Solid-phase method for processing synthetic thermoplastic articles

Abstract

Solid-state branching and / or crosslinking of synthetic thermoplastic articles is achieved using a topical approach. The surface of the article is coated with a composition comprising a polyene and a free radical initiator. The article and applied coating are then heated to induce branching and / or crosslinking in the thermoplastic. This is done below the crystalline melting temperature of the thermoplastic, or, in the case of fabrics, below the melting temperature of the fibers in the fabric. Fabrics treated in such a manner show reduced or no dripping in a vertical burn test.

Description

[Technical Field]

[0001] The present invention generally relates to a method for processing synthetic thermoplastic articles. [Background technology]

[0002] Synthetic thermoplastics such as aliphatic polyamides (commonly known as "nylon"), polyesters, and polyacrylonitriles (PANs) are used, among other things, for the purpose of producing fibers and yarns, which are then knitted or woven to produce cloths. Polyamide cloths are notable for their high strength and abrasion resistance. Polyamide, polyester, and PAN cloths are useful for producing clothing and protective equipment for military, paramilitary, and law enforcement personnel. These cloths are also used to produce a variety of products for use inside homes, offices, and / or other buildings, a variety of products including, among other things, carpets, drapes and curtains, upholstery, bedding, shower curtains, window treatments, wallpaper, and other decorative coverings.

[0003] As thermoplastic materials, polymers such as polyamides, polyesters, and PANs can soften and flow when heated to sufficiently high temperatures. In at least some of the aforementioned applications, it is important to prevent dripping when the article is exposed to an open flame or other heat source. This is often a fire safety issue, as dripped flammable material can cause injury or death by spreading flames or dripping onto people or animals. This concern is reflected in various standard combustion tests, such as ASTM D6413-11, EN 13501-1 Single Burning Item test, and British Standard BS5867 Part 2-Type B test, which evaluate droplet formation under specific ignition conditions.

[0004] Numerous strategies have been devised to improve the performance of thermoplastic articles in standardized combustion tests. These strategies often involve various additives, such as char-forming agents, organophosphorus compounds, organohalogen compounds, hydrated minerals, red phosphorus, and borates. All of these additives have drawbacks. They increase costs, require additional processing steps, and affect physical and / or aesthetic properties. In some cases, they pose exposure or environmental risks. Most have little effect on melting and / or dropping.

[0005] Molded nylon parts can be crosslinked by compounding thermoplastic nylon with polyene compounds (such as triallyl cyanurate, triallyl isocyanurate, and trimethylolpropane trimethacrylate), and then irradiating this compounded material in a mold. See, for example, Non-Patent Document 1. In principle, melting and / or dripping can be reduced by crosslinking thermoplastic polymers, but this process is not feasible for the production of fibers or fabrics on an industrial scale. Similarly, polymers are crosslinked or branched using such polyene compounds in combination with various free radical initiators. This is described, for example, in Patent Document 1 and Non-Patent Document 2. These methods are carried out in a molten state. These methods generate a considerable amount of gel, making them unsuitable for the production of industrial fibers or yarns. These gels clog the spinneret and cause fiber breakage during the spinning and / or subsequent drawing processes. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2019 / 152264 [Non-patent literature]

[0007] [Non-Patent Document 1] Pramanik et al., Radiation Physics and Chemistry,2009,Vol.79,p.199-205 [Non-Patent Document 2] Yang et al., Polymer Testing, 2008, Vol. 27, p. 957-963 [Modes for carrying out the invention]

[0008] The present invention relates to a solid-phase method for processing a synthetic thermoplastic article containing a synthetic thermoplastic component, wherein the synthetic thermoplastic component comprises one or more synthetic thermoplastic resins having a crystal melting temperature of 100°C or higher. That is, the method is a) A step of applying a coating composition to one or more surfaces of the article at a temperature below the crystal temperature of the synthetic thermoplastic resin, and bringing the coating composition into contact with one or more polyamide and / or polyester components of the article, wherein the coating composition comprises (i) one or more polyene compounds having 2 to 6 vinyl groups and a vinyl group equivalent of 125 g / equivalent or less, and (ii) one or more free radical initiators, and an amount of the coating composition sufficient to provide 0.04 kg or more of polyene compounds and 0.005 kg or more of peroxy or azo free radical initiators per 1 kg of synthetic thermoplastic component in the article is applied to the article. b) The coated article is heated to a temperature of 70°C or higher and below the crystal melting temperature of the synthetic thermoplastic resin to decompose the peroxy or azo free radical initiator, to form free radicals, and to generate crosslinks in the aliphatic synthetic thermoplastic resin.

[0009] To our great surprise, the applicant has found that it is possible to induce crosslinking in synthetic thermoplastic resins by applying a coating composition locally and then performing a heating step in a solid state (i.e., below the crystalline melting temperature of the synthetic thermoplastic resin). The ability to crosslink in this method offers very substantial advantages. It eliminates the need to melt-blend crosslinking agents (polyenes and free radical initiators) into the synthetic thermoplastic resin before manufacturing the article. Therefore, special grades of resin are not required, and the cost of compounding them is avoided. Radiation treatment steps, such as those described in Non-Patent Document 1, are unnecessary and therefore can be eliminated. Simple and inexpensive coating and heating equipment can be used. The process is suitable for both continuous and batch operations and can therefore often be implemented in existing production lines.

[0010] The process, in practice, allows for the modification of synthetic thermoplastic articles manufactured using melt processing methods such as melt spinning, extrusion, and blow molding in a simple manner, thereby generating properties in the article (or at least on the treated surface) that are more similar to those of crosslinked thermosetting polymers that are otherwise unsuitable for melt processing operations. One particular advantage is that the treated product generally exhibits reduced or, in some cases, elimination of melting and / or dripping when exposed to flame in a vertical flame test. This is a significant advantage when the article is a cloth or sheet material that constitutes or forms part of personal clothing, protective equipment, and building, furniture, or decorative products.

[0011] The process of the present invention typically does not affect the dimensions or geometric shape of the article, and any resulting changes in size and shape are negligible or, in some cases, nonexistent.

[0012] In a second aspect, the present invention relates to a solid-phase method for reducing the melting, dripping, or both of a cloth, wherein the cloth comprises alone fibers made of a synthetic thermoplastic resin having a crystalline melting temperature of 100°C or higher, or a blend of such fibers with fibers made of a polymer other than a synthetic thermoplastic resin having a crystalline melting temperature of 100°C or higher, wherein the fibers have a melting temperature of 100°C or higher as measured according to ASTM D7138-16. The method comprises the following steps: a) A step of applying a coating composition to one or more surfaces of the cloth at a temperature below the melting temperature of the fibers, wherein the coating composition comprises (i) one or more polyene compounds in an amount of 30 to 99.9 weight percent based on the weight of the coating composition, having 2 to 6 vinyl groups and a vinyl group equivalent of 125 g / equivalent or less, and (ii) one or more free radical initiators, wherein an amount of the coating composition sufficient to provide 0.04 kg or more of polyene compounds and 0.005 kg or more of peroxy or azo free radical initiators per 1 kg of cloth is applied to the article. b) The process includes heating the coated cloth to a temperature of 70°C or higher and below the melting point of the fibers for 1 minute to 2 hours.

[0013] The fabric retains its flexibility and pliability after processing, and in particular, the fibers or filaments do not aggregate to form large clumps. There is little to no change in tactile properties (sometimes referred to as "hand feel"). Airflow is substantially unchanged or only slightly changed.

[0014] A further advantage of the present invention is that the coating composition may further contain additional components that provide beneficial effects. These additional components may include, for example, plasticizers, fabric softeners, dyes, hydrophobic and / or oleophobic treatment agents, and many others.

[0015] The process is particularly suitable for treating fabrics of aliphatic polyamides, polyesters and / or PAN. Fabrics of aliphatic polyamides, polyesters, and / or PAN may, for example, contain fibers of aliphatic polyamides, polyesters, or PAN alone, blends of fibers of aliphatic polyamides, polyesters, and / or PAN with one another, and / or blends of fibers of aliphatic polyamides, polyesters, and / or PAN with fibers consisting of one or more other polymers other than polyamides, polyesters, or PAN, wherein such fibers consisting of other polymers have a melting temperature of 100 °C or higher when measured according to ASTM D7138-16.

[0016] The article to be treated contains one or more synthetic thermoplastic components containing one or more synthetic thermoplastic resins having a crystalline melting temperature of 100 °C or higher. Examples of such synthetic thermoplastic resins include polyamides, polyesters, and PAN. In some embodiments, the synthetic thermoplastic resin constitutes 50% or more, 75% or more, or 90% or more of the total weight of the synthetic thermoplastic component.

[0017] In some embodiments, the synthetic thermoplastic resin is a polyamide or contains a polyamide. The polyamide is aliphatic, i.e., does not contain aromatic groups. It is a thermoplastic organic polymer having repeating units linked by amide bonds. The formula molecular weight per amide group is preferably 500 g / mol or less, preferably 300 g / mol or less. The polyamide has a crystalline melting temperature of 100 °C or higher, preferably 150 °C or higher, when measured according to the capillary method of ISO 3,146:2000. The polyamide may be a polymer of α,ω-amino acids, a copolymer of a dicarboxylic acid and a diamine, a polymer of a cyclic lactam, or any combination of two or more thereof. Examples of useful polyamides include nylon 4, nylon 6, nylon 8, nylon 9, nylon 10, nylon 12, nylon 4 / 6, nylon 5 / 6, nylon 6 / 6, nylon 6 / 9, nylon 10 / 10, and nylon 10 / 12.

[0018] In other embodiments, the synthetic thermoplastic resin is a polyester or contains a polyester. The polyester may or may not contain an aromatic group. It is a thermoplastic polymer having repeating units bonded by ester bonds. The molecular weight per ester group is preferably 500 g / mol or less, preferably 300 g / mol or less. The polyester has a crystal melting temperature of 100 °C or higher, preferably 150 °C or higher, when measured according to the capillary method of ISO 3146:2000. The polyester may be, for example, but not limited to, poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene adipate-co-terephthalate), poly(butylene adipate-co-terephthalate), poly(ethylene succinate), poly(1,4-cyclohexylene-dimethylene terephthalate or poly(butylene succinate).

[0019] In still other embodiments, the synthetic thermoplastic resin is poly(acrylonitrile) or contains it. The synthetic thermoplastic component may contain other materials in addition to the synthetic thermoplastic resin. These may include, for example, but not limited to, other polymers blended with or forming a dispersion with the synthetic thermoplastic resin; fillers and reinforcing agents; rheology modifiers; impact modifiers; plasticizers; colorants; various thermoplastic processing aids (such as lubricants); preservatives; biocides; antioxidants and UV stabilizers, among many others.

[0020] The article may include one or more components that do not contain the synthetic thermoplastic resin. Such other components may be attached to the synthetic thermoplastic component, for example, by an adhesive, mechanically, magnetically, or otherwise. For example, the article may have a multilayer structure having one or more layers made of the synthetic thermoplastic resin and one or more other layers that do not contain any synthetic thermoplastic resin. [[ID=I1]]

[0021] Articles of particular interest include fabrics having fibers (especially one or more aliphatic polyamide fibers, polyester fibers, and PAN fibers) made of one or more synthetic thermoplastic resins having a crystalline melting temperature of 100°C or higher. Such fabrics include fibers and / or yarns made of synthetic thermoplastic resins, which are woven, knitted, intertwined, tied, felted, melt-bonded, or bonded together. Fibers or yarns made of synthetic thermoplastic resins having a crystalline melting temperature of 100°C or higher may be blended with other fibers or yarns made of other materials that are not synthetic thermoplastic resins having a crystalline melting temperature of 100°C or higher. Such other fibers may be, or may include, fibers made of materials such as cotton, elastomer polyurethane (including spandex), cellulose, wool, silk, aramid, polypropylene, polyacetate, and cellulose esters (such as rayon). The fibers have a melting temperature of 100°C or higher, preferably 150°C or higher, according to ASTM D7138-16 Method A (for blends of two or more different fibers) or Method B (for single-component fibers). The fabric may be in the form of a roll product having a width of 100 mm or more (e.g., 300 mm to 7 meters or more), or it may constitute all or part of a finished article such as clothing, curtains, bedding, carpets, wall coverings, etc., or both.

[0022] Step a) of this process involves a coating composition for one or more surfaces of an article, which is brought into contact with one or more synthetic thermoplastic components of the article. The coating composition comprises (i) one or more polyene compounds having 2 to 6 vinyl groups and a vinyl group equivalent of 150 g / equivalent or less, and (ii) one or more free radical initiators. The coating composition is advantageously in liquid form at the temperature at which it is applied to the article, or in the form of a dispersion having a liquid phase containing dispersed solids. If it is a dispersion, the polyene compound and the free radical initiator may each be independently in the liquid phase or the solid phase, or partially in both. The liquid phase of the dispersion may be, for example, the polyene compound or the free radical initiator, or both, or instead, or in addition thereto, the liquid phase may be or contain a carrier or other functional components. In some embodiments, the coating composition is a dispersion of solid free radical initiator particles in a liquid phase containing a liquid polyene compound and optionally one or more other liquid components (such as a carrier and / or other liquid functional components).

[0023] Polyene compounds contain 2 to 6 vinyl groups per molecule. The “vinyl” group for the purposes of the present invention is a -CHR=CHR group, where each R is independently hydrogen, a linear, branched, or cyclic alkyl group having up to 6 carbon atoms, or a phenyl group. The vinyl group is preferably allyl (i.e., part of a larger group having the form -CH2-CHR=CHR), or enone (i.e., part of a larger group having the form -C(O)-CHR=CHR), or both. R is preferably hydrogen in each case.

[0024] In some embodiments, the polyene compounds each contain 2 to 4 vinyl groups per molecule (if more than one), and in certain embodiments, they contain 2 or 3 vinyl groups per molecule.

[0025] Each polyene compound may have a vinyl group equivalent of 125 g / equivalent or less. Examples of suitable polyene compounds include, for example, various compounds corresponding to esters of acrylic acid or methacrylic acid with polyols. These include, for example, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, cyclohexanedimethanol diacrylate, alkoxylated hexanediol diacrylate, neopentyl glycol diacrylate, and propoxylated neopentyl glycol diacrylate. This includes trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, glycerin triacrylate, ethyloxylated and / or propoxylated glycerin triacrylate, pentaerythritol di, tri or tetraacrylate, erythritol di, tri or tetraacrylate, acrylic polyester oligomers, bisphenol A diacrylate, acrylic bisphenol A diglycidyl ether, ethoxylated bisphenol A diacrylate, and corresponding compounds in which the acrylate group is replaced by a methacrylate group. Other suitable acrylate compounds include tris(2-hydroxyethyl) isocyanurate triacrylate oligomers and acrylic urethane oligomers.

[0026] Other suitable polyene compounds are compounds having two or more allyl groups. Examples of these include polyallyl ethers of polyols and polyallyl esters of polycarboxylic acids. Suitable polyallyl ethers include, for example, 1,4-butanediol diallyl ether, 1,5-pentanediol diallyl ether, 1,6-hexanediol diallyl ether, neopentyl glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, tetraethylene glycol diallyl ether, polyethylene glycol diallyl ether, dipropylene glycol diallyl ether, tripropylene glycol diallyl ether, cyclohexanedimethanol diallyl ether, alkoxylated hexanediol diallyl ether, neopentyl glycol diallyl ether, propoxylated This includes opentyl glycol diallyl ether, trimethylolpropane or trialyl ether, ethoxylated trimethylolpropane or trialyl ether, propoxylated trimethylolpropane or trialyl ether, glycerin or trialyl ether, ethyloxylated and / or propoxylated glycerin or trialyl ether, pentaerythritol, tri or tetraallyl ether, erythritol, tri or tetraallyl ether, acrylic polyester oligomer, bisphenol A diacrylate, acrylic bisphenol A diglycidyl ether, ethoxylated bisphenol A diallyl ether, and the like.

[0027] Suitable examples of polyallyl esters include diallyl maleate, diallyl fumarate, diallyl phthalate, diallyl terephthalate, diallyl succinate, and di or triallyl citrate.

[0028] Other useful polyene compounds include triallyl cyanurate and triallyl isocyanurate (TAIC). The free radical initiator is one or more compounds that thermally react and / or decompose to generate free radicals under the conditions of step b) of this process. A free radical initiator that is solid at 22°C is preferred, as are free radical initiators having a 10-hour half-life temperature of 30-70°C or higher (as reported by the free radical initiator manufacturer) and especially a 10-minute half-life temperature of 80-120°C when measured in toluene. The free radical initiator is preferably soluble in water up to about 1 gram or less per liter of water and soluble in toluene up to about 25 grams or more per liter of toluene.

[0029] Azo free radical initiators have been found to be particularly useful. Azo free radical initiators contain an RN=N-R' moiety, where R and R' are organic groups that form carbon-nitrogen bonds to their respective adjacent nitrogen atoms. Examples of azo free radical initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylpentanenitrile), 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitride), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis(2-methylbutyronitrile).

[0030] Other useful free radical initiators include, for example, 1) acyl peroxides (e.g., acetyl peroxide or benzoyl peroxide), 2) alkyl peroxides (e.g., cumyl peroxide, dicumyl peroxide, lauroyl peroxide or t-butyl peroxide), 3) hydroperoxides (e.g., t-butyl hydroperoxide or cumyl hydroperoxide), 4) peresters (e.g., t-butyl perbenzoate), 5) other organic peroxides (e.g., acylalkylsulfonyl peroxides, dialkylperoxydicarbonates, diperoxyketals or ketone peroxides), 6) cyclic ketones and 1,2,4-trioxepane (e.g., as described in U.S. Patent No. 8,334,348), 7) azide compounds, 8) various tetrazines, and 9) various persulfate compounds (e.g., potassium persulfate).

[0031] The polyene compound may constitute, for example, 30% to 99.9% of the total weight of the coating composition. In certain embodiments, the polyene compound constitutes 35% or more, 40% or more, 45% or more, or 50% or more of the total weight of the coating composition. In other specific embodiments, the polyene compound constitutes up to 99.5%, up to 99%, up to 95%, up to 80%, up to 70%, or up to 50% of the total weight of the coating composition.

[0032] The free radical initiator constitutes, for example, 0.1% to 50% of the total weight of the coating composition. In certain embodiments, the polyene compound constitutes 0.5% or more, 1% or more, 2% or more, 3% or more, or 4% or more of the total weight of the coating composition. In other specific embodiments, the polyene compound constitutes up to 25%, up to 15%, up to 10%, up to 7.5%, or up to 6% of the total weight of the coating composition.

[0033] In some embodiments, the polyene compound and the free radical initiator together constitute 35% or more, 45% or more, 50% or more, 60% or more, or 75% or more of the total weight of the coating composition, and up to 100%, up to 98%, or up to 90% of that.

[0034] In some embodiments, the coating composition further comprises one or more terminal vinylpolysiloxanes. The polysiloxane may have a vinyl content of, for example, 0.05 mmol / gram or more, 0.1 mmol / gram or more, and up to 2 mmol / gram, preferably up to 1 mmol / gram, or up to 0.5 mmol / gram. The polysiloxane may contain two or more vinyl groups or three or more vinyl groups per molecule, and up to 10 vinyl groups per molecule, 6 mm 2 / s~1000mm 2 It may have a nominal viscosity of / s (as reported by its manufacturer). Such terminated vinylpolysiloxane products are available from AB Specialty Silicones under the trade name Andisil®. If present, such terminated vinylpolysiloxanes may constitute, for example, 5% or more, 10% or more, or 20% or more of the total weight of the coating composition, and up to 69.9%, up to 60%, or up to 50% thereof.

[0035] In certain embodiments, the coating composition comprises 30-60% by weight, particularly 35-65% by weight, of a polyene compound; 2-10% by weight of a free radical initiator; and one or more terminal vinylpolysiloxanes having the above-described vinyl content of 25-75% by weight. These three components together may constitute, for example, 45-100% or 70-100% of the total weight of the coating composition.

[0036] The coating composition may contain other components besides the aforementioned polyene compounds, free radical initiators, and terminal vinylpolysiloxanes, the other components may function as carriers (i.e., to provide or replenish the liquid phase) and / or perform other specific functions.

[0037] A useful carrier or carrier mixture is a material that is liquid at 22°C or solid at 22°C, but has a melting point of 70°C or less, preferably 50°C or less. The carrier also preferably has a boiling point of 100°C or more, more preferably 125°C or more, and even more preferably 150°C or more. Examples of useful carriers include (i) aliphatic monoalcohols or aliphatic monocarboxylic acids having 14 to 30 carbon atoms; (ii) esters of fatty acids and aliphatic alcohols (the esters having 18 to 48 carbon atoms, preferably 20 to 36 carbon atoms); (iii) polyethers having one or more hydroxyl groups; (iv) polysiloxanes other than terminal vinyl (which may be linear, branched, or cyclic); (v) polysiloxane-poly(alkylene glycol) copolymers; (vi) waxes (e.g., polyethylene wax, beeswax, lanolin, carnauba wax, candelilla wax, oricuri wax, sugarcane wax, jojoba wax, epiticla wax, coconut wax, petroleum wax, paraffin wax, etc.); (vii) fluoropolymers; (viii) solid vegetable oils and / or animal oils or fats; (viii) other organic oligomers or polymers having a pure phase melting point, or softening point, of up to 100°C; or (ix) various plasticizers.

[0038] Aliphatic monoalcohols include saturated aliphatic alcohols such as 1-dodecanol, 1-tetradecanol, 1-hexadecanol, and 1-octadecanol, and aliphatic alcohols have one or more carbon-carbon unsaturated moieties in their aliphatic alcohol chain. Useful esters of fatty acids and fatty alcohols include, for example, hexyl octadecanoate, octyl octadecanoate, dodecyl octadecanoate, and hexadodecyl octadecanoate. The fatty acid and / or aliphatic alcohol portion of the ester may contain one or more carbon-carbon unsaturated moieties.

[0039] Suitable polyethers are polymers of one or more cyclic ethers, such as propylene oxide and tetramethylene glycol. The molecular weight is high enough to produce polymers with a melting point of up to 100°C. The polyether may contain one or more hydroxyl groups. It may be linear or branched. The polyether may contain terminal alkyl ester groups. Specific examples of suitable polyethers include poly(ethylene oxide), monoalkyl esters of poly(ethylene oxide), poly(propylene oxide), monoalkyl esters of poly(propylene oxide), copolymers of ethylene oxide and propylene oxide and their monoalkyl esters, and poly(tetramethylene oxide).

[0040] Useful polysiloxanes include, for example, poly(dimethylsiloxane) and its copolymers. Polysiloxanes may be linear, branched, or cyclic. Useful siloxane-poly(alkylene glycol) copolymers include, for example, poly(dimethylsiloxane-poly(ethylene glycol) copolymers that can have block or graft structures. Particularly preferred polysiloxanes include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and linear or branched polydimethylsiloxane (PDMS) oil, polymethylhydrosiloxane (PMHS) oil, and other liquid cyclomethicones.

[0041] Paraffin or beeswax wax are particularly preferred wax carriers. Stearyl and cetyl alcohols are particularly preferred alcohol carriers and are solid at 22°C. Plasticizers include phthalates, trimellitic acid esters, adipic acid esters, maleic acid esters, benzoic acid esters, terephthalic acid esters, various fatty acid esters, epoxidized vegetable oils, sulfonamides, organophosphates, alkyl citrates, and acetylated monoglycerides.

[0042] The carrier may provide a specific functional contribution to the cured composition. In some embodiments, the carrier provides increased hydrophobicity and / or oleophobicity to the cured composition. It may also perform a plasticizing function. The carrier does not increase flammability.

[0043] The support may also contain low molecular weight organic compounds having a boiling point below 100°C and not being polymerizable unsaturated (i.e., not monomers as described above). These low molecular weight organic compounds include, for example, liquid polyethylene and polyethylene monoalkyl esters such as PPG-14 monobutyl ester; liquid alkanes such as n-hexane, n-pentane, n-heptane, henicosane, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, and triacontane; liquid alcohols such as n-propanol, isopropanol, n-butanol, t-butanol, methanol, and ethanol; fluorinated alkanes such as perfluorohexane, perfluoroheptane, perfluorodecane-pinan, perfluorodecane-octane, and perfluorododecane; and chlorinated alkanes such as isoamyl chloride, isobutyl chloride, and benzyl chloride. Alkanes and chlorinated aromatic compounds; alkanediols and polyalkylene glycosides such as ethylene glycoside, propylene glycoside, diethylene glycoside, triethylene glycoside, dipropylene glycoside, tripylene glycoside, and 1,4-butanediol; liquid esters such as diisopropyl sebacate and glycerol tripalmitate; ketones such as acetone and methyl ethyl ketone; liquid fatty acids such as stearic acid, oleic acid, palmitic acid, and lauric acid; 1-naphthalamine; biphenyl; benzophenone; diphenylamine; 1,2-diphenylethane; maleic anhydride; pyrazine; thymol; glycerin; sorbitol or other sugars; and dibenzylidene sorbitol.

[0044] If present, the carrier may constitute up to 64.9% of the total weight of the coating composition. However, such carriers are preferably present in significantly lower amounts, if any. Preferred amounts are up to 50%, up to 25%, or up to 10%.

[0045] Other examples of such components include one or more free radical curable monomers having exactly one free radical polymerizable group per molecule and a molecular weight of up to 500. Examples of such monomers have one or more hydrocarbyl groups having eight or more carbon atoms, and / or one or more siloxane groups directly or indirectly bonded to the polymerizable group. The hydrocarbyl groups may be partially fluorinated or perfluorinated. The free radical polymerizable group may be any of those polymerized in free radical polymerization, but is preferably a vinyl, acrylate, methacrylate, or chlorosilane group. The solubility of the monomer in water at 30°C is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.25 parts by mass or less, per 100 parts by mass of water. Water is soluble in the monomer to the extent of preferably 2 parts by weight or less, more preferably 1 part by weight or less, and even more preferably 0.25 parts by weight or less, per 100 parts by weight of the monomer at 30°C. Examples of such monomers are further described in International Publication No. 2015 / 127479. Specific examples of monomers include, but are not limited to, one or more of the following: octyl acrylate, octyl methacrylate, decyl acrylate, decyl methacrylate, lauryl acrylate, lauryl methacrylate, octadecyl acrylate, octadecyl methacrylate, 2-(perfluorohexyl)ethyl acrylate, 2-(perfluorooctyl)ethyl acrylate, 2-(perfluorodecyl)ethyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, lauryl methacrylate, stearyl methacrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluorooctyl)ethyltrichlorosilane, vinylsiloxane, and vinylnaphthalene.

[0046] The coating composition may further contain one or more blowing agents. Suitable blowing agents include physical (endothermic) types that are liquid at 22°C but volatilize under curing conditions, and physical types that react to form gases, such as by decomposing under curing reaction conditions. When organic physical blowing agents are present, they are used in small amounts so that the curable composition contains 10% by weight or less, preferably 5% by weight or less, more preferably 2% by weight or less, even more preferably 1% by weight or less, and even more preferably 0.25% by weight or less of an organic compound having a boiling point below 100°C. Chemical blowing agents preferably produce carbon dioxide or nitrogen. Chemical blowing agents include so-called azo types, peroxy blowing agents (peroxyesters, peroxycarbonates, etc.), and certain carbamates and citrate compounds.

[0047] Curable compositions can be prepared simply by mixing the components. The order of addition is generally not important, as long as the free radical initiator is not exposed to temperatures at which it decomposes. A preferred method for forming the composition is to combine them in any order at a temperature of 10°C to 50°C while stirring.

[0048] The coating composition is applied to an article and comes into contact with one or more synthetic thermoplastic components of the article. It can be applied using one of many convenient methods. These convenient methods include, for example, rolling, brushing, spraying, immersing the article in the composition, applying a paddle, and rubbing the composition onto the surface of the article using, for example, an air knife or doctor blade. Particularly useful in continuous industrial processes is applying it to the article using a roller. In such cases, the curable composition is applied to the roller by any convenient method and transferred to the substrate by bringing the substrate into contact with the roller.

[0049] The application temperature (i.e., the temperature of the article at the time of application) is below the crystalline melting temperature of the synthetic thermoplastic resin, or, in the case of fabric, below the melting temperature of the fibers as measured according to the applicable method of ASTM D-7138-16. It is important that the article remains in a solid state throughout the entire process. The application temperature is preferably 70°C or lower, more preferably 50°C or lower, or 35°C or lower. Particularly preferred application temperatures are 10 to 35°C.

[0050] The amount of coating to be applied can be expressed in terms of the weight of the article and / or the surface area to which the coating composition is applied. In some embodiments, the amount of the coating composition is sufficient to provide 0.04 kg to 0.75 kg of polyene compound and 0.005 kg to 0.05 kg of peroxy or azo free radical initiator per 1 kg of synthetic thermoplastic component in the article. When the coating composition is applied to multiple surfaces of the article, the aforementioned weights apply to the total weight of the polyene compound and peroxy or azo free radical initiator in all applied coatings. The amount of the coating composition may be sufficient to provide 0.05 kg or more, 0.06 kg, 0.075 kg or more, or 0.9 kg or more of polyene compound and 0.006 kg or more of peroxy or azo free radical initiator per 1 kg of synthetic thermoplastic component in the article. In some embodiments, the amount of the coating composition is selected to provide 0.6 kg or less, 0.4 kg or less, or 0.3 kg or less of polyene compound and 0.04 kg or less or 0.03 kg or less of peroxy or azo free radical initiator per 1 kg of synthetic thermoplastic component in the article. The total weight of the coating composition may be, for example, 0.05 kg to 1 kg, particularly 0.075 kg to 0.5 kg, of the coating composition per 1 kg of synthetic thermoplastic component in the article.

[0051] Next, the coated article is heated to decompose the peroxyl or azo free radical initiator, forming free radicals and creating crosslinks in a synthetic thermoplastic resin having a crystal melting temperature of 100°C or higher. The heating step is preferably carried out in an oxygen-deficient atmosphere. For the purposes of the present invention, the oxygen-deficient atmosphere is a gas containing 1 mole percent or less of oxygen molecules (O2). The oxygen-deficient atmosphere may contain 0.1 mole percent or less of oxygen molecules. The oxygen-deficient atmosphere may contain 98 mole percent or more, preferably 99 mole percent or more, and more preferably 99.9 mole percent or more of an inert gas, such as nitrogen, argon, carbon dioxide, vapor, helium, or any two or more mixtures thereof.

[0052] The temperature during this heating process is 70°C or higher and below the crystalline melting temperature of the synthetic thermoplastic resin, or, in the case of fabric, below the fiber melting temperature determined according to the applicable method of ASTM D7138-16. The article remains in a solid state during the heating process and shows no change or only negligible change from its original dimensions and geometric shape. Preferred temperatures are 80°C or higher, or 90°C or higher, up to 150°C, or up to 125°C.

[0053] The heating process is preferably carried out in the substantially absence of ionizing radiation, such as ultraviolet radiation, e-beam radiation, or other ionizing radiation, at a dose of 1 kGy or less, 0.1 kGy or less, or 0.01 kGy or less. It is particularly preferable that the articles are not exposed to such ionizing radiation during the heating process, except for any that may be present due to natural background radiation.

[0054] The atmospheric pressure during the heating process may be less than atmospheric pressure, atmospheric pressure, or ultra-atmospheric pressure. Ultra-atmospheric pressure, such as gauge pressure of 689 kPa to 6895 kPa (gauge pressure of 100 to 1000 psi), is advantageous.

[0055] The heating process may be continued for, for example, 1 minute or more, 15 minutes or more, or 30 minutes or more. While periods longer than 2 hours are generally unnecessary, they can be used if more crosslinking is required or if the article is large or thick. During the heating process, the free radical initiator generates free radicals. The free radicals and polyenes crosslink the synthetic thermoplastic resin. Crosslink density generally increases with increasing heating time.

[0056] Crosslinking typically results in changes to the physical and / or thermal properties of the polyamide and / or polyester components of an article. Crosslinked synthetic thermoplastic components may exhibit, among other things, one or more of the following: i) non-melting behavior characteristic of thermosetting resins, ii) delayed ignition, and / or iii) reduced dripping when exposed to an open flame.

[0057] Mechanical properties may also change somewhat as a result of crosslinking. Fabrics treated according to the present invention often show a significant reduction in dripping when subjected to combustion tests such as ASTM D6413-11, EN 13501-1 Single Burning Item test and British Standard BS5867 Part 2-Type B test. Fabrics treated according to the present invention often show slight changes in properties such as airflow, "hand," and drape.

[0058] Various optional components of the coating composition, or their reaction products, may remain with the treated article and form a coating on the treated article, or in some cases, penetrate the synthetic thermoplastic component of the article, or both. Certain carriers, if present, may remain with the treated article and impart functional properties to the treated article. Terminal vinylpolysiloxanes may be polymerized and / or grafted onto the synthetic thermoplastic resin under the conditions of step (b) to impart elasticity.

[0059] The following examples are for illustrative purposes only, and are not intended to limit the scope of the present invention. All parts and percentages are by weight unless otherwise indicated. Example 1 47.5 parts of triallyl isocyanurate and a nominal viscosity of 500 mm² 2 A coating composition is prepared by mixing 47.5 parts of a terminal vinyl polysiloxane polymer having a vinyl content of 0.15 mmol / g and 5 parts of azobisiso (butyronitrile) in a high-shear mixer.

[0060] The coating composition is applied to each surface of the following fabrics using a gravure coater at approximately 35°C to 40°C. The total weight of both coatings is approximately 0.3 kg per kg of fabric. The amount of triallyl isocyanurate applied is approximately 0.1425 kg per kg of fabric, and the amount of azobisuis (butyronitrile) applied is approximately 0.015 kg per kg of fabric.

[0061] Fabric A: Camouflage nylon 6,6 and spandex 98:2 blend, fabric weight 144 g / m 2 . Fabric B: Camouflage pattern, 100% nylon 6,6, fabric weight 48 grams / m 2 .

[0062] Fabric C: Gray, 100% nylon 6,6, fabric weight 50 grams / m 2 . Fabric D: 100% acrylic, fabric weight 287 grams / m 2 . Each of fabrics A, B, and C exhibits a fiber melting temperature greater than 150°C when measured according to ASTM D7138-16. Nylon 6,6 itself has a crystalline melting temperature greater than 150°C.

[0063] After coating, the fabric is then heat-treated in an autoclave at 100 °C for 1 hour under nitrogen (oxygen content less than 100 ppm) at a gauge pressure of 2.76 MPa (400 psig) to produce crosslinks in the nylon.

[0064] Samples of the treated and untreated fabrics are evaluated for air permeability using a DA Atlas M021A air permeability tester and for water repellency using the AATCC TM-022 spray test.

[0065] The treated fabric is also subjected to a vertical burn and drip test as follows: A 7.62 cm (3 inch) × 30.48 cm (12 inch) fabric sample is suspended vertically. A flame 3.81 cm (1.5 inches) high is placed under the lower end of the sample and ignited for 12 seconds, after which it is removed. The flammability and melting / dripping of the burning sample are observed.

[0066] Each of the untreated fabrics melts and forms drips under the conditions of the vertical burn and drip test. After treatment, no melting or dripping is observed in any of the fabric samples. In addition, all the fabrics show a significant improvement in water repellency, increasing from a grade of 0 to 70 for fabric A and from 0 to 100 for fabrics B and C. All the fabrics show a slightly decreased air permeability.

[0067] Example 2 47 parts of triallyl isocyanurate, 25 parts of a terminal vinyl polysiloxane polymer having a nominal viscosity of 500 mm 2 / s and a vinyl content of 0.15 mmol / g, 24 parts of poly(dimethylsiloxane) having a nominal viscosity of 1000 mm 2 / s, and 3 parts of azobisiso(butyronitrile) are mixed in a high-shear mixer to prepare a coating composition.

[0068] The coating composition is applied to each surface of cloth A and cloth B using a gravure coater at approximately 23°C. The total weight of both coatings is approximately 0.3 kg per kg of cloth. The amount of triallyl isocyanurate applied is approximately 0.14 kg per kg of cloth, and the amount of Azobisuis (butyronitrile) applied is approximately 0.009 kg per kg of cloth. After coating, the cloth is heat-treated in an autoclave at 100°C for 30 minutes under nitrogen (oxygen content less than 100 ppm) at a gauge pressure of 2.76 MPa (400 psig) to create crosslinks in the nylon.

[0069] Treated and untreated fabric samples will be evaluated for their breathability, water repellency, and performance in vertical flame drip tests. As mentioned above, each untreated cloth melts and forms a drip under the conditions of the vertical combustion drip test. Even after treatment and 20 wash cycles, no melting or dripping is observed in any of the cloth samples.

[0070] The water-repellent spray rating of fabric A increased from zero to 60 and decreased to 50 after 20 wash cycles. The air permeability of untreated fabric A was 3.49 L / s (7.2 standard cubic feet / min), which remained essentially unchanged after treatment. The air permeability of treated fabric decreased to 1.98 L / s (4.2 CFM) after 20 wash cycles.

[0071] The water-repellent spray rating of fabric B increases from 0 to 60 after treatment. Air permeability decreases from 11.0 L / s (23.3 CFM) to 8.07 L / s (17.1 CFM) after treatment, and further decreases to 6.04 L / s (12.8 CFM) after 20 wash cycles.

[0072] Example 3 A separate sample of fabric A is treated on each surface with one of the following coating compositions and heat-treated for 30 minutes to create crosslinks in the fabric as described in the previous example.

[0073] Composition 3A: 37 parts of triallyl isocyanurate and a nominal viscosity of 500 mm 2 20 parts of a terminal vinyl polysiloxane polymer having a vinyl content of 0.15 mmol / g and a nominal viscosity of 1000 mm² 2 19.5 parts of poly(dimethylsiloxane) containing / s, 2.5 parts of azobisiso(butyronitrile), and 20 parts of melamine cyanurate.

[0074] Composition 3B: 37 parts of triallyl isocyanurate and a nominal viscosity of 500 mm 2 20 parts of a terminal vinyl polysiloxane polymer having a vinyl content of 0.15 mmol / g and a nominal viscosity of 1000 mm² 2 19.5 parts of poly(dimethylsiloxane) containing / s, 2.5 parts of azobisiso(butyronitrile), and 20 parts of melamine polyphosphate.

[0075] In each case, the amount of triallyl isocyanurate applied is approximately 0.111 kg per 1 kg of fabric, and the amount of Azobisuis (butyronitrile) applied is approximately 0.0075 kg per 1 kg of fabric.

[0076] None of the treated samples showed melting or dripping in the combustion test. The permeability was 11.0 L / s (7.2 CFM) for the untreated sample, and only slightly decreased to 2.83 L / s (6.2 CFM) and 3.21 L / s (6.8 CFM) for the samples treated with compositions 3A and 3B, respectively. The water repellency rating was 50 in each case.

[0077] Example 4 46.5 parts of triallyl isocyanurate and a nominal viscosity of 500 mm² 2 A coating composition is prepared by mixing 46.5 parts of a terminal vinyl polysiloxane polymer having a vinyl content of 0.15 mmol / g and 5 parts of azobisiso (butyronitrile) in a high-shear mixer.

[0078] The coating composition is applied to a poly(ethylene terephthalate) cloth weighing 139 grams / m² at approximately 23°C, and then heated for 1 hour as described in the previous example to generate crosslinks in the resin. The amount of triallyl isocyanurate applied is approximately 0.1395 kg per kg of cloth, and the amount of Azobisuis (butyronitrile) is approximately 0.015 kg per kg of cloth. The cloth has a melting temperature greater than 150°C when measured according to ASTM D7138-16. The untreated cloth melts and drips under a vertical combustion test, while the treated cloth does not melt or drip. The air permeability of the treated cloth is 176 L / s (373 CFM) compared to 187 L / s (397 CFM) for the untreated cloth.

[0079] Comparative samples A and B Each surface of cloth A and B is coated with the coating composition and cured in the same general manner as described in the above example. The coating composition is as generally described in U.S. Patent Application Publication No. 2017 / 0029663 and consists of 38% octadecyl acrylate, 11% 1,6-hexanediol diacrylate, 5% dipentaerythritol pentaacrylate, 3% lauryl peroxide, and a nominal viscosity of 10 mm. 2 The composition contains 43% unterminated vinyl poly(dimethylsiloxane) having / s(10CSt). The composition contains only 14% by weight of polyene (1,6-hexanediol and dipentaerythritol pentaacrylate). In each case, the total amount of polyene applied to both combined coatings is about 0.048 kg per kg of fabric, and the total amount of lauryl peroxide is about 0.009 kg per kg of fabric. The fabric thus treated melts and drips when subjected to a vertical combustion test. The large amounts of octadecyl acrylate and poly(dimethylsiloxane) in the coating composition are thought to adversely affect the composition's ability to introduce crosslinking into the fabric, even if a considerable amount of polyene and free radical initiator is provided with the coating.

[0080] Examples 5A-5C Separate samples of cloth B are treated on each surface with one of the following coating compositions at various coating weights as shown in the table below, and then heat-treated for 30 minutes to create crosslinks in the cloth using the method described in the previous example. The thus treated samples are subjected to the combustion test, spray test and permeability test described above, and the results are shown in the table.

[0081] Composition 5A: 92 parts triallyl isocyanurate and 8 parts lauroyl peroxide. Composition 5B: 94 parts triallyl isocyanurate and 6 parts lauroyl peroxide. Composition 5C: 96 parts triallyl isocyanurate and 4 parts lauroyl peroxide.

[0082] [Table 1]

[0083] *This is not an example of the present invention. The data in the table shows the effect of the amount of free radical initiator applied. Application amounts of less than 0.005 kg per kg of fabric are insufficiently effective. Even an application amount of 0.006 kg per kg provides only a slight benefit in sample 5B, although the equivalent amount of free radical initiator applied yields better results when the overall coating weight is higher.

[0084] Example 6 Each surface of cloth D is coated with a coating composition containing 92.6% triallyl isocyanurate and 7.4% lauroyl peroxide. The total coating weight (both sides) is 0.1 kg / kg. The coating weight of polyene is 0.0926 kg / kg, and the coating weight of lauroyl peroxide is 0.0074 kg / kg. Then, 500 mm 2A 0.1 kg / kg total coating weight of 0.1 kg / kg of terminal vinylpolysiloxane is applied, covering each side with a polyene / free radical initiator. The coated cloth is then cured at 135°C for 30 minutes under a nitrogen pressure of 2.07 MPa (400 psig) gauge pressure and an oxygen level of less than 100 ppm. No melting is observed in the combustion test. The treated cloth has a spray grade of 70 and a breathability of 13.4 L / s (28.4 cubic feet / min).

[0085] Similar results were observed when the polysiloxane coating weight was increased to 0.15 kg / kg.

Claims

1. A solid-phase method for processing a synthetic thermoplastic article containing a synthetic thermoplastic component, wherein the thermoplastic component comprises one or more synthetic thermoplastic resins having a crystal melting temperature of 100°C or higher, and the method is a) A step of applying a coating composition to one or more surfaces of an article at a temperature below the crystal melting temperature of the synthetic thermoplastic resin, thereby bringing the coating composition into contact with one or more synthetic thermoplastic components of the article, wherein the coating composition comprises (i) one or more polyene compounds in an amount of 30 to 99.9% by weight, based on the weight of the coating composition, having 2 to 6 vinyl groups and a vinyl group equivalent of 125 g / equivalent or less, and (ii) one or more free radical initiators, wherein an amount of the coating composition sufficient to provide 0.04 kg or more of polyene compounds and 0.005 kg or more of peroxy or azo free radical initiators per 1 kg of the thermoplastic components in the article is applied to the article. b) A step of heating the coated article to a temperature of 70°C or higher and below the crystal melting temperature of the synthetic thermoplastic resin to decompose the peroxy or azo free radical initiator to form free radicals and generate crosslinks in the synthetic thermoplastic resin, The synthetic thermoplastic resin is one or more of aliphatic polyamide, polyester, and polyacrylonitrile, and constitutes 50% or more of the total weight of the synthetic thermoplastic component. The vinyl group is a -CHR=CHR group, where each R is independently a hydrogen, a linear, branched, or cyclic alkyl group having up to six carbon atoms, or a phenyl group, in a solid-phase method.

2. The solid-phase method according to claim 1, wherein the synthetic thermoplastic component comprises one or more thermoplastic aliphatic polyamide resins selected from the group consisting of nylon 4, nylon 6, nylon 8, nylon 9, nylon 10, nylon 12, nylon 4 / 6, nylon 5 / 6, nylon 6 / 6, nylon 6 / 9, nylon 10 / 10, and nylon 10 / 12.

3. The solid-phase method according to claim 1, wherein the synthetic thermoplastic component comprises one or more thermoplastic polyester resins selected from the group consisting of poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene adipate-co-terephthalate), poly(butylene adipate-co-terephthalate), poly(ethylene succinate), poly(1,4-cyclohexylene-dimethylene terephthalate), and poly(butylene succinate).

4. The solid-phase method according to claim 1, wherein the synthetic thermoplastic component comprises one or more thermoplastic polyacrylonitriles.

5. The solid-phase method according to claim 1, wherein the synthetic thermoplastic article is a cloth, and the cloth comprises alone a first fiber made of a synthetic thermoplastic resin having a crystalline melting temperature of 100°C or higher, or a blend of the first fiber and a second fiber made of a polymer other than a synthetic thermoplastic resin having a crystalline melting temperature of 100°C or higher, wherein the second fiber has a melting temperature of 100°C or higher when measured according to ASTM D7138-16.

6. A solid-phase method for reducing the melting, dripping, or both of a cloth, wherein the cloth comprises, alone, first fibers made of a synthetic thermoplastic resin having a crystalline melting temperature of 100°C or higher, or a blend of the first fibers and second fibers made of a polymer other than a synthetic thermoplastic resin having a crystalline melting temperature of 100°C or higher, wherein the second fibers have a melting temperature of 100°C or higher when measured according to ASTM D7138-16, and the method is, a) A step of applying a coating composition to one or more surfaces of the cloth at a temperature below the melting temperature of the second fiber, wherein the coating composition comprises (i) one or more polyene compounds in an amount of 30 to 99.9% by weight, based on the weight of the coating composition, having 2 to 6 vinyl groups and a vinyl group equivalent of 125 g / equivalent or less, and (ii) one or more free radical initiators, wherein an amount of the coating composition sufficient to provide 0.04 kg or more of polyene compounds and 0.005 kg or more of peroxy or azo free radical initiators per 1 kg of cloth is applied to the cloth. b) The process comprises heating the coated cloth to a temperature of 70°C or higher and below the melting temperature of the second fiber for 1 minute to 2 hours, The synthetic thermoplastic resin is one or more of aliphatic polyamide, polyester, and polyacrylonitrile, and constitutes 50% or more of the total weight of the fabric. The vinyl group is a -CHR=CHR group, where each R is independently a hydrogen, a linear, branched, or cyclic alkyl group having up to six carbon atoms, or a phenyl group, in a solid-phase method.

7. The solid-phase method according to claim 6, wherein the aliphatic polyamide is selected from the group consisting of nylon 4, nylon 6, nylon 8, nylon 9, nylon 10, nylon 12, nylon 4 / 6, nylon 5 / 6, nylon 6 / 6, nylon 6 / 9, nylon 10 / 10, and nylon 10 / 12.

8. The solid-phase method according to claim 6, wherein the synthetic thermoplastic resin is selected from the group consisting of poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene adipate-co-terephthalate), poly(butylene adipate-co-terephthalate), poly(ethylene succinate), poly(1,4-cyclohexylene-dimethylene terephthalate), and poly(butylene succinate).

9. The solid-phase method according to claim 6, wherein the synthetic thermoplastic resin is polyacrylonitrile.

10. The polyene compounds mentioned above are 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, cyclohexanedimethanol diacrylate, alkoxylated hexanediol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, and ethoxyl Trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, glycerin triacrylate, ethyloxylated and / or propoxylated glycerin triacrylate, pentaerythritol di, tri or tetraacrylate, erythritol di, tri or tetraacrylate, acrylic polyester oligomer, bisphenol A diacrylate, acrylic bisphenol A diglycidyl ether, ethoxylated bisphenol A diacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate oligomer, acrylic urethane oligomer, 1,4-butanediol diallyl ether, 1,5-pentanediol diallyl ether, 1,6-Hexanediol diallyl ether, neopentyl glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, tetraethylene glycol diallyl ether, polyethylene glycol diallyl ether, dipropylene glycol diallyl ether, tripropylene glycol diallyl ether, cyclohexanedimethanol diallyl ether, alkoxylated hexanediol diallyl ether, neopentyl glycol diallyl ether, propoxylated neopentyl glycol diallyl ether, trimethylolpropane or triallyl ether, ethoxylated trimethylolpropane or triallyl ether, propoxylated trimethylol The solid-phase method according to any one of claims 1 to 9, wherein one or more of the following are selected: propane or trialyl ether, glycerin or trialyl ether, ethoxylated and / or propoxylated glycerin or trialyl ether, pentaerythritol di, tri or tetraallyl ether, erythritol di, tri or tetraallyl ether, acrylic polyester oligomer, bisphenol A diacrylate, acrylic bisphenol A diglycidyl ether, ethoxylated bisphenol A diallyl ether, diallyl maleate, diallyl fumarate, diallyl phthalate, diallyl terephthalate, diallyl succinate, di or trialyl cyanurate, and trialyl isocyanurate.

11. The solid-phase method according to any one of claims 1 to 9, wherein the free radical initiator constitutes 2% to 8% of the total weight of the coating composition.

12. The solid-phase method according to any one of claims 1 to 9, wherein the coating composition further comprises a terminal vinylpolysiloxane having 0.1 mmol to 2 mmol of vinyl groups per gram.

13. The solid-phase method according to any one of claims 1 to 9, wherein the coating composition further comprises 5 to 50% by weight of a terminal vinylpolysiloxane having 0.1 mmol to 2 mmol of vinyl groups per gram.

14. The solid-phase method according to claim 12, wherein the polyene compound, the free radical initiator, and the terminal vinylpolysiloxane having 0.1 mmol to 2 mmol of vinyl groups per gram together constitute 50% to 100% of the total weight of the coating composition.

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