TWI804118B - Actinic radiation-curable compositions containing polyamide - Google Patents

Abstract

Polyamide is combined with one or more actinic radiation-curable compounds to provide compositions, in particular compositions which are liquid at room temperature or which are gels at room temperature but liquids at higher temperatures, which can be cured by exposure to actinic radiation such as UV or visible light to provide articles having improved properties, such as a higher energy at break value, as a result of the inclusion of the polyamide. Such actinic radiation-curable compositions are particularly useful as resins in additive manufacturing processes.

Description

Actinic radiation curable composition comprising polyamide

field of invention

This invention relates to polyamide-containing compositions which can be cured using actinic radiation to provide useful articles, including three-dimensional articles prepared using additive manufacturing techniques.

Background of the invention

Traditionally, three-dimensional (3D) printing techniques of the "fused deposition modeling" type have used thermoplastic resins. The use of such resins limits the achievable resolution to the width of the polymer bead that can be laid. Furthermore, the adhesion between successively printed layers of articles made using thermoplastic resins and 3D printing methods is poor because the mobile polymer chains in the active layer (the printed layer) cannot match the glassy state in the layer before cooling. The polymer chains rewind together, creating a mechanical weakness. While photocurable acrylic systems represent another type of resin that has been used for 3D printed items, such systems typically have a high crosslink density when cured. This produces articles that are poorly resistant to sudden applied stresses and strains, leading to brittle fracture. Therefore, photocurable acrylic resin systems are mainly used only for prototyping applications.

Therefore, great attention will be paid to the development of resin systems for 3D printing and other additive manufacturing applications that alleviate the above-mentioned deficiencies of known thermoplastic resins and photocurable acrylic formulations.

U.S. Patent No. 4,384,011 discloses a radiation-curable resin coating composition, which comprises a specific ratio of soluble polyamide resin dissolved in a solvent and a radiation-polymerizable monomer or the like; and such compositions are used in the production of Use in methods for resin gravure printing plates. Soluble polyamides suitable for such uses include polyamides that have been modified by various types of reactions. In addition, the amount of soluble polyamide resin is relatively high relative to the amount of radiation polymerizable monomeric compound (100 parts by weight soluble polyamide resin to 50-100 parts by weight of radiation polymerizable monomeric compound).

WO 2018/033296 A1 discloses a polymerization-induced phase separation (PIPS) composition for enhancing impact resistance and rheological properties in photocurable resins for 3D printing, such as inks, coatings and adhesives. Such compositions are advantageous in properties such as impact resistance, shear adhesion, and bond strength. The PIPS composition may include components X, Y, and Z, wherein X includes an acrylic monomer; Y includes a copolymer of block A and block B; and Z includes a multifunctional crosslinker. Block copolymers comprising polyamide blocks are not disclosed.

EP 0919873 B1 discloses a photocurable resin composition comprising (A) an acid-modified vinyl-containing epoxy resin; (B) an elastomer (which may be a polyamide-based elastomer); (C) a photopolymerization initiator; (D) a diluent; and (E) a curing agent, and the photocurable resin composition can produce an efficient cured film.

JP 2676662 B2 discloses a photocurable film prepared under low exposure by uniformly dissolving photosensitive aramid and a photopolymerization initiator in an organic solvent substantially composed of a specific polyether compound. The photosensitive polyamide-containing composition is coated on a base material and the coating is dried to form a photosensitive film (dry film) containing photosensitive aromatic polyamide and a photopolymerization initiator. The film is photocured by light irradiation.

Summary of the invention

One aspect of the present invention provides an actinic radiation curable composition comprising: a) at least one polyamide free of actinic radiation curable functional groups; and b) at least one actinic radiation curable compound, wherein the at least one actinic radiation curable compound is liquid at 25°C; Where condition i), condition ii) or condition iii) is satisfied: i) the at least one polyamide is unmodified polyamide or a combination of unmodified polyamides, and the at least one polyamide is completely soluble in the actinic radiation curable composition at 25°C in the thing; ii) at least a portion of the at least one polyamide is present as particles dispersed in the actinic radiation curable composition at 25°C; iii) The actinic radiation curable composition is a gel at 25°C and a liquid at 100°C or higher.

The present invention also provides a method of manufacturing a cured polymer material, wherein the method comprises curing the above-mentioned actinic radiation curable composition with actinic radiation. The cured polymeric material obtained according to these methods is another aspect of the invention.

The present invention further provides a method of manufacturing a three-dimensional article by additive manufacturing, such as by three-dimensional printing, comprising manufacturing a three-dimensional article using the above-mentioned actinic radiation curable composition; and manufactured by such methods three-dimensional objects.

The actinic radiation curable composition of the present invention may be in the form of a homogeneous solution of polyamide in a liquid matrix of one or more actinic radiation curable compounds. In other embodiments, at least a portion of the polyamide may be in the form of particles dispersed in a liquid matrix of one or more actinic radiation curable compounds. Actinic radiation curable compositions can be rapidly cured using photochemical 3D printing techniques to provide high resolution articles with improved mechanical characteristics due to the presence of polyamide as a component of the composition.

Detailed Description of the Preferred Embodiment Exemplary Features of Actinic Radiation Curable Compositions

According to a desirable aspect of the invention (specifically, wherein the actinic radiation curable composition is intended for use in a manufacturing process carried out at ambient temperature, such as an additive manufacturing process), the actinic radiation curable composition is formulated such that It is liquid at 25°C. For example, the actinic radiation curable composition may be a homogeneous liquid at 25°C. However, in other embodiments, the actinic radiation curable composition is formulated such that it is a gel at 25°C, but a liquid at higher temperatures (eg, 120°C).

In embodiments where one or more polyamides are used in the composition that are normally solid at 25°C, the polyamides are completely soluble in the other components of the actinic radiation curable composition. However, according to other aspects of the invention, particles of at least one polyamide are dispersed in a liquid matrix consisting of at least one actinic radiation curable compound. The polyamide component of the composition may be completely or only partially insoluble at 25°C. For example, according to various embodiments of the invention, 0%, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% by weight at 25°C %, at least 90% or 100% of the polyamide component is insoluble. In embodiments where at least a portion of the polyamide component is in the form of undissolved dispersed particles, such particles can be stably dispersed in a liquid matrix of at least one actinic radiation curable compound. The stability of the dispersion can be improved by using a dispersant and/or modifying the polyamide (eg, by modifying the polyamide to introduce functional groups that help stabilize the dispersed polyamide particles). In general, the particle size of the dispersed polyamide particles is preferably kept relatively small, for example, a d50 value of less than 300 μm, less than 250 μm or less than 200 μm and/or a D90 value of less than 400 μm, less than 350 μm or less than 300 μm.

According to a preferred embodiment of the present invention, the actinic The radiation curable composition has a viscosity at 25°C of not more than 100,000 mPa.s, not more than 50,000 mPa.s, not more than 25,000 mPa.s, not more than 10,000 mPa.s, or not more than 5000 mPa.s. Relatively high viscosities may provide satisfactory performance in applications where the curable composition is heated above 25°C, such as in three-dimensional printing operations using machines with heated resin tanks or the like.

The actinic radiation curable composition is converted to a polymeric material upon curing by exposure to an effective amount of actinic radiation, such as ultraviolet or visible light or electron beam radiation. The appearance of the polymeric material can be transparent (transparent), translucent or opaque. Polyamide particles visible to the human eye may be present in a polymeric matrix derived from an actinic radiation curable compound. Polyamides create domains within polymer materials that are invisible to the human eye. For example, a polymeric material may comprise two phases, one phase being polyamide and the other phase being the cured reaction product of one or more actinic radiation curable compounds. Polyamides can also be molecularly dispersed within the polymeric material. For example, a polymeric material may comprise an interpenetrating polymer network. Polyamide

The actinic radiation curable compositions of the present invention comprise one or more polyamides. As used herein, the term "polyamide" refers to a polymer in which amide linkages (-C(=O)NH-) occur along the molecular chain (ie, along the polymer backbone). However, as will be explained in more detail subsequently, the polymer backbone may additionally contain one or more other types of linkages than amide linkages, such as ether linkages and/or ester linkages. In particular, the composition comprises at least one functional group that does not contain any actinic radiation curable functional groups (i.e., functional groups capable of reacting upon exposure to actinic radiation such that the polyamide is covalently incorporated into the polymer matrix, which The polymer matrix is polyamide formed by actinic radiation-induced curing of at least one actinic radiation-curable compound, such as a (meth)acrylate-functional compound, additionally present in the composition. However, in certain embodiments, the actinic radiation curable composition may additionally comprise at least one polyamide bearing at least one actinic radiation curable functional group.

According to certain embodiments, the polyamides that do not contain any actinic radiation curable functional groups (sometimes referred to herein as "non-functionalized polyamides") are aliphatic polyamides. The non-functionalized polyamide may, for example, have a number average molecular weight of at least 5000 g/mol, at least 10,000 g/mol, at least 15,000 g/mol or at least 20,000 g/mol. In other embodiments, the number average molecular weight of the non-functionalized polyamide is no greater than 150,000 g/mol, no greater than 100,000 g/mol, or no greater than 75,000 g/mol. For example, the non-functionalized polyamides used in the present invention may have a number average molecular weight of 10,000 to 100,000 g/mol. The number average molecular weight Mn is measured here according to ISO 16014-1:2012 using gas permeation chromatography (GPC). The product was dissolved in hexafluoropropan-2-ol stabilized with 0.05 M potassium trifluoroacetate and maintained at a concentration of 1 g/L for 24 hours at ambient temperature. The resulting solution was then filtered on a PTFE membrane (0.2 µm porosity) and injected at a flow rate of 1 mL/min in a liquid chromatography system equipped with a set of columns PFG from Polymer Standards Service. The set of columns consisted of a pre-column (50×8 mm in size), a 1000Å column (300×8 mm in size, 7 μm in particle size) and a 100Å column (300×8 mm in size, 7 μm in particle size). Detection is performed using refractive index measurements. The measured molecular weights are given as PMMA equivalents (for calibration).

Polyamides suitable for use in various aspects of the present invention may be modified polyamides. In various other aspects, polyamides that are unmodified polyamides are utilized. Combinations of one or more unmodified polyamides and one or more modified polyamides may also be employed. As used herein, the term "modified polyamide" means a polyamide modified by a chemical reaction to introduce new functional groups or substituents after being produced in a polymerization reaction. Generally, polymerization to form polyamides involves a condensation reaction involving the reaction of one or more polyamines with one or more polycarboxylic acids (or their equivalents); a condensation reaction involving monomers substituted with amine and carboxylic acid groups; or a ring Ring-opening polymerization of lactams. Thus, an "unmodified polyamide" is a polyamide obtained directly by means of a polymerization reaction and not reacted further in such a way as to introduce new functional groups or substituents into the polymer. Such unmodified polyamides are considered modified polyamides if they are subsequently reacted with one or more reagents in such a way as to effect a chemical transformation.

In certain embodiments of the present invention, the actinic radiation curable composition is a homogeneous liquid at 25° C., wherein the non-functionalized polyamide utilized is made completely soluble in the other components of the composition (specifically, One or more actinic radiation curable compounds are present in the composition completely soluble). In such embodiments, the polyamide and the actinic radiation curable compound or mixture of actinic radiation curable compounds may be selected to have solubility parameters capable of providing the actinic radiation curable composition in the form of a homogeneous liquid. However, in other embodiments, the polyamide has only limited solubility at 25°C in the actinic radiation curable composition. In other embodiments, the non-functionalized polyamide is insoluble at 25°C in the other components of the actinic radiation curable composition. In an embodiment where the polyamide is not completely dissolved, the undissolved polyamide or its undissolved portion may exist in the composition in the form of particles, such as dispersed particles, at 25°C.

According to certain advantageous embodiments of the present invention, the actinic radiation curable compound or mixture of actinic radiation curable compounds used as component (b) of the actinic radiation curable composition is selected on the basis of its Hansen solubility parameter, These parameters reflect the physicochemical solubility properties of organic substances, also known as solvating power. Hansen Solubility Parameters can be proposed based on the work of Charles Hansen entitled "Hansen Solubility Parameters: A user's handboo", Second Edition (2007) Boca Raton, Fla.: CRC Press. ISBN 978-O-8493-7248-3 method to calculate. According to this method, three parameters (referred to as "Hansen parameters": _δd , _δp , and _δh ) are sufficient to predict the behavior of a solvent with respect to a given molecule. The parameter δ _d (in MPa ^1/2 ) quantifies the energy of the dispersion force (ie, the van der Waals force) between molecules. The parameter δ _p (in MPa ^1/2 as the unit) represents the energy of the dipole interaction between molecules. Finally, the parameter δ _h (in MPa ^1/2 ) quantifies the energy from intermolecular hydrogen bonds, ie the ability to interact via hydrogen bonds. The sum of the squares of the three parameters is equivalent to the square number of the Hildebrand solubility parameter (δ _tot ). As is known in the art, the Hansen solubility parameter can be used as a way to predict whether one material will dissolve in another material and form a solution. It is based on the concept of "like compatible", wherein a molecule is defined to be "similar" to another molecule if it is bonded to itself in a similar manner. Therefore, the three Hansen solubility parameters can be treated as coordinates in three-dimensional (Hansen) space. The closer together two molecules are in this Hansen space, the more likely they are to form a solution together. The inventors have found that the dispersion parameters δ _d of the non-functionalized polyamide component a) and the actinic radiation curable component b) are sufficiently similar that the Hildebrand solubility parameters for each component depend primarily on δ _p and δ _h , thus, if these parameters are plotted against each other in two-dimensional space, it indicates the solubility of the non-functionalized polyamide component a) in the actinic radiation curable component b).

Where appropriate, all compounds shown on the drawings are suitable as components (a) and (b); other compounds not shown on the drawings (including, for example, other grades of ^PEBAX® elastomers) are also suitable as component (a) and (b). In certain embodiments of the present invention, component (a) and component (b) may have a Hansen solubility parameter δ _p of 7 to 10 MPa ^1/2 and a Hansen solubility parameter of 4.5 to 8.5 MPa ^1/2 δ _h . According to these embodiments and referring to the figures, component (a) can be at least one of PEBAX® 2533, polyamide 12 (PA12), PEBAX® 3533, PEBAX® 4033 and PEBAX® 7433, and component (b ) can be at least one of SR217, SR420, SR423D, SR506D, SR9075, SR504D, SR567P, SR261, SR789, SR285, SR239EU, and CN1964CG. All such products are commercially available from their assignees.

In certain embodiments, the actinic radiation curable composition can be a gel at 25°C, which can be heated (for example, to 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, or 140°C). °C) and/or when combined with a suitable non-reactive solvent or combination of non-reactive solvents. As used herein, the term "gel" can be defined as a colloidal system in which the dispersed phase is liquid and the dispersion medium is solid. A gel can be an immobile semisolid, in other words, it does not flow under its own weight. At 25°C, the gel may be homogeneous, transparent and/or flexible. The actinic radiation curable composition can be heated to reduce its viscosity, for example during a 3D printing operation, to facilitate handling. According to certain embodiments, the actinic radiation curable composition may be maintained in a chamber or tank and heated to a temperature to reduce the viscosity of the actinic radiation curable composition. For example, the actinic radiation curable composition may be heated to a temperature above the melting point of component a).

According to certain embodiments, the composition comprises at least one thermoplastic polyamide. In other embodiments, the composition includes at least one polyamide that is a thermoplastic elastomer.

According to various aspects of the invention, the non-functionalized polyamide may be a linear polyamide. However, branched polyamides may also be used. Non-functionalized polyamides can have end groups that are carboxylic acid groups, amine groups, or both carboxylic acid groups and amine groups. In addition to actinic radiation curable end groups such as (meth)acrylate end groups, other types of end groups may also or alternatively be present.

Non-functionalized polyamides suitable for use in the present invention include any of the homopolyamides and copolyamides known in the art, such as polyamide 6,6, polyamide 6,10, polyamide 6,10, Amide 10,10, Polyamide 6,12, Polyamide 4,6, Polyamide 6, Polyamide 11, and Polyamide 12.

Block copolymers consisting of at least one polyamide block are also suitable as non-functionalized polyamides in the present invention. Such block copolymers additionally comprise at least one block that is not a polyamide block (hereinafter sometimes referred to as a non-polyamide block), such as at least one polyester block, at least one polyether-ester block, segment, at least one polyether block or at least one polyorganosiloxane block. At least one polyamide block may constitute a "hard" block (e.g., a block having a glass transition temperature (Tg) of 30° C. or greater), while at least one block other than a polyamide block may constitute a "hard" block. Soft blocks (for example, blocks with a Tg of less than 30°C, especially blocks with a Tg of 0°C or lower).

Suitable polyamide blocks include blocks of any of the homopolyamides and copolyamides known in the art, such as polyamide 6,6, polyamide 6,10, polyamide 10,10, polyamide 6,12, polyamide 4,6, polyamide 6, polyamide 11 and polyamide 12.

The number average molecular weight of the polyamide blocks is not particularly limited and may vary as desired to impart certain characteristics to either or both the actinic radiation curable composition and the cured product obtained therefrom. For example, the one or more polyamide blocks may have a number average molecular weight of at least 400 g/mol or at least 500 g/mol, and/or a number average molecular weight of no more than 20,000 g/mol or no more than 10,000 g/mol. According to certain embodiments, the number average molecular weight of the polyamide blocks may be 400 to 20,000 g/mol or 500 to 10,000 g/mol.

As mentioned previously, the non-polyamide blocks may, for example, be selected from the group consisting of: polyether blocks (blocks containing multiple ether linkages in the polymer backbone), polyester blocks (polymer A block containing multiple ester bonds in the main chain), a polyether-ester block (a block containing multiple ether bonds and ester bonds in the polymer main chain) and a polyorganosiloxane block (a polymer main chain A block containing multiple -O-Si(R) ₂ -bonds in which each R is an organic moiety such as methyl). Accordingly, block polymers useful in the present invention include, but are not limited to, polyamide-polyether block copolymers, polyamide-to-polyester block copolymers, polyamide-polyether-polyester block copolymers And polyamide-polyorganosiloxane block copolymers.

Suitable polyether blocks include especially polyoxyalkylene blocks, such as blocks formed by ring-opening polymerization of alkylene oxides, such as ethylene oxide, propylene oxide, oxetane and tetrahydrofuran. In certain embodiments, although the polyoxyalkylene blocks are homopolymeric (i.e., comprise structurally consistent repeat units), copolymeric blocks composed of two or more different oxyalkylene repeat units Sections are also possible. Suitable polyether blocks include, but are not limited to, polyethylene glycol blocks (which may also be referred to as polyoxyethylene blocks), polypropylene glycol blocks (which may also be referred to as polyoxypropylene blocks), poly Propylene glycol blocks (which may also be referred to as polyoxytrimethylene blocks) and polybutylene glycol blocks (which may also be referred to as polyoxytetramethylene blocks). The polyether blocks may also be blocks comprising a central non-ether moiety, such as a bisphenol moiety, substituted with a polyoxyalkylene moiety, such as a polyoxyethylene moiety. For example, the polyether blocks may be ethoxylated bisphenol A blocks.

One or more polyester blocks may also be present in polyamides suitable for use in the present invention, wherein the polyamides are block copolymers. Such polyester blocks may be aliphatic polyester blocks, although aromatic polyester blocks may also be used.

In other embodiments, one or more of the non-polyamide blocks may be polyorganosiloxane blocks, such as polydimethylsiloxane blocks.

The number average molecular weight of the non-polyamide blocks is not particularly limited and may vary as desired to impart certain characteristics to either or both the actinic radiation curable composition and the cured product obtained therefrom. For example, the one or more non-polyamide blocks may have a number average molecular weight of at least 200 g/mol or at least 300 g/mol, and/or a number average molecular weight of not more than 6000 g/mol or not more than 3000 g/mol . According to certain embodiments, the number average molecular weight of the non-polyamide blocks may be 200 to 6000 g/mol or 300 to 3000 g/mol.

Block copolymers comprising at least one polyamide block and at least one non-polyamide block may comprise, for example, 5 to 95% by weight of polyamide blocks and 5 to 95% by weight, based on the weight of the block copolymer Non-polyamide blocks, 10 to 90% by weight polyamide blocks and 10 to 90% by weight non-polyamide blocks or 15 to 85% by weight polyamide blocks and 15 to 85% by weight non-polyamide blocks block.

In certain embodiments, the polyamide is a block copolymer comprising a single non-polyamide block (e.g., a polyether or polyester block) and two polyamide blocks, wherein the non-polyamide block The segments form the central block and the polyamide blocks form the block ends, having the general structure ABA, where one = polyamide block and B = non-polyamide block). However, in other embodiments, the polyamide is a block copolymer comprising a single non-polyamide block and a single polyamide block, having the general structure AB, where A=polyamide block and B=polyamide block ether blocks. In other embodiments, the non-functionalized polyamide is a multi-block copolymer comprising two or more non-polyamide blocks and two or more polyamide blocks, the blocks being Alternately arranged and corresponding to the general structure (AB) _n , wherein A=polyamide block, B=non-polyamide block, and n=2 or greater integer.

Methods of making block copolymers comprising one or more polyamide blocks and one or more non-polyamide blocks are well known in the art and any of such methods can be used to make The polyamide block copolymer of the present invention.

Exemplary polyamide block copolymers suitable for use in the present invention are described, for example, in the following published patent application, the disclosure of which is incorporated herein by reference in its entirety for all purposes: US 2015/0166746 A1; US 2016/0369098 A1; and US 2016/0251484 A1.

Combinations of two or more different polyamides can be utilized in the present invention. As used herein, the term "polyamide component" refers to all components of an actinic radiation curable composition that are polyamides (whether a single polyamide or a combination of polyamides).

The amount of the polyamide component present in the actinic radiation curable composition can be varied as desired or needed to achieve the effect of the actinic radiation curable composition and the product obtained therefrom after curing by exposure to actinic radiation. A property or characteristic of one or both of the cured products. For example, the actinic radiation curable composition may comprise at least 0.5%, at least 1%, at least 2%, at least 5%, or at least 10% by weight polyamide, based on the total weight of the actinic radiation curable composition. . According to certain embodiments, the actinic radiation curable composition may consist of no more than 50 wt%, no more than 40 wt%, or no more than 30 wt% polyamide, based on the total weight of the actinic radiation curable composition.

In other aspects of the invention, the actinic radiation curable composition comprises up to 30 parts by weight polyamide per 100 parts by weight actinic radiation curable compound (in the case of more than one actinic radiation curable compound, each 100 parts by weight of the total amount of actinic radiation curable compound). In other aspects, the actinic radiation curable composition may comprise at least 0.5 parts by weight polyamide per 100 parts by weight actinic radiation curable compound. For example, in certain embodiments, the actinic radiation curable composition may comprise 0.5 to 25 parts by weight polyamide per 100 parts by weight actinic radiation curable compound. In one embodiment, the actinic radiation curable composition may comprise 0.5 to 20, 0.5 to 15, 0.5 to 10, 0.5 to 8, or 0.5 to 6 parts by weight polyamide per 100 parts by weight of actinic radiation curable compound. In another embodiment, the actinic radiation curable composition may contain 5 to 25 parts by weight, 8 to 25 parts by weight, 10 to 25 parts by weight, or 15 to 25 parts by weight of polyamide per 100 parts by weight of actinic radiation curable compound. Amide. actinic radiation curable compound

In addition to one or more polyamides, the actinic radiation curable compositions of the present invention comprise one or more actinic radiation curable compounds. Such actinic radiation curable compounds include compounds comprising one or more functional groups capable of participating in a polymerization or curing reaction upon exposure to actinic radiation such that the The covalent bonding of the functional groups of the polymers forms the polymer matrix. Suitable functional groups for this purpose include ethylenically unsaturated functional groups such as (meth)acrylate functional groups (i.e., acrylate functional groups, methacrylate functional groups), (meth)acrylamide functional groups (i.e., acrylamide functional groups, methacrylamide functional groups), cyanoacrylate functional groups, methylene malonate functional groups, itaconate functional groups, vinyl functional groups, vinyl functional groups, Ether functional groups and their analogs. The actinic radiation curable compounds used in the present invention may have a single such actinic radiation curable functional group per molecule, or may have two, three, four or more actinic radiation curable functional groups per molecule . If the actinic radiation curable compound comprises two or more actinic radiation curable functional groups per molecule, such functional groups may be the same or different.

As described in more detail below, the actinic radiation curable compound can be monomeric or oligomeric in character. Suitable (meth)acrylate functional compounds include, for example, (meth)acrylate functional monomers and (meth)acrylate functional oligomers.

According to certain embodiments of the present invention, the actinic radiation curable composition comprises at least one (meth)acrylate functionalized monomer or oligomeric monomer comprising two or more (meth)acrylate functional groups per molecule. Polymer. Examples of suitable (meth)acrylate functional monomers containing two or more (meth)acrylate functional groups per molecule include acrylate and methacrylate esters of polyols (containing two or more (eg, 2 to 6) hydroxyl organic compounds). Specific examples of suitable polyols include _C2-20 alkanediols (diols with _C2-10 alkylene groups may be preferred, where the carbon chain may be branched; for example ethylene glycol, propylene glycol, 1,2 -Propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, butylene glycol (1,4-butanediol), 1,5-pentanediol, 1 ,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, cyclohexane-1,4-dimethanol, bisphenol and hydrogenated bisphenol , and alkoxylated (for example, ethoxylated and/or propoxylated) derivatives thereof, wherein, for example, 1 to 20 molar alkylene oxides, such as ethylene oxide and/or propylene oxide, have been with 1 mole of diol); diethylene glycol; glycerol; alkoxylated glycerol; triethylene glycol; dipropylene glycol; tripropylene glycol; trimethylolpropane; alkoxylated trimethylolpropane; (trimethylolpropane); alkoxylated bis(trimethylolpropane); pentaerythritol; alkoxylated pentaerythritol; dipentaerythritol; alkoxylated dipentaerythritol; cyclohexanediol; alkoxylated cyclohexane Diol; Cyclohexane Dimethanol; Alkoxylated Cyclohexane Dimethanol; Norcamphene Dimethanol; Alkoxylated Norborne Dimethanol; Norbornane Dimethanol; ; Polyols containing aromatic rings; Cyclohexane-1,4-dimethanol ethylene oxide adducts; Bisphenol ethylene oxide adducts; Hydrogenated bisphenol ethylene oxide adducts; Bisphenol rings Propylene oxide adduct; hydrogenated bisphenol propylene oxide adduct; cyclohexane-1,4-dimethanol propylene oxide adduct; sugar alcohol and alkoxylated sugar alcohol. Such polyols may be fully or partially esterified (by (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride or the like), provided that such polyols contain at least Two (meth)acrylate functional groups. As used herein, the term "alkoxylated" refers to compounds in which one or more epoxides, such as ethylene oxide and/or propylene oxide, have been combined with reactive hydrogen-containing groups of base compounds such as polyols (eg, hydroxyl) to form one or more oxyalkylene moieties. For example, 1 to 25 moles of epoxide can be reacted per mole of base compound. According to certain aspects of the invention, the molecular weight of the (meth)acrylate functional monomer used may be relatively low (eg, 100 to 1000 g/mol).

Any of the (meth)acrylate functional oligomers known in the art may also be used in the actinic radiation curable compositions of the present invention. According to certain embodiments, such oligomers comprise two or more (meth)acrylate functional groups per molecule. The number average molecular weight of such oligomers can vary widely, eg, from about 500 to about 50,000.

Suitable (meth)acrylate functionalized oligomers include, for example, polyester (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyether (meth)acrylate oligomers Polyurethane (meth)acrylate oligomer, Acrylic (meth)acrylate oligomer, Polydiene (meth)acrylate oligomer, Polycarbonate (meth)acrylate Acrylate oligomers, polyamide (meth)acrylate oligomers, and combinations thereof. Such oligomers can be selected and used in combination with one or more (meth)acrylate functional monomers to tune or tune the properties of cured resins prepared using the actinic radiation curable compositions of the present invention.

Exemplary polyester (meth)acrylate oligomers include the reaction products of acrylic or methacrylic acid or mixtures thereof with hydroxyl terminated polyester polyols. In particular, where the polyester polyol is difunctional, the reaction process can be carried out such that all or substantially all of the hydroxyl groups of the polyester polyol have been (meth)acrylated. Polyester polyols can be produced by polycondensation of polyhydroxy-functional components (specifically, diols) with polycarboxylic acid-functional compounds (specifically, dicarboxylic acids and anhydrides). The polyhydroxy-functional component and the polycarboxylic acid-functional component may each have a linear, branched, cycloaliphatic or aromatic structure and may be used individually or in admixture.

Examples of suitable epoxy (meth)acrylate oligomers include reaction products of acrylic or methacrylic acid or mixtures thereof with glycidyl ethers or esters.

Suitable polyether (meth)acrylate oligomers include, but are not limited to, acrylic or methacrylic acid or mixtures thereof and polyether alcohols that are polyether polyols such as polyethylene glycol, polypropylene glycol, or polybutylene glycol. condensation reaction products. Suitable polyether alcohols may be linear or branched substances comprising ether linkages and terminal hydroxyl groups. Polyether alcohols can be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides with starter molecules. Suitable starter molecules include water, polyhydroxy functional materials, polyester polyols and amines.

Polyurethane (meth)acrylate oligomers (sometimes referred to as "urethane (meth)acrylate oligomers") that can be used in the multi-component system of the present invention ) include those based on aliphatic and/or aromatic polyester polyols and polyether polyols with aliphatic and/or aromatic polyester diisocyanates and polyether diisocyanates, terminated by (meth)acrylate end groups Urethane. Suitable polyurethane (meth)acrylate oligomers include, for example, aliphatic polyester urethane diacrylate and tetraacrylate oligomers, aliphatic polyether urethane diacrylate Acrylate and tetraacrylate oligomers, and aliphatic polyester/polyether urethane diacrylate and tetraacrylate oligomers.

In various embodiments, polyurethane (meth)acrylate oligomers can be prepared by combining aliphatic and/or aromatic diisocyanates with OH group-terminated polyester polyols (including aromatic, aliphatic and mixed aliphatic/aromatic polyester polyols), polyether polyols, polycarbonate polyols, polycaprolactone polyols, dimethicone polyols or polybutadiene polyols or Their combination reacts to form an isocyanate-functionalized oligomer, which is then reacted with a hydroxyl-functionalized (meth)acrylate such as hydroxyethyl acrylate or hydroxyethyl methacrylate to provide prepared with terminal (meth)acrylate groups. For example, a polyurethane (meth)acrylate oligomer may contain two, three, four or more (meth)acrylate functional groups per molecule.

Suitable acrylic (meth)acrylate oligomers (also sometimes referred to in the art as "acrylic oligomers") include oligomers that can be described as species having an oligomeric acrylic acid backbone that The chain is functionalized with one or more (meth)acrylate groups, which may be located at the end of the oligomer or pendant to the acrylic backbone. The acrylic backbone can be a homopolymer, a random copolymer or a block copolymer comprising repeat units of acrylic monomers. (Meth)acrylic monomers can be any monomeric (meth)acrylates, such as C1-C6 alkyl (meth)acrylates; and functionalized (meth)acrylates, such as those with hydroxyl, carboxylic acid and/or Or epoxy (meth)acrylate. Acrylic (meth)acrylate oligomers can be prepared using any procedure known in the art, such as by oligomerizing monomers, at least a portion of which are modified by hydroxyl, carboxylic acid and/or Epoxy functionalization (e.g. hydroxyalkyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized oligomer intermediate which is subsequently combined with one or more The (meth)acrylate-containing reactants react to introduce the desired (meth)acrylate functional groups.

Exemplary (meth)acrylate functionalized monomers and oligomers may include ethoxylated bisphenol A di(meth)acrylate; triethylene glycol di(meth)acrylate; ethylene glycol di(meth)acrylate; (Meth)acrylate; Tetraethylene glycol di(meth)acrylate; Polyethylene glycol di(meth)acrylate; 1,4-Butanediol diacrylate; 1,4-Butanediol diacrylate Methacrylate; Diethylene glycol diacrylate; Diethylene glycol dimethacrylate; 1,6-Hexanediol diacrylate; 1,6-Hexanediol dimethacrylate; Neopentyl dimethacrylate Alcohol diacrylate; Neopentyl glycol di(meth)acrylate; Polyethylene glycol (600) dimethacrylate (where 600 refers to the approximate number average molecular weight of the polyethylene glycol moiety); Polyethylene glycol (200) Diacrylate; 1,12-Dodecanediol Dimethacrylate; Tetraethylene Glycol Diacrylate; Triethylene Glycol Diacrylate; 1,3-Butanediol Dimethacrylate ; tripropylene glycol diacrylate; polybutadiene diacrylate; methylpentanediol diacrylate; polyethylene glycol (400) diacrylate; ethoxylated ₂ bisphenol A dimethacrylate; Oxylated ₃ Bisphenol A Dimethacrylate; Ethoxylated ₃ Bisphenol A Diacrylate; Cyclohexanedimethanol Dimethacrylate; Cyclohexanedimethanol Diacrylate; Ethoxylated ₁₀ Bisphenol A dimethacrylate (where the number after "ethoxylated" is the average number of oxyalkylene moieties per molecule); dipropylene glycol diacrylate; ethoxylated ₄ bisphenol A dimethacrylate Esters; Ethoxylated ₆ Bisphenol A Dimethacrylate; Ethoxylated ₈ Bisphenol A Dimethacrylate; Alkoxylated Hexylene Glycol Diacrylate; Alkoxylated Cyclohexanedimethanol Diacrylate; Dodecane Diacrylate; Ethoxylated ₄ Bisphenol A Diacrylate; Ethoxylated ₁₀ Bisphenol A Diacrylate; Polyethylene Glycol (400) Dimethacrylate; Polypropylene Glycol (400) Dimethacrylate; Metal Diacrylate; Modified Metal Diacrylate; Metal Dimethacrylate; Polyethylene Glycol (1000) Dimethacrylate; Butadiene; Propoxylated ₂ Neopentyl Glycol Diacrylate; Ethoxylated ₃₀ Bisphenol A Dimethacrylate; Ethoxylated ₃₀ Bisphenol A Diacrylate; Alkoxylated Neopentyl Diacrylate Alcohol Diacrylate; Polyethylene Glycol Dimethacrylate; 1,3-Butanediol Diacrylate; Ethoxylated ₂ Bisphenol A Dimethacrylate; Dipropylene Glycol Diacrylate; Ethoxylated ₄ Bisphenol A diacrylate; Polyethylene glycol (600) diacrylate; Polyethylene glycol (1000) dimethacrylate; Tricyclodecane dimethanol diacrylate; Propoxylated neopentyl glycol Diacrylates, such as propoxylated _2- neopentyl glycol diacrylate; diacrylate ester of alkoxylated aliphatic alcohol trimethylolpropane trimethacrylate; trimethylolpropane triacrylate; cf. (2-Hydroxyethyl)isocyanurate triacrylate; Ethoxylated ₂₀ Trimethylolpropane Triacrylate; Pentaerythritol Triacrylate; Ethoxylated ₃ Trimethylolpropane Triacrylate; Oxylated ₃ -Trimethylolpropane Triacrylate; Ethoxylated ₆ -Trimethylolpropane Triacrylate; Propoxylated ₆ -Trimethylolpropane Triacrylate; Ethoxylated ₉ -Trimethylolpropane Propane Triacrylate; Alkoxylated Trifunctional Acrylate; Trifunctional Methacrylate; Trifunctional Acrylate; Propoxylated _3- Glyceryl Triacrylate; Propoxylated _5.5 -Glyceryl Triacrylate; Ethoxylated _15- trimethylolpropane triacrylate; trifunctional phosphate; trifunctional acrylate; pentaerythritol tetraacrylate; di-trimethylolpropane tetraacrylate; ethoxylated _4- pentaerythritol tetraacrylate; Oxyethylene tetraacrylate; dipentaerythritol pentaacrylate; pentaacrylate; epoxy acrylate oligomer; epoxy methacrylate oligomer; acrylate urethane oligomer; amine Formate methacrylate oligomer; Acrylic polyester oligomer; Polyester methacrylate oligomer; Stearyl methacrylate oligomer; Acrylic acrylate oligomer; Perfluorinated Acrylate oligomers; perfluorinated methacrylate oligomers; amine acrylate oligomers; amine-modified polyether acrylate oligomers; and amine methacrylate oligomers.

The actinic radiation curable compositions of the present invention may comprise one or more (meth)acrylate functionalized compounds comprising a single acrylate or methacrylate functional group per molecule (referred to herein as "mono(meth)acrylate ) acrylate-functionalized compounds"). Any such compound known in the art may be used.

Examples of suitable mono(meth)acrylate functionalized compounds include, but are not limited to, aliphatic alcohols (where the aliphatic alcohol may be linear, branched, or cycloaliphatic and may be monoalcohol, diol, or polyol, limited to Mono(meth)acrylates with only one hydroxyl group (meth)acrylated); mono(meth)acrylates of aromatic alcohols such as phenol, including alkylated phenols; alkaryl alcohols ( mono(meth)acrylates such as benzyl alcohol); mono(meth)acrylates of oligomeric and polymeric diols such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol and polypropylene glycol ) acrylates; mono(meth)acrylates of diols, oligomeric diols, monoalkyl ethers of polymeric diols; alkoxylated (e.g. ethoxylated and/or propoxylated) aliphatic Alcohols (of which the aliphatic alcohols may be straight-chain, branched or cycloaliphatic and may be mono-, di- or polyols, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is passed through (meth)acrylate Mono(meth)acrylates of alkoxylated (for example, ethoxylated and/or propoxylated) aromatic alcohols (such as alkoxylated phenols) mono(meth)acrylates; caprolactone mono(meth)acrylate; and analogs thereof.

The following compounds are specific examples of mono(meth)acrylate functionalized compounds suitable for use in the curable compositions of the present invention: methyl (meth)acrylate; ethyl (meth)acrylate; (meth)acrylic acid n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate ; Isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; Cetyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2- and 3-hydroxypropyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; base) 2-ethoxyethyl acrylate; 2- and 3-ethoxypropyl (meth)acrylates; tetrahydrofuryl (meth)acrylates; alkoxylated tetrahydrofuryl (meth)acrylates; ( Isocamphoryl methacrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; Isodecyl acrylate: 2-Phenoxyethyl (meth)acrylate: Lauryl (meth)acrylate; Isocamphoryl (meth)acrylate; 2-Phenoxyethyl (meth)acrylate; Alkoxy Alkoxylated nonylphenol (meth)acrylate; Alkoxylated nonylphenol (meth)acrylate; Cyclotrimethylolpropane (meth)acrylate; Trimethylcyclohexanol (meth)acrylate; Diethylene glycol monomethyl ether (meth)acrylate; Diethylene glycol monoethyl ether (meth)acrylate; Diethylene glycol monobutyl ether (meth)acrylate; Triethylene glycol monoethyl ether (methyl) ) acrylates; ethoxylated lauryl (meth)acrylates; methoxypolyethylene glycol (meth)acrylates; and combinations thereof.

In a preferred embodiment, at least one actinic radiation curable compound comprises at least one sterically hindered (meth)acrylate monomer.

The sterically hindered (meth)acrylate monomer may have one or two (meth)acrylate groups, preferably one (meth)acrylate group, more preferably an acrylate group. The sterically hindered (meth)acrylate monomer may contain a cyclic moiety and/or a tertiary butyl group. Cyclic moieties can be monocyclic, bicyclic or tricyclic, including bridged, fused and/or spiro ring systems. A cyclic moiety can be carbocyclic (all ring atoms are carbon) or heterocyclic (at least one ring atom is a heteroatom, such as N, O or S). The cyclic moiety can be aliphatic, aromatic, or a combination of aliphatic and aromatic. In particular, the cyclic moiety can comprise a ring or ring system selected from the group consisting of cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof. More specifically, the cyclic moiety may comprise a ring or ring system selected from the group consisting of phenyl, cyclopentyl, cyclohexyl, norbornyl, tricyclodecanyl, dicyclopentadienyl, oxiranyl , oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, dioxanyl, dioxaspirodecanyl and dioxasiroundecyl. The ring or ring system may be optionally substituted with one or more groups selected from the group consisting of hydroxy, alkoxy, alkyl, hydroxyalkyl, cycloalkyl, aryl, alkylaryl and arylalkyl .

其中 符號

表示附接至包含(甲基)丙烯酸酯官能基之部分的連接點， 切割鍵

表示單鍵或雙鍵； 且各環原子可任擇地經選自以下之一或多個基團取代：羥基、烷氧基、烷基、羥基烷基、環烷基、芳基、烷基芳基及芳基烷基。 In particular, the cyclic moiety can correspond to one of the following formulae:

where the symbol

Indicates the point of attachment to a moiety containing a (meth)acrylate functional group, cleavage bond

Represents a single bond or a double bond; and each ring atom may be optionally substituted by one or more groups selected from: hydroxyl, alkoxy, alkyl, hydroxyalkyl, cycloalkyl, aryl, alkyl Aryl and arylalkyl.

Specifically, the sterically hindered (meth)acrylate monomer comprises a cyclic moiety, such as a moiety comprising an aliphatic ring, especially an aliphatic ring selected from the group consisting of cyclohexane, tricyclodecane, tetrahydrofuran, camphene alkanes, 1,3-dioxolanes and 1,3-dioxanes.

Examples of sterically hindered (meth)acrylate monomers are tertiary butyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, nonylphenol (Meth)acrylate, Isocamphoryl (meth)acrylate, tertiary butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, (meth) ) dicyclopentadienyl acrylate, tricyclodecane methanol mono(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, tetrahydrofuryl (meth)acrylate, cyclic trimethylol propaneformyl (meth)acrylate (CTFA, also known as 5-ethyl-1,3-dioxan-5-yl)methyl (meth)acrylate), (meth)acrylic acid (2 ,2-Dimethyl-1,3-dioxolan-4-yl)methyl ester, (2-ethyl-2-methyl-1,3-dioxolane (meth)acrylic acid Alk-4-yl)methyl esters, glycerol formal methacrylate, their alkoxylated (ie ethoxylated and/or propoxylated) derivatives and mixtures thereof.

In particular, at least one actinic radiation curable compound comprises a sterically hindered (meth)acrylate monomer selected from the group consisting of nonylphenol (meth)acrylate, isobornyl (meth)acrylate, ( Tertiary butylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, tricyclodecane methanol mono(meth)acrylate, tricyclodecane dimethanol dimethanol (Meth)acrylates, tetrahydrofuryl (meth)acrylates, cyclic trimethylolpropaneformyl (meth)acrylates and mixtures thereof.

The sterically hindered (meth)acrylate monomers may comprise at least 10 wt %, 10 wt % to 90 wt %, 20 wt % to 85 wt %, 30 wt % to 80 wt%, 40 wt% to 75 wt%, or 50 wt% to 70 wt%.

In a preferred embodiment, at least one actinic radiation curable compound comprises at least one acyclic (meth)acrylate monomer.

The acyclic (meth)acrylate monomer may have one or two (meth)acrylate groups, preferably two (meth)acrylate groups. Acyclic (meth)acrylate monomers may be alkoxylated, especially alkoxylated or propoxylated.

Examples of acyclic (meth)acrylate monomers are lauryl (meth)acrylate, behenyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexyl Diol di(meth)acrylates, 1,10-decanediol di(meth)acrylates and their alkoxylated (i.e. ethoxylated and/or propoxylated) derivatives and mixtures thereof .

The acyclic (meth)acrylate monomer may comprise at least 5 wt%, 5 wt% to 60 wt%, 8 wt% to 55 wt%, 10 wt% to 50 wt% of the total weight of the curable composition, 15% to 45% by weight or 20% to 40% by weight.

In a preferred embodiment, the at least one actinic radiation curable compound comprises at least one urethane (meth)acrylate.

The urethane (meth)acrylate may have one or two (meth)acrylate groups, preferably two (meth)acrylate groups. The urethane (meth)acrylate may be an aliphatic urethane (meth)acrylate, especially an aliphatic urethane di(meth)acrylate.

The urethane (meth)acrylate monomer may comprise at least 10 wt%, 10 wt% to 90 wt%, 15 wt% to 85 wt%, 20 wt% to 80 wt% of the total weight of the curable composition %, 25% to 75% by weight or 30% to 70% by weight.

In an especially preferred embodiment, the at least one actinic radiation curable compound comprises at least one (meth)acrylate-functional monomer and at least one (meth)acrylate-functional oligomer; in particular , at least one actinic radiation curable compound comprising: - at least one sterically hindered (meth)acrylate monomer such as nonylphenol (meth)acrylate, isobornyl (meth)acrylate, tertiary butylcyclohexyl (meth)acrylate, ( 3,3,5-Trimethylcyclohexyl methacrylate, Tricyclodecane methanol mono(meth)acrylate, Tricyclodecane dimethanol di(meth)acrylate, Tetrahydrofuranyl(meth)acrylate Acrylates, cyclic trimethylolpropaneformyl (meth)acrylates and mixtures thereof; and - at least one urethane (meth)acrylate, such as an aliphatic urethane (meth)acrylate.

The sterically hindered (meth)acrylate monomer may comprise at least 10 wt%, 10 wt% to 100 wt%, 15 wt% to 95 wt%, 20 wt% to 90% by weight, 25% to 85% by weight, or 30% to 80% by weight.

The urethane (meth)acrylate may comprise at least 10%, 10% to 100%, 15% to 95%, 20% to 90% by weight of the total weight of the actinic radiation curable compound %, 25% to 85% by weight or 30% to 80% by weight. Photoinitiator

In certain embodiments of the present invention, the actinic radiation curable compositions described herein include at least one photoinitiator and are curable by radiant energy (visible light, ultraviolet light). A photoinitiator can be considered any type of substance that, upon exposure to radiation, such as actinic radiation, forms a species that initiates the reaction and cure of the polymerized organic species present in the curable composition. Suitable photoinitiators include free radical photoinitiators as well as cationic photoinitiators and combinations thereof.

、氧蒽酮、吖啶衍生物、吩

衍生物、喹㗁啉衍生物及三

化合物。Free radical polymerization initiators are substances that form free radicals when irradiated. The use of free radical photoinitiators is especially preferred. Non-limiting classes of free radical photoinitiators suitable for use in curable compositions of the present invention include, for example, benzoin, benzoin ether, acetophenone, benzyl, benzyl ketal, anthraquinone, phosphine oxide, alpha -Hydroxyketone, phenylglyoxylate, α-aminoketone, benzophenone, 9-oxosulfur

, Oxyanthrone, acridine derivatives, phen

derivatives, quinoline derivatives and three

compound.

If the photoinitiator is present in the actinic radiation curable composition, the typical concentration is up to about 15% by weight, based on the total weight of the curable composition. For example, the actinic radiation curable composition may comprise a total of 0.1% to 10% by weight photoinitiator, based on the total weight of the curable composition. non reactive solvent

According to certain embodiments of the present invention, actinic radiation curable compositions are formulated to be free or substantially free of non-reactive solvents. As used herein, the term "non-reactive solvent" means a solvent that is not curable by actinic radiation in contrast to the actinic radiation curable compounds present in the composition. However, non-reactive solvents may react with one or more components of the composition via other mechanisms.

For example, the actinic radiation curable composition may contain less than 5%, less than 2%, less than 1%, less than 0.5%, less than 0.1%, or even 0% by weight of the total weight of the composition. solvent.

For certain applications, however, it may be desirable to include substantial amounts of one or more non-reactive solvents in the actinic radiation curable composition. For example, non-reactive solvents can be used to help dissolve one or more components of the composition (especially the polyamide component) and/or reduce the viscosity of the composition. The type of non-reactive solvent that can be used is not limited, provided that it does not interfere with the ability to cure the composition by exposing the composition to actinic radiation. Suitable non-reactive solvents include, for example, ketones (eg, acetone), esters, ethers, alcohols (including halogenated alcohols, such as fluorinated alcohols), aromatic hydrocarbons, and the like, and combinations thereof. For example, the actinic radiation curable composition can be formulated to include at least 0.5%, at least 1%, at least 2%, or at least 5% by weight of one or more non-reactive solvents, based on the total weight of the composition. According to other embodiments, the actinic radiation curable composition comprises at most 90 wt%, at most 80 wt%, at most 70 wt%, at most 60 wt%, at most 50 wt%, at most 40 wt%, based on the total weight of the composition, Up to 30%, up to 25%, or up to 20% by weight of non-reactive solvent. For example, the actinic radiation curable composition may comprise 1% to 50% by weight or 1% to 25% by weight of non-reactive solvent.

The non-reactive solvent, if present, can be a volatile non-reactive solvent or a non-volatile reactive solvent. As used herein, the term "volatile" means a substance whose boiling point at atmospheric pressure does not exceed 100°C and the term "nonvolatile" means a substance whose boiling point at atmospheric pressure exceeds 100°C. Combinations of volatile and non-volatile solvents may also be employed.

It is also within the scope of the present invention to use one or more non-reactive solvents that aid in dissolving certain components (particularly polyamide components) when formulating a composition where the composition components (including the non-reactive solvent) in combination Thereafter, at least a portion of the non-reactive solvent is then removed to provide a final formulated actinic radiation curable composition suitable for the desired application (eg, build-up fabrication). For example, the components of the composition can be combined and then subjected to processing steps such as mixing and/or heating to obtain a homogeneous product or solution, wherein the non-reactive solvent is then removed by suitable means such as distillation or vacuum stripping at least part of it. other optional additives

Depending on the particular desired end use application and desired properties of the actinic radiation curable composition and cured product obtained therefrom, one or more other additives may optionally be present in the composition. Such additives may for example be selected from the group consisting of chain transfer agents, light blockers (opacifiers), wetting agents (surface tension modifiers), matting agents, colorants, dyes, pigments, adhesion promoters , fillers, rheology modifiers/formulations, leveling or leveling agents, thixotropic agents, plasticizers, light absorbers, light stabilizers, dispersants, antioxidants, antistatic agents, lubricants, devitrification Agents, defoamers, polymerization inhibitors and combinations thereof, including any additives commonly used in coatings, sealants, adhesives, molding, 3D printing, additive manufacturing or ink technology.

、羥基苯基三

、蘇丹(Sudan) I、溴百里酚藍、2,2'-(2,5-噻吩二基)雙(5-三級丁基苯并㗁唑) (以商標「Benetex OB Plus」銷售)及苯并三唑紫外光吸收劑。The actinic radiation curable compositions of the present invention may contain one or more photoblockers (sometimes referred to in the art as absorbers), especially when the curable composition is used as a three-dimensional light source involving photocuring of the curable composition. In the case of resin in the printing method. The light blocking agent can be any such substance known in 3D printing technology, including, for example, non-reactive pigments and dyes. For example, the light blocking agent can be a visible light blocking agent or a UV light blocking agent. Examples of suitable photoblockers include, but are not limited to: titanium dioxide, carbon black, and organic UV light absorbers such as hydroxybenzophenones, hydroxyphenylbenzotriazoles, oxalanilides, benzophenones, 9-oxo sulfur

, hydroxyphenyl tri

, Sudan (Sudan) I, bromothymol blue, 2,2'-(2,5-thiophenediyl)bis(5-tertiary butylbenzoxazole) (sold under the trademark "Benetex OB Plus") And benzotriazole UV absorber.

The amount of photoblocker can vary as desired or as appropriate for a particular application. Generally, if the actinic radiation curable composition includes a photoblocker, it is present at a concentration of 0.001% to 10% by weight of the curable composition. Manufacturing method

The actinic radiation curable compositions of the present invention may be prepared by any suitable method. For example, the various desired components can be simply combined and mixed. Where it is desired to achieve some degree of dissolution of the polyamide components, such dissolution may be facilitated by various means, such as heating and/or vigorous stirring of the combined components. Homogenization methods can also be used. Additionally, one or more solvents may be utilized to facilitate dissolution of the polyamide components, as previously described. In one embodiment, the finely powdered polyamide is slowly added to the other components of the composition at a temperature of 20°C to 90°C while mixing. The resulting actinic radiation curable composition may then be stored under suitable protective conditions until required for use thereof to form an article or cured product.

The present invention also relates to a method of manufacturing an actinic radiation curable composition according to the invention, wherein the method comprises mixing at least one polyamide, at least one actinic radiation curable compound and at least one compound capable of dissolving at least one polyamide The volatile solvents are combined to provide an initial mixture and at least a portion of the volatile solvent is removed from the initial mixture to provide an actinic radiation curable composition. Uses of Actinic Radiation Curable Compositions

As previously mentioned, actinic radiation curable compositions prepared according to the present invention may comprise one or more photoinitiators and be photocurable. In certain other embodiments of the present invention, the actinic radiation curable compositions described herein do not include any initiators and are curable (at least in part) with electron beam energy.

The actinic radiation curable compositions described herein may be compositions that cure by means of free radical polymerization, cationic polymerization, or other types of polymerization. In particular embodiments, the curable composition is photocured (ie, cured by exposure to actinic radiation, such as light, especially visible, UV, near-UV, infrared, and/or near-infrared light).

The present invention relates to a method of producing a cured product, also called cured polymeric material, wherein the method comprises curing the actinic radiation curable composition of the present invention. In particular, actinic radiation curable compositions can be cured by exposing the composition to radiation. More specifically, actinic radiation curable compositions can be cured by exposing the composition to UV light, near UV light, visible light, infrared light, and/or near infrared light radiation or electron beams. The cured product obtained by the method of the present invention can be ink, coating, sealant, adhesive, molded article or 3D printed article.

End-use applications for curable compositions include, but are not limited to, inks, coatings, adhesives, build-up resins (such as 3D printing resins), molding resins, sealants, composites, antistatic layers, electronic applications, Recycled materials, smart materials that can detect and respond to stimuli, and biomedical materials.

Advantageously, as measured by ASTM D256-10 (2018), by photocuring a similar actinic radiation curable composition having the same composition as the actinic radiation curable composition but without at least one polyamide The cured polymeric material obtained with the actinic radiation curable composition of the present invention has a higher fracture energy than the cured polymeric material obtained.

Accordingly, the present invention relates to a method for increasing the fracture energy of a cured polymer material obtained by photocuring an actinic radiation curable composition, wherein the method comprises, prior to photocuring, at least one Polyamides with radiation curable functional groups are added to the actinic radiation curable composition. In particular, the radiation curable composition comprises at least one actinic radiation curable compound that is liquid at 25°C.

The present invention also relates to the use of polyamides free of actinic radiation curable functional groups to increase the fracture energy of cured polymeric materials obtained by photocuring actinic radiation curable compositions. In particular, the radiation curable composition comprises at least one actinic radiation curable compound that is liquid at 25°C.

Specifically, the cured product can be a 3D-printed item. A 3D-printed item can be defined as an item obtained with a 3D-printing machine using a computer-aided design (CAD) model or a digital 3D model. In particular, a 3D-printed article can be obtained by a method of manufacturing a 3D-printed article, which method comprises printing a 3D article with the actinic radiation curable composition of the present invention.

Specifically, the method may include layer-by-layer or continuous printing of 3D objects. Multiple layers of actinic radiation curable compositions according to the present invention may be applied to the surface of a substrate; the multiple layers may be cured simultaneously (e.g. by exposure to a single dose of radiation) or the layers may be curable under actinic radiation Another layer of composition is sequentially cured before being applied. The actinic radiation curable compositions described herein are useful as resins in 3D printing applications. Accordingly, the present invention relates to a method of manufacturing a three-dimensional object by additive manufacturing, which comprises using the actinic radiation curable composition of the invention to manufacture a three-dimensional object.

The actinic radiation curable compositions described herein are suitable for use in a process known as thermal 3D printing, in which the composition can be extruded in a manner similar to 3D fabrication in the fused filament process and simultaneously or later exposed with actinic radiation. solidified. Any 3D printing process as described herein can be performed at a temperature suitable to achieve the desired viscosity.

Cured compositions prepared from actinic radiation curable compositions as described herein are useful, for example, in three-dimensional articles (wherein the three-dimensional article may consist essentially of or consist of the cured composition), coated articles (wherein the substrate Coated with one or more layers of a cured composition, including encapsulated articles in which the substrate is completely covered by the cured composition), laminated or adhered articles (where the first component of the article is laminated or adhered by means of the cured composition In the second component), a composite article or a printed article (where a cured composition is used to emboss graphics or the like on a substrate such as a substrate comprising paper, plastic and/or metal).

Curing of the actinic radiation curable composition according to the invention may be carried out by any suitable method, such as free radical and/or cationic polymerization. One or more initiators, such as free radical initiators (eg, photoinitiators that generate free radical species when irradiated), may be present in the actinic radiation curable composition. Prior to curing, the actinic radiation curable composition may be applied to the substrate surface in any known conventional manner, such as by spraying, knife coating, rolling, casting, drum coating, dipping, and the like, and combinations thereof . Indirect application using a transfer printing process can also be used. Application to the substrate surface can be performed at ambient temperature (eg, room temperature) or at elevated temperature. For example, if the actinic radiation curable composition is a solid (such as a gel) at ambient temperature, it can be heated to a temperature effective to liquefy the actinic radiation curable composition to facilitate application to the substrate surface temperature. Such embodiments of the invention may be used, for example, in three-dimensional printing operations or the like employing machines with heated resin tanks or chambers, or in extrudable actinic radiation curable compositions and then later cured or In the process of solidification during the extrusion step.

The substrate may be any commercially relevant substrate, such as a high surface energy substrate or a low surface energy substrate, such as a metal substrate or a plastic substrate, respectively. Such substrates may comprise metal, paper, cardboard, glass, thermoplastics such as polyolefins, polycarbonate, acrylonitrile butadiene styrene (ABS) and blends thereof, composites, wood, leather and their combination. When used as an adhesive, the actinic radiation curable composition can be placed between two substrates and subsequently cured, whereby the cured composition bonds the substrates together to provide an adhesive article. Actinic radiation curable compositions according to the present invention may also be formed or cured in bulk (for example, an actinic radiation curable composition may be cast into a suitable mold and then cured).

Curing can be accelerated or facilitated by supplying energy to the actinic radiation curable composition, such as by exposing the actinic radiation curable composition to a radiation source, such as visible or UV light, infrared radiation, and/or electron beam radiation . Thus, a cured composition can be considered a reaction product of an actinic radiation curable composition that is cured to form an actinic radiation curable composition. Curable compositions can be partially cured by exposure to actinic radiation, wherein further curing is achieved by heating the partially cured article. For example, an article formed from a curable composition (eg, a 3D printed article) may be heated at a temperature of 40°C to 120°C for a period of 5 minutes to 12 hours.

Multiple layers of actinic radiation curable compositions according to the present invention may be applied to the surface of a substrate; the multiple layers may be cured simultaneously (e.g. by exposure to a single dose of radiation) or the layers may be curable under actinic radiation Another layer of composition is sequentially cured before being applied.

The actinic radiation curable compositions described herein are useful as resins in 3D printing applications.

The present invention relates to a method of manufacturing a three-dimensional article by additive manufacturing, which comprises using the actinic radiation curable composition of the present invention to manufacture a three-dimensional article. After the lamination fabrication step, the three-dimensional article may be subjected to a further step of post-curing using at least one of actinic radiation or heat. After the lamination fabrication step, the actinic radiation cured polymer phase in the three-dimensional article may be removed from the three-dimensional article using at least one of thermal degradation or washing with an organic solvent. After removal of the actinic radiation-cured polymer phase, the polyamide phase can remain in the three-dimensional article, and the polyamide phase can then be subjected to thermal sintering.

Three-dimensional (3D) printing, which is a type of additive manufacturing, is the process of making 3D digital models by the growth of building materials. 3D printed object systems are produced by using computer-aided design (CAD) data of the object through the sequential construction of two-dimensional (2D) layers or slices corresponding to the cross-section of the 3D object. Stereolithography (SL) is a type of additive manufacturing in which a liquid resin is hardened by selective exposure to radiation to form 2D layers. Radiation may be in the form of electromagnetic waves or electron beams. The most commonly used energy sources are ultraviolet, visible light or infrared radiation.

The inventive actinic radiation curable compositions described herein can be used as 3D printing resin formulations, ie, compositions intended for the manufacture of three-dimensional objects using 3D printing techniques. Such three-dimensional articles may be freestanding/self-supporting and may consist essentially of or consist of cured actinic radiation curable compositions according to the invention. The three-dimensional object may also be a composite material comprising at least one component consisting essentially of or consisting of a solidified composition as mentioned previously and comprising one or more materials other than such solidified composition At least one additional component (such as a metallic component or a thermoplastic component). The actinic radiation curable compositions of the present invention are particularly suitable for use in digital photoprinting (DLP), but other types of three-dimensional (3D) printing can also be implemented using the curable compositions of the present invention (e.g., SLA, inkjet) method. The actinic radiation curable composition of the present invention can be used in a three-dimensional printing operation together with another material that acts as a support or support for an article formed from the actinic radiation curable composition of the present invention.

Therefore, the actinic radiation curable composition of the present invention is suitable for implementing various types of three-dimensional manufacturing or printing techniques, including methods of constructing three-dimensional objects in a step-by-step or layer-by-layer manner. In such methods, layer formation may be performed by solidification (curing) of the actinic radiation curable composition upon exposure to radiation, such as visible light, UV or other actinic radiation. For example, a new layer can be formed on the top surface of the growing object or the bottom surface of the growing object. The actinic radiation curable composition according to the invention can also advantageously be used in a process for the production of three-dimensional objects by additive manufacturing, wherein the process is carried out continuously. For example, objects can be generated from liquid interfaces. A suitable method of this type is sometimes referred to in the art as a "continuous liquid interface (or interphase) production (or printing)" ("CLIP") method. Such methods are described, for example, in WO 2014/126830; WO 2014/126834; WO 2014/126837; and Tumbleston et al., "Continuous Liquid Interface Production of 3D Objects", Science vol. 347, No. 6228, pp. 1349-1352 . (March 20, 2015), the entire disclosure of which is incorporated herein by reference in its entirety for all purposes.

When stereolithography is performed above an oxygen-permeable build window, articles can be produced using the actinic radiation curable composition according to the invention by creating an oxygen-containing "dead zone" during the CLIP process, which The cured article is a thin uncured layer of curable composition between the window and the surface of the cured article. In such processes, actinic radiation is used to curable compositions in which curing (polymerization) is inhibited by the presence of molecular oxygen; such inhibition is typically observed, for example, in curable compositions capable of curing by free radical mechanisms. The desired dead zone thickness can be maintained by selecting various control parameters such as photon flux and optical and curing properties of the curable composition. The CLIP process is performed by projecting a series of continuous actinic radiation (e.g., UV) patterns through an oxygen-permeable actinic radiation (e.g., UV) transparent window beneath a bath that maintains the actinic radiation-curable composition in liquid form An image (which may be generated, for example, by a digital light processing imaging unit). The liquid interface below the advancing (growing) item is maintained by the dead zone created above the window. The cured article is continuously withdrawn from the actinic radiation curable composition bath above the dead zone, which can be compensated for by feeding an additional amount of the curable composition into the bath to compensate for the possible actinic radiation curing and incorporation into the growing article. The amount of curing composition to supplement.

The present invention relates to a method of manufacturing a three-dimensional object, comprising: a) applying a first layer of the actinic radiation curable composition according to the invention to the surface; b) at least partially curing the first layer to provide a cured first layer; c) applying a second layer of the actinic radiation curable composition onto the cured first layer; d) at least partially curing the second layer to provide a cured second layer adhered to the cured first layer; Steps c) and d) are repeated as many times as necessary to accumulate a three-dimensional object consisting of the actinic radiation curable composition in cured form.

Although the curing step may be performed by any suitable means, and in some cases the means will depend on the components present in the curable composition, in some embodiments of the invention, the curing step is achieved by exposing the layer to be cured to Curing is effected with an effective amount of radiation, especially actinic radiation (eg, electron beam radiation, UV radiation, visible light, etc.). The formed three-dimensional article can be heated to achieve thermal curing.

Accordingly, in various embodiments, the present invention provides a method of fabricating a three-dimensional article comprising the steps of: a) providing (eg coating) a first layer of an actinic radiation curable composition according to the invention and in liquid form onto a surface; b) imagewise exposing the first layer to actinic radiation to form a first exposed imaged cross-section, wherein the radiation has an intensity and duration sufficient to cause at least partial curing of the layer in the exposed areas; c) providing (eg, coating) another layer of actinic radiation curable composition onto the previously exposed imaged cross-section; d) image-wise exposing the further layer to actinic radiation to form a further imaged cross-section, wherein the radiation is of a magnitude sufficient to cause at least partial curing of the further layer in the exposed regions and to cause the further layer to differ from the previously exposed imaged cross-section. the strength and duration of the adhesion; e) Steps c) and d) are repeated the required number of times to accumulate three-dimensional objects.

After printing a 3D object, it can be subjected to one or more post-processing steps. The post-processing step may be selected from one or more of the following steps: removal of any printed support structures, washing with water and/or organic solvents to remove residual resin, and post-treatment using heat treatment and/or actinic radiation simultaneously or sequentially. solidified. Post-processing steps can be used to convert newly printed items into finished functional items ready for their intended application.

In one embodiment, the method of manufacturing a three-dimensional object comprises the step of heating the actinic radiation curable composition above the melting point of the at least one polyamide of component a).

Therefore, the method of manufacturing a three-dimensional object may include the following steps: a') heating the actinic radiation curable composition according to the invention to a temperature above the melting point of component a); b') applying a first layer of heated actinic radiation curable composition to the surface; c') cooling the first layer to a temperature below the melting point of component a) to obtain a cooled first layer; d') at least partially solidifying the cooled first layer to provide a solidified first layer; e') applying a second layer of heated actinic radiation curable composition onto the cured first layer; f') cooling the second layer to a temperature below the melting point of component a), resulting in a cooled second layer; g') at least partially curing the second layer to provide a cured second layer adhered to the cured first layer; h') Steps e'), f') and g') are repeated as many times as necessary to accumulate a three-dimensional object consisting of said actinic radiation curable composition in cured form.

In particular, steps c') and d') can be carried out simultaneously and steps f') and g') can be carried out simultaneously.

The invention also relates to a method of producing a three-dimensionally printed article using digital light projection, stereolithography or multi-jet printing, comprising irradiating an actinic radiation curable composition according to the invention in a layer-by-layer manner to form a three-dimensional print thing. Aspects of the invention

Exemplary aspects of the invention can be summarized as follows: Aspect 1: An actinic radiation curable composition comprising: a) at least one polyamide free of actinic radiation curable functional groups; and b) at least one actinic radiation curable compound, wherein the at least one actinic radiation curable compound is liquid at 25°C; Where condition i), condition ii) or condition iii) is satisfied: i) the at least one polyamide is unmodified polyamide or a combination of unmodified polyamides, and the at least one polyamide is completely soluble in the actinic radiation curable composition at 25°C in the thing; ii) at least a portion of the at least one polyamide is present as particles dispersed in the actinic radiation curable composition at 25°C; iii) The actinic radiation curable composition is a gel at 25°C and a liquid at 100°C or higher.

Aspect 2: The actinic radiation curable composition of aspect 1, wherein the actinic radiation curable composition comprises at most 30 parts by weight of polyamide per 100 parts by weight of actinic radiation curable compound.

Aspect 3: The actinic radiation curable composition according to Aspect 1 or Aspect 2, wherein the actinic radiation curable composition comprises 0.5 to 25 parts by weight of polyamide per 100 parts by weight of the actinic radiation curable compound.

Aspect 4: The actinic radiation curable composition according to any one of aspects 1 to 3, wherein the actinic radiation curable composition is a homogeneous liquid at 25°C.

Aspect 5: The actinic radiation curable composition according to any one of Aspects 1 to 3, wherein condition iii) is satisfied.

Aspect 6: The actinic radiation curable composition according to any one of aspects 1 to 3, wherein condition ii) is satisfied, and the at least one polyamide particle is dispersed in the at least one actinic radiation curable compound in the liquid matrix.

Aspect 7: The actinic radiation curable composition of any one of Aspects 1 to 6, wherein the at least one actinic radiation curable compound comprises at least one actinic radiation curable compound selected from the group consisting of Compounds: (meth)acrylate functionalized compounds, cyanoacrylates, methylenemalonates, itaconates, and combinations thereof.

Aspect 8: The actinic radiation curable composition of any of Aspects 1 to 7, wherein the at least one actinic radiation curable compound comprises at least one (meth)acrylate functionalized oligomer.

Aspect 9: The actinic radiation curable composition of any one of Aspects 1 to 8, wherein the at least one actinic radiation curable compound comprises at least one (meth)acrylic acid selected from the group consisting of Ester-functionalized compounds: polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, amine (meth)acrylate oligomer, epoxy (meth)acrylate Oligomers, urethane (meth)acrylate oligomers, and combinations thereof.

Aspect 10: The actinic radiation curable composition according to any one of Aspects 1 to 9, wherein the viscosity of the actinic radiation curable composition at 25° C. is not more than 100,000 mPa.s.

Aspect 11: The actinic radiation curable composition of any one of Aspects 1 to 10, wherein the at least one polyamide comprises at least one polyamide consisting of at least one polyamide block and at least one block copolymer selected from the group consisting of: polyester block, polysiloxane block, polyether-ester block, polyether block and polyorganosilicon oxane block.

Aspect 12. The actinic radiation curable composition of any one of Aspects 1 to 11, wherein the at least one polyamide comprises at least one polyamide consisting of at least one polyamide block and at least one block copolymer selected from the group consisting of: polyethylene glycol block, polypropylene glycol block, polybutylene glycol block, polydimethylsiloxane block and ethoxylated bisphenol A block.

Aspect 13: The actinic radiation curable composition of any one of Aspects 1 to 12, wherein the at least one polyamide block is a polyamide block selected from the group consisting of: polyamide Amine 6,6, Polyamide 6,10, Polyamide 10,10, Polyamide 6,12, Polyamide 4,6, Polyamide 6, Polyamide 11, and Polyamide 12.

Aspect 14: The actinic radiation curable composition of any one of Aspects 1 to 13, wherein the at least one polyamide comprises at least one polyamide that is a thermoplastic elastomer and is Block copolymers consisting of at least one polyamide block and at least one polybutylene glycol block selected from the group consisting of polyamide 6,6, polyamide 6,10, polyamide Amine 10,10, Polyamide 6,12, Polyamide 4,6, Polyamide 6, Polyamide 11, and Polyamide 12.

Aspect 15: The actinic radiation curable composition of any one of Aspects 1 to 14, wherein the actinic radiation curable composition is curable by exposure to at least one of ultraviolet light, visible light, and electron beam radiation And solidified.

Aspect 16: The actinic radiation curable composition of any one of Aspects 1 to 15, wherein the at least one polyamide comprises at least one polyamide having a number average molecular weight of 10,000 to 100,000 g/mol.

Aspect 17: The actinic radiation curable composition of any one of Aspects 1 to 16, wherein the at least one polyamide comprises at least one polyamide selected from the group consisting of: polyamide 6 , 6, polyamide 6,10, polyamide 10,10, polyamide 6,12, polyamide 4,6, polyamide 6, polyamide 11 and polyamide 12.

Aspect 18: The actinic radiation curable composition of any one of Aspects 1 to 17, further comprising at least one photoinitiator.

Aspect 19: The actinic radiation curable composition of any one of Aspects 1 to 18, wherein the actinic radiation curable composition comprises less than 0.1% by weight of the actinic radiation curable composition Non-reactive solvent.

Aspect 20: The actinic radiation curable composition of any one of Aspects 1 to 19, wherein the actinic radiation curable composition does not contain a non-reactive solvent.

Aspect 21: The actinic radiation curable composition of any one of Aspects 1 to 20, wherein condition i) is satisfied, and the actinic radiation curable composition further comprises at 25° C. effective to make the at least one The amount of at least one non-reactive solvent in which the polyamide is completely soluble in the actinic radiation curable composition.

Aspect 22: The actinic radiation curable composition of any one of Aspects 1 to 21, wherein the at least one polyamide is partially dissolved in the at least one actinic radiation curable compound at 25°C.

Aspect 23: The actinic radiation curable composition of any of Aspects 1 to 22, wherein the at least one polyamide comprises at least one polyamide that is a thermoplastic material.

Aspect 24: The actinic radiation curable composition of any one of Aspects 1 to 23, wherein the at least one polyamide comprises at least one polyamide that is a thermoplastic elastomer.

Aspect 25: The actinic radiation curable composition of any one of Aspects 1 to 24, wherein component a) and component b) have a Hansen solubility parameter δp of 7 to 10 MPa ^1/2 and 4.5 to Hansen solubility parameter δh of 8.5 MPa ^1/2 .

Aspect 26: The actinic radiation curable composition of any one of Aspects 1 to 25, wherein the actinic radiation curable composition is selected from the group consisting of adhesives, sealants, coatings , 3D printing and additive manufacturing resins, inks and molding resins.

Aspect 27: A method of making a cured polymeric material, wherein the method comprises curing the actinic radiation curable composition of any one of Aspects 1 to 26 with actinic radiation.

Aspect 28: The method of Aspect 27, wherein the method utilizes at least one of ultraviolet light or visible light.

Aspect 29: A cured polymer material obtained according to the method of Aspect 27 or Aspect 28.

Aspect 30: The cured polymeric material of Aspect 29, wherein, as measured by ASTM D256-10 (2018), is identical to the actinic radiation curable composition by making the composition without the at least one The cured polymer material has a higher fracture energy than the cured polymer material obtained by photocuring similar actinic radiation curable compositions of polyamides.

Aspect 31: A method of manufacturing a three-dimensional article by additive manufacturing, comprising using the actinic radiation curable composition according to any one of aspects 1-26 to manufacture the three-dimensional article.

Aspect 32: The method of Aspect 31, wherein after the lamination fabrication step, the three-dimensional article is subjected to a further step of post-curing using at least one of actinic radiation or heat.

Aspect 33: The method of Aspect 31 or Aspect 32, wherein after the lamination fabrication step, the actinic radiation curing in the three-dimensional article is removed from the three-dimensional article using at least one of thermal degradation or washing with an organic solvent polymer phase.

Aspect 34: The method of Aspect 33, after removing the actinic radiation-cured polymer phase, a polyamide phase remains in the three-dimensional article, and the polyamide phase is then subjected to thermal sintering.

Aspect 35: A method of manufacturing a three-dimensional article, comprising: a) applying a first layer of the actinic radiation curable composition according to any one of aspects 1 to 26 to the surface; b) curing the first layer to provide a cured first layer; c) coating a second layer of the actinic radiation curable composition onto the cured first layer; d) curing the second layer to provide a cured second layer adhered to the cured first layer; e) repeating steps c) and d) as many times as necessary to accumulate a three-dimensional object consisting of the actinic radiation curable composition in cured form.

Aspect 36: The method of Aspect 35, wherein the actinic radiation curable composition is heated above the melting point of the a) at least one polyamide free of actinic radiation curable functional groups.

Aspect 37: A method of manufacturing a three-dimensionally printed article using digital light projection, stereolithography, or multi-jet printing, comprising irradiating the actinic radiation curable composition according to any one of Aspects 1 to 26 in a layer-by-layer manner object to form the 3D printed object.

Aspect 38: A method of manufacturing a three-dimensional article, comprising: a) heating the actinic radiation curable composition according to any one of aspects 1 to 26 to a temperature above the melting point of component a); b) applying a first layer of heated actinic radiation curable composition to the surface; c) cooling the first layer to a temperature below the melting point of component a), resulting in a cooled first layer; d) solidifying the cooled first layer to provide a solidified first layer; e) applying a second layer of heated actinic radiation curable composition onto the cured first layer; f) cooling the second layer to a temperature below the melting point of component a), resulting in a cooled second layer; g) curing the second layer to provide a cured second layer adhered to the cured first layer; h) repeating steps e), f) and g) as many times as necessary to accumulate a three-dimensional object consisting of the actinic radiation curable composition in cured form.

Aspect 39: The method of Aspect 38, wherein steps c) and d) are performed simultaneously and steps f) and g) are performed simultaneously.

Aspect 40: A method of making the actinic radiation curable composition according to any one of aspects 1 to 26, wherein the method comprises combining at least one polyamide, at least one actinic radiation curable compound, and a compound capable of dissolving at least At least one volatile solvent of a polyamide to provide an initial mixture and at least a portion of the volatile solvent is removed from the initial mixture to provide the actinic radiation curable composition.

Within this specification, the embodiments have been described in such a manner that a clear and concise description can be written, but it is intended and understood that the embodiments may be combined or separated in various ways without departing from the invention. For example, it should be understood that all preferred features described herein apply to all aspects of the invention described herein.

In some embodiments, the invention herein may be construed to exclude acts that do not substantially affect the actinic radiation curable composition, methods for making the actinic radiation curable composition, use of the actinic radiation curable composition Any element or process step that is the basic and novel feature of the method and of the articles made from the actinic radiation curable composition. Additionally, in some embodiments, the invention may be construed excluding any element or process step not described herein.

Although the invention is illustrated and described herein with reference to particular embodiments, the invention is not intended to be limited to the details shown. In fact, various modifications may be made in detail within the scope and scope of equivalents of the claims and without departing from the invention. EXAMPLES Example 1: Composition of mixtures of polyamides (PEBAX® grades 2533 and 4023, Arkema) and actinic radiation curable compounds (SARTOMER® CN1964CG; SR210CG; SR506D, both from Arkema) containing no actinic radiation curable functional groups compatibility

These materials are: SARTOMER ^® PRO22456: 10 wt % PEBAX ^® 2533 in SARTOMER ^® SR506D SARTOMER ^® PRO22457: 10 wt % PEBAX ^® 4023 in SARTOMER ^® SR506D

PRO22456 and PRO22457 were prepared by melting Pebax pellets in a pot at 110°C (for PEBAX® 2533) or 120°C (for PEBAX® 4023). Then preheated monomer SR506D was added while stirring at 1000 ppm MEHQ and under ₀₂ . SARTOMER ^® SR210CG: polyethylene glycol (200) dimethacrylate (PEG200DMA) SARTOMER ^® SR506D: isobornyl acrylate (IBOA) SARTOMER ^® CN1964CG: urethane dimethacrylate

Tables 1-3 show the mixing conditions and compatibility results for various combinations of polyamide and actinic radiation curable compound. Amounts of polyamides, oligomers and monomers are given in parts by weight. % PEBAX in the formulation is expressed as % by weight of PEBAX based on the total weight of the formulation. [Table 1] Table 1: Examples 1A-1D example 1A 1B 1C (control) 1D Polyamide PRO22456 10 10 - - PRO22457 - - - 10 oligomer CN1964CG 30 50 50.4 50 monomer SR210CG 50 - - - SR506D - 40 49.5 40 total 90 100 99.9 100 PEBAX% in the preparation 1.1 1 0 1 Blending method (manual blending unless specified) Heat separately at 110°C, then mix together and heat at 110°C for 5 minutes Heat separately at 110°C, then mix together and heat at 110°C for 30 minutes, then mix every 5 minutes Mix and heat at 110°C for 10 minutes Heat separately at 110°C, then mix together and heat at 110°C for 30 minutes, then mix every 5 minutes just after mixing (hot) liquid with small agglomerates liquid with small agglomerates liquid liquid with small agglomerates After 30 minutes at 20-25°C liquid with small agglomerates liquid with small agglomerates liquid liquid with small agglomerates After 24 hours at 20-25°C gelled liquid with small agglomerates liquid gelled [Table 2] Table 2: Examples 1E - 1H example 1E 1F 1G 1H Polyamide PRO22456 20 35 50 15 PRO22457 - - - - oligomer CN1964CG 30 30 30 30 monomer SR210CG - - - - SR506D 50 35 20 55 total 100 100 100 100 PEBAX% in the preparation 2 3.5 5 1.5 Blending method (manual blending unless specified) Mix with Dispermill Discovery 200 at 75°C and 800 rpm for 20 minutes, then heat to 110°C for 15 minutes just after mixing (hot) lumpy lumpy lumpy liquid with some lumps After 30 minutes at 20-25°C liquid start to gel gelled liquid After 24 hours at 20-25°C gelled gelled gelled gelled [table 3] Table 3: Examples 1I-1K example 1I 1J 1K Polyamide PRO22456 20 30 50 PRO22457 - - - oligomer CN1964CG - - - monomer SR210CG - - - SR506D 80 70 50 total 100 100 100 PEBAX% 2 3 5 Blending method (manual blending unless specified) Heat separately at 110°C, then mix together and heat at 110°C for 30 minutes, then mix every 5 minutes just after mixing (hot) liquid liquid liquid After 30 minutes at 20-25°C liquid with small agglomerates start to gel start to gel After 24 hours at 20-25°C gelled gelled gelled

The above results show that the addition of polyamides to actinic radiation curable compounds generally provides liquids or liquids with small agglomerates while still hot immediately after mixing. However, the mixture almost always produced a homogeneous gel after cooling at room temperature for 24 hours. Either of these forms is expected to be suitable as a medium for additive manufacturing. Example 2: Properties of Cured Formulations:

This example is based on dispersing PEBAX powder in an oligomer or monomer blend. Four different formulations were prepared by combining powders of polyamides without actinic radiation curable functional groups with four different actinic radiation curable compounds. The amount of polyamide is expressed as weight percent polyamide based on the weight of the formulation. All preparations and testing were performed at room temperature and are described in detail below.

Use a Glass-Col Rugged Rotator for mixing. The samples were cured in silicone molds under an LED conveyor at full intensity, 395 nm wavelength, 50 rpm with two passes for each sample. The test proceeds as follows:

Viscosity was measured prior to curing using a Brookfield disc rheometer. Tensile properties after curing were measured using an Instron according to the procedure in ASTM D638.

The results and properties after curing are shown in Table 4 with the exception of viscosity, which was measured on the mixture before curing. [Table 4] Table 4: Properties of Example 2 Formulation and Cured Amount of polyamide*, wt% Actinic Radiation Curable Compound: N3xtDimension ^® P-121 Viscosity before curing (mPa.s) Tensile strength (MPa) Elongation(%) Modulus (MPa) Fracture energy (kg.m ² .s ^-2 ) Polyamide state 0% 50 47.1 7.8 900 0.144 1% 47.4 21.4 3.3 699.6 0.186 dispersion 3% 49.2 20.1 3.3 649.8 0.185 dispersion 5% 57.6 21.3 4 584.3 0.235 dispersion Actinic Radiation Curable Compound: N3xtDimension ^® I-150 0% 46000 15.8 50 172.4 1.68 - 1% 49225 19.2 36.6 243.3 3.112 to dissolve 3% 12071 14.55 34.75 177.65 2.0655 to dissolve 5% 6522 17.7 22.3 246.2 1.627 to dissolve 10% 9121 12.9 31.6 149.1 1.94 mix Actinic Radiation Curable Compound: N3xtDimension ^® P-220 0% 1425 36.1 4.9 990.5 0.1 - 10% 2009 16.9 3.9 486.2 0.219 - 20% 4920 16.6 4.1 466.1 0.206 - Actinic Radiation Curable Compound: N3xtDimension ^® F-230 0% 550 12.6 39.9 162.6 0.8 - 10% 566 10.4 29.6 146.5 1.506 dispersion 20% 944 14.1 18.6 214 1.123 dispersion *PEBAX ^® 9002 from Arkema

These results show that the fracture energy of all samples incorporating polyamide was increased (higher than the control). In general, the opacity of all samples incorporating polyamide increased. Improved (lower than control) viscosity prior to curing was observed in the mixture of polyamide and actinic radiation curable compounds P-220 and 1-150. Example 3: Properties of 4-tert-butylcyclohexyl acrylate with 17 wt% polyamide compared to 100% 4-tert-butylcyclohexyl acrylate

The samples were prepared by first mixing 4-tertiary butylcyclohexyl acrylate (TBCHA) ( ^SARTOMER® SR217, Arkema) with 17 wt% polyamide ( ^PEBAX® 2533, Arkema) by weight of the composition. The first step was melting the Pebax pellets in a pot at 110°C or 120°C, followed by the addition of preheated monomer SR217 in a second step at 1000 ppm MEHQ with stirring under _O2 . This preparation was then mixed together with 4 wt% photopolymerization initiator (Irgacure ^® TPO-L, BASF) at 110°C. These are compared to pure 4-tert-butylcyclohexyl acrylate also combined with 4 wt% of the same photopolymerization initiator. The samples were cured under the LED conveyor at full intensity, 395 nm wavelength, with 5 passes per side at 5 m/min for each sample. When post-curing, it was carried out in an oven at 120° C. for 2 hours. The properties were compared using dynamic analysis (DMA) as well as three-point bending. Cured samples of a blend of 4-tert-butylcyclohexyl acrylate and 17 wt% polyamide were post-cured with heat, and their properties were measured by DMA and three-point bending. The results are presented in Table 5. [table 5] Table 5: Results of Example 3 example 3A 3B 3C (control) Polyamide, wt% in TBCHA 17 17 0 deal with light curing only Light curing and post curing light curing only DMA - Torque Tα (i.e., maximum temperature transition) °C -40/-8 -40/-3 31 E' at 200℃ Flow above 40°C Flow above 40°C Flow/slip above 40°C Three-point bending test (2 mm/min) Fracture stress, MPa 9.6 7.3 17 standard deviation 1.0 0.9 4 Fracture deflection (mm) 4.8 5.8 4.9 standard deviation 0.9 1.1 1.1 Flexural modulus (GPa) 363 415 1337 standard deviation 30 37 99

(none)

[Fig. 1] is a graph of two Hansen parameters applicable to various compounds used herein as components (a) and (b), namely the parameter δh (in MPa ^1/2 ), which is quantified from the molecular The energy of the hydrogen bond between them; the comparison parameter, the parameter δp (also in MPa ^1/2 unit), which represents the energy of the dipole interaction between molecules.

Claims (24)

An actinic radiation curable composition comprising: a) at least one polyamide free of actinic radiation curable functional groups; and b) at least one actinic radiation curable compound, wherein the at least one actinic radiation The curable compound is liquid at 25°C; wherein the actinic radiation curable composition comprises up to 30 parts by weight of polyamide per 100 parts by weight of actinic radiation curable compound, and the polyamide comprises at least one polyamide , which is a block copolymer consisting of at least one polyamide block and at least one block which is not a polyamide block; and wherein condition i), condition ii) or condition iii) is satisfied: i) the at least one polyamide is unmodified polyamide or a combination of unmodified polyamides, and the at least one polyamide is completely soluble in the actinic radiation curable composition at 25°C; ii ) at least a portion of the at least one polyamide is present as particles dispersed in the actinic radiation curable composition at 25°C; iii) the actinic radiation curable composition is a gel at 25°C and at 100 Liquid at ℃ or higher. The actinic radiation curable composition according to claim 1, wherein the actinic radiation curable composition comprises 0.5 to 25 parts by weight of polyamide per 100 parts by weight of actinic radiation curable compound. The actinic radiation curable composition according to claim 1, wherein the actinic radiation curable composition comprises 0.5 to 10 parts by weight of polyamide per 100 parts by weight of actinic radiation curable compound. The actinic radiation curable composition according to claim 1, wherein condition iii) is satisfied. The actinic radiation curable composition according to claim 1, wherein the condition ii) is satisfied, and the particles of the at least one polyamide are dispersed in the liquid matrix of the at least one actinic radiation curable compound. The actinic radiation curable composition according to claim 1, wherein the at least one actinic radiation The radiation curable compound comprises at least one actinic radiation curable compound selected from the group consisting of (meth)acrylate functionalized compounds, cyanoacrylates, methylene malonates, itaconic acid Esters and combinations thereof. The actinic radiation curable composition according to claim 1, wherein the at least one actinic radiation curable compound comprises at least one sterically hindered (meth)acrylate monomer. The actinic radiation curable composition according to claim 7, wherein the sterically hindered (meth)acrylate monomer comprises a cyclic moiety. The actinic radiation curable composition as claimed in item 7, wherein the sterically hindered (meth)acrylate monomer system is selected from: tertiary butyl (meth)acrylate, 2-phenoxy (meth)acrylate ethyl ethyl ester, benzyl (meth)acrylate, nonylphenol (meth)acrylate, isobornyl (meth)acrylate, tertiary butylcyclohexyl (meth)acrylate, (meth)acrylic acid 3,3,5-Trimethylcyclohexyl ester, Dicyclopentadienyl (meth)acrylate, Tricyclodecane methanol mono(meth)acrylate, Tricyclodecane dimethanol di(meth)acrylate ester, tetrahydrofuryl (meth)acrylate, cyclic trimethylolpropaneformyl (meth)acrylate (CTFA, also known as (meth)acrylate 5-ethyl-1,3-di

Alkyl-5-yl)methyl ester), (meth)acrylate (2,2-dimethyl-1,3-dioxolan-4-yl)methyl ester, (meth)acrylate (2- Ethyl-2-methyl-1,3-dioxolan-4-yl)methyl ester, glycerol formal methacrylate, its alkoxylated derivatives and mixtures thereof. The actinic radiation curable composition according to claim 7, wherein the sterically hindered (meth)acrylate monomer accounts for at least 10% by weight of the total weight of the actinic radiation curable composition. The actinic radiation curable composition of claim 1, wherein the at least one actinic radiation curable compound comprises at least one urethane (meth)acrylate. The actinic radiation curable composition according to claim 11, wherein the urethane (meth)acrylate is an aliphatic urethane (meth)acrylate. The actinic radiation curable composition according to claim 11, wherein the urethane (meth)acrylate monomer accounts for at least 10% by weight of the total weight of the curable composition. The actinic radiation curable composition according to claim 1, wherein the at least one actinic radiation curable compound comprises at least one (meth)acrylate functionalized monomer and at least one (meth)acrylate functionalized oligosaccharide Polymer. The actinic radiation curable composition according to claim 1, wherein the at least one actinic radiation curable compound comprises: - at least one sterically hindered (meth)acrylate monomer; and - at least one urethane (meth)acrylates. The actinic radiation curable composition as claimed in claim 1, wherein the at least one polyamide comprises at least one polyamide, the at least one polyamide is composed of at least one polyamide block and at least one selected from the group consisting of Block copolymers composed of groups of blocks: polyester blocks, polysiloxane blocks, polyether-ester blocks, polyether blocks, and polyorganosiloxane blocks. The actinic radiation curable composition as claimed in claim 1, wherein the at least one polyamide comprises at least one polyamide, the at least one polyamide is composed of at least one polyamide block and at least one selected from the group consisting of Block copolymers composed of blocks composed of groups: polyethylene glycol blocks, polypropylene glycol blocks, polybutylene glycol blocks, polydimethylsiloxane blocks and ethoxylated bisphenol A block. The actinic radiation curable composition as claimed in claim 1, wherein the at least one polyamide comprises at least one polyamide selected from the group consisting of: polyamide 6,6, polyamide 6,10, Polyamide 10,10, Polyamide 6,12, Polyamide 4,6, Polyamide 6, Polyamide 11, and Polyamide 12. The actinic radiation curable composition according to claim 1, wherein the actinic radiation curable composition comprises less than 0.1% by weight of non-reactive solvent based on the weight of the actinic radiation curable composition. The actinic radiation curable composition of claim 1, wherein the at least one polyamide is partially dissolved in the at least one actinic radiation curable compound at 25°C. A method of making a cured polymeric material, wherein the method comprises the use of actinic The radiation cures the actinic radiation curable composition of any one of claims 1 to 20. A cured polymer material obtained by the method as claimed in claim 21. A method of manufacturing a three-dimensional article by additive manufacturing, comprising using the actinic radiation curable composition according to any one of claims 1 to 20 to manufacture the three-dimensional article. The method of claim 23, wherein after the lamination manufacturing step, the three-dimensional article is subjected to a further step of post-curing using at least one of actinic radiation or heat.

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