002] Bamboo is an important renewable non-wood forest resource with the characteristics of fast growth, short harvesting cycle and high mechanical strength. It has important value in social, economic, ecological and cultural aspects. In the natural environment, the main components of the cell wall in bamboo are similar to those of wood, consisting of cellulose, hemicellulose and lignin. Compared with wood, the cell cavity of bamboo is rich in nutrients such as sugars, starch, fat and protein, making it more susceptible to infection and damage by mold. Studies have shown that mold usually does not destroy the cell wall structure of bamboo or reduce its mechanical strength, but it will affect its appearance color and natural texture to a certain extent, reducing the economic value and service life of bamboo products. In addition, long-term exposure to mold environment will seriously affect physical health. The spores produced by most molds can cause respiratory infections and even allergic reactions. For example, the aflatoxin secreted by Aspergillus flavus has a strong carcinogenic and carcinogenic effect; Aspergillus niger can cause lung, skin, gastrointestinal infections and other problems. The use of mold inhibitors to inhibit the occurrence of mold in bamboo is one of the important measures to achieve efficient and long-term utilization of bamboo.

[0003] Although organic mildew inhibitors for wood and bamboo are commonly used for soaking, painting or pressurized impregnation, their mildew-proofing effect is often significantly affected by high-temperature thermal degradation, oxidative degradation or accelerated degradation in alkaline environments of mildew inhibitors during the high-temperature hot-pressing process of artificial boards or reconstituted bamboo. For example, the reconstituted bamboo mildew-proof modifier developed by CN107584622A combines azoles, isothiazolinones and pyrethroids to provide good mildew resistance, but it will degrade to a certain extent under high-temperature hot pressing. In the field of artificial boards, CN114946868A provides an organic-inorganic composite mildew inhibitor composed of isothiazolinone compounds, borax and nano-titanium dioxide, which has low toxicity and environmental advantages, but the inorganic component has the defect of insufficient long-term stability.

[0004] However, whether it is the anti-mildew treatment of reconstructed bamboo or artificial boards, the existing organic mildew inhibitors are insufficiently stable in high temperature and alkaline environments, and the anti-mildew effect still has bottlenecks such as short effectiveness and weak efficacy, which requires further improvement and optimization. Summary of the invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art, provide a composite mildew preventer for wood and bamboo with thermal alkali coupling stability, and a preparation method and application thereof, reduce the oxidative degradation and thermal degradation of organic mildew preventers for wood and bamboo under high temperature and alkaline conditions, and give bamboo good mildew resistance.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] A composite mildew preventer for wood and bamboo materials with thermal alkali coupling stability, comprising the following raw material components in parts by weight:

[0008]

[0009] As a further improvement to the above application steps:

[0010] Preferably, the following raw material components are included by weight:

[0011]

[0012] Preferably, the following raw material components are included by weight:

[0013]

[0014] Preferably, the organophosphoric acid antioxidant includes one or more of tris(2,4-tert-butylphenyl)phosphate, diisodecylphenylphosphonate, triphenyl phosphate, diphenyldecyl phosphate, triphenyl phosphite, phosphite, and hydroxyethylidene diphosphonic acid.

[0015] Preferably, the polymerization inhibition type heat stabilizer includes one or both of 2,6-di-tert-butyl-4-methylphenol and 2,4,6-trimethylphenol.

[0016] Preferably, the surfactant includes one or more of polyoxyethylene vegetable oil, polyoxyethylene alkyl aryl ether, polyoxyethylene lauryl ether, polyoxyethylene lanolin alcohol ether, polyoxyethylene sorbitan monooleate, and polyoxyethylene monolaurate.

[0017] As a general inventive concept, the present invention also provides a method for preparing the aforementioned wood-bamboo composite mildew inhibitor with thermal alkali coupling stability, comprising the following steps:

[0018] The isothiazolinone organic mildew preventer is dissolved in diethylene glycol and mixed evenly, heated and maintained at 40-60°C, an organic phosphoric acid antioxidant, an inhibitory heat stabilizer, a surfactant and water are added, stirred evenly, and a composite mildew preventer for wood and bamboo with thermal alkali coupling stability is prepared.

[0019] As a further improvement of the above technical solution: after adding an organic phosphoric acid antioxidant, an inhibitory heat stabilizer and a surfactant, stir at a rotation speed of 200-2000 rpm for 5-10 minutes, then add water and stir at a rotation speed of 200-2000 rpm for 10-20 minutes.

[0020] As a general inventive concept, the present invention also provides the aforementioned wood-bamboo composite mildew preventer with thermal alkali coupling stability and the use of the wood-bamboo composite mildew preventer with thermal alkali coupling stability prepared according to the aforementioned preparation method in bamboo mildew prevention treatment.

[0021] As a further improvement to the above technical solution: the application method comprises the following steps:

[0022] S1, soaking the bamboo bundle in a heat-alkali coupled stabilized wood-bamboo composite mildew inhibitor, and drying the bamboo bundle until the moisture content is 8-12%;

[0023] S2. Assemble a plurality of bamboo bundles, and hot press them for 6-15 minutes at a hot pressing pressure of 1-1.5 MPa and a temperature of 120-150° C. to obtain recombined bamboo.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The wood-bamboo composite mildew preventer with heat-alkali coupling stability of the present invention (heat-alkali coupling stability means that the mildew preventer has good stability under the condition of high temperature and alkaline environment. Such environment will be generated when the phenolic resin adhesive and the lignin adhesive are hot-pressed and formed, and these two adhesives, especially the phenolic resin, are adhesives commonly used in wood-bamboo composite materials), improves the antioxidant performance and thermal stability of the wood-bamboo composite mildew preventer by jointly using an organic phosphoric acid antioxidant and an inhibitory heat stabilizer, inhibits the degradation of the wood-bamboo composite mildew preventer due to the mildew preventer in an alkaline environment and high temperature treatment, thereby reducing the decrease in the mildew resistance of the wood-bamboo composite material to which the wood-bamboo composite mildew preventer is added due to the hot pressing process. DETAILED DESCRIPTION

[0026] The present invention will be described in further detail below. Unless otherwise specified, the instruments or materials used in the present invention are commercially available.

[0027] Example 1

[0028] The composite mildew preventer for wood and bamboo materials with heat-alkali coupling stability of the present embodiment includes the following raw material components in parts by weight: 0.2 parts of isothiazolinone organic mildew preventer (CMIT), 3.8 parts of diethylene glycol, 1.5 parts of organic phosphoric acid antioxidant (phosphite), 1.5 parts of inhibitory heat stabilizer (2,6-di-tert-butyl-4-methylphenol), 5 parts of surfactant (polyoxyethylene alkyl aryl ether), and 88 parts of water.

[0029] The preparation method of a composite mildew preventer for wood and bamboo materials with thermal alkali coupling stability of the present embodiment comprises the following steps: dissolving 0.5 g of 5-chloro-2-methylisothiazolinone (CMIT) in 10.0 g of diethylene glycol, mixing evenly, taking out 4.0 g, heating and maintaining at 40-60° C. (50° C. in the present embodiment), then adding 1.5 g of phosphite, 1.5 g of 2,6-di-tert-butyl-4-methylphenol and 5.0 g of polyoxyethylene alkyl aryl ether thereto, stirring at a rotation speed of 400 rpm for 10 min, then adding 88.0 g of water thereto, and stirring at a rotation speed of 400 rpm for another 20 min, to obtain a composite mildew preventer for wood and bamboo materials with thermal alkali coupling stability.

[0030] The present embodiment provides an application method of a wood-bamboo composite mildew inhibitor with thermal-alkali coupling stability, comprising the following steps:

[0031] A bamboo bundle with a thickness of 2 mm and a moisture content of 10% is immersed in the heat-alkali coupled stable wood-bamboo composite mildew inhibitor of this embodiment. The pressure during the immersion treatment is 0.5-0.8 MPa (the immersion pressure in this embodiment is 0.5 MPa), and the immersion time is 2-10 min (the immersion time in this embodiment is 5 min). After immersion, the bamboo bundle is taken out for drying. The drying temperature is controlled at 60-80° C. (60° C. in this embodiment) and the drying time is 24-48 h (36 h in this embodiment) until the moisture content of the bamboo bundle is reduced to 8-12% (10% in this embodiment). Phenolic resin is used as an adhesive. The bamboo bundle is assembled into reconstituted bamboo under the conditions of hot pressing pressure of 1.2 MPa, hot pressing temperature of 140° C., and hot pressing time of 6 min.

[0032] Example 2

[0033] The composite mildew preventer for wood and bamboo materials with heat-alkali coupling stability of the present embodiment includes the following raw material components in parts by weight: 0.2 parts of isothiazolinone organic mildew preventer (DCOIT), 3.8 parts of diethylene glycol, 2.5 parts of organic phosphoric acid antioxidant (diisodecyl phenyl phosphonate), 2.5 parts of inhibition type heat stabilizer (2,6-di-tert-butyl-4-methylphenol), 7 parts of surfactant (polyoxyethylene alkyl aryl ether), and 84 parts of water.

[0034] The preparation method of a composite mildew preventer for wood and bamboo materials with thermal alkali coupling stability of the present embodiment comprises the following steps: dissolving 0.5 g of 4,5-dichloro-N-octyl-4-isothiazoline-3-one (DCOIT) in 10.0 g of diethylene glycol, mixing evenly, taking out 4.0 g, heating and maintaining at 40-60° C. (50° C. in the present embodiment), then adding 2.5 g of diisodecyl phenyl phosphonate, 2.5 g of 2,6-di-tert-butyl-4-methylphenol and 7.0 g of polyoxyethylene alkyl aryl ether thereto, stirring at a rotation speed of 400 rpm for 10 min, then adding 84.0 g of water thereto, and stirring at a rotation speed of 400 rpm for another 20 min, to obtain a composite mildew preventer for wood and bamboo materials with thermal alkali coupling stability.

[0035] This embodiment provides an application method of a wood-bamboo composite mildew inhibitor with thermal alkali coupling stability, and its application steps are the same as those in Example 1.

[0036] Example 3

[0037] The composite mildew preventer for wood and bamboo materials with heat-alkali coupling stability of the present embodiment includes the following raw material components by weight: 0.1 parts of isothiazolinone organic mildew preventer (OIT), 1.9 parts of diethylene glycol, 2.5 parts of organophosphate antioxidant (hydroxyethylidene diphosphonic acid), 4 parts of inhibitory heat stabilizer (2,4,6-trimethylphenol), 5 parts of surfactant (polyoxyethylene sorbitan monooleate), and 86.5 parts of water.

[0038] The preparation method of a composite mildew preventer for wood and bamboo materials with thermal alkali coupling stability of the present embodiment comprises the following steps: dissolving 0.5 g of 2-octyl-4-isothiazoline-3-one (OIT) in 10.0 g of diethylene glycol, mixing evenly, taking out 2.0 g, heating and maintaining at 40-60° C. (50° C. in the present embodiment), then adding 2.5 g of hydroxyethylidene diphosphonic acid, 4.0 g of 2,4,6-trimethylphenol and 5.0 g of polyoxyethylene sorbitan monooleate thereto, stirring at a rotation speed of 1000 rpm for 6 min, then adding 86.5 g of water thereto, and stirring at a rotation speed of 400 rpm for another 20 min, to obtain a composite mildew preventer for wood and bamboo materials with thermal alkali coupling stability.

[0039] This embodiment provides an application method of a wood-bamboo composite mildew inhibitor with thermal alkali coupling stability, and its application steps are the same as those in Example 1.

[0040] Example 4

[0041] The composite mildew preventer for wood and bamboo materials with heat-alkali coupling stability of the present embodiment includes the following raw material components by weight: 0.1 parts of isothiazolinone organic mildew preventer (CMIT), 1.9 parts of diethylene glycol, 2.5 parts of organic phosphoric acid antioxidant (hydroxyethylidene diphosphonic acid), 4 parts of inhibitory heat stabilizer (2,6-di-tert-butyl-4-methylphenol), 5 parts of surfactant (polyoxyethylene monolaurate), and 86.5 parts of water.

[0042] The preparation method of a composite mildew preventer for wood and bamboo materials with thermal alkali coupling stability of the present embodiment comprises the following steps: dissolving 0.5 g of 5-chloro-2-methylisothiazolinone (CMIT) in 10.0 g of diethylene glycol, mixing evenly, taking out 2.0 g, heating and maintaining at 40-60° C. (50° C. in the present embodiment), then adding 2.5 g of hydroxyethylidene diphosphonic acid, 4.0 g of 2,6-di-tert-butyl-4-methylphenol and 5.0 g of polyoxyethylene monolaurate thereto, stirring at a rotation speed of 1500 rpm for 5 min, then adding 86.5 g of water thereto, and stirring at a rotation speed of 400 rpm for another 20 min, to obtain a composite mildew preventer for wood and bamboo materials with thermal alkali coupling stability.

[0043] This embodiment provides an application method of a wood-bamboo composite mildew inhibitor with thermal alkali coupling stability, and its application steps are the same as those in Example 1.

[0044] Comparative Example 1

[0045] The composite mildew preventer for wood and bamboo materials in the comparative example lacks an inhibitory heat stabilizer and an organophosphate antioxidant, and comprises the following raw material components by weight: 0.1 parts of an isothiazolinone organic mildew preventer (OIT), 1.9 parts of diethylene glycol, 0 parts of an organophosphate antioxidant, 0 parts of an inhibitory heat stabilizer, 5 parts of a surfactant (polyoxyethylene alkyl aryl ether), and 93 parts of water.

[0046] The preparation method of a composite mildew preventive for wood and bamboo in the comparative example comprises the following steps: dissolving 0.5 g of 2-octyl-4-isothiazoline-3-one (OIT) in 10.0 g of diethylene glycol, mixing evenly, taking out 2.0 g, heating and maintaining at 40-60° C. (50° C. in the comparative example), then adding 5.0 g of polyoxyethylene sorbitan monooleate and 93.0 g of water thereto, and stirring at a rotation speed of 400 rpm for another 20 min to obtain the composite mildew preventive for wood and bamboo.

[0047] The application method of the composite mildew preventive for wood and bamboo materials in this comparative example has the same application steps as those in Example 1.

[0048] Comparative Example 2

[0049] The composite mildew preventer for wood and bamboo materials in the comparative example lacks an inhibitory heat stabilizer and comprises the following raw material components by weight: 0.2 parts of an isothiazolinone organic mildew preventer (CMIT), 3.8 parts of diethylene glycol, 1.5 parts of an organic phosphoric acid antioxidant (phosphite), 0 parts of an inhibitory heat stabilizer, 5 parts of a surfactant (polyoxyethylene alkyl aryl ether), and 89.5 parts of water.

[0050] The preparation method of a composite mildew preventive for wood and bamboo in the comparative example comprises the following steps: dissolving 0.5 g of 5-chloro-2-methylisothiazolinone (CMIT) in 10.0 g of diethylene glycol, mixing evenly, taking out 4.0 g, heating and maintaining at 40-60° C. (50° C. in the comparative example), then adding 1.5 g of phosphite and 5.0 g of polyoxyethylene alkyl aryl ether thereto, stirring at a rotation speed of 400 rpm for 10 min, then adding 89.5 g of water thereto, stirring at a rotation speed of 400 rpm for another 20 min, to obtain the composite mildew preventive for wood and bamboo.

[0051] The application method of the composite mildew preventive for wood and bamboo materials in this comparative example has the same application steps as those in Example 1.

[0052] Comparative Example 3

[0053] The composite mildew preventer for wood and bamboo materials in the comparative example lacks an organic phosphoric acid antioxidant and includes the following raw material components by weight: 0.2 parts of an isothiazolinone organic mildew preventer (CMIT), 3.8 parts of diethylene glycol, 0 parts of an organic phosphoric acid antioxidant, 1.5 parts of an inhibitory heat stabilizer (2,6-di-tert-butyl-4-methylphenol), 5 parts of a surfactant (polyoxyethylene alkyl aryl ether), and 89.5 parts of water.

[0054] The preparation method of a composite mildew preventive for wood and bamboo of the comparative example comprises the following steps: dissolving 0.5 g of 5-chloro-2-methylisothiazolinone (CMIT) in 10.0 g of diethylene glycol, mixing evenly, taking out 4.0 g, heating and maintaining at 40-60° C. (50° C. in the comparative example), then adding 1.5 g of 2,6-di-tert-butyl-4-methylphenol and 5.0 g of polyoxyethylene alkyl aryl ether thereto, stirring at a rotation speed of 400 rpm for another 10 min, and then adding 89.5 g of water thereto to obtain a high temperature resistant composite mildew preventive for wood and bamboo.

[0055] The application method of the composite mildew preventive for wood and bamboo materials in this comparative example has the same application steps as those in Example 1.

[0056] Comparative Example 4

[0057] The composite mildew preventer for wood and bamboo materials of the comparative example uses resveratrol to replace the organophosphate antioxidant, and comprises the following raw material components by weight: 0.1 parts of isothiazolinone organic mildew preventer (OIT), 1.9 parts of diethylene glycol, 2.5 parts of resveratrol, 4 parts of inhibitory heat stabilizer (2,4,6-trimethylphenol), 5 parts of surfactant (polyoxyethylene monolaurate), and 86.5 parts of water.

[0058] The preparation method of a composite mildew preventive for wood and bamboo in the comparative example comprises the following steps: dissolving 0.5 g of 2-octyl-4-isothiazoline-3-one (OIT) in 10.0 g of diethylene glycol, mixing evenly, taking out 2.0 g, heating and maintaining at 40-60° C. (50° C. in the comparative example), then adding 2.5 g of resveratrol, 4.0 g of 2,4,6-trimethylphenol and 5.0 g of polyoxyethylene sorbitan monooleate thereto, stirring at a rotation speed of 1000 rpm for 6 min, then adding 86.5 g of water thereto, and stirring at a rotation speed of 400 rpm for another 20 min, to obtain the composite mildew preventive for wood and bamboo.

[0059] The application method of the composite mildew preventive for wood and bamboo materials in this comparative example has the same application steps as those in Example 1.

[0060] Comparative Example 5

[0061] The composite mildew preventer for wood and bamboo materials of the comparative example uses dibutyltin maleate to replace the polymerization inhibition type heat stabilizer, and comprises the following raw material components by weight: 0.1 parts of isothiazolinone organic mildew preventer (OIT), 1.9 parts of diethylene glycol, 2.5 parts of organic phosphonic acid antioxidant (hydroxyethylidene diphosphonic acid), 4 parts of polymerization inhibition type heat stabilizer (dibutyltin maleate), 5 parts of surfactant (polyoxyethylene monolaurate), and 86.5 parts of water.

[0062] The preparation method of a composite mildew preventer for wood and bamboo materials in the comparative example comprises the following steps: dissolving 0.5 g of 2-octyl-4-isothiazoline oxazoline-3-one (OIT) in 10.0 g of diethylene glycol, mixing evenly, taking out 2.0 g, heating and maintaining at 40-60° C. (50° C. in the comparative example), then adding 2.5 g of hydroxyethylidene diphosphonic acid, 4.0 g of dibutyltin maleate and 5.0 g of polyoxyethylene monolaurate thereto, stirring at a rotation speed of 1000 rpm for 6 min, then adding 86.5 g of water thereto, and stirring at a rotation speed of 400 rpm for another 20 min, to obtain the composite mildew preventer for wood and bamboo materials.

[0063] The application method of the composite mildew preventive for wood and bamboo materials in this comparative example has the same application steps as those in Example 1.

[0064] Comparative Example 6

[0065] The composite mildew preventer for wood and bamboo materials in this comparative example uses a relatively large amount of an organic phosphoric acid antioxidant, and includes the following raw material components in parts by weight: 0.2 parts of an isothiazolinone organic mildew preventer (DCOIT), 3.8 parts of diethylene glycol, 10 parts of an organic phosphoric acid antioxidant (diisodecyl phenyl phosphonate), 2.5 parts of an inhibitory heat stabilizer (2,6-di-tert-butyl-4-methylphenol), 7 parts of a surfactant (polyoxyethylene alkyl aryl ether), and 76.5 parts of water.

[0066] The preparation method of a composite mildew preventive for wood and bamboo materials in the comparative example comprises the following steps: dissolving 0.5 g of 4,5-dichloro-N-octyl-4-isothiazoline-3-one (DCOIT) in 10.0 g of diethylene glycol, mixing evenly, taking out 4.0 g, heating and maintaining at 40-60° C. (50° C. in the comparative example), then adding 10.0 g of diisodecyl phenyl phosphonate, 2.5 g of 2,6-di-tert-butyl-4-methylphenol and 7.0 g of polyoxyethylene alkyl aryl ether thereto, stirring at a rotation speed of 400 rpm for 10 min, then adding 76.5 g of water thereto, and stirring at a rotation speed of 400 rpm for another 20 min, to obtain the composite mildew preventive for wood and bamboo materials.

[0067] The application method of the composite mildew preventive for wood and bamboo materials in this comparative example has the same application steps as those in Example 1.

[0068] Comparative Example 7

[0069] The composite mildew preventive for wood and bamboo materials in this comparative example uses a relatively large amount of an inhibitory heat stabilizer, and includes the following raw material components in parts by weight: 0.2 parts of an isothiazolinone organic mildew preventive (DCOIT), 3.8 parts of diethylene glycol, 2.5 parts of an organic phosphoric acid antioxidant (diisodecyl phenyl phosphonate), 10 parts of an inhibitory heat stabilizer (2,6-di-tert-butyl-4-methylphenol), 7 parts of a surfactant (polyoxyethylene alkyl aryl ether), and 76.5 parts of water.

[0070] The preparation method of a composite mildew preventive for wood and bamboo materials in the comparative example comprises the following steps: dissolving 0.5 g of 4,5-dichloro-N-octyl-4-isothiazoline-3-one (DCOIT) in 10.0 g of diethylene glycol, mixing evenly, taking out 4.0 g, heating and maintaining at 40-60° C. (50° C. in the comparative example), then adding 2.5 g of diisodecyl phenyl phosphonate, 10.0 g of 2,6-di-tert-butyl-4-methylphenol and 7.0 g of polyoxyethylene alkyl aryl ether thereto, stirring at a rotation speed of 400 rpm for 10 min, then adding 76.5 g of water thereto, and stirring at a rotation speed of 400 rpm for another 20 min, to obtain the composite mildew preventive for wood and bamboo materials.

[0071] The application method of the composite mildew preventive for wood and bamboo materials in this comparative example has the same application steps as those in Example 1.

[0072] Comparative Example 8

[0073] The composite mildew preventive for wood and bamboo materials of the comparative example adopts sodium polyoxyethylene fatty alcohol ether sulfate as a surfactant, and comprises the following raw material components in parts by weight: 0.2 parts of isothiazolinone organic mildew preventive (DCOIT), 3.8 parts of diethylene glycol, 2.5 parts of organic phosphoric acid antioxidant (diisodecyl phenyl phosphonate), 4 parts of inhibition type heat stabilizer (2,6-di-tert-butyl-4-methylphenol), 7 parts of surfactant (sodium polyoxyethylene fatty alcohol ether sulfate), and 82.5 parts of water.

[0074] The preparation method of a composite mildew preventive for wood and bamboo materials in the comparative example comprises the following steps: dissolving 0.5 g of 4,5-dichloro-N-octyl-4-isothiazoline-3-one (DCOIT) in 10.0 g of diethylene glycol, mixing evenly, taking out 4.0 g, heating and maintaining at 40-60° C. (50° C. in the comparative example), then adding 2.5 g of diisodecyl phenyl phosphonate, 4.0 g of 2,6-di-tert-butyl-4-methylphenol and 7.0 g of sodium fatty alcohol polyoxyethylene ether sulfate thereto, stirring at a rotation speed of 400 rpm for 10 min, then adding 82.5 g of water thereto, and stirring at a rotation speed of 400 rpm for another 20 min, to obtain the composite mildew preventive for wood and bamboo materials.

[0075] The application method of the composite mildew preventive for wood and bamboo materials in this comparative example has the same application steps as those in Example 1.

[0076] The basic parameter performance test of the wood and bamboo composite mildew preventer was conducted to detect the performance of the prepared wood and bamboo composite mildew preventer from five aspects, including appearance, average particle size, centrifugal stability, and storage stability. The average particle size was measured using a Delsa Nano C laser particle size analyzer. The centrifugal stability was measured by taking 10.0 g of each of the wood and bamboo composite mildew preventers stabilized by thermal alkali coupling in Examples 1-4 and the wood and bamboo composite mildew preventers in Comparative Examples 1-8, respectively, and placing them in a centrifuge and centrifuging them at a speed of 3000 r / min for 30 minutes to observe the stability of the wood and bamboo composite mildew preventer. The results are shown in Table 1:

[0077] Table 1 Basic parameters and performance of wood and bamboo composite mildew inhibitors in various embodiments and comparative examples

[0078]

[0079] The results show that the particle sizes of all the embodiments and comparative examples are between 28 nm and 80 nm, and the centrifugal stability and storage stability are maintained well.

[0080] Stability test of wood and bamboo composite mildew preventer: 10.0 g of each of the wood and bamboo composite mildew preventer of Examples 1-4 and Comparative Examples 1-8 were taken, mixed with phenolic resin adhesive in a ratio of 30:70, placed in a culture dish, and heat treated in an environment of 180° C. for 20 min. Then, methanol was used to dissolve the effective ingredients in the composite mildew preventer stabilized by heat alkali coupling. HPLC was used to test the effective ingredient content in the composite bamboo mildew preventer before and after the heat treatment, and the thermal degradation rate of the effective ingredient was calculated. The results are shown in Table 2:

[0081] Table 2 Thermal degradation rate of effective components of composite mildew inhibitor for wood and bamboo materials in various embodiments and comparative examples by heat treatment combined with alkali treatment

[0082]

[0083] The results show that the active ingredients of Comparative Example 1 without adding an organic phosphate antioxidant and an inhibitory heat stabilizer are largely degraded, and the active ingredients of Comparative Example 3 without adding an organic phosphate antioxidant and Comparative Example 2 without adding an inhibitory heat stabilizer are also largely pyrolyzed, proving that a single organic phosphate antioxidant or an inhibitory heat stabilizer cannot prevent the active ingredients of the mildew inhibitor from being degraded, while Examples 1-4 can reduce the degradation rate of the active ingredients caused by the combined treatment of heat and alkali at 180°C to less than 9%, proving that the combined use of an organic phosphate antioxidant and an inhibitory heat stabilizer can effectively improve the stability of the mildew inhibitor. The active ingredients of Comparative Example 4 with resveratrol replacing the organic phosphate antioxidant and Comparative Example 5 with dibutyltin maleate replacing the inhibitory heat stabilizer are also largely degraded, indicating that the types of organic phosphate antioxidants and inhibitory heat stabilizers of the present invention are superior in improving the stability of the mildew inhibitor, and not any type of antioxidant or stabilizer can achieve the technical effect that the present invention can achieve. Comparative Example 6, in which the amount of organic phosphoric acid antioxidant is relatively large, and Comparative Example 7, in which the amount of polymerization inhibition type heat stabilizer is relatively large, prove that the amount of organic phosphoric acid antioxidant and polymerization inhibition type heat stabilizer used in the present invention is closely related to whether the stability of the mildew inhibitor can be improved, and not any ratio of organic phosphoric acid antioxidant and polymerization inhibition type heat stabilizer can achieve the technical effect that the present invention can achieve. Comparative Example 8 proves that the type of surfactant of the present invention has a synergistic effect with the organic phosphoric acid antioxidant and polymerization inhibition type heat stabilizer.

[0084] The anti-mildew performance test of the reconstructed bamboo treated with the composite anti-mildew agent for wood and bamboo materials was conducted. The anti-mildew performance of the plywood was tested with reference to the standard GB / T 18261-2013 "Test Method for the Effectiveness of Anti-mildew Agents against Wood Mold and Discoloration Fungi", where the infection value of 0 means that there are no mycelium or mildew spots on the surface of the test piece; the infection value of 1 means that the infection area of ​​the test piece surface is <1 / 4; the infection value of 2 means that the infection area of ​​the test piece surface is 1 / 4 to 1 / 2; the infection value of 3 means that the infection area of ​​the test piece surface is 1 / 2 to 3 / 4; the infection value of 4 means that the infection area of ​​the test piece surface is >3 / 4. The results are shown in Table 3:

[0085] Table 3 Infection value of reconstituted bamboo treated with composite antifungal agent for wood and bamboo

[0086]

[0087] The results show that the recombinant bamboo formed by hot pressing after being treated with bamboo bundles in Comparative Example 1 without the combined treatment of organophosphate antioxidant and polymerization inhibitor heat stabilizer has an infection value of 4 for both Aspergillus niger and Trichoderma viride after one month of fungal attack, indicating that the effective ingredients in the antifungal agent have been degraded under the action of heat and alkali coupling, and can no longer provide antifungal performance for the recombinant bamboo. The antifungal properties of Comparative Examples 2 and 3 are also not good, which also shows that the single use of organophosphate antioxidant or polymerization inhibitor heat stabilizer cannot effectively improve the antifungal properties of the recombinant bamboo composite antifungal agent. At the same time, the antifungal properties of Comparative Examples 4-8 are also not good. The type of organophosphate antioxidant, the amount of organophosphate antioxidant, the polymerization inhibitor heat stabilizer and the type of surfactant of the present invention have a synergistic effect. Examples 1-4 combined with organophosphate antioxidant and polymerization inhibitor heat stabilizer can give the recombinant bamboo good antifungal properties.

[0088] Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Any technician familiar with the art can make many possible changes and modifications to the technical solution of the present invention by using the technical content disclosed above without departing from the scope of the technical solution of the present invention, or modify it into an equivalent embodiment of equivalent changes. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention should fall within the scope of protection of the technical solution of the present invention.

Claims

1. A composite mildew preventer for wood and bamboo materials with thermal alkali coupling stability, characterized in that: The invention comprises the following raw material components by weight:

2. The wood-bamboo composite mildew inhibitor with heat-alkali coupling stability according to claim 1, characterized in that: The invention comprises the following raw material components by weight:

3. The wood-bamboo composite mildew inhibitor with heat-alkali coupling stability according to claim 2, characterized in that: The invention comprises the following raw material components by weight:

4. The wood-bamboo composite mildew inhibitor with heat-alkali coupling stability according to any one of claims 1 to 3, characterized in that: The organic phosphoric acid antioxidant includes one or more of tris(2,4-tert-butylphenyl)phosphate, diisodecylphenylphosphonate, triphenyl phosphate, diphenyldecyl phosphate, triphenyl phosphite, phosphite, and hydroxyethylidene diphosphonic acid.

5. The wood-bamboo composite mildew inhibitor with heat-alkali coupling stability according to any one of claims 1 to 3, characterized in that: The polymerization inhibition type heat stabilizer includes one or two of 2,6-di-tert-butyl-4-methylphenol and 2,4,6-trimethylphenol.

6. The wood-bamboo composite mildew inhibitor with heat-alkali coupling stability according to any one of claims 1 to 3, characterized in that: The surfactant includes one or more of polyoxyethylene vegetable oil, polyoxyethylene alkyl aryl ether, polyoxyethylene lauryl ether, polyoxyethylene lanolin alcohol ether, polyoxyethylene sorbitan monooleate, and polyoxyethylene monolaurate.

7. A method for preparing the composite mildew inhibitor for wood and bamboo materials with thermal alkali coupling stability according to any one of claims 1 to 6, characterized in that: The following steps are involved: The isothiazolinone organic mildew preventer is dissolved in diethylene glycol and mixed evenly, heated and maintained at 40-60°C, an organic phosphoric acid antioxidant, an inhibitory heat stabilizer, a surfactant and water are added, stirred evenly, and a composite mildew preventer for wood and bamboo with thermal alkali coupling stability is prepared.

8. The method for preparing the composite wood-bamboo mildew inhibitor with heat-alkali coupling stability according to claim 7, characterized in that: After adding an organic phosphoric acid antioxidant, an inhibitory heat stabilizer and a surfactant, the mixture is stirred at a rotation speed of 200-2000 rpm for 5-10 minutes, and then water is added and stirred at a rotation speed of 200-2000 rpm for 10-20 minutes.

9. Use of the composite mildew preventer for wood and bamboo materials with heat-alkali coupling stability according to any one of claims 1 to 6 and the composite mildew preventer for wood and bamboo materials with heat-alkali coupling stability prepared by the preparation method according to claim 7 or 8 in mildew prevention treatment of bamboo materials.

10. The use according to claim 9, characterized in that: The following steps are involved: S1, soaking the bamboo bundle in a heat-alkali coupled stabilized wood-bamboo composite mildew inhibitor, and drying the bamboo bundle until the moisture content is 8-12%; S2. Assemble a plurality of bamboo bundles, and hot press them for 6-15 minutes at a hot pressing pressure of 1-1.5 MPa and a temperature of 120-150° C. to obtain recombined bamboo.

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