JP2016501320A - Decorative paper containing self-dispersing pigments - Google Patents

Abstract

The present disclosure provides a decorative paper comprising a self-dispersing pigment, the self-dispersing pigment having an isoelectric point of at least about 8, more typically from about 8 to about 10, And (a) hydrolyzing the aluminum compound or the basic aluminate and depositing the surface of the hydrous alumina in order, and (b) A step of adding a bifunctional compound, the bifunctional compound comprising an anchor group for linking the bifunctional compound to the surface of the pigment, and a basic amine group comprising a primary, secondary or tertiary amine; And a step of adding a bifunctional compound comprising: Typically, the inorganic particles are titanium dioxide TiO2. These decorative papers containing self-dispersing pigments are useful for making paper laminates.

Description

  The present disclosure relates to self-dispersing inorganic particles, particularly titanium dioxide pigments, and to their use in decorative paper and to paper laminates made from such paper.

  It is generally well known in the art that paper laminates are suitable for a variety of applications including table and desk tops, counter tops, wall panels, floor surface materials and the like. Paper laminates have a wide variety of uses as described above because they can be extremely durable and can be used in a wide variety of building materials (both appearance and feel) including wood, stone, marble, and tiles. This is because it can be similar and can be decorated with images and colors.

  Typically, a paper laminate is made by infiltrating various types of resin from decorative paper into paper, collecting several layers of one or more types of laminated paper, and changing the resin to a cured state. It is made by gathering paper into an integral core structure. The type of resin and laminate paper used, and the composition of the final assembly, will be largely determined by what the laminate is ultimately used for.

  The decorative paper laminate can be made by using the decorated paper layer as the portion of the paper layer visible from the outside of the integral core structure. The remaining portion of the core structure typically includes various supporting paper layers with one or more highly opaque intermediate layers between the decorative layer and the supporting layer. May be included. Thereby, the appearance of the supporting layer does not adversely affect the appearance of the decorative layer.

  Paper laminates can be manufactured by both low pressure and high pressure lamination processes.

  Decorative paper usually includes a filler such as titanium dioxide to increase the brightness and opacity of the paper. Typically, these fillers are incorporated into the fibrous paper web by being added to the wet end.

  Often seen in the process of making decorative paper, pigments are in a form that is detrimental to the formation of a paper substrate, and components of the furnish such as wet strength resins and / or paper fibers. It is a situation where they interact. Such adverse interactions can be manifested in the form of loss in the tensile strength of paper (in wet or dry state), or a mottled appearance in the finished sheet, or poor opacity. Therefore, there is a need for self-dispersing pigments that have improved compatibility with papermaking furnish components.

In a first aspect, the present disclosure provides a decorative paper comprising a self-dispersing pigment, the self-dispersing pigment having an isoelectric point of at least about 8, more typically from about 8 to about 10, Inorganic particles having a silica treated product and an outermost treated product, more typically a titanium dioxide (TiO ₂ ) pigment, the outer treated product in order:
(A) hydrolyzing an aluminum compound or basic aluminate and depositing a surface of hydrous alumina;
(B) a step of adding a bifunctional compound, wherein the bifunctional compound is:
i. An anchor group linking the bifunctional compound to the surface of the pigment, and ii. Adding a bifunctional compound comprising a basic amine group comprising a primary, secondary, or tertiary amine.

  In a first aspect, the present disclosure provides a self-dispersing pigment, wherein the anchor group is a carboxylic acid functional group comprising acetate or a salt thereof; malonate, succinate, glutarate, adipate, or Dicarboxylic acid groups including their salts; oxoanion functional groups including phosphates, phosphonates, sulfates, or sulfonates; or substituted 1,3-diketones or substituted 3-ketoamides.

In a first aspect, the present disclosure provides a self-dispersing pigment, wherein the basic amine group is ammine; N-methyl, ethyl, propyl, butyl, cyclopentyl, or cyclohexyl Amines; or mixed dialkylamines such as N, N-dimethyl, diethyl, dipropyl, dibutyl, dicyclopentyl, dicyclohexylamine, or N, N-methylethyl, and more typically used amine groups are , Ammine (—NH ₂ ), N-methylamine, or N, N-dimethylamine.

In a first aspect, the present disclosure provides a self-dispersing pigment, the self-dispersing pigment further comprising a linking group that chemically bonds an anchor group to a basic amine group, the linking group comprising: Including:
(A) an alkyl chain having 1 to 8 carbon atoms, more typically 1 to 4 carbon atoms;
(B) polyetheramines comprising poly (oxyethylene), poly (oxypropylene), or mixtures thereof, whereby the weight average molecular weight of the linking group is from about 220 to about 2000; for example, Jeffamine® D , ED and EDR series; or
(C) A carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, or a sulfur atom at the bonding position between the anchor group.

  In a first aspect, the present disclosure provides a self-dispersing pigment, wherein the bifunctional compound comprises an α-omega amino acid, such as β-alanine, γ-aminobutyric acid, and ε-aminocaproic acid; , Α-amino acids such as arginine, aspartic acid, or salts thereof.

In a first aspect, the present disclosure provides a self-dispersing pigment, wherein the bifunctional compound is:
(I) an aminomalonate derivative having the following structure:

式中、Ｘは、上述のように、アンカー基を塩基性アミン基に化学的に結合する連結基であり、
Ｒ’及びＲ”はそれぞれ独立して、水素、アルキル、シクロアルキル、アルキル−アリル、アルケニル、シクロアルケニル、アルケン、アルキレン、アリーレン、アルキルアリーレン、アリルアルキレン又はシクロアルキレンから選択され；
Ｒ₁及びＲ₂は、それぞれ独立して水素、アルキル、シクロアルキル、アルケニル、シクロアルケニル、アルケン、アルキレン、又はシクロアルキレンから選択され；且つ
ｎ＝０〜５０である、アミノマロネート誘導体；
（ｉｉ）以下の構造を有するアミノスクシネート誘導体であって：

In the formula, as described above, X is a linking group that chemically bonds an anchor group to a basic amine group,
R ′ and R ″ are each independently selected from hydrogen, alkyl, cycloalkyl, alkyl-allyl, alkenyl, cycloalkenyl, alkene, alkylene, arylene, alkylarylene, allylalkylene or cycloalkylene;
R ₁ and R ₂ are each independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, alkylene, or cycloalkylene; and an aminomalonate derivative where n = 0-50;
(Ii) an aminosuccinate derivative having the following structure:

式中、Ｘは、上述のように、アンカー基を塩基性アミン基に化学的に結合する連結基であり、
Ｒ’及びＲ”はそれぞれ独立して、水素、アルキル、シクロアルキル、アルキル−アリル、アルケニル、シクロアルケニル、アルケン、アルキレン、アリーレン、アルキルアリーレン、アリルアルキレン又はシクロアルキレンから選択され；
Ｒ₁及びＲ₂は、それぞれ独立して水素、アルキル、シクロアルキル、アルケニル、シクロアルケニル、アルケン、アルキレン、又はシクロアルキレンから選択され；且つ
ｎ＝０〜５０である、アミノスクシネート誘導体；
（ｉｉｉ）以下の構造を有する２，４−ペンタンジオン誘導体であって：

In the formula, as described above, X is a linking group that chemically bonds an anchor group to a basic amine group,
R ′ and R ″ are each independently selected from hydrogen, alkyl, cycloalkyl, alkyl-allyl, alkenyl, cycloalkenyl, alkene, alkylene, arylene, alkylarylene, allylalkylene or cycloalkylene;
R ₁ and R ₂ are each independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, alkylene, or cycloalkylene; and an amino succinate derivative, wherein n = 0-50;
(Iii) a 2,4-pentanedione derivative having the following structure:

式中、Ｘは、上述のように、アンカー基を塩基性アミン基に化学的に結合する連結基であり、
Ｒ₁及びＲ₂は、それぞれ独立して水素、アルキル、シクロアルキル、アルケニル、シクロアルケニル、アルケン、アルキレン、及びシクロアルキレンから選択され；且つ
ｎ＝０〜５０である、２，４−ペンタンジオン誘導体；又は
（ｉｖ）以下の構造を有する３−ケトブタンアミド誘導体であって：

In the formula, as described above, X is a linking group that chemically bonds an anchor group to a basic amine group,
2,4-pentanedione derivatives wherein R ₁ and R ₂ are each independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, alkylene, and cycloalkylene; and n = 0-50 Or (iv) a 3-ketobutanamide derivative having the following structure:

式中、Ｘは、アンカー基を塩基性アミン基に化学的に結合する連結基であり、且つ
Ｒ₁及びＲ₂は、それぞれ独立して水素、アルキル、シクロアルキル、アルケニル、シクロアルケニル、アルケン、アルキレン、及びシクロアルキレンから選択される、３−ケトブタンアミド誘導体、を含む。

Wherein X is a linking group that chemically bonds the anchor group to the basic amine group, and R ₁ and R ₂ are each independently hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, 3-ketobutanamide derivatives selected from alkylene and cycloalkylene.

  In a first aspect, the present disclosure provides a self-dispersing pigment, wherein X is a methylene, oxyethane, or oxypropane group, where n = 0-50; or an oxoethylene monomer and an oxopropylene monomer A polyetheramine copolymer containing both.

  In a first aspect, the present disclosure provides a slurry comprising a self-dispersing pigment, the slurry comprising 10% of pigment solids, and the pH of the pigment slurry is less than about 7, more typically about 5 to 5. About 7.

In a first aspect, the present disclosure provides a self-dispersing pigment having a surface area of at least 15 m ² / g.

  “Self-dispersing pigment” means when the zeta potential of the pigment is the dominant force to keep the pigment particles separate (ie dispersed in the aqueous phase) It is the pigment which has the property to be. This force can be strong enough to separate weakly agglomerated pigment particles when suspended in an aqueous medium under low shear conditions. The zeta potential varies as a function of the pH and ionic strength of the solution, and the pigment particles ideally maintain a sufficient charge level to provide a repulsive force that keeps the particles separate and suspended. It is.

  In the present disclosure, “comprising” specifically refers to the presence of the recited feature, completeness, process, or component as referred to, It is to be construed as not excluding the presence or addition of one or more features, whole objects, steps, or components, or groups thereof. Also, the term “comprising” is intended to include examples encompassed by the terms “consisting essentially of” and “consisting of”. . Similarly, the term “consisting essentially of” is intended to include examples encompassed by the term “consisting of”.

  In this disclosure, if an amount, concentration, or other value or parameter is given as a range, a typical range, or a list of typical upper and typical lower values, All ranges formed from any pair of upper limits or typical values of any range and lower limits or typical values of any range, whether or not separately disclosed It should be understood that it is specifically disclosed. Where a numerical range is cited herein, the range includes both ends of the range and all integers and fractions within the range, unless otherwise indicated. Even when a range is defined, the scope of the present disclosure is not limited to a specific value.

In the present disclosure, for example, the singular forms “a”, “an”, and “the” used include a plurality of instruction objects unless the content is clearly specified. That is, for example, “a (indefinite) TiO ₂ particle”, “the (definite article) TiO ₂ particle” or “a (indefinite article) TiO ₂ particle” includes a plurality of TiO ₂ particles. Including.

Inorganic particles:
The inorganic particles are typically inorganic metal oxide or mixed metal oxide pigment particles, more typically titanium dioxide particles, which can be pigments or nanoparticles, typically inorganic metal oxides. Alternatively, inorganic particles, which are mixed metal oxide particles, and more typically titanium dioxide particles, enhance their compatibility within the decorative paper furnish. The term inorganic particles refers to an inorganic particulate material that is dispersed throughout the final product, such as a decorative paper composition, to impart color and opacity to the product. Some examples of inorganic particles include ZnO, TiO ₂ , SrTiO ₃ , BaSO ₄ , PbCO ₃ , BaTiO ₃ , Ce ₂ O ₃ , Al ₂ O ₃ , CaCO ₃ , and ZrO _2. Not limited.

Titanium dioxide pigment:
Titanium dioxide (TiO ₂ ) pigments useful in the present disclosure can be in the rutile form or the pyrite crystalline form, but the rutile form is typical. It is usually made by a chloride process or a sulfate process. In the chloride process, TiCl ₄ is oxidized into TiO ₂ particles. In the sulfate process, sulfuric acid and ore containing titanium are dissolved and the resulting solution is passed through a series of steps to obtain TiO ₂ . Both the sulfate process and the chloride process are described in more detail in The Pigment Handbook Volume 1, 2nd Edition, John Wiley & Sons, NY (1988), for related teachings. This application is hereby incorporated by reference as if fully set forth.

  By the term “pigment” it is meant that the titanium dioxide particles are of an average size of less than about 1 micron. Typically, the particles have an average size of about 0.020 to about 0.95 microns, more typically about 0.050 to about 0.75 microns, most typically about 0. 0.075 to about 0.50 microns. Also typical are pigments having a specific gravity in the range of about 3.5 to about 6 g / cc.

  Surface treatment may be applied to the untreated titanium dioxide pigment. By “surface treatment” is meant that the titanium dioxide pigment particles are contacted with a compound described herein and the compound is adsorbed on the surface of the titanium dioxide particles, or at least one compound and The reaction product with the titanium dioxide particles exists on the surface as an adsorbed species or is chemically bonded to the surface. The compound, its reaction product, or a combination thereof may be present on the surface of the pigment as a single layer, or as a continuous two-layer or discontinuous two-layer treatment, particularly a coating.

For example, titanium dioxide particles, typically pigment particles, can have one or more surface treatments. A silica-treated product is present on the surface of the titanium dioxide pigment. The outermost treatment can be obtained by performing the following procedures in sequence:
(A) hydrolyzing an aluminum compound or basic aluminate so as to deposit a surface of hydrous alumina;
(B) Add a bifunctional compound containing the following groups:
(I) an anchor group for linking the bifunctional compound to the pigment surface; and (ii) a basic amine group comprising a primary, secondary, or tertiary amine.

Silica-treated product:
Inorganic particles, particularly titanium dioxide particles, may contain at least one silica-treated product. The silica treatment is about 0.1 wt% to about 20 wt%, typically about 1.5 wt% to about 11 wt%, more typically based on the total weight of the treated titanium dioxide particles. Specifically, it may be present in an amount of about 2% to about 7% by weight. The treated product can be applied by a method known to those skilled in the art. A typical method of adding the silica treatment to the TiO ₂ particles is by a wet treatment similar to that disclosed in US Pat. No. 5,993,533. An alternative method of adding the silica treatment to the TiO ₂ particles is by depositing exothermic silica on the exothermic titanium dioxide particles, as described in US Pat. No. 5,992,120, or Some are by co-oxidizing silicon chloride with titanium tetrachloride, as described in US Pat. No. 5,562,764 and US Pat. No. 7,029,648, the disclosures of which are incorporated herein by reference. Has been incorporated by reference. Other pyrolytic deposition metal oxide treatments include using doped aluminum alloys that are then oxidized to produce volatile metal chlorides that are deposited on the pigment particle surface in the gas phase. . Co-oxidation of the metal chloride species yields the corresponding metal oxide. That is, for example, the use of a silicon-aluminum alloy results in silica deposition. International Patent Application Publication No. 2011 / 059938A1 describes this processing procedure in more detail and is incorporated by reference into the present disclosure.

In one specific embodiment, a slurry comprising silica-treated titanium dioxide particles and water is prepared by a process that includes the following steps. The process includes providing a slurry of titanium dioxide particles mixed in water, but the slurry is typically 25 wt% to about 35 wt%, more typically based on its total weight. Is present in an amount of about 30% TiO ₂ . The slurry is then heated to about 30 to about 40 degrees Celsius, more typically 33 to 37 degrees Celsius, and the pH is about 3.5 to about 7.5, more typically about 5.0 to Adjust to about 6.5. A soluble silicate such as sodium silicate or potassium silicate is then added to the slurry, but the pH is between about 3.5 and about 7.5, more typically about 5.0 to Maintained between about 6.5. Next, stirring is performed for at least about 5 minutes, typically at least about 10 minutes, but no more than 30 minutes to facilitate precipitation of the silica onto the titanium dioxide particles. Commercially available water-soluble sodium silicate, in which the weight ratio of SiO ₂ / Na ₂ O is about 1.6 to about 3.75 and varies from 32 to 54% of the weight of the solids, is further diluted. The most practical, whether or not diluted. The slurry should typically be acidic while adding an effective portion of soluble silicate to attach porous silica to the titanium dioxide particles. The acid used may be any acid such as HCl, H ₂ SO ₄ , HNO ₃ or H ₃ PO ₄ , but has a dissociation constant high enough to precipitate silica and the acidity of the slurry Used in an amount sufficient to maintain the conditions. Compounds such as TiOSO ₄ or TiCl ₄ that hydrolyze to form acids may be used. Instead of adding all the acid first, soluble silicate and acid may be added simultaneously as long as the acidity of the slurry is typically maintained at a pH value below about 7.5. After the acid is added, the slurry should be maintained at a temperature not exceeding 50 degrees Celsius for at least 30 minutes before proceeding to further additions.

  The treated product is about 3 to about 14% by weight, more typically about 5 to about 12.0% by weight, and even more typically 10.5%, based on the total weight of the titanium dioxide particles, particularly the titanium dioxide core particles. Corresponds to weight percent silica.

Outer treatment:
The aluminum compound or basic aluminate results in a hydrous alumina treatment at least about 3% based on the total weight of the treated titanium dioxide particles, on the surface of the titanium dioxide particles, typically the outermost surface. Typically, about 4.5 to about 7% alumina is produced. Some suitable aluminum compounds and basic aluminates include aluminum sulfate hydrate, aluminum chloride hydrate or aluminum nitrate hydrate, and alkali aluminate, but more typically Sodium aluminate or potassium aluminate can be mentioned.

  Bifunctional compounds include anchor groups that link the bifunctional compound to the surface of the pigment, typically the outermost surface, and basic amine groups including primary, secondary, or tertiary amines. Anchor groups include carboxylic acid functional groups including acetate or salts thereof; dicarboxylic acid groups including malonate, succinate, glutarate, adipate or salts thereof; oxo including phosphate, phosphonate, sulfate, or sulfonate Includes diketones such as anionic functional groups, or C3-substituted 2,4-pentanediones or substituted or 3-ketobutanamide derivatives. The bifunctional compound is present in an amount of less than 10% by weight, more typically from about 0.4% to about 3%, based on the weight of the treated pigment.

  Substituents on basic amine groups are hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, alkylene, or cycloalkylene, more typically short chain alkyls including methyl, ethyl, or propyl, and even more Typically selected from the group consisting of ammine.

  Bifunctional compounds may include α-omega amino acids such as β-alanine, γ-aminobutyric acid, and ε-aminocaproic acid and α-amino acids such as lysine, arginine, aspartic acid, or salts thereof. .

  Alternatively, the bifunctional compound comprises an aminomalonate derivative of the following structure:

式中、Ｘは、アンカー基を塩基性アミン基に化学的に結合する連結基であり、
Ｒ’及びＲ”はそれぞれ独立して、水素、アルキル、シクロアルキル、アルキル−アリル、アルケニル、シクロアルケニル、アルケン、アルキレン、アリーレン、アルキルアリーレン、アリルアルキレン、又はシクロアルキレンから選択され、より典型的には、水素、炭素原子数が１〜８のアルキル、炭素原子数が６〜８のアリルから選択され、また、更により典型的には、Ｒ’及びＲ”は水素、メチル、又はエチルから選択される、
Ｒ₁及びＲ₂はそれぞれ独立して、水素、アルキル、シクロアルキル、アルケニル、シクロアルケニル、アルケン、アルキレン、又はシクロアルキレン、より典型的にはメチル、エチル、又はプロピルを含む短鎖アルキル、及び更により典型的にはアンミンよりなる群から選択され、
ｎ＝０〜５０である。

In the formula, X is a linking group that chemically bonds an anchor group to a basic amine group,
R ′ and R ″ are each independently selected from hydrogen, alkyl, cycloalkyl, alkyl-allyl, alkenyl, cycloalkenyl, alkene, alkylene, arylene, alkylarylene, allylalkylene, or cycloalkylene, more typically Is selected from hydrogen, alkyl having 1 to 8 carbon atoms, allyl having 6 to 8 carbon atoms, and even more typically, R ′ and R ″ are selected from hydrogen, methyl, or ethyl To be
R ₁ and R ₂ are each independently hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, alkylene, or cycloalkylene, more typically short chain alkyls including methyl, ethyl, or propyl, and further Typically selected from the group consisting of ammine,
n = 0 to 50.

  Typically, when X is methylene, n = 1-8, and more typically n = 1-4. When X is oxymethylene or oxypropylene, n is in the range of 2.5-50, more typically in the range of 6-18. Some examples of aminomalonate derivatives include methyl and ethyl esters of 2- (2-aminoethyl) malonic acid, more typically methyl esters of 2- (2-aminoethyl) dimethylmalonate and Ethyl ester is included.

  The bifunctional compound may alternatively comprise an aminosuccinate derivative of the following structure:

式中、Ｘは、アンカー基を塩基性アミン基に化学的に結合する連結基であり、
Ｒ’及びＲ”はそれぞれ独立して、水素、アルキル、シクロアルキル、アルキル−アリル、アルケニル、シクロアルケニル、アルケン、アルキレン、アリーレン、アルキルアリーレン、アリルアルキレン、又はシクロアルキレンから選択され、より典型的には、水素、炭素原子数が１〜８のアルキル、炭素原子数が６〜８のアリルから選択され、また、更により典型的には、Ｒ’及びＲ”は水素、メチル、又はエチルである、
Ｒ₁及びＲ₂はそれぞれ独立して、水素、アルキル、シクロアルキル、アルケニル、シクロアルケニル、アルケン、アルキレン、又はシクロアルキレン、より典型的にはメチル、エチル、又はプロピルを含む短鎖アルキル、及び更により典型的にはアンミンよりなる群から選択され、
及び
ｎ＝０〜５０である。

In the formula, X is a linking group that chemically bonds an anchor group to a basic amine group,
R ′ and R ″ are each independently selected from hydrogen, alkyl, cycloalkyl, alkyl-allyl, alkenyl, cycloalkenyl, alkene, alkylene, arylene, alkylarylene, allylalkylene, or cycloalkylene, more typically Is selected from hydrogen, alkyl having 1 to 8 carbon atoms, allyl having 6 to 8 carbon atoms, and even more typically, R ′ and R ″ are hydrogen, methyl or ethyl ,
R ₁ and R ₂ are each independently hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, alkylene, or cycloalkylene, more typically short chain alkyls including methyl, ethyl, or propyl, and further Typically selected from the group consisting of ammine,
And n = 0 to 50.

  Typically, when X is methylene, n = 1-8, and more typically n = 1-4. When X is oxymethylene or oxypropylene, n is in the range of 2.5-50, more typically in the range of 6-18. Some examples of amino succinate derivatives include N-substituted aspartic acid, more typically methyl and ethyl esters of N- (2-aminoethyl) aspartic acid.

  The bifunctional compound may alternatively comprise an acetoacetate derivative of the following structure:

式中、Ｘは、アンカー基を塩基性アミン基に化学的に結合する連結基であり、
Ｒ₁及びＲ₂はそれぞれ独立して、水素、アルキル、シクロアルキル、アルケニル、シクロアルケニル、アルケン、アルキレン、又はシクロアルキレン、より典型的にはメチル、エチル、又はプロピルを含む短鎖アルキル、及び更により典型的にはアンミンよりなる群から選択され、
及び
ｎ＝０〜５０である。

In the formula, X is a linking group that chemically bonds an anchor group to a basic amine group,
R ₁ and R ₂ are each independently hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, alkylene, or cycloalkylene, more typically short chain alkyls including methyl, ethyl, or propyl, and further Typically selected from the group consisting of ammine,
And n = 0 to 50.

  Typically, when X is methylene, n = 1-8, and more typically n = 1-4. When X is oxymethylene or oxypropylene, n is in the range of 2.5-50, more typically in the range of 6-18. An example of an acetoacetate derivative is 3- (2-aminoethyl) -2,4-pentanedione.

  The bifunctional compound may alternatively comprise a 3-ketoamide (amide acetate) derivative of the following structure:

式中、Ｘは、アンカー基を塩基性アミン基に化学的に結合する連結基であり、
Ｒ₁及びＲ₂はそれぞれ独立して、水素、アルキル、シクロアルキル、アルケニル、シクロアルケニル、アルケン、アルキレン、又はシクロアルキレン、より典型的にはメチル、エチル、又はプロピルを含む短鎖アルキル、及び更により典型的にはアンミンよりなる群から選択され、
及び
ｎ＝０〜５０である。

In the formula, X is a linking group that chemically bonds an anchor group to a basic amine group,
R ₁ and R ₂ are each independently hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, alkylene, or cycloalkylene, more typically short chain alkyls including methyl, ethyl, or propyl, and further Typically selected from the group consisting of ammine,
And n = 0 to 50.

  Typically, when X is methylene, n = 1-8, and more typically n = 1-4. When X is oxymethylene or oxypropylene, n is in the range of 2.5-50, more typically in the range of 6-18. Some examples of amide acetate derivatives include ethylenediamine and diethylenetriamineamide, more typically N- (2-aminoethyl) -3-oxobutanamide.

  The tendency to increase the isoelectric point of the pigment is proportional to the amount of amine functionality imparted to the surface of the pigment, so the molar amount of the bifunctional compound added to 100 g of the treated pigment is added to the added N It is appropriate to express it as millimole percent of For example, the amount of bifunctional compound used to effectively increase the isoelectric point of the pigment ranges from 2 to 10 mmol%, more typically from 4 to 8 mmol%. It is a range. Therefore, for the preferred low molecular weight bifunctional compound β-alanine, an applied amount of 5 mmol% translates to 0.45 wt%. In contrast, in the high molecular weight example, a 3-ketobutanamide Jeffamine ED-2003 (molecular weight less than 2000) adduct requires 10.4 wt% to achieve an amine equivalent of 5 mmol%. .

The bifunctional compound further includes a linking group that chemically bonds the anchor group to the basic amine group, which includes the following:
(A) an alkyl group having 1 to 8 carbon atoms, more typically 1 to 4 carbon atoms;
(B) a polyetheramine comprising poly (oxyethylene) or poly (oxypropylene), or mixtures thereof, whereby the weight average molecular weight of the linking group is from about 220 to about 2000; or (c) an anchor group A carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, or a sulfur atom at the connecting position of Some examples of (b) include the Jeffamine® D, ED, and EDR series.

  In one specific embodiment, in the bifunctional compound used to prepare the self-dispersing pigment, does X contain a methylene group, oxyethane group, or oxypropane group where n = 0-50? Or polyetheramine copolymers comprising both oxoethylene and oxopropylene monomers.

In slurries made with self-dispersing pigments, the pigment solids contain at least about 10%, more typically 35%, and the pH of the pigment slurry is less than about 7, more typically about 5%. ~ 7. Self-dispersible pigment, the surface area is at least 15 m ² / g, more typically 25~35m ² / g.

  Alternatively, the treated inorganic particles, in particular titanium dioxide particles, may comprise at least one further oxidized product (eg alumina, zirconia or ceria), aluminosilicate, or aluminophosphate. This alternative treatment is about 0.1 wt.% To about 20 wt.%, Typically about 0.5 wt.% To about 5 wt.%, Based on the total weight of the treated titanium dioxide particles. Typically, it may be present in an amount of about 0.5% to about 1.5% by weight. The treated product can be applied by a method known to those skilled in the art.

Typically, the provided oxidation treatment may be in at least two layers, the first layer being at least about 3.0%, and more based on the total weight of the treated titanium dioxide particles. Typically about 5.5 to about 6% alumina and at least about 1%, more typically about 1.5% to about 3.0, based on the total weight of the treated titanium dioxide particles. % Phosphorus pentoxide, P ₂ O ₅ . In certain specific embodiments, the second layer of oxide on the titanium dioxide pigment is at least about 1.5%, more typically about, based on the total weight of the treated titanium dioxide particles. It contains 6% to about 14%, even more typically about 9.5% to about 12% silica.

  Titanium dioxide pigments prior to surface treatment are as in US Pat. Nos. 4,461,810, 4,737,194, and International Patent Application Publication No. 2004/061013, the disclosures of which are incorporated by reference into this disclosure, One type or two or more types of metal oxide and / or a phosphatized surface treatment product may be carried. These coatings can be applied using techniques known to those skilled in the art.

  Typical are titanium dioxide pigments coated with phosphatized metal oxides, for example titanium dioxide pigments coated with phosphatized alumina and phosphatized alumina / ceria oxide.

  Included in suitable commercial examples of titanium dioxide pigments are alumina-coated titanium dioxide pigments such as R700 and R706 (available from EI du Pont de Nemours and Company, Wilmington, Del.), Alumina / For example, R796 + (available from EI du Pont de Nemours and Company, Wilmington, Del.), And titanium dioxide pigments coated with alumina / phosphate / ceria R794 (available from EI duPont de Nemours and Company, Wilmington, Del.).

Process for preparing treated titanium dioxide particles The process for preparing a self-dispersing pigment comprises the following steps:
(A) preparing inorganic particles treated with silica, particularly TiO ₂ pigment particles;
(B) A step of adding an aqueous aluminum salt and adding the following bifunctional compound containing i and ii to form an aqueous solution:
an anchor group linking the bifunctional compound to the surface of the pigment, and ii a basic amine group comprising a primary, secondary, or tertiary amine;
(C) adding a base to the mixture obtained in step (b) and raising the pH to about 4 to about 9 to form a turbid solution; and (d) the mixture obtained in step (c). Adding to the slurry of inorganic particles treated with silica, in particular TiO ₂ pigment particles treated with silica, so that the hydrous alumina and the bifunctional compound contain the outermost surface treated product. Silica treated TiO ₂ particles can be prepared by treating the TiO ₂ particles using several different techniques to form a silica treated product thereon. For example, wet processing, depositing exothermic oxide on exothermic titanium dioxide particles, by the method described in US Pat. No. 5,992,120, or US Pat. No. 5,562,764 and US Pat. It can be prepared by co-oxidizing metal tetrachloride with titanium tetrachloride as described in US 7,029,648. The contents of these patent documents are incorporated into the present disclosure by reference. Other pyrolytic deposition metal oxide treatments include using doped aluminum alloys that are then oxidized to produce volatile metal chlorides that are deposited on the pigment particle surface in the gas phase. . Co-oxidation of the metal chloride species yields the corresponding metal oxide.

  In the formation of the outermost treatment, the acidic aluminum salt includes aluminum sulfate hydrate or aluminum nitrate hydrate, more typically aluminum chloride hydrate, and the base is sodium hydroxide, sodium carbonate. Or more typically comprises ammonium hydroxide. Starting with the amount of bifunctional compound chosen to give the desired isoelectric point of the pigment, the accompanying amount of acidic aluminum salt has a molar ratio of bifunctional compound to Al of less than 3, more typically Is selected to be about 1 to about 2.5. Thus, a mixture that is more hydrolyzed and more likely to deposit is used to increase the surface of the pigment. Less preferred here are aluminum complexes of bidentate ligands such as the anion of acetylacetone (ie 2,4-pentanedione). Such complexes are well known from coordination chemistry literature, and tri (acetylacetonato) aluminum complexes are known for their stability (boiling point is 314 degrees Celsius) and nonpolar, but in water It is insoluble.

  The titanium dioxide particles can be surface treated in any number of ways well known to those skilled in the art, as exemplified in the above incorporated references. For example, the treatment can be applied by injector treatment, addition to a micronizer, or simply by mixing with a slurry of titanium dioxide.

  Surface-modified titanium dioxide is a suitable technique known in the art at a concentration of less than about 10% by weight, typically about 3 to about 5% by weight, based on the total weight of the dispersion. Can be dispersed in water. An example of a suitable dispersion technique is sonication. The surface modified titanium dioxide of the present disclosure is cationic. The isoelectric point of the surface modified titanium dioxide of the present disclosure, determined by the pH value when the zeta potential value is zero, is greater than 8, typically greater than 9, even more typically. Is in the range of about 9 to about 10. The isoelectric point can be determined using the zeta potential measurement method described in the examples below. Depending on the amount of bifunctional compound deposited, the isoelectric point can be controlled to at least 8.0, more typically 8.0-9.0, which is important during factory processing and decorative paper production. In addition, it may be advantageous in that it facilitates the dispersion and / or soft aggregation of the particulate composition. A high isoelectric point means that the pigment particles are cationically charged under the conditions when the pigment particles are introduced into the furnish of the decorative paper. The surface of the cationic pigment is sufficiently charged at a pH of less than 7, but tends to interact with the anion-charged paper fiber, while being difficult to adsorb the cationic wet strength resin. ing.

  Typically, the particle-to-particle surface treatment is substantially homogeneous. This means that a certain amount of alumina or aluminophosphate is linked to the surface of each core particle, but the difference between the particles at the alumina and phosphate levels is very low. , All particles interact in the same way as water, organic solvent, or dispersant molecules (ie all particles interact with the chemical environment in a common way, to a common degree) That's what it means. Typically, the treated titanium dioxide particles are completely dispersed in water and form a slurry in less than 10 minutes, more typically less than about 5 minutes. "Completely dispersed" means that the dispersion consists of individual particles or a small group of particles (hard aggregate) created during the particle formation stage, and all soft aggregates are individually It is reduced to particles.

  After treatment by this process, the pigment is recovered by known procedures, which include neutralization of the slurry and, optionally, filtration, washing, drying, and often dry milling such as micronization. Process. However, drying is not always necessary. This is because the product slurry can be used directly to prepare a paper dispersion in which water is the liquid phase.

Applications Treated titanium dioxide particles can be used in paper laminates. The paper laminate of the present disclosure is useful for flooring, furniture, counter tops, artificial wood surface materials, and artificial stone surfaces.

Decorative Paper The decorative paper may include fillers such as treated titanium dioxide and other fillers prepared as described above. Some examples of other fillers include talc, zinc oxide, kaolin, calcium carbonate, and mixtures thereof.

The filler component of the decorative paper is about 10% to about 65% by weight, especially 30% to 45% by weight, based on the total weight of the decorative paper. The basis weight of the base portion of the decorative paper, 30g / m ² ~ about 300 g / m ^2, may range especially ^{90g / m 2 ~110g / m 2} . The basis weight is selected as a function of that particular application.

  To form a sheet of paper, a suspension of titanium dioxide can be mixed with the pulp. For example, sawn pulp such as eucalyptus pulp is mixed into an aqueous dispersion. The pH of the pulp dispersion is typically from about 6 to about 8, more typically from about 7 to about 7.5. Such pulp dispersion can be used to form paper by conventional techniques.

  Coniferous wood pulp (long fiber pulp) or hardwood pulp such as eucalyptus (short fiber pulp), and mixtures thereof are useful as pulp to produce the decorative paper base. It is also possible to use cotton fibers or a mixture of all these types of pulp. Mixtures of coniferous wood and hardwood pulp with a ratio of about 10:90 to about 90:10, and particularly about 30:70 to about 70:30 may be useful. The pulp beating degree is 20 degrees to about 60 degrees SR according to the Shopper Leaguer type testing machine.

  The decorative paper may also contain a cationic polymer, but such cationic polymers may contain epichlorohydrin and tertiary amines or quaternary ammonium compounds, but such quaternary ammoniums. The compound is for example chlorohydroxypropyltrimethylammonium chloride or glycidyltrimethylammonium chloride. Most typically, the cationic polymer is a quaternary ammonium compound. Cationic polymers such as wet strength agents are also useful, including polyamide / polyamine epichlorohydrin resins, other polyamine derivatives, or polyamide derivatives, cationic polyacrylates, modified melamine formaldehyde resins, or cationized starch. Yes, can be added to form a dispersion. Other resins include, for example, diallyl phthalate, epoxide resin, urea formaldehyde resin, urea-acrylic ester copolyester, melamine formaldehyde resin, melamine phenol formaldehyde resin, phenol formaldehyde resin, poly (meth) acrylate and / or Unsaturated polyester resin. The cationic polymer is present in an amount of about 0.5 to about 1.5% by weight of the dry polymer relative to the total dry weight of pulp fibers used in the paper.

  Fixing aids, wet strength improvers, fixing agents, sizing agents (internal and surface), fixing agents, and other materials such as organic and inorganic color pigments, dyes, optical brighteners, and dispersants are also Useful to form dispersions and may be added as needed to achieve the desired final properties of the paper. Fixing aids are added to minimize the loss of titanium dioxide and other fine components during the papermaking process. This necessitates additional costs, as is the case with other additives such as wet strength improvers.

  Examples of paper used in paper laminates are US Pat. No. 6,599,592, the disclosure of which is incorporated by reference for all purposes as if fully set forth in the present disclosure, and US Pat. No. 5,679,219. No. 6,706,372, and US Pat. No. 6,783,631 can be found in the above incorporated references including, but not limited to:

  As indicated above, paper typically contains many components, including, for example, various pigments, fixing agents, and wet strength improvers. Pigments, for example, impart desired properties such as opacity and whiteness to the final product paper, and a widely used pigment is titanium dioxide.

  The treated titanium dioxide particles can be used to prepare decorative paper in any conventional manner, but at least a portion of all the titanium dioxide pigments typically used in such papermaking. Is replaced by a treated titanium dioxide pigment.

  As indicated above, the decorative paper according to the present disclosure is opaque and the cellulosic pulp-based sheet comprises no more than about 45 wt.%, More typically about 10 wt.% To about 45 wt. More typically from about 25% to about 42% by weight, the titanium dioxide pigment component comprises all or some of the treated titanium dioxide particles according to the present disclosure. In one exemplary embodiment, the treated titanium dioxide pigment component is at least about 25% by weight (based on the weight of the titanium dioxide pigment component), and more typically at least about 40% by weight of the present disclosure. Of treated titanium dioxide pigment. In other exemplary embodiments, the titanium dioxide pigment component consists essentially of the treated titanium dioxide pigment of the present disclosure. In yet another exemplary embodiment, the titanium dioxide pigment component substantially comprises only the treated titanium dioxide pigment of the present disclosure.

Paper Laminates Paper laminates according to the present disclosure can be made by any conventional process well known to those skilled in the art, as described in many previously incorporated references.

  Typically, the process of making paper laminates begins with raw materials, which are impregnating resins such as phenolic and melamine resins, brown paper (eg, kraft paper), and premium Printing paper (laminated paper according to the present disclosure).

  The brown paper functions as a carrier for the impregnating resin, supplements the strength of the final laminate and increases the thickness. High-grade paper is a decorative sheet. For example, it may be a full color, a pattern printed, or a wood grain printed.

  In industrial scale processes, a roll of paper is typically loaded onto a spindle at the “wet end” of a resin processor and impregnated with resin. High-quality (decorative) surface paper is treated with a transparent resin such as melamine resin so as not to affect the (decorative) appearance of the paper surface. Since the appearance is not important for brown paper, it may be treated with a colored resin such as a phenolic resin.

  Two methods are commonly used to impregnate paper with resin. The usual (and fastest and most efficient) method is called “reverse roll coating”. In this process, the paper is drawn between two large rollers, with one roller applying a thin resin coating on one side of the paper. This thin coating is given time to penetrate the paper while it is transported towards the drying oven. Almost all brown paper is processed by a reverse roll process, because the process is more efficient and can be applied to a complete coating with less resin and less waste. is there.

  Another method is the “dipping and squeezing” process, where the paper is drawn into a resin vat and then squeezed out of excess resin through a roller. Surface (decorative) paper is usually impregnated with resin by a dipping and squeezing process, which allows the impregnating resin to be coated thicker and the final lamination, although the process is slower This is because the surface characteristics of the object, such as durability, antifouling property, and heat resistance can be improved.

  After impregnating the resin, the paper (as a continuous sheet) is passed through a drying (processing) oven to a “dry end” where it is cut into a plurality of sheets.

  The paper impregnated with the resin should have a consistent thickness so that irregularities in the final laminate can be avoided.

  In an assembly that collects the components of the laminate, the top surface is typically a face sheet, since the appearance of the final laminate is primarily determined by the face sheet. However, an uppermost “surface” sheet that becomes substantially transparent when solidified may be placed over the decorative sheet. This is for example to add depth to the appearance of the final laminate and to increase the wear resistance of the laminate.

  In a laminate in which the surface paper is a single color with a light color, an additional sheet of high-quality white paper may be placed under the printed surface sheet. By doing so, the amber phenolic filler sheet can be prevented from interfering with the color of the bright surface.

  The touch of the surface of the laminate is determined by a plate that is inserted into the press with a build-up of textured paper and / or materials. Typically, a steel plate is used, with a well polished plate having a glossy finish, and a plate etched into irregularities has a matte finish.

  The final buildup is sent to a press machine, and each buildup (a pair of laminates) is separated from the next buildup by the steel plate. In the press machine, pressure is applied to build up by a water tank pump or the like. Low pressure and high pressure methods are used to make the paper laminate. Typically, pressures of at least 5 MPa (800 psi), and sometimes as much as 10.34 MPa (1500 psi), are applied, while superheated water or steam is passed through a built-in jacket in the press to 121 degrees Celsius (Fahrenheit). 250 degrees). Build-up is maintained under these temperature and pressure conditions for a period of time (typically about 1 hour) during which time the resin in the paper impregnated with resin re-liquefies and flows. This is the time required to solidify and combine the stacked stacks of paper into a single sheet of final decorative laminate.

  When the laminate is removed from the press, the laminate sheets are separated and trimmed to the desired size of the final product. Typically, the back side of the laminate is also roughened (eg, by sanding) and bonded to one or more substrates, such as plywood, hard fiberboard, particleboard, composite, etc. In order to provide a good adhesive surface. As those skilled in the art will appreciate, the need and choice of substrate and adhesive will depend on the desired end use of the laminate.

  The following examples, i.e. exemplary and exemplary descriptions of embodiments of the present disclosure, are not intended to limit the scope of the present disclosure. Various modifications, alternative constructions, and equivalents may be employed without departing from the true spirit and scope of the appended claims.

Characterization of isoelectric points using ZetaProbe (Colloidal Dynamics):
A 4% solids slurry of pigment was placed in an analytical cup. Electrokinetic acoustic (ESA) and pH probes were submerged in the stirred pigment suspension. Next, titration of the stirred suspension was performed using 2N KOH as the base titrant and 2N HNO ₃ as the acid titrant. Mechanical parameters were selected to titrate the acid containing leg to pH 4 and titrate the base containing leg to pH 9. The zeta potential was determined from the dynamic fluidity spectrum of the particles measured using the electrokinetic acoustic technique described by O'Brien et al. ^* . The isoelectric point of the pigment is typically determined by interpolating along the pH / zeta potential curve where the zeta potential is equal to zero.

^* O'Brien R. W. , Cannon D. W. , Rowlands W. N. J. et al. Colloid Interface Sci. 173, 406-418 (1995).
O'Brien R.M. W. Jones A. , Rowlands W. N. Colloids and Surfaces A 218, 89-101 (2003).

(Example 1):
200 g of a 30% (w / w) slurry of titanium dioxide pigment coated with alumina (DuPont R-796) is placed in a jacketed 250 mL beaker and heated to 55 degrees Celsius. During the surface treatment, the slurry is agitated using a propeller blade attached to an overhead stirrer. The measured pH value of this slurry at 55 degrees Celsius is 5.5. 14.6 g of sodium silicate sol with a 28.7% SiO ₂ content (about 7% SiO ₂ based on the weight of the pigment) is placed in a 20 cc syringe. The sol is added at a rate of 0.7 mL / min so that the time required to complete the addition is within 20 minutes. During the addition of the silicate, the pH is maintained in the range of 5.0-5.5 by simultaneously adding 20% HCl solution. After the silicate addition is complete, the mixture is held at its pH and temperature for 30 minutes. 18.8 g of 43% sodium aluminate sol (24% Al ₂ O ₃ content, approximately 7% Al ₂ O ₃ based on pigment weight) is placed in a 20 cc syringe. The sol is added at a rate such that the addition occurs within 10 minutes. The pH is allowed to rise to 10, while maintaining pH 10 by starting to add 20% HCl solution. After this period, 0.68 g (7 mmol%) of 3- (2-aminoethyl) -2,4-pentanedione is added to the stirred slurry. The pH is adjusted to 10 and held in that state for 30 minutes. After this time, the pH is lowered to 5.5 by further addition of 20% HCl and held at pH 5.5 for 30 minutes. The slurry is vacuum filtered through a Buchner funnel fitted with Whatman # 2 filter paper. The resulting cake is washed with 4 × 100 mL deionized water, transferred onto a Petri dish and dried at 110 degrees Celsius for 16 hours. Crush the dried cake with a mortar and pestle. A slurry with a solid content of 10% of this pigment is expected to have a pH of 6.5. The slurry having a solid content of 4% is expected to have an isoelectric point (ZetaProbe) of 8.9. As a comparative example, the R-796 pigment at the start point alone had an isoelectric point of 6.9.

(Example 2):
200 g of a 30% (w / w) slurry of titanium dioxide pigment coated with alumina (DuPont R-796) is placed in a jacketed 250 mL beaker and heated to 55 degrees Celsius. The slurry is agitated using a propeller blade attached to an overhead stirrer. 14.6 g of sodium silicate sol with a 28.7% SiO ₂ content (about 7% SiO ₂ based on the weight of the pigment) is placed in a 20 cc syringe. The sol is added at such a rate that the addition is complete within 20 minutes. During the addition of the silicate, the pH is maintained in the range of 5.0-5.5 by simultaneously adding 20% HCl solution. After the silicate addition is complete, the mixture is held at its pH and temperature for 30 minutes. 18.8 g of 43% sodium aluminate sol (24% Al ₂ O ₃ content, approximately 7% Al ₂ O ₃ based on pigment weight) is placed in a 20 cc syringe. The sol is added at a rate such that the addition occurs within 10 minutes. The pH is allowed to rise to 10, while maintaining pH 10 by starting to add 20% HCl solution. After the addition of the aluminate is complete, 3.4 g (5 mmol%) of Jeffamine® ED-900 plus 3-oxobutanamide is added to the stirred slurry. The pH is adjusted to 10 and maintained for 30 minutes. After this time, the pH is lowered to 5.5 by further addition of 20% HCl and held at pH 5.5 for 30 minutes. As described in Example 1, the slurry is filtered, washed, dried and comminuted. A slurry with a solid content of 10% of this pigment is expected to have a pH of 6.5. The slurry having a solid content of 4% is expected to have an isoelectric point (ZetaProbe) of 8.9.

(Example 3):
3330 g of a 30% solids (w / w) R-796 slurry (ie, sufficient to produce about 1 Kg of dry pigment) was placed in a 5 L stainless steel pail, 55 degrees Celsius Heat on a hot plate. Stir the slurry all the time using a propeller blade attached to an overhead stirrer. 242 g of sodium silicate sol with 28.7% SiO ₂ content (about 7% SiO ₂ based on pigment weight) is placed in a dropping funnel set on a pail can. The silica sol is added at such a rate that the time required to complete the addition is within 20 minutes. During the addition of the silicate, the pH is maintained in the range of 5.0-5.5 by simultaneously adding 20% HCl solution. After the silicate addition is complete, the mixture is held at its pH and temperature for 30 minutes. Next, 310 g of 43% sodium aluminate sol (about 7% Al ₂ O ₃ based on the weight of the pigment) is added in the same manner. The addition rate is controlled so that the contents in the funnel are added within 20 minutes. The pH is allowed to rise to 10, while maintaining pH 10 by starting to add 20% HCl solution. After the addition of the aluminate is complete, 8.2 g (5 mmol%) of N- (2-aminoethyl) -3-oxobutanamide is added to the stirred slurry. The pH is adjusted to 10 and maintained for 30 minutes. After this time, the pH is lowered to 5.5 by further addition of 20% HCl and held for 30 minutes. The slurry is vacuum filtered through a large Buchner funnel fitted with Whatman # 2 filter paper. The resulting cake is washed with deionized water until the conductivity of the filtrate drops below 0.2 mS / cm. The wet cake is transferred to an aluminum pan and dried at 110 degrees Celsius for 16 hours. The dried cake is crushed and sieved through a 325 mesh screen. The final grinding of this material is carried out by means of a steam jet mill. A slurry with a solid content of 10% of this pigment is expected to have a pH of 6.5. The slurry having a solid content of 4% is expected to have an isoelectric point (ZetaProbe) of 8.9.

(Example 4):
A slurry of 40% dry solid, silica-containing cationized self-dispersing pigment was added to 300 g of deionized water while stirring continuously with a high speed disperser equipped with a Cowles blade. Created. A 1 N hydrochloric acid solution is added with gentle agitation until pH 5 is reached. The pigment is then dispersed for 10 minutes at 5000 rpm. Reduce speed to 1000 rpm, check pH and maintain by continuing to add 1 normal HCl to pH 5.0 (± 0.2 units) for at least 1 minute. Next, a thin pulp stock containing 0.625% eucalyptus pulp and a commercially available polyamide / polyamine wet strength resin such as Kymene® 617 (WSR, 0.75% dry based on dry pulp) The resin weight) is blended. The pH measurement of the thin pulp material is 5.9. The furnish is assembled by adding 6.4 g of 40% TiO ₂ slurry to 300 g of thin pulp stock with stirring. Using 0.1 normal NaOH, the pH is adjusted upwards to 7.0-7.2. An aliquot of 0.12 g colloidal silica is added with stirring as a yield improver before being added to a commercial handmade paper forming machine (Rapid-Kothen from PTI). The handmade paper produced by this process contained 40% ash and had a basis weight of 101 gsm. This corresponds to a TiO ₂ first pass survival rate of 70%.

Comparative Example 1:
A slurry of DuPont's R-796 + pigment in 35% (w / w) solids in deionized water is treated with 10% sodium hydroxide solution to a pH of 9-9.5. To do. A Cowl's blade is attached to a high-speed disperser, and the slurry is dispersed by operating at 5000 rpm for 10 minutes. Check the pH and keep adding 10% sodium hydroxide for at least 1 minute to maintain a pH of 9.2 (± 0.2 units). 4.3 g of slurry is stirred into a thin pulp stock (300 g) containing 0.625% eucalyptus pulp and Kymene® 617 WSR (0.75% dry resin weight based on dry pulp) Added while. Add another equal amount of WSR, stir for 1 minute, and immediately transfer this paper forming mixture to a commercial handmade paper forming machine (Rapid-Kothen from PTI). The machine automatically forms a sheet and dehydrates the sheet. The formed sheet is removed from the machine and dried at 93 degrees Celsius for 10 minutes under reduced pressure. The basis weight and the proportion of TiO _{2 in} the sheet are then determined. In the above recipe, the amount of TiO ₂ dispersion added to the thin pulp raw material is changed to adjust the proportion of ash and correct the residual rate of the pigment. In this way, a handmade paper sheet having a basis weight of 95 to 100 gsm and 40% ash can be produced.

Claims (23)

A decorative paper comprising a self-dispersing pigment, wherein the self-dispersing pigment has an isoelectric point of at least about 8, more typically from about 8 to about 10, Including the inorganic particles, the outermost processed material in order,
(A) a step of hydrolyzing an aluminum compound or a basic aluminate and depositing a surface of hydrous alumina; and (b) a step of adding a bifunctional compound, wherein the bifunctional compound is:
i. An anchor group linking the bifunctional compound to the surface of the pigment, and ii. A decorative paper prepared by adding a bifunctional compound comprising a basic amine group comprising a primary, secondary, or tertiary amine.   The decorative paper according to claim 1, further comprising an opaque cellulose pulp-based sheet.   The decorative paper according to claim 1, further comprising an impregnating resin.   The decorative paper according to claim 3, wherein the impregnating resin is a phenol resin or a melamine resin. The inorganic _{particles, ZnO, TiO 2, SrTiO 3} , BaSO 4, PbCO 3, BaTiO 3, Ce 2 O 3, Al 2 O 3, CaCO 3, or ZrO _2, the decorative paper according to claim 1. The inorganic particles have a surface area of at least 10 m ² / g, preferably, greater than 15 m ² / g, a self-dispersion TiO ₂ pigment, decorative paper according to claim 5.   The anchor group is a carboxylic acid functional group, a dicarboxylic acid group, an oxoanion functional group, a 1,3-diketone, a 3-ketoamide, a 1,3-diketone derivative, or a 3-ketoamide derivative. Decorative paper as described.   The decorative paper according to claim 7, wherein the carboxylic acid functional group includes acetate or a salt thereof, and the dicarboxylic acid group includes malonate, succinate, glutarate, adipate, or a salt thereof.   The diketone is 2,4-pentanedione, 3- (2-aminoethyl) -2,4-pentanedione, or C-3 substituted with an ammine- or amine-containing functional group or a salt thereof. The decorative paper according to claim 6, which is a derivative of 4-pentanedione.   The decorative paper of claim 7, wherein the oxoanion functional group comprises a substituted phosphate, phosphonate, sulfate, or sulfonate.   The basic amine is ammine; N-alkylamine having 1 to 8 carbon atoms; N-cycloalkylamine having 3 to 6 carbon atoms; N, N-dialkylamine having 2 to 16 carbon atoms; A self-dispersing pigment according to claim 3, comprising an N, N-dicycloalkylamine having 6 to 12 carbon atoms; or a mixture of alkyl and cycloalkyl substituents. The bifunctional compound further includes a linking group _Xn that chemically bonds the anchor group to the basic amine group, and the linking group includes an alkyl chain having 1 to 8 carbon atoms, poly (oxy) Ethylene) or poly (oxypropylene), or a polyetheramine containing a mixture thereof, whereby the linking group has a weight average molecular weight of about 220 to about 2000, and includes carbon atoms, oxygen atoms, nitrogen atoms, phosphorus atoms Or the decorative paper of Claim 6 in which a sulfur atom comprises the coupling | bonding position between the said coupling group and the said anchor group. The bifunctional compound is
(I) an aminomalonate derivative having the following structure:

Wherein X is a linking group that chemically bonds the anchor group to the basic amine group;
R ′ and R ″ are each independently selected from hydrogen, alkyl, cycloalkyl, alkyl-allyl, alkenyl, cycloalkenyl, alkene, alkylene, arylene, alkylarylene, allylalkylene or cycloalkylene;
R ₁ and R ₂ are each independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, alkylene, or cycloalkylene;
n = 0 to 50;
(Ii) an aminosuccinate derivative having the following structure:

Wherein X is a linking group that chemically bonds the anchor group to the basic amine group;
R ′ and R ″ are each independently selected from hydrogen, alkyl, cycloalkyl, alkyl-allyl, alkenyl, cycloalkenyl, alkene, alkylene, arylene, alkylarylene, allylalkylene or cycloalkylene;
R ₁ and R ₂ are each independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, alkylene, or cycloalkylene;
n = 0 to 50;
(Iii) a 2,4-pentanedione derivative having the following structure:

In the formula, X is a linking group that chemically bonds an anchor group to a basic amine group,
R ₁ and R ₂ are each independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, alkylene, and cycloalkylene;
n = 0 to 50; or (iv) a 3-ketobutanamide derivative having the following structure:

In the formula, X is a linking group that chemically bonds an anchor group to a basic amine group,
R ₁ and R ₂ are each independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkene, alkylene, and cycloalkylene;
The decorative paper according to claim 6, wherein n = 0 to 50. The linking group “X” is:
An alkyl chain having 1 to 8 carbon atoms; including (b) poly (oxyethylene) or poly (oxypropylene), or mixtures thereof, whereby the weight average molecular weight of the linking group is from about 220 to about 2000 14. A decorative paper according to claim 13, comprising a polyetheramine copolymer comprising: (c) both an oxoethylene monomer and an oxopropylene monomer. 14. The decorative paper according to claim 13, wherein R ′ and R ″ are hydrogen, methyl, or ethyl, and R ₁ and R ₂ are hydrogen, methyl, ethyl, or propyl.   The decorative paper according to claim 13, wherein the aminomalonate derivative is a methyl ester of 2- (2-aminoethyl) malonic acid or an ethyl ester of 2- (2-aminoethyl) malonic acid.   The decorative paper according to claim 13, wherein the aminosuccinate derivative is a methyl ester of N-substituted aspartic acid or an ethyl ester of N-substituted aspartic acid.   The decorative paper according to claim 13, wherein the 3-ketobutanamide (amide acetate) derivative is ethylenediamineamide or diethylenetriamineamide.   The aluminum compound is made from a salt comprising aluminum chloride, aluminum sulfate, or aluminum nitrate, or mixtures thereof, or the basic aluminate is made from a source comprising sodium aluminate or potassium aluminate. Item 7. A decorative paper according to item 6. The decorative paper according to claim 6, wherein the self-dispersing TiO ₂ pigment further includes at least one oxidation-treated product including aluminum oxide, silicon dioxide, zirconium oxide, cerium oxide, aluminosilicate, or aluminophosphate. .   Using a wet treatment process; using pyrogenic silica deposition on pyrogenic titanium dioxide particles; by co-oxidation of silicon tetrachloride with titanium tetrachloride; or by pyrolysis using doped aluminum alloys 4. The decorative paper of claim 3, wherein the treated silica is formed by a metal oxide treatment (a treatment that is subsequently oxidized to produce volatile metal chlorides deposited on the pigment particles).   The decorative paper according to claim 21, wherein the wet treatment uses a soluble silicate such as sodium silicate or potassium silicate. The self-dispersing titanium dioxide pigment comprises a first oxide layer comprising at least about 4% Al ₂ O ₃ and at least about 1.5% P ₂ O ₅ based on the total weight of the treated pigment; a second layer of at least about 3% of SiO _2, more preferably about 5% to 7% of SiO _2, based on the total weight of pigment processed, at least about 3% of Al ₂ O ₃ and at least The decorative paper according to claim 6, comprising an outermost layer comprising about 5 mmol% of the bifunctional compound.