JP2008514599A - Wax emulsion preservative composition and production method - Google Patents

Abstract

（式中、Ｒ^１は、Ｃ_１〜Ｃ_６アルキルで場合により置換されることが可能である、チアゾリル、イソチアゾリルまたはチアジアゾリルなどの、窒素および硫黄を含有する複素環であることが可能であり、Ｒ^２は、水素またはＣ_１〜Ｃ_６アルキル、特に水素であることが可能であり、ｎは、０、１、２または３であり、Ｒ^３のそれぞれの例は、独立して、水素、Ｃ_１〜Ｃ_６アルキル、フェノキシ、Ｃ_１〜Ｃ_６アルコキシ、ハロ、アミノ、Ｃ_１〜Ｃ_６アルキルアミノ、ジＣ_１〜Ｃ_６アルキルアミノ、イミダゾリル、チアゾリル、イソチアゾリル、チアジアゾリル、チエニル、フリル、ピリル、ナフチル、フェニル、ハロフェニル、Ｃ_１〜Ｃ_６アルキルフェニルまたはＣ_１〜Ｃ_６アルコキシフェニルであることが可能である。）を有する防腐剤を含む、乳剤。この防腐剤は、乳剤が形成された後に乳剤に添加することができる。この乳剤は、石膏ボードまたは石膏木材繊維ボードなどの石膏製品に組み込むことができる。この石膏製品は、石膏、水および乳剤を含有するスラリーを固体製品に成形することにより製造できる。リグノセルロース材料と結合剤とを混合して混合物を作成し、この混合物を特定の形状に固化して複合製品を成形することにより製造されるリグノセルロース複合製品の耐水性を改善する方法は、上記のように、この混合物に乳剤を添加することを含むことができる。Water as continuous phase, wax as discontinuous phase, emulsifier and general structure: (I)

Wherein R ¹ can be a nitrogen and sulfur containing heterocycle, such as thiazolyl, isothiazolyl or thiadiazolyl, optionally substituted with C ₁ -C ₆ alkyl; R ² can be hydrogen or C ₁ -C ₆ alkyl, especially hydrogen, n is 0, 1, 2 or 3, and each example of R ³ is independently hydrogen, C ₁ -C ₆ alkyl, phenoxy, C ₁ -C ₆ alkoxy, halo, amino, C ₁ -C ₆ alkylamino, di-C ₁ -C ₆ alkylamino, imidazolyl, thiazolyl, isothiazolyl, thiadiazolyl, thienyl, furyl, pyryl , naphthyl, phenyl, _halophenyl, it can be a C 1 -C ₆ alkylphenyl or _C 1 -C ₆ alkoxyphenyl.) It contains a preservative that has, emulsion. This preservative can be added to the emulsion after it has been formed. This emulsion can be incorporated into gypsum products such as gypsum board or gypsum wood fiber board. This gypsum product can be produced by molding a slurry containing gypsum, water and emulsion into a solid product. A method for improving the water resistance of a lignocellulose composite product produced by mixing a lignocellulosic material and a binder to form a mixture and solidifying the mixture into a specific shape to form a composite product is described above. Adding an emulsion to the mixture.

Description

  Gypsum (calcium sulfate dihydrate) is very often used in the manufacture of industrial and building products (especially gypsum board and gypsum wood fiber (GWF) products) due to its certain properties. Gypsum is an abundant and generally inexpensive raw material that can be cast, molded or otherwise formed into useful shapes by dehydration and rehydration processes. The basic raw material for producing gypsum board is calcium sulfate (gypsum) hemihydrate, usually called stucco, which is produced by heat-converting dihydrate to remove the aqueous phase.

  The manufacture of gypsum products generally involves preparing a gypsum-containing slurry containing gypsum and other components of the final product, then processing to remove water from the slurry, and shaping and drying the remaining solids as desired. Including processing into shapes. The gypsum slurry must be poured onto a paper substrate in the production of gypsum board. In a continuous process, the slurry / substrate combination is then sized by passing between rollers. Simultaneously with the sizing treatment step, a paper backing is placed on the sized gypsum slurry. Therefore, the gypsum slurry must have sufficient fluidity so that a properly sized gypsum board can be produced. Flowability refers to the ability of the gypsum slurry to flow.

  In the production of gypsum board, it is also important that the gypsum slurry can be foamed to a limited extent. Foaming refers to this ability to foam. As the gypsum slurry and paper substrate pass through the sizing roller, a certain amount of gypsum slurry is backflowed and deposited in the roller nip so that a steady flow of gypsum is delivered to the sizing roller. Foamability is important for this ability to reverse the gypsum slurry at the roller nip. Although a shaped plate can be used without a master roll, foaming is important for adjusting the density of the final product. Due to the continuous nature of the gypsum board manufacturing process, the gypsum slurry flows over the substrate and then passes through a sizing roller, so that the range of gypsum slurry flow after sizing is to maintain the final product dimensions of the gypsum board Is important to. The time for which the gypsum slurry stops flowing is called the preset time. Preset time is therefore an important characteristic of gypsum slurry. The setting time of the gypsum slurry is also an important property. The setting time refers to the time required for the gypsum slurry to dry under heating to the final solid gypsum board. As is known in the art, in a continuous gypsum board manufacturing process, it is important that the gypsum slurry has a consistent setting time.

  Unlike gypsum board production, gypsum wood fiber (GWF) product production is facilitated by conventional papermaking processes. The process of felting dilute aqueous dispersions of various fiber materials with water is a known industrial production process for producing many types of paper and board products. In this method, an aqueous dispersion of fibers, a binder, and other necessary or desirable components are placed on a moving, perforated support wire, such as a Fourdrinier or Oliver mat molding machine, for dehydration. Shed. This dispersion is first dewatered by gravity and then dehydrated by vacuum suction. The wet mat is then compressed to a specific thickness between the roll and support wire to remove additional water. The compressed mat is then dried in a heated convection or forced air dryer and the dried material is cut into the desired dimensions. The production of gypsum wood fiber products is similarly done using a wet end face box spray mechanism to spread the gypsum wood fiber slurry onto the vacuum wire to create the first mat, dewatering with a series of vacuum belt rolls, and then It can be compressed and placed in a kettle for final dehydration. Gypsum wood fiber products are paper-free cores that do not include face paper and backing paper, but have similar performance and use as compared to conventional exterior products currently available.

  Gypsum absorbs water, thereby reducing the strength of the product in which the gypsum is used and causing harmful biological activities such as growth of mold, fungi, etc. in the product and on the product surface. Conventional products such as normal gypsum board, gypsum tile, gypsum block, gypsum mold have a relatively low resistance to water. For example, if a normal gypsum board is immersed in water, it immediately absorbs a significant amount of water and loses its strength significantly. Tests have shown that when a 2 inch by 4 inch cylindrical gypsum board core is immersed in water at about 70 ° F., the cylinder shows 36% moisture absorption after 40 minutes of immersion.

  Attempts to impart water resistance to gypsum board include incorporating asphalt, metal soap, resin and wax additives into the aqueous gypsum slurry. The resulting material was difficult to use and important properties were difficult to control. Polysiloxane-based systems have also been used as an attempt to impart water resistance to gypsum boards. The final gypsum product is also coated with a water resistant coating or film. One specific example of past attempts to obtain water resistant gypsum products is spraying molten paraffin, wax or asphalt into an aqueous gypsum slurry.

  Examples of other prior art attempts to obtain water-resistant gypsum products include an aqueous gypsum slurry with a wax (such as paraffin wax) and a relative ratio of about 1 to about 10 parts asphalt to 1 part wax. The addition of an asphalt emulsion. Polyvinyl alcohol has been used in an attempt to provide a room temperature system used to impart water resistance to gypsum.

  Some emulsions, in particular corn, sago, wheat, rice, etc., combined with other chemical compounds such as sodium lignosulfate, polymerized alkylphenols of C24 or higher and various waxes and added complexing agents such as sodium borate Contains typical starch species. This system shows significant advantages over conventional wax emulsions, but manifests as a decrease in pH due to bacterial activity resulting from the degradation of sodium lignosulfate during long-term storage, and a small amount of separation at the water / wax interface. Due to the viscosity changes that occur with temperature and aging, as well as the changes that occur in single and combination, it has many defects such as lower utilization than expected utilization in a blender.

  The panel board industry includes, but is not limited to, plywood, OSB (Oriented Strand Board) (commonly referred to as chipboard or wafer board), generally referred to herein as lignocellulose composite products, medium Includes density fiber board, particle board and other products. In each of these composite products and timber (cut, processed wood pieces used as building materials) (referred to generically herein as “lignocellulosic products”), moisture absorption or “uptake” and swelling ( Both of these have a detrimental effect on the usefulness of the product. For example, in plywood used for floor lining, swelling results in distortion or deformation in the final wood or tile facing. A similar problem occurs with swollen OSBs used as roof members applied to areas exposed to moisture. These composite board panels, like trees and other lignocellulosic products, can be stored in the field as a result of water uptake (which reduces the biological degradation resulting from growth and invasion of bacteria, fungi and insects). It is also known to deteriorate in the field.

  A lignocellulose composite product is usually produced by hot pressing a lignocellulosic material, a wax and a thermosetting resin. This refers to a conventional bonding process. This wax is a sizing treatment agent for improving the water resistance of the composite product. This resin is a binder that collects materials including composites and thereby molds them into a unified shape. Resole is commonly used as a binding resin for lignocellulose composite products.

  In a conventional hot-pressure manufacturing method for lignocellulose composite products, the lignocellulosic material is mixed in a blender or blender with phenolic resin and other ingredients. The resulting blend or mixture is usually compressed at a pressure above atmospheric pressure and a temperature above room temperature to produce a composite. The lignocellulosic material used to manufacture the mat can be selected from the group consisting of wood fibers, wood flakes, wood strands, wood chips, wood particles and mixtures thereof. The lignocellulosic materials listed here are referred to in the art as wood furnish. However, it is known that other wood finishes such as straw, bagasse, bark, recycled wood fiber, recycled paper fiber and mixtures thereof can also be used. A wood finish once mixed or mixed with a phenolic resin is then molded onto a support material to create a preform with a shape approximating the finished product. The preform is then placed on a hot-pressed caul board where a finished product is produced by applying a pressure above atmospheric pressure and a temperature above room temperature. The phenol resin is polymerized by the high temperature and pressure, and the preform is bonded to form a finished product. This hot pressing method is further described in US Pat. No. 4,433,120 to Shui-Tung Chiu.

  There remains a need for additives that are useful in imparting resistance to the growth of organisms on gypsum products and that are economical to use. When adding a biocide to a gypsum product, it is common to spray mold resistant chemicals on the surface of the product and / or on the backing paper. There also remains a need for useful and effective preservatives for lignocellulose composite products.

(Summary of Invention)
The above described and other features are exemplified by the following detailed description.

  Water as continuous phase, wax as discontinuous phase, emulsifier and general structure

（式中、Ｒ^１は、Ｃ_１〜Ｃ_６アルキルで場合により置換されることが可能である、チアゾリル、イソチアゾリルまたはチアジアゾリルなどの、窒素および硫黄を含有する複素環であることが可能であり、Ｒ^２は、水素またはＣ_１〜Ｃ_６アルキル、特に水素であることが可能であり、ｎは、０、１、２または３であり、Ｒ^３のそれぞれの例は、独立して、水素、Ｃ_１〜Ｃ_６アルキル、フェノキシ、Ｃ_１〜Ｃ_６アルコキシ、ハロ、アミノ、Ｃ_１〜Ｃ_６アルキルアミノ、ジＣ_１〜Ｃ_６アルキルアミノ、イミダゾリル、チアゾリル、イソチアゾリル、チアジアゾリル、チエニル、フリル、ピリル、ナフチル、フェニル、ハロフェニル、Ｃ_１〜Ｃ_６アルキルフェニルまたはＣ_１〜Ｃ_６アルコキシフェニルであることが可能である。）
を有する防腐剤を含む、乳剤。

Wherein R ¹ can be a nitrogen and sulfur containing heterocycle, such as thiazolyl, isothiazolyl or thiadiazolyl, optionally substituted with C ₁ -C ₆ alkyl; R ² can be hydrogen or C ₁ -C ₆ alkyl, especially hydrogen, n is 0, 1, 2 or 3, and each example of R ³ is independently hydrogen, C ₁ -C ₆ alkyl, phenoxy, C ₁ -C ₆ alkoxy, halo, amino, C ₁ -C ₆ alkylamino, di-C ₁ -C ₆ alkylamino, imidazolyl, thiazolyl, isothiazolyl, thiadiazolyl, thienyl, furyl, pyryl , Naphthyl, phenyl, halophenyl, C ₁ -C ₆ alkylphenyl or C ₁ -C ₆ alkoxyphenyl.
An emulsion comprising a preservative having:

  The process for making a wax emulsion involves making an emulsion that does not contain a preservative as defined herein and then adding the preservative to it.

  The gypsum product includes gypsum and preservatives as defined herein.

  A method for producing a gypsum product includes making a slurry from a wax-in-water emulsion containing gypsum, water, and a preservative as described herein, and molding the slurry into a solid product.

  A method for improving the water resistance of a lignocellulosic composite product produced by mixing a lignocellulosic material and a binder to form a mixture and solidifying the mixture into a specific shape to form a composite product is described below. Adding an emulsion as defined herein to the mixture.

  Produced by mixing a lignocellulosic material and a binder to form a mixture, adding the emulsion defined herein to the mixture, and molding the mixture and the emulsion contained in the mixture into a solid product. , Lignocellulose composite products.

(Detailed description of the invention)
Certain preservatives have been found to be particularly useful in wax emulsions, particularly those used in the manufacture of gypsum products and wood fiber boards and other lignocellulose composite products.

  The preservatives described herein are useful for inhibiting the growth of organisms, for example, the growth of molds, fungi, etc. on gypsum products. As used herein, “preservatives” include biocides such as fungicides, fungicides, algicides, fungicides, or combinations thereof. Typical preservatives include the compositions described in US Pat. No. 3,370,957 to Wagner et al. (Which is incorporated herein in its entirety), which has the general structure (I)

（式中、Ｒ^１は、Ｃ_１〜Ｃ_６アルキルで場合により置換されることが可能である、チアゾリル、イソチアゾリルまたはチアジアゾリルなどの、窒素および硫黄を含有する複素環であることが可能であり、Ｒ^２は、水素またはＣ_１〜Ｃ_６アルキル、特に水素であることが可能であり、ｎは、０、１、２または３であり、Ｒ^３のそれぞれの例は、独立して、水素、Ｃ_１〜Ｃ_６アルキル、フェノキシ、Ｃ_１〜Ｃ_６アルコキシ、ハロ、アミノ、Ｃ_１〜Ｃ_６アルキルアミノ、ジＣ_１〜Ｃ_６アルキルアミノ、イミダゾリル、チアゾリル、イソチアゾリル、チアジアゾリル、チエニル、フリル、ピリル、ナフチル、フェニル、ハロフェニル、Ｃ_１〜Ｃ_６アルキルフェニルまたはＣ_１〜Ｃ_６アルコキシフェニルなどであることが可能である。）に関する防腐剤を開示している。

Wherein R ¹ can be a nitrogen and sulfur containing heterocycle, such as thiazolyl, isothiazolyl or thiadiazolyl, optionally substituted with C ₁ -C ₆ alkyl; R ² can be hydrogen or C ₁ -C ₆ alkyl, especially hydrogen, n is 0, 1, 2 or 3, and each example of R ³ is independently hydrogen, C ₁ -C ₆ alkyl, phenoxy, C ₁ -C ₆ alkoxy, halo, amino, C ₁ -C ₆ alkylamino, di-C ₁ -C ₆ alkylamino, imidazolyl, thiazolyl, isothiazolyl, thiadiazolyl, thienyl, furyl, pyryl can be naphthyl, phenyl, _halophenyl, that is like C 1 -C ₆ alkylphenyl or _C 1 -C ₆ alkoxyphenyl ) Discloses a preservative on.

  Certain embodiments of fungicides have general structures (II) and (III)

（式中、Ｒ^１、Ｒ^２およびＲ^３は先に定義したものである。）を有するものを含む。

(Wherein R ¹ , R ² and R ³ are as defined above).

  Typical fungicides having the structure (I) are 2- (4′-thiazolyl) benzimidazole, 2- [3 ′-(1 ′, 2 ′, 5′-thiadiazolyl) benzimidazole, 2- (4 '-Thiazolyl) -5-methoxybenzimidazole, 2- (4'-thiazolyl) -5-phenoxybenzimidazole hydrochloride, 2- (2'-methyl-4'-thiazolyl) benzimidazole, 2- [4'- (1 ′, 2 ′, 3′-thiadiazolyl)] benzimidazole, 1-acetyl-2- (4′-thiazolyl) -5-phenylbenzimidazole, 2- (4′-isothiazolyl) benzimidazole, 2- (4 '-Thiazolyl) -6-fluorobenzimidazole, 2- (4'-thiazolyl) -5-aminobenzimidazole, 2- (2'-thiazolyl) -5- 1'-imidazolyl) benzimidazole, 2- (4'-isothiazolyl) -5-chlorobenzimidazole, 2- (4'-thiazolyl) -5-phenylbenzimidazole, 2- [4 '-(1', 2 ' , 3′-thiadazolyl)]-5- (4′-tolyl) benzimidazole, 1-acetyl-2- (2′-thiazolyl) -5-phenylbenzimidazole, 1-methyl-2- (2′-isothiazolyl) -5- (2'-methoxyphenyl) benzimidazole, 2- (4'-isothiazolyl) -5-furylbenzimidazole, 2- (4'-thiazolyl) -5- (4'-fluorophenyl) benzimidazole hydrochloride 2- (4′-thiazolyl) -5-bromobenzimidazole, 2- (4′-thiazolyl) -5-chlorobenzimidazole 2- (2′-thiazolyl) -5-methoxybenzimidazole, 2- (4′-thiazolyl) -5- (2′-fluorophenyl) benzimidazole hydrochloride, 2- [3 ′-(1 ′, 2 ′) 5′-thiadiazolyl) 1-5-methylthiobenzimidazole, 2- (4′-thiazolyl) -5,6-difluorobenzimidazole, 1-benzoyl-2- (4′-thiazolyl) benzimidazole, 2- (2 '-Thiazolyl) -5- (2'-pyryl) benzimidazole, 1-methyl-2- (4'-isothiazolyl) benzimidazole hydrochloride, 2- (4'-thiazolyl) -5-phenoxybenzimidazole, 2- [3 ′-(1 ′, 2 ′, 5′-thiadiazolyl) 1-5-methoxybenzimidazole, 1-ethyl-2- (4′-thiazolyl) -5 -(2'-thiazolyl) benzimidazole, 1-acetyl-2- [3 '-(1', 2 ', 5'-thiadiazolyl)]-5- (2 "-furyl) benzimidazole, 2- (4' -Thiazolyl) -4-fluorobenzimidazole hydrochloride, 2- (2'-thiazolyl) benzimidazole, 1-acetyl-2- (4'-thiazolyl) benzimidazole and combinations thereof. In certain embodiments described below, thiabendazole (2- (4′-thiazolyl) benzimidazole) has been found to be effective in inhibiting the growth of species on gypsum board, and thus, in general, benzimidol. The utility of the compounds and other preservatives described herein has been demonstrated.

  Preferably, the preservative is added to the wax emulsion as the last component. That is, the preservative is “post-added” to the already formed wax emulsion. The preservative should be present in the wax emulsion in an amount of 0.01 to 10%, optionally 0.1 to 5%, for example 0.2 to 4% by weight of the wax emulsion (% by weight). Can do. The preservative may be added in any convenient form, such as a hydrated paste containing 100% solids or a water dilution system such as 25 to 50% active thiabendazole. The preservative is preferably added with stirring, which is believed to disperse the preservative completely in the discontinuous wax phase of the emulsion. One or more of these biocides or others described below can optionally be used in an amount corresponding to about 0.0025% to about 0.2% by weight of the final gypsum product. The preservative is post-added to all desired wax emulsions with vigorous stirring where the aqueous phase is a continuous phase in an amount ranging from 0.01 to 5% (percent). The resulting wax emulsion can be used in the production of gypsum products and has a significant effect on the desired properties of the final product, ie strength, adhesion at the adhesive surface, and (if applicable) water resistance Not shown. Emulsions can be added to gypsum and water mixtures without adversely affecting the properties of the mixture, which is necessary for the production of gypsum products such as gypsum board and GWF. Such properties include fluidity, moldability and cure time. In the manufacture of gypsum wallboard products, imparting water resistance to the final product is important in order to limit the maximum moisture absorption achieved by the wallboard in the established board soaking test. For example, the American Standards for Testing Materials ASTM 1396 and its supplements describe such tests.

  Generally, the preservative is an emulsion containing a combination of stearic / oleic acid and an amine whose amine structure can be described as TEA, DEA, AMP, morpholine and other known fatty acid amine systems; lignin sulfate or lignin sulfone. Emulsions in which acid salts act as surfactants in combination with various waxes; and starch compounds and metal salts and calcium phenolates, branched long chain alkylphenol calcium, long linear alkylphenol calcium, amine-containing / free maleic acid It can be used in wax emulsions emulsified with various wax emulsions useful in the manufacture of gypsum products, including emulsions comprising complex polymers and complex mixtures of long chain (C30 or higher) alkylphenols and waxes or combinations of waxes. By way of example, but not by way of limitation, some of such emulsions are shown below. The addition of the preservative, when incorporated into a gypsum slurry, maintains the properties desired for the final product, i.e., strength, adhesion at the adhesive surface, and (if applicable) water resistance. An emulsion is provided that imparts resistance to mold and other biological activities that occur in In addition, it has been found that the use of these preservatives provides a strong product strength compared to the use of other preservatives.

  The wax emulsions containing the preservatives described herein can also be added to resins used in the manufacture of various panel boards that do not contain gypsum.

  In one embodiment, the preservative can be used in wax emulsions containing starch (optionally complexed starch). In one embodiment, such an emulsion can include wax, alkylphenol, polynaphthalene sulfonic acid, alkali metal hydroxide and complexed starch. The polynaphthalenesulfonic acid and the alkali metal hydroxide react to form a salt of polynaphthalenesulfonic acid. Such emulsions are (a) mixed with wax and alkylphenol to obtain a first premix; (b) mixed with polynaphthalene sulfonic acid, alkali metal hydroxide, water and complexed starch to obtain a second It can be produced by obtaining a premix; (c) mixing the first premix and the second premix to obtain a mixture; and (d) homogenizing the mixture.

  Waxes useful for making the various embodiments of the present invention can be selected from any commercially available wax having a melting point of about 120 ° F to about 150 ° F, preferably about 135 ° F to about 145 ° F. Such waxes are usually low volatility and exhibit a weight loss of less than about 10% during standard thermogravimetric analysis. Also, the oil content of these waxes is usually less than about 1% by weight. These waxes are relatively high molecular weight and have an average chain length of C36 (ie, 36 carbon chain length) or higher.

  In certain embodiments, it is useful to saponify one or more of the waxes. In this way, the saponified wax acts as an added surfactant. Useful waxes in this regard are limited to waxes having a certain acid or saponification number and having a melting point greater than about 180 ° F. Such saponification of the wax can be achieved by mixing the wax with a strongly basic substance such as ammonium hydroxide or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Waxes that can be saponified in the production of the emulsions described herein include waxes from coal liquefaction, vegetable waxes, oxidized waxes obtained by processing or refining slack waxes, scale waxes or crude oils. For example, saponifiable waxes include montan wax, carnauba wax, beeswax, bayberry-myle tol wax, candelilla wax, caranda coconut wax, castor wax, esparto wax, wood wax, ouricure wax, retano (letamo) celli. Includes minbi wax, shellac, whale wax, sugarcane wax, wool / lanolin wax, and the like. The alkali metal hydroxide can be added in the form of a highly concentrated aqueous solution that can contain about 45% by weight alkali metal hydroxide. Ammonium hydroxide can be added in solid form. Some or all of the saponifier can also be reacted in situ with the dispersant and / or other components of the emulsion. Ammonium hydroxide may be opposed due to the ammonia odor it emits, but ammonium hydroxide is considered advantageous because, in addition to wax saponification, the emulsion used in the emulsion This is because ammonia serves as a formaldehyde scavenger, which can reduce formaldehyde emissions from the final composite product. The combination of ammonium hydroxide and formaldehyde also improves the ammonium hydroxide odor, so in some embodiments, for this purpose, for example, formaldehyde in an amount of about 0.02 to about 0.1 wt. Can be added to the emulsion. In addition, ammonium hydroxide is particularly advantageous when using the emulsion in lignocellulosic materials including northern wood species, ie, pine, poplar, and the like. The amount of strongly basic substance required to saponify the wax can be calculated based on the saponification values of the five waxes. For example, the saponification number divided by 1000 is equal to the grams of potassium hydroxide added to 1 gram of wax.

  Suitable unsaponifiable waxes are above about 120 ° F. (eg, about 49 ° C.), such as from about 120 ° F. to about 165 ° F. (about 49 ° C. to about 74 ° C.), optionally from about 120 ° F. to about 150 ° C. A wax having a melting point of from about F (about 49 ° C. to about 66 ° C.), and preferably from about 135 ° F. to about 145 ° F. (about 57 ° C. to about 63 ° C.). Suitable unsaponifiable waxes include paraffin wax, slack wax and scale wax. Such waxes are commercially available as low volatility showing a weight loss of less than about 10% by weight during standard thermogravimetric analysis. Also, the oil content of these waxes is usually less than about 5% by weight, preferably less than about 1% by weight. Some of these waxes are of relatively high molecular weight and have an average chain length of C36 (ie 36 carbon chain length) or more. Paraffin wax is usually a straight chain hydrocarbon obtained from light lubricating oil distillates and having an average chain length of mainly 20 to 30 carbon atoms. Suitable paraffin waxes include Wax 3816 available from Honeywell / Astor (Duluth, Georgia). Slack wax is a petroleum wax having an oil content of 3% to 50% by weight. Suitable slack waxes include Exxon 600 slack wax and Ashland 200 slack wax, and combinations of 50 parts Exxon 600 slack wax and 50 parts Ashland 200 slack wax.

  The starch used in the emulsion of the present invention is a complex starch. The starch can be complexed in situ during the preparation of the emulsion, or the starch can be pre-complexed before being added to the emulsion. The starch is preferably complexed by mixing starch with a complexing agent such as a borate compound, molybdate compound or molybdenum compound. For example, a preferred borate compound is sodium tetraborate decahydrate. For example, a preferred molybdate compound is ammonium heptamolybdate. For example, a preferred molybdenum compound is molybdenum disulfide. Other compounds useful for complexing starch are ammonium borate, ammonium pentaborate, potassium pentaborate, potassium tetraborate, lithium tetraborate and magnesium borate compounds; ammonium dimolybdate, heptamolybdenum Ammonium acid, barium molybdate, calcium molybdate, lithium molybdate, magnesium molybdate, sodium molybdate and potassium molybdate; and other molybdenum compounds.

  Starch useful for producing the complexed starch of the present invention includes, but is not limited to, corn, rice, wheat, potato, sago and other starches.

  The ratio of complexing agent (borate compound, molybdate compound, or molybdenum compound) to starch is important for the functionality of the complexed starch in the emulsion. It has been found that the ratio of complexing agent (borate compound, molybdate compound or molybdenum compound) to starch can be reduced to 1:20 by weight. The ratio can be as high as 1: 3.5, however, at this and higher ratios, a higher amount in the emulsion to maintain the desired balance of properties in the gypsum mixture and final gypsum product. Of complex starch is required. These desired properties include flowability, moldability and water resistance.

  Borate compounds, molybdate compounds and molybdenum compounds are surprisingly effective complexing agents. Examples of useful complexing agents include, but are not limited to, sodium borate (borax), magnesium borate and other borate compounds, ammonium molybdate, sodium molybdate, magnesium molybdate and other molybdates Includes salt compounds, molybdenum disulfide and other molybdenum compounds. The ratio of complexing agent (eg, sodium tetraborate decahydrate, sodium molybdate dehydrate, molybdenum disulfide, or other compound) to the modified starch is determined by the board / slurry process, ie, foam aid and slurry. It greatly affects the adjustment of other properties required for the compatibility of the additive.

  Incorporation of alkylphenols in the emulsion has been found useful to achieve low moisture absorption in gypsum products. As used herein, “alkylphenol” refers to a phenolic compound having a long chain alkyl group. Long chain alkyl groups can be straight or branched. The long chain alkyl group can be C24-C34 (24-34 carbon chain length), preferably C24-C28. Such alkylphenols contain long chain C24-C34 (24-34 carbon chain length) polymerized methylene linked alkylphenols, phenol salts, calcium phenolate, branched long chain alkylphenol calcium, linear long chain alkylphenol calcium and amine substituents. / Contains no maleic acid complex polymer.

  The alkyl group of the alkylphenol can be derived from the corresponding olefin. For example, a C26 alkyl group is derived from a C26 alkene (preferably a 1-alkene), a C34 alkyl group is derived from a C34 alkene, and a mixed chain length group is derived from a corresponding mixture of olefins. However, if the alkyl group is an alkyl group having at least about 30 carbon atoms, the alkyl group is 2-10 carbons such as ethylene, propylene, butene-1, isobutene, butadiene, isoprene, 1-hexene and 1-octene. It can be an aliphatic group (or a mixture of such groups) produced from homo- or interpolymers of mono- and diolefins having atoms (eg, copolymers, terpolymers). Aliphatic hydrocarbyl groups can also be derived from halogenated (eg, chlorinated or brominated) analogs of such homopolymers or copolymers. However, such groups are not compatible with monomeric high molecular weight alkenes (eg 1-tetracontene) and chlorinated and hydrochloride analogs thereof, aliphatic petroleum fractions, especially paraffin waxes and their decomposed, chlorinated analogs. And other supplies such as hydrochloride analogs, white oils, synthetic alkenes such as those produced by the Ziegler-Natta process (eg, poly (ethylene) grease) and other sources known to those skilled in the art Can be derived from the source. Unsaturation of the hydrocarbyl group can be reduced or removed, if desired, by hydrogenation by methods known in the art. Production by methods and materials substantially free of chlorine or other halogens is sometimes preferred for environmental reasons. There can be two or more alkyl groups, but typically each aromatic nucleus of an aromatic group contains 2 or 3 or less. Most typically, there is only one hydrocarbyl group for one aromatic moiety, especially when the hydrocarbyl-substituted phenol is based on a single benzene ring.

One example of a useful alkylphenol emulsion described _herein, Lubrizol Chem under the trade name 319H that are listed C 24 _{-C 34} polymerized methylene coupled alkyl phenol. Corp. (Wycliffe, Ohio). Various other commercially available alkylphenols that can be used in these emulsions include (identified by any identification number in Table 1 below).

  In this specification, alkylphenol and the reaction product of alkylphenol with any other component of the saponifier or emulsion are referred to as alkylphenol components.

  Such emulsions provide an alternative to the use of sodium lignosulfate or sodium lignosulfonate, previously used as both cosurfactant and dispersion aid, and biocides to inhibit biological activity The need for is further reduced. (However, the preservatives described herein could be used in emulsions containing lignosulfate or lignosulfonate.) Starch: borate, or starch: molybdate, or starch: molybdenum compound. The ratio of can be from about 4: 1 to about 20: 1 by weight.

  The emulsion heats the wax and surfactant ("wax mixture") in one container and water, complexing agent (borate compound, molybdate compound, or molybdenum compound) and corn starch (in the other container) It can be produced by heating a “water mixture”). Both mixtures were heated to about 185 ° (85 ° C.) with agitation. The wax mixture was then poured into the water mixture while stirring. The resulting mixture was then placed in a homogenizer.

  For homogenization, a micelle size distribution of about 0.6 microns to about 1.8 microns is preferably achieved. However, the micelle size distribution can range from about 0.5 microns to about 2.5 microns. This level of homogenization can be achieved, for example, by operating at about 2,000 to about 4,000 psi using a double orifice homogenizer.

  The homogenized mixture is preferably cooled after the homogenization step.

  Most preferably, the homogenized mixture is cooled from approximately 185 ° F. to about 100 ° F. This can be accomplished by passing the homogenized mixture through a cooling coil immersed in water maintained at room temperature.

  More specifically, by mixing water, a complexing agent (ie, borate compound, molybdate compound, or molybdenum compound) and starch to produce a complexed starch useful in certain embodiments, Emulsions can be made. Polynaphthalene sulfonic acid and potassium hydroxide are added to the aqueous solution of complexed starch. The mixture is brought to a temperature of about 185 ° F. to about 205 ° F. and is maintained until the starch achieves maximum gelation, which typically occurs in about 20 to about 30 minutes. Polymerized alkylphenol is incorporated into the wax compound and the temperature is about 185 ° F to about 205 ° F. The wax phase is then added to the water phase and reacted to form a surfactant in situ. This combination and reaction of polymerized alkylphenol and polynaphthalene sulfonic acid forms a surfactant / dispersant that acts to modify the wax crystals and resists the wax crystals from sticking together and bonding together. And keep the wax crystals separate until the wax crystals migrate due to the polarity of the gypsum. The reaction is then homogenized at a pressure of about 2,000 to about 4,000 psi and then cooled at a predetermined rate to adjust the stability and viscosity of the final wax emulsion. The homogenized composition exits the homogenizer at a temperature of about 135 ° F to about 145 ° F. The mixture is then cooled from about 80 ° F. to about 110 ° F. The cooling rate is adjusted so as not to cause wax recrystallization and solution breakage.

  By combining the modified starch compound with the other described compounds and utilizing them in appropriate proportions, a low viscosity system can be created in which a wide range of solids from about 40% to about 60% by weight is available. .

  In certain embodiments using a single wax additive, it has been found that the binary surfactant system provides an emulsion that is stable at both room temperature and elevated temperature. Such a stable emulsion can be added to hot or boiling water, for example, without the emulsion separating or coagulating.

  One example of a binary surfactant is a combination of dodecylisopropanolamine benzene sulfonate and a nonionic ethoxylated arylphenol.

  Dodecylisopropanolamine benzene sulfonate is available from Unichema (Wilmington, Del.) Under the trade name SD1121. One non-ionic ethoxylated arylphenol is available from Ethox Corp. , (Ethox 2938 available from Greenville, SC). Alternatively, alkoxylated fatty acid esters can be combined with dodecylisopropanolamine benzene sulfonate to form a binary surfactant system. One alkoxylated fatty acid ester is Ethox 2914, also available from Ethox Corp. In certain embodiments of the present invention, dispersion aids or flow modifiers have also been found useful in maintaining the flowability of the gypsum / emulsion mixture. Such dispersants are strong lipophiles and are therefore excellent antifoams. One such dispersant is poly (oxy-1,2-ethanediyl), α-phenyl-ω-hydroxystyrenate.

  Emulsions can be produced by combining and homogenizing a single wax, a binary surfactant system, an alkylphenol and a complexed starch. An example is shown in Table 1 below.

  Other wax emulsions that can contain the preservatives disclosed herein can be described as (1) a single stearic / oleic acid and amine structure as TEA, DEA, AMP, morpholine and other fatty amines. Combinations with amines and (2) those containing lignin sulfate or lignin sulfonate that act as surfactants in combination with various waxes.

  Emulsions can be made by mixing and homogenizing two or more waxes, cosurfactants, alkylphenols and complexed starch. A typical composition range for the two wax emulsions is shown in Table 2 below.

  Table 3 below shows examples of emulsions made according to the binary wax embodiment.

  The emulsions in Table 3 can be mixed with water and gypsum added to the water emulsion mixture. This water / emulsion / gypsum mixture can then be formed into a gypsum product.

  In another embodiment, a wax emulsion useful for making a gypsum product can include lignosulfonate or lignosulfate, as shown in Table 4 below.

  In yet another embodiment, useful wax emulsions can contain carboxymethylcellulose. Such emulsions are useful for lignocellulose products. One example of a carboxymethylcellulose-containing wax emulsion for use in gypsum slurries useful in the manufacture of gypsum products includes a non-saponifiable wax, a saponified wax, an alkylphenol component, a dispersant / surfactant, a carboxymethylcellulose component and water. In certain embodiments, the non-saponifiable wax can comprise from about 33% to about 35% by weight of the emulsion, the saponified wax can comprise from about 3% to about 5% by weight of the emulsion, The alkylphenol component can comprise from about 0.5% to about 2.5% by weight of the emulsion, the dispersant can comprise from about 0.5% to about 2% by weight of the emulsion, and carboxymethylcellulose. The components can comprise from about 0.2% to about 5% by weight of the emulsion.

  The emulsions described herein include a wax component that includes an unsaponifiable wax and a saponifiable wax.

  Suitable saponifiable waxes have an acid value or saponification number and a melting point above about 180 ° F. (about 82 ° C.).

  Preferably, the wax does not contain more than about 5% by weight of polar compounds as impurities.

  The wax component can be present in an amount from about 25 weight percent to about 50 weight percent, preferably from about 30 weight percent to about 40 weight percent, based on the total weight of the emulsion. Preferably, the wax component comprises a combination of unsaponifiable and saponifiable waxes that exhibit a melting point of about 120 ° F. or higher. The unsaponifiable wax can comprise from about 25% to about 44% by weight of the total weight of the emulsion, and the saponifiable wax comprises from about 0.5% to about 5% by weight of the total weight of the emulsion. Can do. A preferred combination of waxes is a paraffin wax such as Honeywell 3816 as the first wax and a saponifiable wax such as montan wax. In one embodiment, the wax component comprises paraffin wax in an amount of about 25% to about 45%, preferably about 30% to about 40% by weight and about 2.5% by weight, based on the total weight of the emulsion. % To about 5% by weight, preferably about 3.5% to about 4.5% by weight of saponifiable wax.

  In order to saponify the saponifiable wax, the strongly basic compound described herein is added to the emulsion mixture. The saponifying agent can be added in an amount from about 0.15% to about 4.5%, optionally from about 0.5% to about 3% by weight of the emulsion. High concentration aqueous saponifier may optionally be added in an amount of about 0.5 to about 3% by weight of the emulsion. Ammonium hydroxide can be added in solid form in an amount of from about 0.15 to about 3% by weight of the emulsion. The amount of saponifying agent can vary based on the type of saponifiable wax used or the type of wood. As a result of the addition of the saponifying agent, the emulsions described herein can have a pH of about 8.5 to about 12.5, such as a pH of about 8.5 to about 9.5.

  Typical carboxymethylcellulose materials useful for these emulsions have a molecular carbon chain length of about 20 to about 50 carbons. An example of a suitable carboxymethylcellulose is sodium carboxymethylcellulose available from Penn Carbose (Somerset, PA) under the trade name LT-30 and is described as having a carbon chain length of about 26 to 30 carbons. . Other suitable carboxymethylcellulose materials include Penn Carboxe LT-20 and LT-42. Carboxymethylcellulose, and the product in which it reacts with the saponifying agent or any other other component in the emulsion, is referred to herein as the “carboxymethylcellulose component”.

  Polynaphthalene sulfonates are useful in the emulsions described herein and are not bound by theory, but are believed to act as dispersants / surfactants. The salt can be an in situ reaction product of polynaphthalene sulfonic acid and a saponifying agent such as an alkali metal hydroxide. One commercially available polynaphthalene sulfonic acid is DISAL GPS, which is available from Handy Chemical (Montreal, Quebec, Canada). These acids and acid salts are collectively referred to as the polynaphthalene sulfonic acid component, and more broadly (including surrogate materials) as the dispersant / surfactant. The dispersant / surfactant can comprise from about 0.1% to about 5%, optionally from about 0.25% to about 5% by weight of the emulsion.

It has been found that incorporation of alkylphenols in the emulsion facilitates achieving low water absorption in lignocellulose composite products. Preferably, the alkylphenol is selected such that the average carbon chain length of the alkyl moiety is comparable, i.e., approximately the same or close to that of carboxymethylcellulose. For example, alkylphenols having an average chain length of about C ₂₄ to about C ₃₄ can be used in emulsions containing carboxymethyl cellulose (eg, Carbose LT-30 carboxymethyl cellulose) having an average chain length of about 26 to about 32 carbons.

  The amount of alkylphenol component present in the emulsion is from about 0.25% to about 10% by weight, and optionally from about 0.5% to about 2.5% by weight, based on the total weight of the emulsion. .

  One method of making the emulsions described herein is attributed to time, energy, worker and production efficiency. This method involves mixing the components of the emulsion in a single container and then transporting the mixture to a homogenizer under the following conditions. The advantage of this method is that the emulsion mixture is produced in a single container. There is no need to prepare and store separately in different containers before mixing a partial mixture of emulsion components.

In one embodiment of the “single container” method, an unsaponifiable wax (eg, 3816 wax, further described below) is melted, eg, melted at a temperature about 10 ° F. above its melting point. And add water at a temperature at which the wax does not solidify. The container is then charged as in the following example.
a. Charging a melt unsaponifiable wax (eg, 3816 wax) at a temperature of about 189 ° F to about 192 ° F (about 87 ° C to about 89 ° C);
b. Start heating and stirring,
c. Charging melt saponifiable wax and alkylphenol with stirring;
d. Charge most of the water (eg 95%), keep stirring,
e. Charging a dispersant / surfactant (eg, DISAL polynaphthalene sulfonic acid, further described elsewhere herein), carboxymethylcellulose and a saponifier;
f. Charge the remaining water (preferably including the water that is used to clean the tube and subtracted from the whole),
g. The tank temperature is, for example, about 190 ° F to about 210 ° F (about 88 ° C to about 100 ° C).
h. Continue stirring for about 30 to about 150 minutes while maintaining the temperature.
i. Apply to homogenizer at about 1500 to about 3500 PSI (about 10 megapascals (MPa) to about 24 MPa),
j. In some cases, cooling is performed in a process of performing heat radiation twice, including first heat radiation between the outlet temperature from the homogenizer and a temperature above the ambient temperature and second heat radiation to the ambient (storage) temperature. For example, to achieve a first heat release of about 10 ° F. to about 20 ° F. below the homogenizer outlet temperature, for example, the emulsion composition is transferred from the homogenizer to a cooler and then optionally stirred, for example, Transfer to a cooling tank to achieve a second heat release that is about 5 ° F to about 15 ° F lower. In one embodiment, the first heat release is generated by cooling from about 130 ° F. to about 110 ° F., and the second heat release is generated by cooling from about 110 ° F. to about 70 ° F.

  While not being bound by a particular theory, the use of two heat-dissipating cooling steps allows for the formation of emulsion formation and proceeds to completion. As a result, the viscosity of the emulsion is more stable over time, and the emulsion is more stable when subjected to shear stirring than when a single heat-dissipating cooling step is used. In an alternative method of making the emulsion, a first premix comprising a molten wax and an alkylphenol is produced, and a second premix (aqueous premix) comprising water, carboxymethylcellulose and polynaphthalene sulfonic acid and a saponifier is produced, The first and second premixes are then mixed in a mixing tank for a time sufficient for the wax to saponify (eg, 1 to 3 hours), and the resulting mixture is then transferred to a homogenizer and cooled as described above. Batch methods that can be used can be used.

  Examples of component ranges in some embodiments of the emulsions described herein are shown in Table 5 below.

  Table 6 below provides examples of component proportions in certain embodiments of the emulsions described herein.

  Such emulsions can have a viscosity of about 10 to about 100 centipoise as measured with a Brookfield viscometer. One sample emulsion had a viscosity of 9 cps at about 40% solids.

  The emulsions described herein and other emulsions are useful in the manufacture of gypsum products when incorporated into gypsum slurries, and the preservatives described herein can be used for all of them.

  The following components: 33% G wax (paraffin wax), 3.3% montan wax, 0.5% alkylphenol, 0.5% Disal, 0.75% potassium hydroxide, 0.01% ammonium heptamolybdate, starch A wax emulsion formulation was prepared using 0.09%, polyfon H (lignosulfonic acid, sodium salt) 0.5% and water 61.35%. To this wax emulsion was added 0.2% thiabendazole sold under the trade name MC-2 by Superme Chemical (Cumming, GA). This wax emulsion was used for the production of gypsum products. The resulting gypsum product was tested according to ASTM D3273. During this 4 week test, samples of the material of interest such as gypsum board were placed at a constant temperature of about 90 ° F. (32.2 ° C.) and a relative humidity of 95% to 98% for potting soil and fungi. Place in closed chamber with culture. Observe the condition of the test sample weekly and measure the degree of filamentous fungus growth. Samples produced as described above showed no growth of organisms during the first week of testing.

  In other tests, test emulsions as described above were used to make particleboard coupon samples containing urea-formaldehyde binders. Some of the test emulsions contained 1% by weight thiabendazole of the emulsion wax and others contained 2% by weight. To the furnish that produces the specimen, an amount of 0.4 solid weight percent of the furnish was added. Some of the coupons were immersed in water for 24 hours prior to testing. For testing purposes, constant humidity conditions (72 ° F (22.2 ° C), 72% relative humidity (RH)), outdoor roof environmental conditions (exposed to the atmosphere but directly exposed to rainfall) Were immersed), various immersed and non-immersed specimens were placed in various environments, including indoors in uncontrolled warehouses, and laboratory environments beside water baths. Similarly prepared and treated control coupons were also in these environments. After the first week, the control specimen showed growth of the organism visible to the naked eye, but after the sixth week, the sample piece made with thiabendazole showed no visible growth on it.

  Without being bound by any particular theory, a sample of gypsum product made with a wax emulsion containing thiabendazole has been found to have a crystal believed to be thiabendazole in a visual comparison with other gypsum products. It is thought to indicate that it is embedded in a solid. This is because thiabendazole and the above related compounds are crystallized as the gypsum slurry is wetted by the wax in the gypsum and then dehydrated to form a gypsum product and the wax emulsion is destroyed. It is believed that the preservative returns to its crystalline form and is embedded in the gypsum crystals. Thus, the preservative is impregnated in the gypsum crystal structure rather than simply present on the surface of the product or present in discontinuous discrete agglomeration of the wax that can remain after the wax emulsion is broken. It can be said that they are connected. The preservative is considered to be less likely to leach from the gypsum crystal internal structure than from the surface of the gypsum product or from the agglomeration of the wax, so by incorporating the preservative into the gypsum, Is extended. This may be a factor contributing to the enhanced product strength found in gypsum product samples containing this preservative.

  Effective amounts of any of the other preservatives can also optionally be used in the gypsum product. Preservatives including, for example, fungicides / fungicides, fungicides or other biocides may optionally be included in the gypsum product by incorporating the preservatives in the emulsion or in the gypsum-containing slurry. it can. One example of a preservative suitable for gypsum products is the fungicide / antifungal agent marketed as METASOL D3TA, which contains 3,5-dimethyl-tetrahydro-1,3,5,2H thiadiazin-2-thione. is there. METASOL D3TA is available from Ondo-Nalco (Houston, TX). The fungicide can include any commercially available fungicide including formaldehyde. Other suitable biocides include bis-thio-benzene, propiconazole and bis (tributyltin) oxide.

  For example, useful for lignocellulosic products, including GWF products and other gypsum products (containing wood fibers or other lignocellulosic materials), and preservatives associated with thiabendazole and / or lignocellulosic products described herein Preservatives that can optionally be used in addition to the agent may be inorganic or organic, for example, biocides such as insecticides, fungicides, fungicides and one or more of the biocides. Combinations including the above can be included. The biocide can be selected according to (1) the target organism, (2) solubility characteristics, (3) temperature and pH stability, and other conditions found in the production of composite materials. Biocides include substances that kill or inhibit the growth of microorganisms such as filamentous fungi, myxomycetes, fungi, bacteria. Insecticides, fungicides and fungicides are all examples of biocides. Anti-fungal agents include substances that kill fungi or inhibit growth. Bactericides include agents that kill bacteria. An insecticide is a drug that kills insects. Further specific examples of biocides include, but are not limited to, chlorinated hydrocarbons, organometallics, halogen releasing compounds, metal salts, organosulfur compounds and phenols. Preferred biocides include, but are not limited to, chromated copper arsenate (CCA) such as ammoniacal copper quaternary ammonium (ACQ), ammoniacal copper zinc arsenate (ACZA), bis (dimethylcarbamic acid) copper (CDDC), ammoniacal copper citrate and copper azole, copper naphthenate, zinc naphthenate, quaternary ammonium salt, pentachlorophenol, tebuconazole (TEB), chlorothalonil (CTL), chlorpyrifos, isothiazolone, propiconazole, etc. Of triazoles, pyrethroids and other insecticides, imidicloprid, oxine copper and the like, as well as combinations comprising one or more of the biocides. In addition to organic biocides, use nanoparticles with different release rates incorporating inorganic preservatives such as boric acid, sodium borate, zinc, zinc borate, silica borate, copper and zinc salts can do.

  Suitable common fungicides are, for example, 3-isothiazolone, 3-iodo-2-propynylbutylcarbamate, 1,2-dibromo-2,4-dicyanobutane, methylene-bis-thio-cyanate (MBT), 2 -Thiocyano-methylthiobenzothiazole, tetrachloroisophthalonitrile, 5-bromo-5-nitro-1,3-dioxane, 2-bromo-2-nitropropane-1,3-diol, 2,2-di-bromo- 3-nitrilopropionamide (DBNPA), N, N′-dimethylhydroxyl-5,5′-dimethyl-hydantoin, bromochlorodimethylhydantoin, 1,2-benzisothiazolin-3-one, 4,5-tri-methylene- 2-methyl-3-isothiazolone, 5-chloro-2- (2,4-dichlorophenoxy) -phen 3,4,4'-trichlorocarbanilide, copper naphthenate, 8-hydroxy-quinoline copper, zinc borate, boric acid, trimethyl boron, zinc oxide, glutaraldehyde, 1,4-bis (bromo- Acetoxy) -2-butene, 4,5-dichloro-1,1-dithiacyclopenten-3-one, chlorothalonil, quaternary ammonium-based compounds and combinations comprising one or more of the above fungicides.

  Suitable fungicides are, for example, zinc dimethyldithiocarbamate, 2-methyl-4-tert-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N , N-dimethyldichlorophenylurea, copper thiocyanate, N- (fluorodichloromethylthio) phthalimide, N, N-dimethyl-N′-phenyl-N′-fluorodichloromethylthiosulfamide; 2-pyridinethiol-1-oxide Copper, sodium and zinc salts; tetraethylthiuram disulfide, 2,4,6-trichlorophenyl-maleimide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine, diiodomethyl p-tolylsulfone, phenyl ( Bispyridyl) bismuth dichloride, 2- (4-thiazo L) -benzimidazole, pyridine triphenylborane, phenylamide, halopropargyl compound, propiconazole, cyproconazole, tebuconazole and 2-haloalkoxyaryl-3-isothiazolone (2- (4-trifluoromethoxyphenyl) -3 -Isothiazolone, 2- (4-trifluoromethoxy-phenyl) -5-chloro-3-isothiazolone, 2- (4-trifluoromethoxyphenyl) -4,5-dichloro-3-isothiazolone, and the like Includes combinations comprising one or more of the agents.

  The fungicides include, for example, felbum, diram, maneb (manganese ethylenedithiocarbamate), mancozeb, dineb (zinc ethylenebisdithiocarbamate), propineb, metam, thiram, dinebu and polyethylene thiuram disulfide complexes, dazomet, and these Dithiocarbamic acid and derivatives such as mixtures of copper salts; nitrophenol derivatives such as dinocup, binapacryl and 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate; captan holpet, gliodin, dithianone, thioquinox, benomyl, thiabendazole, vinorozoline , Iprodione, prosimidone, triadimenol, triadimephone, viteltanol, fluoroimide, triarimol, cycloheximide, ethyl Heterocyclic structures such as mol, dodemorph, dimethomorph, tifluzamide and quinomethionate; various fungicides such as chloranil, dicron, chloronebu, tricamba, dichlorane and polychloronitrobenzene; antifungal antibiotics such as griseofulvin, kasugamycin and streptomycin; Various antifungal agents such as dodine, methoxyl, 1-thiocyano-2,4-dinitrobenzene, 1-phenyl-thiosemicarbazide, thiophanate methyl and simoxanyl; acyls such as flaxil, ciprofram, off race, benalaxyl and oxadixyl Alanine; phenylbenzamide derivatives such as those disclosed in fluazinam, flumetober, EP578,586-A, EP550,788- And amino acid derivatives such as valine derivatives disclosed in the above, and methoxyacrylates such as methyl (E) -2- (2- (6- (2-cyanophenoxy) pyrimidin-4-yloxy) phenyl) -3-methoxyacrylate , Benzo (1,2,3) thiadiazole-7-thiocarboxylic acid S-methyl ester, propamocarb, imazalyl, carbendazim, microbutanyl, fenbuconazole, tridemorph, pyrazophos, phenalimol, fenpiclonyl, pyrimethanil, and one of the fungicides It can be an agricultural fungicide such as a combination comprising one or more.

  A fungicide / antifungal combination can be included in the preservative composition. One example of a fungicide / antifungal agent is METASOL D3TA, which is 3,5-dimethyl-tetrahydro-1,3,5,2H-thiadiazine-2 available from Ondo-Nalco (Houston, TX). -Thion.

  Suitable insecticides include, for example, acephate, aldicarb, α-cypermethrin, azine phosmethyl, bifenthrin, binapacryl, buprofezin, carbaryl, carbofuran, cartap, chlorpyrifos, chlorpyrifosmethyl, clofentezin, cyfluthrin, cyhexatin, cypermethrin, ciphenothrin, Deltamethrin, demeton, demeton-S-methyl, demeton-O-methyl, demeton-S, demeton-S-methylsulfoxide, demefion-O, demefione-S, diarihol, diazinon, dicophore, dicrotophos, diflubenzuron, dimethoate, dinocup, endosulfan , Endothion, Esfenvalerate, Ethiophene Carb, Ethion, Ethoate Methyl, Etoprop, Etrimfos Phenamifos, Phenazafurol, Fenbutazin oxide, Fenitrothion, Phenoxycarb, Fensulfothione, Fenthion, Fenvalerate, Flucycloxuron, Flufenoxuron, Fulvalonate, Honofos, Phosmethylan, Furatiocarb, Hexithiazox, Isazophos, Isofenphos, Isoxathione, Methamidophos, methidathion, methiocarb, methomyl, methylparathion, mevinphos, mexacarb, monocrotofos, nicotine, ometoate, oxamyl, parathion, permethrin, folate, hosalon, phosmet, phosphamidone, pirimicarb, pirimiphosethyl, profenophos, promecarve pirmelet , Rotenone, tebufenozide, temefos, Includes combinations comprising TEPP, terbufos, thiodicarb, tolcrofosmethyl, triazamate, triazophos, bamidthione and one or more of the pesticides.

  Termicides can be used in addition to other insecticides as long as the properties of the other insecticides are not impaired. Termiticides include permethrin, imidacloprid, etopfenprox, and combinations comprising one or more of the above agents.

  Specific examples of suitable preservatives are didecyldimethylammonium chloride (DDAC), BARDAP (N, N-didecyl-N-methylpolyoxyethylammonium propionate), copper benzalkonium chloride or N-alkylbenzyldimethylammonium chloride. Alkyl ammonium compounds such as (BKC); metal salts of naphthenic acid such as copper naphthenate (NCU) or zinc naphthenate (NZN); metal salts of versatic acid such as zinc versatate; cyproconazole [(2RS, 3RS; 2RS, 3SR) -2- (4-chlorophenyl) -3- (cyclopropyl-1- (1H-1,2,4-triazol-1-yl) butan-2-01], tebuconazole [(RS) -1 -P-chlorophenyl-4,4-dimethyl-3- (1H-1,2,4-tri Sol-1-ylmethyl) pentane-3-01], propiconazole [1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2, , 4-triazole], 1- [2- (2 ′, 4-dichlorophenyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole-1-ethanol or 1- [2- ( 2 ′, 4′-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole-1-ethanol and other triazole compounds; and IF-1000 [4- Organic iodine compounds such as chlorophenyl-3-iodopropargyl formal], IPBC [3-iodo-2-propynyl-N-butylcarbamate] and Combinations comprising one or more serial preservatives.

  Lignocellulose preservatives can be used in combination. Preferred combinations include cyproconazole and DDAC, cyproconazole and BARDAP, tebuconazole and propiconazole, and the like.

  Compounds that are effective in inhibiting or preventing the growth of soil bacteria that decay wood and fungi that decay wood (mainly fungi that decay wood such as Chaetomium globosum) can also be used as preservatives . Such compounds include p-cumylphenol (PCP) and salts thereof (p-cumylphenol sodium salt, p-cumylphenolethylamine salt, etc.) and combinations comprising one or more of the wood preservatives. Including. PCP inhibits the growth of soil bacteria, ascomycetes and imperfect fungi that decay wood, and is useful as an antifungal and termiticide. PCP is therefore particularly preferred. PCP can exhibit a sufficient effect on wood materials with a throughput (applied amount) of about 200 to 1,000 grams / cubic meter wood (g / m 3).

  All ranges described herein are inclusive and combinable, for example, “about 120 ° to about 165 ° F., sometimes 135 ° to 145 ° F.” is about 120 ° to about 145 ° F. , Including all endpoints and intermediate values, including about 130 ° to about 150 ° F., and combinations thereof. In this specification, terms such as “first” and “second” do not refer to any order, quantity, or importance, but are used to distinguish one element from another. As used herein, the terms “a” and “an” are not meant to limit the amount, but indicate that there is at least one of the cited items.

  While particular embodiments and best modes of the invention have been described herein, these embodiments are for illustrative purposes only. It will be apparent to those skilled in the art that modifications can be made without departing from the spirit of the invention and the scope of the appended claims.

Claims (14)

Water as continuous phase, wax as discontinuous phase, emulsifier and general structure

Wherein R ¹ can be a nitrogen and sulfur containing heterocycle, such as thiazolyl, isothiazolyl or thiadiazolyl, optionally substituted with C ₁ -C ₆ alkyl; R ² can be hydrogen or C ₁ -C ₆ alkyl, especially hydrogen, n is 0, 1, 2 or 3, and each example of R ³ is independently hydrogen, C ₁ -C ₆ alkyl, phenoxy, C ₁ -C ₆ alkoxy, halo, amino, C ₁ -C ₆ alkylamino, di-C ₁ -C ₆ alkylamino, imidazolyl, thiazolyl, isothiazolyl, thiadiazolyl, thienyl, furyl, pyryl , Naphthyl, phenyl, halophenyl, C ₁ -C ₆ alkylphenyl or C ₁ -C ₆ alkoxyphenyl.
An emulsion comprising a preservative having:   The emulsion of claim 1 wherein the preservative comprises a benzimidazole compound.   The emulsion of claim 1 wherein the preservative comprises thiabendazole.   4. Emulsion according to any one of claims 1 to 3, wherein the preservative comprises from 0.01 to 10% by weight of the emulsion.   The emulsion according to any one of claims 1 to 3, comprising an unsaponifiable wax, a saponifiable wax, an alkylphenol, polynaphthalenesulfonic acid, carboxymethylcellulose, a saponifying agent and water.   At least one wax in an amount of from about 25% to about 40% by weight based on the total weight of the emulsion; a saponifiable wax in an amount of from about 2.5% to about 4.5% by weight based on the total weight of the emulsion. Alkylphenols in an amount of from about 0.25% to about 10.0% by weight based on the total weight of the emulsion; polyphenols in an amount of from about 0.25% to about 5.0% by weight based on the total weight of the emulsion. 4. Naphthalene sulfonic acid, comprising from about 55% to about 65% water by weight, from about 0.5% to about 1 amount of alkali metal hydroxide, based on the total 10 weights of the emulsion. Any one emulsion.   33% by weight unsaponifiable wax, 3% by weight saponifiable wax, 0.5% by weight alkylphenol, 0.5% by weight polynaphthalenesulfonic acid, 0.2% by weight carboxymethylcellulose, saponifier and water. An emulsion according to any one of claims 1 to 3, comprising. General structure

Wherein R ¹ can be a nitrogen and sulfur containing heterocycle, such as thiazolyl, isothiazolyl or thiadiazolyl, optionally substituted with C ₁ -C ₆ alkyl; R ² can be hydrogen or C ₁ -C ₆ alkyl, especially hydrogen, n is 0, 1, 2 or 3, and each example of R ³ is independently hydrogen, C ₁ -C ₆ alkyl, phenoxy, C ₁ -C ₆ alkoxy, halo, amino, C ₁ -C ₆ alkylamino, di-C ₁ -C ₆ alkylamino, imidazolyl, thiazolyl, isothiazolyl, thiadiazolyl, thienyl, furyl, pyryl , naphthyl, phenyl, _halophenyl, it can be a C 1 -C ₆ alkylphenyl or _C 1 -C ₆ alkoxyphenyl.) To produce an emulsion which does not contain a preservative with, and followed comprises adding the the preservative in the emulsion method of wax emulsion.   9. The method of claim 8, comprising adding a pasty preservative.   9. The method of claim 8, comprising adding the preservative in the form of a mixture of preservative and water in an amount of about 25% by weight of the water-preservative mixture. Gypsum and general structure

Wherein R ¹ can be a nitrogen and sulfur containing heterocycle, such as thiazolyl, isothiazolyl or thiadiazolyl, optionally substituted with C ₁ -C ₆ alkyl; R ² can be hydrogen or C ₁ -C ₆ alkyl, especially hydrogen, n is 0, 1, 2 or 3, and each example of R ³ is independently hydrogen, C ₁ -C ₆ alkyl, phenoxy, C ₁ -C ₆ alkoxy, halo, amino, C ₁ -C ₆ alkylamino, di-C ₁ -C ₆ alkylamino, imidazolyl, thiazolyl, isothiazolyl, thiadiazolyl, thienyl, furyl, pyryl , Naphthyl, phenyl, halophenyl, C ₁ -C ₆ alkylphenyl or C ₁ -C ₆ alkoxyphenyl.
A gypsum product comprising a preservative having: Plaster, water and general structure

Wherein R ¹ can be a nitrogen and sulfur containing heterocycle, such as thiazolyl, isothiazolyl or thiadiazolyl, optionally substituted with C ₁ -C ₆ alkyl; R ² can be hydrogen or C ₁ -C ₆ alkyl, especially hydrogen, n is 0, 1, 2 or 3, and each example of R ³ is independently hydrogen, C ₁ -C ₆ alkyl, phenoxy, C ₁ -C ₆ alkoxy, halo, amino, C ₁ -C ₆ alkylamino, di-C ₁ -C ₆ alkylamino, imidazolyl, thiazolyl, isothiazolyl, thiadiazolyl, thienyl, furyl, pyryl , Naphthyl, phenyl, halophenyl, C ₁ -C ₆ alkylphenyl or C ₁ -C ₆ alkoxyphenyl.
A method for producing a gypsum product, comprising: forming a slurry from a wax-in-water emulsion containing a preservative having the following: and forming the slurry into a solid product.   This is a method for improving the water resistance of a lignocellulose composite product produced by mixing a lignocellulose material and a binder to form a mixture and solidifying the mixture into a selected shape to form a composite product. And adding the emulsion of claim 1 to the mixture.   By mixing a lignocellulosic material and a binder to form a mixture, adding the emulsion of claim 1 to the mixture, and molding the mixture and the emulsion contained therein into a solid product; Lignocellulose composite product produced.