Fusing Agents Description The present invention relates to a fusing agent, comprising a compound of formula (I), a three-dimensional (3D) printing kit including the compound of formula (I) and a method for three-dimensional (3D) printing, including selectively applying the fusing agent on at least a portion of the build material layer and the use of the compound of formula (I) as almost colourless IR absorbers in 3D printing.

Description of the related art

EP1648686A1 relates to a method of selectively combining particulate material, for ex- ample plastics material by sintering, comprises providing a layer (10) of particulate ma- terial, providing radiation, for example using a radiation source (12), over the layer (10), and varying the absorption of the provided radiation across a selected surface portion of the layer (10) to combine a po-tion of the material of the layer (10). The method may comprise varying radiation absorption by varying the intensity of the radiation incident on the surface portion of the layer (10), or alternatively may comprise varying the radia- tion absorptive properties of the particulate material over the selected surface portion of the layer (10), for example by printing a radiation absorbent material (50, Fig. 5) onto the surface portion.

EP1740367A1 relates to a method and device for production of three-dimensional ob- jects by means of electromagnetic radiation and application of an absorber by means of an ink-jet method.

EP0802178A2 describes Schiff base quinone complexes which are useful as anti-fad- ing agents and filter dyes. The anti-fading agents are applicable to heat developable photosensitive materials, silver halide photosensitive materials, and optical recording materials.

W02007062183 describes a radiation absorbing compound, said compound compris- ing:

, wherein: (a) R ¹ , R ² , R ³ and R ⁴ are independently selected from the group consisting of: alkyl, branched alkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, alkoxy, halogen, dialkyla- mino, polyoxyalkylene, carboxyl, acyl, and hydrogen; and

(b) n is from about 1 to about 4; and (c) wherein the M is selected from one or more of the following: K, Cs, Bi, Sb, Zr, and

Mo and its use for laser welding of thermoplastics and in IR reflecting fabrics..

W02008054550 describes a compound, said compound comprising: wherein:

(a) R ¹ , R ² , R ³ and R ⁴ are independently selected from the group consisting of: alkyl, branched alkyl, cycloalkyl, aryl, substituted aryl, heteroaryl, alkoxy, halogen, dialkyla- mino, polyoxyalkylene, carboxyl, acyl, and hydrogen; and

(b) n is from about 1 to about 4; and

(c) wherein the M comprises in part an element that is selected from one or more of the following: Si, Zr, Bi, Sb, Ce, Cs, K, Mo, especially Si, Zr. They are useful in optical re- cording media, thermal writing display, laser printing, laser filters, IR photography, med- ical applications, plastic reheat, laser welding, laser marking and for protective goggles for welding and for protection from lasers in military applications.

WO2019/199328 discloses a kit for three-dimensional printing comprising:

(I) a perimeter membrane composition comprising: a powder build material; and

(II) a three-dimensional part composition comprising: the powder build material, a fusing agent, and a detailing agent.

It is highly desirable for NIR absorbing compounds used in 3 dimensional (3D) printing to have strong NIR absorbance (absorption maximum at 800 to 1200 nm, especially 900 to 1100 nm) yet have minimal visible light absorbance (i.e. , absorbance between 400 nm and 700 nm). In addition, the NIR absorbing compounds should be thermally stable (high thermal fastness properties) and should not degrade before having ab- sorbed the irradiation.

Examples of the three-dimensional (3D) printing method disclosed herein utilize Multi Jet Fusion Printing (MJFP). During MJFP, a layer of a build material (also referred to as build material particles) is exposed to radiation, but a selected region (in some in- stances less than the entire layer) of the build material is fused and hardened to be- come a layer of a 3D part(s) or object(s). Some fusing agents used in MJFP tend to have significant absorption (e.g., 80%) in the 700 nm - 1400 nm light absorbing range. This absorption generates heat suitable for fusing during 3D printing, which leads to 3D parts having mechanical integrity and rela- tively uniform mechanical properties (e.g., strength, elongation at break, etc.). This ab- sorption, however, results in strongly colored, e.g., black, 3D parts. In some instances, it may not be necessary to generate strongly colored parts. Rather, it may be appropri- ate to generate a part that is clear, white, off-white, or some color other than black.

To meet the MJFP process(es) for a fusing agent and printing colorless or white parts, a near-infrared compound should be physically and chemically stable, compatible with ink vehicles and co-solvents to give a good jetting performance, and colorless after printing and have a high IR absorbance.

The compound(s) should be sufficiently soluble or compatible in the medium in which it is used. Further, the compound should be sufficiently thermally and oxidatively stable to facilitate incorporation and use in the desired application without excessive degrada- tion during the desired lifetime of the absorber.

In a first aspect, the invention relates to a fusing agent, comprising (A) a compound of formula (I), wherein n is an interger of 1 to 4;

R ¹ , R ² , R ³ and R ⁴ are independently of each other a hydrogen atom, a halogen atom, a cyano group, a C ₁ -C ₂₅ alkyl group, a C ₂ -C ₂₅ alkenyl group, a C ₂ -C ₂₅ alkynyl group, a C ₁ - C ₂₅ alkoxy group, a C ₁ -C ₂₄ haloalkyl group, a C ₁ -C ₂₅ alkylcarbonyl group, a C ₁ -C ₂₅ car- bamoyl group, a C ₁ -C ₂₅ acylamino group, a C ₁ -C ₂₅ alkoxycarbonyl group, an optionally substituted C ₃ -C ₁₂ cycloalkyl group, an optionally substituted C ₆ -C ₁₀ aryl group, an op- tionally substituted C ₆ -C ₁₀ -aryloxy, an optionally substituted C ₆ -C ₁₀ -aryl-C ₁ -C ₁₀ -alkylene group, or an optionally substituted C ₂ -C ₉ heteroaryl group, and R ^2’ and R ^3’ are a hydrogen atom, or

R ² and R ^2’ and/or R ³ and R ^3’ together form a group of formula ;

M is selected from Mg, Ca, Sr, Ba, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Ti, Sc, Y, Zr, Hf, V, Mn, Fe, Co, Ni, Cu, Zn, Ce, and the lanthanoides, such as, for example, La, Eu, Pr, Nd, Sm, Gd, Tb, Dy and Yb; especially M is selected from Mg, Ca, Al, Ga, Si, Ge, Ti and the lanthanoides;

R ⁵ has the meaning of R ¹ ;

(B) a fusing agent vehicle; and

(C) optionally one, or more components selected from the group consisting of co-sol- vents), humectant(s), surfactant(s), antimicrobial agent(s), anti-kogation agent(s), and/or chelating agent(s).

In a second aspect, the invention relates to a three-dimensional (3D) printing kit, comprising: a build material including:

(i) a thermoplastic polymer and

(ii) the fusing agent according to the present invention to be applied to at least a portion of the build material composition during 3D printing, the fusing agent including the com- pound of formula (I) to absorb electromagnetic radiation to coalesce the thermoplastic polymer in the at least one portion as well as a method for three-dimensional (3D) printing, comprising:

(i) applying a build material to form a build material layer,

(ii) pre-heating the build material to a temperature ranging from about 50°C to about 400°C; (iii) selectively applying the fusing agent according to the present invention on at least a portion of the build material layer; and

(iv) exposing the build material and the fusing agent to infrared radiation to form the 3D object(s) or part(s) by fusing the build material and the fusing agent; and

(v) repeating (i), (ii), (iii), and/or (iv).

The build material is preferably selected from polyamides (PAs) (e.g., PA 11 / nylon 11 , PA 12 / nylon 12, PA 6 / nylon 6, PA 8 / nylon 8, PA 9 / nylon 9, PA 6,6 / nylon 6,6, PA 6,12 / nylon 6, 12, PA 8, 12 / nylon 8, 12, PA 9, 12 / nylon 9, 12, or combinations thereof); polyethylene, polyethylene terephthalate (PET), and an amorphous variation of these materials; polystyrene, poly-acetals, polypropylene, polycarbonate, polyester, thermal polyurethanes, other engineering plastics, and blends of any two or more of the polymers; and core shell polymer particles of the polymers.

In a third aspect, the invention relates to a consumable material for use in an additive manufacturing system, the consumable material comprising: at least one polymer, at least one compound of formula (I), wherein n, R ¹ , R ² , R ³ , R ^2’ , R ^3’ , R ^2” , R ^3” , R ⁴ and M are defined above, or below.

In a fourth aspect, the invention relates to a consumable assembly for use in an extru- sion-based additive manufacturing system, the consumable assembly comprising: a container portion; a consumable filament at least partially retained by the container portion, the consuma- ble filament comprising: at least one polymer, comprising at least one compound of formula (I), wherein n, R ¹ , R ² , R ³ , R ^2’ , R ^3’ , R ^2” , R ^3” , R ⁴ and M are defined above, or below.

In a fifth aspect, the invention relates to a a method for producing an article by means of an additive manufacturing method from the consumable material according to the present invention, comprising at least temporarily exposing the consumable material according to infrared radiation in the wavelength range between 700 nm and 1700 nm, especially 700 nm to 1300 nm.

In a sixth aspect, the invention relates to an article, obtainable by the method(s) accord- ing to the present invention.

In a seventh aspect, the invention relates to the use of a compound of formula

(I) in 3D printing, wherein n, R ¹ , R ² , R ³ , R ^2’ , R ^3’ , R ^2” , R ^3” , R ⁴ and M are defined above, or below.

The compound of formula (I) is preferably a compound of formula (lb), or

(Ic), wherein

M, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are defined above or below. Compounds of formula (la) are more preferred than compounds of formula (lb) and (Ic). The two substituents R ⁵ in for- mula (lb) and (Ic) can be different, but are preferably the same and are a hydrogen atom, or a C ₁ -C ₂₅ alkyl group.

In a preferred embodiment the present invention is directed to compounds of formula

(la’), wherein M is selected from Mg, Ca, Si, Ge and Ti, especially Mg, Si, Ge and Ti; or compounds of formula (la”), wherein M is a lanthanoide, espe- cially La, Eu, Pr, Nd, Sm, Gd, Tb, Dy and Yb, very especially Pr.

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are defined above, or below. R ¹ , R ² , R ³ and R ⁴ are preferably the same and are a C ₁ -C ₂₅ alkyl group, a C ₅ -C ₇ cycloal- kyl group, a C ₆ -C ₁₀ aryl group, which is substituted by one, two, or three C ₁ -C ₁₂ alkyl groups, or Alternatively, R ¹ and R ² are the same and are a C ₁ -C ₂₅ alkyl group and R ³ and R ⁴ are a hydrogen atom. Alternatively, R ¹ and R ² are the same and are a C ₁ -C ₂₅ alkyl group, R ³ is a cyano group and R ⁴ is a hydrogen atom. Alternatively, R ¹ and R ² are the same and are a C ₁ -C ₂₅ alkyl group, R ³ is a halogen atom and R ⁴ is a hydrogen atom. More preferably, R ¹ , R ² , R ³ and R ⁴ are the same and are a group of formula , wherein R ^c and R ^e are independently selected from a C ₁ -C ₄ alkyl group, and R ^d is H, or a C ₁ -C ₁₂ alkyl group; where the sum of the carbon atoms of the R ^c , R ^d and R ^e radicals is an integer from 3 to 19, a cyclohexyl group, or an adamantyl group. Most preferred, R ¹ , R ² , R ³ and R ⁴ are the same and are an isopropyl group, a tert-amyl group, a 1 ,1 ,3,3-tetramethylbutyl (tert-octyl) group, a 2,2-dimethyl-1-propanyl (neopen- tyl) group, a tert-butyl group, a cyclohexyl group, or an adamantyl group.

The ligand LH in ML _n (= compound of formula (I)) is preferably selected from



Examples of the compounds of formula (la’) and (la”) are shown in the tables below: The compounds of formula (I) are known, or can be prepared according to known pro- cedures. Refrence is made, for example, to W02007062183, W02008054550 and US5925777.

Compounds A-1 to A-12, B-1 to B-12, C-1 to C-12, D-1 to D-12, E-1 to E-12, F-1 to F- 12 and G-1 to G-12 are more preferred than compounds H-1 to H-12 and 1-1 to 1-12.

The particle size distribution of the compound of formula (I) is typically characterized by having a D(v, 0.5) value of most 0.8 pm, in particular at most 0.5 pm and especially at most 0.3 pm, e.g. in the range from 10 to 800 nm, in particular from 10 to 500 nm, more particularly in the range from 10 to 300 nm, as determined by static light scattering. In the suspension, the particles of the compound of formula (I), may however form loose agglomerates and thus the apparent particle size may be larger. However, the particle size distribution of primary particles of the compound of formula (I), which form the ag- glomerate, is usually characterized by having a D(v, 0.5) in the above ranges.

Compounds of formula (I) that are suitable for the inventive fusing agents can be ob- tained e.g. from chemical synthesis or commercial sources having already an appropri- ate particle size distribution as well as a median particle diameter D(v 0.5) in the afore- mentioned ranges. In case the particles of the compound of formula (I) to be used are too coarse, the particle size can be reduced by using established particle communition methods, including in particular communition techniques involving water or an organic solvent and grinding media like beads or inorganic salts. Suitable methods and devices are known and have been described e.g. in Perry's Chemical Engineers' Handbook,

7th ed. McGraw Hill 1997, 20-31 to 20-38, and the literature cited therein, and are com- mercially available, e.g. from Netzsch Feinmahltechnik, FHZ GmbH, Hosokawa-Alpine AG, Willy A. Bachofen AG Maschinenfabrik, Coperion and Buhler GmbH.

The compound of formula (I) present in the suspension of the fusing agent may be sub- jected to a desagglomeration. Thereby agglomerates of the pigment particles contained in the suspension will be broken up. Desagglomeration (sometimes also spelled dis- agglomeration) can be achieved by applying strong shear forces to the suspension, e.g. by using a disperser or homogenizer, such as a disc homogenizers or rotor stator homogenizers, or by applying ultrasound. Suitable homogenizers are well known and commercially available, e.g. from Netzsch Feinmahltechnik or from IKA-Werke GmbH&Co. KG. The application of ultrasound for desagglomeration of particles in the liquid phase has been frequently described e.g. in WO 99/32220 or by U Teipel et al., Int. J. Mineral Processing Vol. 74, Supplement (2004), S183-S190. The desagglomera- tion is typically continued until an particle size distribution as well as a median particle diameter D(v 0.5) within the aforementioned ranges is obtained. The term C ₁ -C ₂₅ alkyl denominates a group of linear or branched saturated hydrocarbon radicals having from 1 to 25 carbon atoms. Examples of alkyl include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylpro- pyl (isopropyl), 1 , 1 -dimethylethyl (tert.-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3- methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1 -dimethyl propyl, 1,2-dime- thylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dime- thylbutyl, 1,2-dimethylbutyl, 1,3-dimethyl butyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, 1 , 1 ,3,3-tetra- methylbutyl (tert-octyl), nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneico- syl, docosyl and in case of nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneico- syl, docosyl their isomers, in particular mixtures of isomers such as "isononyl", "iso- decyl". Examples of C ₁ -C ₄ alkyl are for example methyl, ethyl, propyl, 1-methylethyl, bu- tyl, 1 -methylpropyl, 2-methylpropyl or 1,1 -dimethylethyl.

The term "C ₁ -C ₂₅ haloalkyl" as used herein denotes straight-chain or branched C ₁ -C ₂₅ alkyl as defined above, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms, fluorine, bromine, chlorine or iodine, particularly chlo- rine, or fluorine. Examples are chloromethyl, dichloromethyl, trichloromethyl, fluorome- thyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodi- fluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluo- roethyl, 2,2,2-trichloroethyl and pentafluoroethyl.

The term "C ₁ -C ₂₅ alkoxy" as used herein denotes straight-chain or branched C ₁ -C ₂₅ alkyl as defined above bound to the remainder of the molecule through an oxygen. Exam- ples for C ₁ -C ₄ -alkoxy are methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1- methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy.

The term "C ₁ -C ₁₂ cycloalkyl" as used herein denotes a mono-, bi- or tricyclic cycloalkyl radical which is unsubstituted or substituted by one or more radicals R ^x , for example 1, 2, 3 or 4 R ^x radicals, wherein R ^x is defined below. Examples of C ₃ -C ₁₂ cycloalkyl include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclohexadecyl, 1-adamantyl and norbornyl (= bicyclo[2.2.1]heptyl).

The term "C ₆ -C ₁₀ aryl" as used herein denotes phenyl or naphthyl which is unsubstituted or substituted by one or more radicals R ^x . The term "C ₆ -C ₁₀ aryloxy" as used herein denotes phenoxy and naphthyloxy which is unsubstituted or substituted by one or more radicals R ^x .

The term "alkylene" or "alkanediyl" as used herein denotes a straight-chain or branched alkyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.

The term "C ₆ -C ₁₀ aryl-C ₁ -C ₁₀ alkylene" (which may also be referred to as aralkyl) as used herein refers to C ₆ -C ₁₀ aryl-substituted alkyl radicals having at least one unsubstituted or substituted aryl group, as defined herein. The alkyl group of the aralkyl radical may be interrupted by one or more nonadjacent groups selected from O, S and NR ^y , wherein R ^y is as defined below. C ₆ -C ₁₀ -aryl-C ₁ -C ₁₀ -alkylene is preferably phenyl-C ₁ -C ₁₀ - alkylene, more preferably phenyl-C ₁ -C ₄ -alkylene, for example benzyl, 1-phenethyl, 2- phenethyl, 1-phenprop-1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl, 2-phen- but-1-yl, 3-phenbut-1-yl, 4-phenbut-1-yl, 1-phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl or 4-phenbut-2-yl; preferably benzyl and 2-phenethyl.

The term "heteroaryl" as used herein refers to heteroaromatic, monocyclic, or bicyclic condensed system with 5, 6, 7, 8, 9, 10, 11, or 12 ring members in which at least one of the rings is aromatic and which contains 1, 2, 3 or 4 heteroatoms selected from N, S or O which is unsubstituted or substituted by one or more radicals R ^x . Monocyclic he- taryl groups are preferably 5- or 6-membered hetaryl groups comprising 1 , 2 or 3 het- eroatoms selected from O, S or N such as 2-furyl (furan-2-yl), 3-furyl (furan-3-yl), 2- thienyl (thiophen-2-yl), 3-thienyl (thiophen-3-yl), 1 H-pyrrol-2-yl, 1 H-pyrrol-3-yl, pyrrol-1 - yl, imidazol-2-yl, imidazol-1-yl, imidazol-4-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, py- razol-5-yl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothi- azolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1,2,4- oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thi- adiazol-5-yl, 1,3,4-thiadiazol-2-yl, 4H-[1,2,4]-triazol-3-yl, 1 ,3,4-triazol-2-yl, 1,2,3-triazol- 1 -yl, 1,2,4-triazol-1-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-tria- zin-3-yl. Bicyclic throughout aromatic heteroaryl is 9- or 10-membered and contains 1,

2, 3 or 4 heteroatoms selected from O, S or N. Examples are quinolinyl, isoquinolinyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, benzox- azolyl, benzisoxazolyl, benzthiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, benzotriazinyl.

R ^x is selected from a linear or branched C ₁ -C ₂₅ alkyl group, a linear or branched C ₁ - C ₂₅ fluoroalkyl group, a linear or branched C ₁ -C ₂₅ alkoxy group, fluorine and chlorine, es- pecially a linear or branched C ₁ -C ₁₂ alkyl group. R ^y is hydrogen, a a linear or branched C ₁ -C ₂₅ alkyl group, C3-Ci2cycloalkyl, heteroaryl, or C ₆ -C ₁₀ -aryl.

The compound of formula (I) is present in an amount ranging from about 0.1 wt% to about 10 wt% based on the total weight of the fusing agent.

The co-solvent is present in an amount ranging from about 0 wt% to about 20 wt% based on the total weight of the fusing agent. Some examples of co-solvents can include 2-pyrrolidinone, hydroxyethyl-2-pyrrolidone, diethylene glycol, triethylene glycol, 2-methyl-1, 3-propanediol, tetraethylene glycol, tripropylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol bu- tyl ether, dipropylene glycol butyl ether, triethylene glycol butyl ether, 1,2-hexanediol, 2- hydroxyethyl pyrrolidinone, 2-hydroxyethyl-2-pyrrolidinone, 1,6-hexanediol, and combi- nations thereof.

The balance of the fusing agent is water. As an example, deionized water may be used. The composition of the fusing agents is, for example, described in W02020005200, WO2019245589, WO2019245518, WO2019245517, WO2019245535,

WO20 19245534, WO2019245516 and US2019382429.

Fusing Agent Vehicles As used herein, “FA vehicle” may refer to the liquid in which the compound of formula (I) is dispersed or dissolved to form the fusing agent. A wide variety of FA vehicles, in- cluding aqueous and non-aqueous vehicles, may be used in the fusing agent. In some examples, the FA vehicle may include water alone or a non-aqueous solvent alone with no other components. In other examples, the FA vehicle may include other compo- nents, depending, in part, upon the applicator that is to be used to dispense the fusing agent.

Examples of other suitable fusing agent components include dispersant(s), co-sol- vents), humectant(s), surfactant(s), silane coupling agent(s), antimicrobial agent(s), anti-kogation agent(s), and/or chelating agent(s).

The solvent of the fusing agent may be water or a non-aqueous solvent (e.g., ethanol, acetone, n-methyl pyrrolidone, aliphatic hydrocarbons, etc.). In some examples, the fusing agent consists of the energy absorber and the solvent (without other compo- nents). In these examples, the solvent makes up the balance of the fusing agent. Classes of organic co-solvents that may be used in a water-based fusing agent include aliphatic alcohols, aromatic alcohols, diols, glycol ethers, polyglycol ethers, 2-pyrrol- idones, caprolactams, formamides, acetamides, glycols, and long chain alcohols.

Examples of these co-solvents include primary aliphatic alcohols, secondary aliphatic alcohols, 1 ,2-alcohols, 1 ,3-alcohols, 1 ,5-alcohols, 1 ,6-hexanediol or other diols (e.g.,

1 ,5-pentanediol, 2-methyl-1 ,3-propanediol, etc.), ethylene glycol alkyl ethers, propyl- ene glycol alkyl ethers, higher homologs (C ₆ -C ₁₂ ) of polyethylene glycol alkyl ethers, tri- ethylene glycol, tetraethylene glycol, tripropylene glycol methyl ether, N- alkyl caprolac- tams, unsubstituted caprolactams, both substituted and unsubstituted formamides, both substituted and unsubstituted acetamides, and the like. Other examples of organic co-solvents include dimethyl sulfoxide (DMSO), isopropyl alcohol, ethanol, pentanol, acetone, or the like.

Other examples of suitable co-solvents include water-soluble high-boiling point sol- vents, which have a boiling point of at least 120°C, or higher. Some examples of high- boiling point solvents include 2-pyrrolidone (i.e. , 2-pyrrolidinone, boiling point of about 245°C), 1 -methyl-2-pyrrolidone (boiling point of about 203°C), N-(2- hydroxyethyl)-2- pyrrolidone (boiling point of about 140°C), 2-methyl-1 ,3-propanediol (boiling point of about 212°C), and combinations thereof.

The co-solvent(s) may be present in the fusing agent in a total amount ranging from about 1 wt% to about 50 wt% based upon the total weight of the fusing agent, depend- ing upon the jetting architecture of the applicator. In an example, the total amount of the co-solvent(s) present in the fusing agent is 25 wt% based on the total weight of the fusing agent.

The co-solvent(s) of the fusing agent may depend, in part, upon the jetting technology that is to be used to dispense the fusing agent. For example, if thermal inkjet print- heads are to be used, water and/or ethanol and/or other longer chain alcohols (e.g., pentanol) may be the solvent (i.e. makes up 35 wt% or more of the fusing agent) or co- solvents. For another example, if piezoelectric inkjet printheads are to be used, water may make up from about 25 wt% to about 30 wt% of the fusing agent, and the solvent (i.e., 35 wt% or more of the fusing agent) may be ethanol, isopropanol, acetone, etc. The co-solvent(s) of the fusing agent may also depend, in part, upon the build material composition that is being used with the fusing agent. For a hydrophobic powder (such as a polyamide-like materials), the FA vehicle may include a higher solvent content in order to improve the flow of the fusing agent into the build material composition.

The FA vehicle (fusing agent) may also include humectant(s). In an example, the total amount of the humectant(s) present in the fusing agent ranges from about 3 wt% to about 10 wt%, based on the total weight of the fusing agent. An example of a suitable humectant is ethoxylated glycerin having the following formula: H _a (0CH ₂ CH ₂ )0H ₂ C-H ₂ C(0(CH ₂ CH ₂ 0) _b H)-H ₂ C(0(CH ₂ CH ₂ 0) _c H) in which the total of a+b+c ranges from about 5 to about 60, or in other examples, from about 20 to about 30. An example of the ethoxylated glycerin is LIPONIC® EG-1 (LEG-1, glycereth-26, a+b+c=26, available from Lipo Chemicals).

In some examples, the FA vehicle (fusing agent) includes surfactant(s) to improve the jettability of the fusing agent. Examples of suitable surfactants include a self-emulsifia- ble, non-ionic wetting agent based on acetylenic diol chemistry (e.g., SURFYNOL® SEF from Air Products and Chemicals, Inc.), a non-ionic fluorosurfactant (e.g., CAP- STONE® fluorosurfactants, such as CAPSTONE® FS-35, from Chemours), and com- binations thereof. In other examples, the surfactant is an ethoxylated low-foam wetting agent (e.g., SURFYNOL® 440 or SURFYNOL® CT-111 from Air Products and Chemi- cal Inc.) or an ethoxylated wetting agent and molecular defoamer (e.g., SURFYNOL® 420 from Air Products and Chemical Inc.). Further examples of suitable defoamers that can be used include FoamStar® and Foamaster® defoamers, such as FoamStar® ED 2522, FoamStar® ED 2526, FoamStar® ED 2527, FoamStar® SI 2210, FoamStar® SI 2220, FoamStar® SI 2242, FoamStar® SI 2250, FoamStar® SI 2260, FoamStar® SI 2270, FoamStar® SI 2280, FoamStar® SI 2292, FoamStar® ST 2410, FoamStar® ST 2420, FoamStar® ST 2422, FoamStar® ST 2434, FoamStar® ST 2436, FoamStar®

ST 2438, FoamStar® ST 2439, FoamStar® ST 2445, or FoamStar® ST 2446, espe- cially Foamstar® SI 2280 (available from BASF SE). Still other suitable surfactants in- clude non-ionic wetting agents and molecular defoamers (e.g., SURFYNOL® 104E from Air Products and Chemical Inc.) or water-soluble, non-ionic surfactants (e.g., TERGITOL™ TMN-6, TERGITOL™ 15-S-7, or TERGITOL™ 15-S-9 (a secondary al- cohol ethoxylate) from The Dow Chemical Company or TEGO® Wet 510 (polyether si- loxane) available from Evonik Industries).

The compound of formula (I) may, in some instances, be dispersed with a dispersant. As such, the dispersant helps to uniformly distribute the compound of formula (I) throughout the fusing agent. Examples of suitable dispersants include polymer or small molecule dispersants, charged groups attached to the surface of the compound of for- mula (I), or other suitable dispersants. Some specific examples of suitable dispersants include a water-soluble acrylic acid polymer (e.g., CARBOSPERSE® K7028 available from Lubrizol), water-soluble styrene-acrylic acid copolymers/resins (e.g., JONCRYL© 298, JONCRYL® HPD 396 (styrene acrylic resin solution in MEA (mono-ethanol amine)), JONCRYL® HPD 671 (styrene-acrylic resin), JONCRYL® 678, JONCRYL® 680, JONCRYL® 683, JONCRYL® 690, etc. available from BASF SE), a block copoly- mer with pigment affinic groups, or water-soluble styrene-maleic anhydride copoly- mers/resins, such as, for example, DISPERBYK®-190 (available from BYK), Dispex® Ultra PA 4550, Dispex® Ultra PA 4560, Dispex® Ultra PA 4590, Dispex® Ultra PX 4585, Dispex® Ultra PX 4575, Dispex® 4620, Dispex® AA 4125, Dispex® AA 4135, Dispex® AA 4040 (available from BASF SE).

Whether a single dispersant is used or a combination of dispersants is used, the total amount of dispersant(s) in the fusing agent may range from about 10 wt% to about 200 wt% based on the weight of the compound of formula (I) in the fusing agent.

Whether a single surfactant is used or a combination of surfactants is used, the total amount of surfactant(s) in the fusing agent may range from about 0.01 wt% to about 10 wt% based on the total weight of the fusing agent. In an example, the total amount of surfactant(s) in the fusing agent may be about 3 wt% based on the total weight of the fusing agent.

An anti-kogation agent may be included in the fusing agent that is to be jetted using thermal inkjet printing. Kogation refers to the deposit of dried printing liquid (e.g., fusing agent) on a heating element of a thermal inkjet printhead. Anti- kogation agent(s) is/are included to assist in preventing the buildup of kogation.

A silane coupling agent may also be added to the fusing agent. Examples of suitable silane coupling agents include the SILQUEST® A series manufactured by Momentive. Whether a single silane coupling agent is used or a combination of silane coupling agents is used, the total amount of silane coupling agent(s) in the primer fusing agent may range from about 0.1 wt% to about 50 wt% based on the weight of the compound of formula (I) in the fusing agent.

Examples of suitable anti-kogation agents include oleth-3-phosphate (e.g., commer- cially available as CRODAFOS™ 03A or CRODAFOS™ N-3 acid from Croda), or a combination of oleth-3-phosphate and a low molecular weight (e.g., < 5,000) poly- acrylic acid polymer (e.g., commercially available as CARBOSPERSE™ K- 7028 Poly- acrylate from Lubrizol).

Whether a single anti-kogation agent is used or a combination of anti-kogation agents is used, the total amount of anti-kogation agent(s) in the fusing agent may range from greater than 0.20 wt% to about 0.65 wt% based on the total weight of the fusing agent. In an example, the oleth-3-phosphate is included in an amount ranging from about 0.20 wt% to about 0.60 wt%, and the low molecular weight polyacrylic acid polymer is in- cluded in an amount ranging from about 0.005 wt% to about 0.03 wt%.

The FA vehicle may also include antimicrobial agent(s). Suitable antimicrobial agents include biocides and fungicides. Example antimicrobial agents may include the NU- OSEPT™ (Troy Corp.), UCARCIDE™ (Dow Chemical Co.), ACTICIDE® B20 (Thor Chemicals), ACTICIDE® M20 (Thor Chemicals), ACTICIDE® MBL (blends of 2-methyl- 4-isothiazolin-3-one (MIT), 1 ,2-benzisothiazolin-3-one (BIT) and Bronopol) (Thor Chemicals), AXIDE™ (Planet Chemical), NIPACIDE™ (Clariant), blends of 5-chloro-2- methyl-4-isothiazolin-3-one (CIT or CM IT) and MIT under the tradename KATHON™ (Dow Chemical Co.), and combinations thereof. Examples of suitable biocides include an aqueous solution of 1 ,2-benzisothiazolin-3-one (e.g., PROXEL® GXL from Arch Chemicals, Inc.), quaternary ammonium compounds (e.g., BARDAC® 2250 and 2280, BARQUAT® 50-65B, and CARBOQUAT® 250-T, all from Lonza Ltd. Corp.), and an aqueous solution of methylisothiazolone (e.g., KORDEK® MLX from Dow Chemical Co.).

In an example, the fusing agent may include a total amount of antimicrobial agents that ranges from about 0.05 wt% to about 1 wt%. In an example, the antimicrobial agent(s) is/are a biocide(s) and is/are present in the fusing agent in an amount of about 0.25 wt% (based on the total weight of the fusing agent).

Chelating agents (or sequestering agents) may be included in the FA vehicle to elimi- nate the deleterious effects of heavy metal impurities. Examples of chelating agents in- clude ammonia, disodium ethylenediaminetetraacetic acid (EDTA-Na), ethylene dia- mine tetra acetic acid (EDTA), and methylglycinediacetic acid (e.g., TRILON® M from BASF Corp.).

When a single chelating agent, or a combination of chelating agents is used, the total amount of chelating agent(s) in the fusing agent may range from 0.001 wt% to 2 wt% based on the total weight of the fusing agent. In an example, the chelating agent(s) is/are present in the fusing agent in an amount of about 0.04 wt% (based on the total weight of the fusing agent).

Jetting methods

The method of using the fusing agent can comprise adding the fusing agent described above to a build material deposited on a substrate during 3D printing.

The adding of the fusing agent to the build material can include jetting the fusing agent onto the build material to form a 3D object(s) or part(s).

Jetting the fusing agent to form 3D object(s) or part(s) can include:

((i) applying a build material to form a build material layer,

(ii) pre-heating the build material to a temperature ranging from about 50°C to about 400°C;

(iii) selectively applying the fusing agent according to the present application on at least a portion of the build material layer; and

(iv) exposing the build material and the fusing agent to infrared radiation to form the 3D object(s) or part(s) by fusing the build material and the fusing agent; and

(v) repeating (i), (ii), (iii), and/or (iv). Build Material(s)

The build material can be a powder, a liquid, a paste, or a gel. Examples of build mate- rial can include semi-crystalline thermoplastic materials with a wide processing window of greater than 5°C (e.g., the temperature range between the melting point and the re- crystallization temperature). Some specific examples of the build material can include polyamides (PAs) (e.g., PA 11 / nylon 11 , PA 12 / nylon 12, PA 6 / nylon 6, PA 8 / ny- lon 8, PA 9 / nylon 9, PA 6,6 / nylon 6,6, PA 6,12 / nylon 6, 12, PA 8, 12 / nylon 8, 12, PA 9, 12 / nylon 9, 12, or combinations thereof). Other specific examples of the build material can include polyethylene, polyethylene terephthalate (PET), and an amor- phous variation of these materials. Still other examples of suitable build materials can include polystyrene, polyacetals, polypropylene, polycarbonate, polyester, thermal pol- yurethanes, other engineering plastics, and blends of any two or more of the polymers listed herein. Core shell polymer particles of these materials may also be used.

The build material can have a melting point ranging from about 50°C to about 400°C. As examples, the build material may be a polyamide having a melting point of 180°C, or thermal polyurethanes having a melting point ranging from about 100°C to about 165°C.

The build material can be made up of similarly sized particles or differently sized parti- cles. In some examples, the build material can include particles of two different sizes. The term "size," as used herein with regard to the build material, refers to the diameter of a spherical particle, or the average diameter of a non-spherical particle (e.g., the av- erage of multiple diameters across the particle). In an example, the average size of the particles of the build material can range from about 0.1 pm to about 100 pm, or from about 1 pm to about 80 pm, or from about 5 pm to about 50 pm.

Build Material Additive(s)

In some examples, the build material can include, in addition to polymer particles, a charging agent, a flow aid, or combinations thereof. Charging agent(s) may be added to suppress tribo-charging. Examples of suitable charging agent(s) include aliphatic amines (which may be ethoxylated), aliphatic amides, quaternary ammonium salts (e.g., behentrimonium chloride or cocam idopropyl betaine), esters of phosphoric acid, polyethylene glycol esters, or polyols. Some suitable commercially available charging agents include HOSTASTAT® FA 38 (natural based ethoxylated alkylamine), HOS- TASTAT® FE2 (fatty acid ester), and HOSTASTAT® HS 1 (alkane sulfonate), each of which is available from Clariant Int. Ltd.).

In an example, the charging agent is added in an amount ranging from 0.001 wt% to 5 wt% based upon the total weight of the build material. Flow aid(s) may be particularly beneficial when the particles of the build material are less than 25 pm in size. The flow aid can improve the flowability of the build material by reducing the friction, the lateral drag, and the tribocharge buildup (by increasing the particle conductivity). Examples of flow aids can include tricalcium phosphate (E341 ), powdered cellulose (E460(ii)), magnesium stearate (E470b), sodium bicarbonate (E500), sodium ferrocyanide (E535), potassium ferrocyanide (E536), calcium ferrocya- nide (E538), bone phosphate (E542), sodium silicate (E550), silicon dioxide (E551 ), calcium silicate (E552), magnesium trisilicate (E553a), talcum powder (E553b), sodium aluminosilicate (E554), potassium aluminum silicate (E555), calcium aluminosilicate (E556), bentonite (E558), aluminium silicate (E559), stearic acid (E570), or polydime- thylsiloxane (E900).

The flow aid can be added in an amount ranging from 0.001 wt% to 5 wt% based upon the total weight of the build material.

Layer(s) of the build material can be applied in a fabrication bed of a 3D printer. The applied layer(s) can be exposed to heating, which can be performed to pre-heat the build material. Thus, the heating temperature may be below the melting point of the build material. As such, the temperature selected can depend upon the build material that is used. As examples, the heating temperature may be from about 5°C to about 50°C below the melting point of the build material. In an example, the heating tempera- ture can range from about 50°C to about 400°C. In another example, the heating tem- perature can range from about 150°C to about 170°C.

Pre-heating the layer(s) of the build material may be accomplished using any suitable heat source that exposes all of the build material to the heat.

Examples of the heat source can include a thermal heat source or an electromagnetic radiation source (e.g., infrared (IR), microwave, or combination thereof).

After pre-heating the layer(s) of the build material, the fusing agent herein can be se- lectively applied on at least a portion of the build material in the layer(s).

The fusing agent described herein can be dispensed from an inkjet printhead, such as a thermal inkjet printhead or a piezoelectric inkjet printhead. The printhead can be a drop-on-demand printhead or a continuous drop printhead.

The printhead may include an array of nozzles through which drops of the fusing agent described herein can be ejected. In some examples, printhead can deliver variable size drops of the fusing agent.

Before or after selectively applying the fusing agent described herein on the portion(s) of the build material, colored ink(s) can be applied to portion(s) of the build material. After the fusing agent and in some instances the colored ink(s) are selectively applied in the specific portions of the layer(s) of the build material, the entire object(s) or part(s) is exposed to infrared radiation.

The infrared radiation can be emitted from a radiation source, such as an I R (e.g., near-IR) curing lamp, or IR (e.g., near-IR) light emitting diodes (LED), or lasers with specific IR or near-IR wavelengths. Any radiation source may be used that emits a wavelength in the infrared spectrum, for example near-infrared spectrum. The radiation source may be attached, for example, to a carriage that also holds the printhead(s).

The carriage may move the radiation source into a position that is adjacent to the fabri- cation bed containing the 3D printed object(s) or part(s). The radiation source may be programmed to receive commands from a central processing unit and to expose the layer(s) of the build material including the fusing agent to the infrared radiation.

The length of time the radiation is applied for, or energy exposure time, may be de- pendent, for example, on characteristics of the radiation source, characteristics of the build material, and/or characteristics of the fusing agent(s).

The fusing agent described herein can enhance the absorption of the radiation, convert the absorbed radiation to thermal energy, and promote the transfer of the thermal heat to the build material in contact therewith. In an example, the fusing agent can suffi- ciently elevate the temperature of the build material above the melting point(s), allowing curing (e.g., sintering, binding, or fusing) of the build material particles to take place. The completed 3D printed object(s) or part(s) may be removed from the fabrication bed and any uncured build material may be removed from the 3D part(s) or object(s). The uncured build material may be washed and then reused.

3D Printing Using Fusing Agent(s)

A 3D printing system for forming the 3D object(s) or part(s) can include a supply bed (including a supply of the build material described above), a delivery piston, a roller, a fabrication bed (having a contact surface), and a fabrication piston. Each of these phys- ical elements may be operatively connected to a central processing unit of the 3D print- ing system. The central processing unit (e.g., running computer readable instructions stored on a non- transitory, tangible computer readable storage medium) can manipu- late and transform data represented as physical (electronic) quantities within the print- er's registers and memories in order to control the physical elements to create the 3D object(s) or part(s). The data for the selective delivery of the build material described above and the fusing agent described above may be derived from a model of the 3D object(s) or part(s) to be formed.

The delivery piston and the fabrication piston may be the same type of piston, but are programmed to move in opposite directions. In an example, when a first layer of the 3D object(s) or part(s) is to be formed, the delivery piston may be programmed to push a predetermined amount of the build material out of the opening in the supply bed and the fabrication piston may be programmed to move in the opposite direction of the de- livery piston in order to increase the depth of the fabrication bed. The delivery piston can advance enough so that when the roller pushes the build material into the fabrica- tion bed and onto the contact surface, the depth of the fabrication bed is sufficient so that a layer of the build material may be formed in the bed. The roller can be capable of spreading the build material into the fabrication bed to form the layer, which is relatively uniform in thickness. In an example, the thickness of the layer can range from about 1 pm to about 1000 pm, although thinner or thicker layers may also be used.

The roller can be replaced by other tools, such as a blade that may be used for spread- ing different types of powders, or a combination of a roller and a blade.

After the layer of the build material is deposited in the fabrication bed, the layer can be exposed to heating. Heating can be performed to pre-heat the build material, and thus a heating temperature below the melting point of the build material can be useful. As such, the temperature selected can depend upon the build material that is used. As ex- amples, the heating temperature may be from about 5°C to about 50°C below the melt- ing point of the build material. In an example, the heating temperature can range from about 50°C to about 400°C. In another example, the heating temperature can range from about 150°C to about 170°C.

Pre-heating the layer of the build material may be accomplished using any suitable heat source that exposes all of the build material in the fabrication bed to the heat. Ex- amples of the heat source include a thermal heat source or an electromagnetic radia- tion source (e.g., infrared (IR), microwave, or combinations thereof).

After pre-heating the layer, the fusing agent can be selectively applied on a portion of the build material in the layer. The fusing agent may be dispensed from an inkjet print- head. One or multiple printheads may be used that span the width of the fabrication bed. The printhead may be attached to a moving XY stage or a translational carriage that moves the printhead adjacent to the fabrication bed in order to deposit the fusing agent in targeted area(s). The printhead may be programmed to receive commands from the central processing unit and to deposit the fusing agent according to a pattern of a cross-section for the layer of the 3D object(s) or part(s) that is to be formed. As used herein, the cross-section of the layer of the object(s) or part(s) to be formed refers to the cross-section that is parallel to the contact surface.

In an example, the printhead can selectively apply the fusing agent on those portion(s) of the layer that are to be fused to become the first layer of the 3D object(s) or part(s). As an example, if the first layer is to be shaped like a cube or cylinder, the fusing agent can be deposited in a square pattern or a circular pattern, respectively, on at least a portion of the layer of the build material.

Examples of fusing agents include water-based dispersions having a compound of for- mula (I) (e.g., an active material). The dye or pigment in the fusing agent can include any color in addition to the compound of formula (I) described hereinabove.

The aqueous nature of the fusing agent can allow the fusing agent to penetrate, at least partially, into the layer of the build material. The build material may be hydropho- bic, and the presence of a co-solvent and/or a surfactant in the fusing agent may assist in obtaining wetting behavior.

It is to be understood that a single fusing agent may be selectively applied to form the layer of the 3D object(s) or part(s), or multiple fusing agents may be selectively applied to form the layer of the 3D object(s) or part(s). After the fusing agent is/are selectively applied on the targeted portion(s), a detailing agent may be selectively applied on the same and/or on different portion(s) of the build material. The detailing agent can include a colorant, a surfactant, a co-solvent, and a balance of water. In some examples, the detailing agent can include these compo- nents, and no other components. In some instances, the detailing agent can exclude specific components, such as additional colorants (e.g., pigment(s)). In some other ex- amples, the detailing agent can further include an anti-kogation agent, a biocide, or combinations thereof. The detailing agent can prevent or reduce cosmetic defects (e.g., color and white patterns) by adding the colorant, which diffuses into and dyes the build material particles at least at the edge boundary.

The colorant in the detailing agent may be a dye of any color having substantially no absorbance in a range of 650 nm to 2500 nm. By "substantially no absorbance" it is meant that the dye absorbs no radiation having wavelengths in a range of 650 nm to 2500 nm, or that the dye absorbs less than 10% of radiation having wavelengths in a range of 650 nm to 2500 nm. The dye can also be capable of absorbing radiation with wavelengths of 650 nm or less. As such, the dye in the detailing agent can absorb at least some wavelengths within the visible spectrum, but absorb little or no wavelengths within the near-infrared spectra. This is in contrast to the active material in the fusing agent, which can absorb wavelengths within the near-infrared spectra. As such, the colorant in the detailing agent may not substantially absorb the fusing radiation, and thus may not initiate melting and fusing of the build material in contact therewith when the layer is exposed to the fusing radiation.

The above 3D printing stages can be repeated in different orders to obtain the 3D printed object(s) or part(s). After the application or desired lifetime, remainders of the absorber can easily be photobleached by means of a laser or any other suitable light source.

In some examples, the detailing agent described above can be the same as the col- ored ink(s) described above.

Unless otherwise stated, references herein to "wt%" of a component are to the weight of that component as a percentage of the whole composition comprising that compo- nent.

In addition, the present invention is directed to a consumable material for use in an ad- ditive manufacturing system, the consumable material comprising: at least one polymer comprising:

at least one compound of formula (I), wherein n, R ¹ , R ² , R ³ , R ^2’ , R ^3’ , R ^2” , R ^3” , R ⁴ and M are defined above.

In addition, the present invention is directed to a consumable assembly for use in an extrusion-based additive manufacturing system, the consumable assembly comprising: a container portion; a consumable filament at least partially retained by the container portion, the consuma- ble filament comprising: at least one polymer, at least one compound of formula (I), wherein n, R ¹ , R ² , R ³ , R ^2’ , R ^3’ , R ^2” , R ^3” , R ⁴ and M are defined above.

The consumable filament may have a core comprising the at least one polymer and a coating comprising the at least one compound of formula (I).

The at least one polymer may be a meltable polymer which is selected from the group consisting of polyurethane, polyester, polyalkylene oxide, plasticized PVC, polyamide, protein, PEEK, PEAK, polypropylene, polyethylene, thermoplastic elastomer, POM, polyacrylate, polycarbonate, polymethylmethacrylate, polystyrene or a combination of at least two of these.

A method for producing an article by means of an additive manufacturing method from the consumable material comprises at least temporarily exposing the consumable material to infrared radiation in the wavelength range between 700 nm and 1700 nm, especially 700 nm to 1200 nm.

The present invention is also directed to an article obtainable by the method.

If a standard test is mentioned herein, unless otherwise stated, the version of the test to be referred to is the most recent at the time of filing this patent application.

All amounts disclosed herein and in the examples below are in wt% unless indicated otherwise.

To further illustrate the present disclosure, examples are given herein. It is to be under- stood that these examples are presented for illustrative reasons and are not to be con- strued as limiting the scope of the present disclosure.

Examples Example 1

4.0 g of compound A-1 , 1.0 g Dispex® Ultra PX 4585 and 75 g Joncryl 678 (99%) were dispersed in a Skandex apparatus (Co. Lau, Type: BA-S 20, DA-S 200) with 110 g sili- con aluminium zirconium mixed oxide (SAZ) beads (ø 1.0-1.25 mm) in a 200 mL jar for 90 min. After cooling to room temperature the beads were filtered of and the mill base diluted to 1% pigment concentration of compound A-1. A drawdown was prepared with a 12 or 24 pm spiral wirebar on PET foil and paper (Algro Finess 2000, 70 g/m ² (Sappi Alfeld GmbH)). The achieved film showed a strong IR absorption.

Suitable dispersing additives: Dispex® Ultra PA 4550, Dispex® Ultra PA 4560,

Dispex® Ultra PA 4590, Dispex® Ultra PX 4585, Dispex® Ultra PX 4575, Dispex® 4620, Dispex® AA 4125, Dispex® AA 4135, Dispex® AA 4040.

Compound A-1 may be replaced by compound B-1, or compound C-1.

Example 2

4.0 g of compound A-1 and 75 g Joncryl 678 (99%) were dispersed in a Skandex appa- ratus (Co. Lau, Type: BA-S 20, DA-S 200) with 110 g silicon aluminium zirconium mixed oxide (SAZ) beads (ø 1.0-1.25 mm) in a 200 mL jar for 90 min. After cooling to room temperature the beads were filtered of and the mill base diluted to 1% pigment concentration of compound A-1. A drawdown was prepared with a 12 or 24 pm spiral wirebar on PET foil and paper (Algro Finess 2000, 70 g/m ² (Sappi Alfeld GmbH)). The achieved film showed a strong IR absorption.

Compound A-1 may be replaced by compound B-1, or compound C-1.

Further fusing agents are shown in the table below.

Joncryl® product(s) available from BASF. Surfynol® SEF is available from Air Prod- ucts. Crodafos™ is available from Croda. Trilon® M is available from BASF. Proxel® GXL is available from Arch Chemicals. Kordex® ML is available from the Dow Chemi- cal Company.

Water based formulation of an IR absorber for 3D printing Formulation A:

Cpd. G-1 was dispersed by help of SAZ beads in 15.5% pigment concentration in an ink consisting of 19% Joncryl® HPD 671 in triethylene glycol, ammonia and water (pH about 9.5). After dispersing the ink was diluted with a let down varnish consisting of 24% Joncryl® HPD 671 in ammonia and water to a 1% pigment concentration. A draw- down (14 pm spiral wirebar) was prepared on algro finess paper.

Formulation B:

Cpd. G-1 was premixed with 19% Dispex® Ultra PX 4585 and 4% Foamstar® SI 2280, then dispersed by help of SAZ beads in 15% pigment concentration in an ink consisting of 20% Joncryl HPD 671 in triethylene glycol, ammonia and water (pH about 9.5). After dispersing the ink was diluted with a let down varnish consisting of 24% Joncryl® HPD 671 in ammonia and water to a 1% pigment concentration. A drawdown (14 pm spiral wirebar) was prepared on algro finess paper. Comparison of formulation A and B in remission at 770 nm:

Formulation Relative IR absorption Formulation A 100%

Formulation B 107%

Formulation, containing Dispex® Ultra PX 4585, show higher IR absorption.

Formulation C: Cpd. 1-1 was premixed with 0.5% Foamstar® ED 2522, then dispersed by help of SAZ beads in 17% pigment concentration in an ink consisting of 20% Joncryl HPD 396 MEA in triethylene glycol and water. After dispersing the ink was diluted with a let down var- nish consisting of 26% Joncryl® HPD 396 MEA in ammonia and water to a 1% pigment concentration. A drawdown (14 pm spiral wirebar) was prepared on algro finess paper. Formulation D:

Cpd. 1-1 was premixed with 3.5% Dispex® Ultra PX 4585 and 0.5% Foamstar® ED 2522, then dispersed by help of SAZ beads in 16% pigment concentration in an ink consisting of 20% Joncryl® HPD 396 MEA in triethylene glycol and water. After dis- persing the ink was diluted with a let down n varnish consisting of 26% Joncryl® HPD 396 MEA in water to a 2% pigment concentration. A drawdown (14 pm spiral wirebar) was prepared on algro finess paper.

Comparison of formulation C and D in remission at 840 nm:

Formulation Relative I R ab- sorption

Formulation C 100%

Formulation D 102%

Formulation D, containing Dispex® Ultra PX 4585, show higher IR absorption.

Formulation E:

Cpd. D-1 was premixed with 3% Dispex Ultra® PX 4585 and 0.4% Foamstar® ED 2522, then dispersed by help of SAZ beads in 15% pigment concentration in an ink consisting 19% Joncryl® HPD 671 in triethylene glycol, ammonia and water (pH about 9.5). After dispersing the ink was diluted with a let down varnish consisting of 26% Joncryl® HPD 671 in water to a 2% pigment concentration. A drawdown (14 pm spiral wirebar) was prepared on algro finess paper.

Formulation F:

Cpd. D-1 was premixed with 3.5% Dispex Ultra® PX 4585 and 0.5% Foamstar® ED 2522, then dispersed by help of SAZ beads in 16% pigment concentration in an ink consisting of 16% Joncryl® HPD 396 MEA in triethylene glycol and water. After dis- persing the ink was diluted with a let down varnish consisting of 26% Joncryl® HPD 396 MEA in water to a 2% pigment concentration. A drawdown (14 pm spiral wirebar) was prepared on algro finess paper.

Comparison of formulation C and D in remission at 810 nm:

Formulation Relative I R ab- sorption

Formulation F 100%

Formulation E 108%

Formulation E, containing Dispex® Ultra PX 4585 and Joncryl® HPD 671, show higher IR absorption.