CN111808462B - Flame-retardant UV (ultraviolet) coating and preparation method thereof - Google Patents
Flame-retardant UV (ultraviolet) coating and preparation method thereof Download PDFInfo
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- CN111808462B CN111808462B CN202010559533.9A CN202010559533A CN111808462B CN 111808462 B CN111808462 B CN 111808462B CN 202010559533 A CN202010559533 A CN 202010559533A CN 111808462 B CN111808462 B CN 111808462B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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Abstract
The invention relates to the technical field of coatings, in particular to a flame-retardant UV coating and a preparation method thereof. The preparation raw material of the UV coating consists of a component A and a component B; the component A is UV resin; the component B comprises 2-15 parts by weight of vinyl phosphate, 6-30 parts by weight of diluent monomer and 2-10 parts by weight of photoinitiator; the weight ratio of the UV resin to the vinyl phosphate is (5-8): 1. the invention provides a flame-retardant UV coating, which is characterized in that a vinyl phosphate ester, a diluent monomer and UV resin are added for photocuring, a phosphorus-containing functional group with a flame-retardant effect is bonded with the UV resin in a chemical bond mode and is uniformly distributed in a coating film, so that the prepared UV coating has good flame-retardant property, and the vinyl phosphate ester is added to have good effects on various properties of the UV coating, such as adhesion, pencil hardness, aging resistance, water resistance, oil resistance and the like.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a flame-retardant UV coating and a preparation method thereof.
Background
The UV resin is also called photosensitive resin, and is an oligomer which can be quickly subjected to physical and chemical changes in a short time after being irradiated by light, and then is crosslinked and cured. The UV resin is a photosensitive resin having a relatively low molecular mass, and has a reactive group capable of UV, such as an unsaturated double bond or an epoxy group. The UV resin is widely applied to the fields of printing ink paper products, paint coatings, adhesives and the like due to the characteristics of cleanness, energy conservation and environmental protection. The UV resin is a matrix resin of the UV coating, and is compounded with a photoinitiator, a reactive diluent and various auxiliary agents to form the UV coating. The UV coating is the earliest example of the industrial large-scale successful application of the photo-curing technology, and is also the product with the largest production and sale quantity in the current photo-curing industry field, the scale is far larger than that of the photo-curing ink and the photo-curing adhesive, wherein acrylic resin, modified acrylic resin and the like are widely applied in the UV coating, but the Limit Oxygen Index (LOI) of the UV resin is low, the fire is easily caused, and the UV coating is limited in many special fields.
The organic phosphorus flame retardant has the advantages of low smoke, no toxicity, low halogen, no halogen and the like, accords with the development direction of the flame retardant, and has good development prospect. The organic phosphorus flame retardant includes phosphate, phosphite, phosphate, organic phosphorus salt, and also phosphorus heterocyclic compounds and polymer phosphate (phosphonate), but the most widely used is phosphate and phosphonate, and the research and development of phosphorus flame retardant is underway, and many reports are reported every year, mainly focusing on the latter two. The action mechanism of the organic phosphorus flame retardant is that the flame retardant can generate a cross-linked solid substance or a carbonized layer with a more stable structure when being heated. The formation of the carbonized layer can prevent the polymer from further pyrolysis on the one hand and prevent the thermal decomposition products in the carbonized layer from entering the gas phase to participate in the combustion process on the other hand.
Among them, there are very few research and development reports on flame retardant UV materials, and almost all are additive flame retardant methods: for example, patent CN201310457228 provides a flame retardant UV photo-curable coating and a preparation method thereof; CN201910374416 provides a production process of a high-performance flame-retardant UV paint; CN201910931992 provides a halogen-free flame retardant UV curable acrylate pressure-sensitive adhesive, a pressure-sensitive adhesive tape, and a preparation method thereof, and these patents adopt military affairs to add an organic phosphorus flame retardant to realize the flame retardant effect of the material. However, such flame retardants are not completely effective in forming an integral body with the material, and if the flame retardant and the material are not uniformly mixed, the flame retardant effect is greatly impaired. By adopting a reactive flame-retardant mode, the flame retardant and the UV resin are subjected to chemical reaction to form a whole with the material, so that the highest efficiency of flame retardance is a key point, and the development of the flame-retardant UV resin can greatly expand the application field of the UV resin.
Disclosure of Invention
In order to solve the problems, the invention provides a flame-retardant UV coating in a first aspect, wherein the UV coating is prepared from a raw material consisting of a component A and a component B;
the component A is UV resin;
the component B comprises, by weight, 0.5-15 parts of vinyl phosphate, 6-30 parts of a diluent monomer and 2-10 parts of a photoinitiator;
the weight ratio of the UV resin to the vinyl phosphate is (5-8): 1.
in a preferred embodiment of the present invention, the UV resin is selected from one of acrylic resin, modified acrylic resin, polyester resin and modified polyester resin.
In a preferred embodiment of the present invention, the vinyl phosphate is a chain monovinyl phosphate a or a chain bisvinyl phosphate B;
the structural formula of the chain-shaped monovinyl phosphate A is shown as a formula 1:
the structural formula of the chain-shaped divinyl phosphate B is shown as a formula 2:
r is selected from one of alkoxy, aryloxy, alkyl and aryl, R1One of hydrogen atom, alkyl, cycloalkyl, aryl and derivatives thereof, and n is 1-20.
In a preferred embodiment of the present invention, R is selected from C1-C20 alkoxy, aryloxy, C1-C20 alkyl and aryl, and R is selected from C1-C20 alkoxy1One selected from hydrogen atom, C1-C20 alkyl, cycloalkyl, aryl and derivatives thereof.
In a preferred embodiment of the present invention, the vinyl phosphate is a cyclic monovinyl phosphate or a cyclic bisvinyl phosphate F.
In a preferred embodiment of the present invention, the cyclic monovinyl phosphate is selected from one of cyclic monovinyl phosphate C, cyclic monovinyl phosphate D, and cyclic monovinyl phosphate E;
the structural formula of the cyclic monovinyl phosphate C is shown as a formula 3:
the structural formula of the cyclic monovinyl phosphate D is shown as the formula 4:
the structural formula of the cyclic monovinyl phosphate E is shown as a formula 5:
R2one selected from hydrogen atom, alkyl, aryl and cycloalkyl; r3Is selected from one of hydrogen atom, alkyl, aryl and cycloalkyl.
As a preferred embodiment of the present invention, R2One selected from hydrogen atom, C1-C20 alkyl, aryl and cycloalkyl; r3One selected from hydrogen atom, C1-C20 alkyl, aryl and cycloalkyl.
As a preferred technical scheme of the invention, the structural formula of the cyclic divinyl phosphate F is shown as a formula 6:
as a preferable technical scheme of the invention, the component B also comprises an auxiliary agent, and the auxiliary agent comprises one or more of a delustering agent, a flatting agent, a pigment, a filler, a dispersing agent and a defoaming agent.
The second aspect of the invention provides a preparation method of the flame-retardant UV coating, which comprises the following steps:
and mixing the preparation raw materials of the UV coating to obtain the UV coating.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a flame-retardant UV coating, which is characterized in that a vinyl phosphate ester, a diluent monomer and UV resin are added for photocuring, a phosphorus-containing functional group with a flame-retardant effect is bonded with the UV resin in a chemical bond mode and is uniformly distributed in a coating film, so that the prepared UV coating has good flame-retardant property, and the vinyl phosphate ester is added to have good effects on various properties of the UV coating, such as adhesion, pencil hardness, aging resistance, water resistance, oil resistance and the like.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides a flame-retardant UV coating, which is prepared from a raw material comprising a component A and a component B;
the component A is UV resin;
the component B comprises, by weight, 0.5-15 parts of vinyl phosphate, 6-30 parts of a diluent monomer and 2-10 parts of a photoinitiator;
the weight ratio of the UV resin to the vinyl phosphate is (5-8): 1.
in a preferred embodiment, the preparation raw material of the UV coating consists of an A component and a B component;
the component A is UV resin;
the component B comprises 7-12 parts by weight of vinyl phosphate, 7-28 parts by weight of diluent monomer and 2-10 parts by weight of photoinitiator;
the weight ratio of the UV resin to the vinyl phosphate is (5-8): 1.
in a preferred embodiment, the preparation raw material of the UV coating is composed of an A component and a B component;
the component A is UV resin;
the component B comprises 8 parts of vinyl phosphate, 24 parts of diluent monomer and 8 parts of photoinitiator in parts by weight;
the weight ratio of the UV resin to the vinyl phosphate is 7: 1.
[ A component ]
In one embodiment, the UV resin of the present invention is one selected from the group consisting of an acrylic resin, a modified acrylic resin, a polyester resin, and a modified polyester resin.
The acrylic resin is a generic term for polymers of acrylic acid, methacrylic acid and derivatives thereof. The acrylic resin is thermosetting acrylic resin, the thermosetting acrylic resin has a certain functional group in the structure, and forms a net structure through the reaction with functional groups such as amino, epoxy, double bonds and the like during paint preparation, so that the acrylic resin has excellent fullness, gloss, hardness, solvent resistance and weather resistance, and does not change color or turn yellow during high-temperature baking. The acrylic resin is not particularly limited in the present invention, and is known in the art.
The modified acrylic resin is obtained by modifying acrylic resin, such as organic silicon modification, organic fluorine modification, epoxy modification, polyurethane modification, organic fluorine-silicon modification, nano material modification, polyester modification and the like; in a preferred embodiment, the modified acrylic resin is selected from one of epoxy acrylic resin, aliphatic polyurethane acrylic resin and polyester acrylic resin. Examples of the epoxy acrylic resin include, but are not limited to, B-100M, B-102, B-102M, B-106, B-113, B-123, B-151, B-153, B-163, B-165, B-186, B-191A, B-196S of Boxing New materials science and technology Co., Ltd, LR9019 of Basff, AgiSyn 1010, AgiSyn 1030, AgiSyn 1050; examples of the polyester acrylic resin include, but are not limited to, B-509B, B-519, B-520, B-522, B-5226, B-530, B-531, B-535, B-536, B-546, B-560, B-570, B-574C, B-590, Tesman's NeoRad P-11, NeoRad P-50, NeoRad P-56, AgiSyn 705, AgiSyn 707, AgiSyn 716, AgiSyn 720, AgiSyn 730, AgiSyn 740, and AgiSyn 9771; examples of aliphatic urethane acrylic resins include, but are not limited to, B-2051, B-210D, B-2111-5396, B-215, B-216, B-221, B-226, B-268M, B-270, B-286, B-296, B-368, B-371, B-375, Isesman AgiSyn 230A2, AgiSyn 230A3, AgiSyn 230T1, AgiSyn 242, AgiSyn 2421, AgiSyn 298, AgiSyn 530, AgiSyn 536, NeoRad U-10-15H, NeoRad U-10-15T, Pasteur Larou mer 9033; the modified acrylic resin is not particularly limited in the present invention, and is known in the art.
The polyester resin is a general term for a high molecular compound obtained by polycondensation of a diol or a diacid or a polyol and a polyacid. Polyesters can be classified into saturated polyesters and unsaturated polyesters. The saturated polyester is synthesized by adopting the method that unsaturated bonds except benzene rings are not contained in the raw materials. The polyester resin is unsaturated polyester resin. In addition, when the polyester resin is synthesized, if some other structures are introduced through chemical modification, the polyester resin can have properties which are not possessed originally, the purpose of improving and highlighting certain properties is achieved, and special application property requirements are met, for example, epoxy, acrylic acid and organic silicon are adopted for modification, so that the modified polyester resin is obtained. The present invention is not limited to polyester resins and modified polyester resins, and is well known in the art.
[ B component ]
Vinyl phosphate ester
In one embodiment, the vinyl phosphate ester of the present invention is a chain monovinyl phosphate ester a or a chain bisvinyl phosphate ester B;
the structural formula of the chain-shaped monovinyl phosphate A is shown as a formula 1:
the structural formula of the chain-shaped divinyl phosphate B is shown as a formula 2:
r is selected from one of alkoxy, aryloxy, alkyl and aryl, R1One of hydrogen atom, alkyl, cycloalkyl, aryl and derivatives thereof, and n is 1-20.
Examples of alkoxy groups include, but are not limited to, C1-C20 alkoxy groups.
Examples of aryloxy groups include, but are not limited to, phenoxy, benzyloxy, naphthoxy; in one embodiment, the aryloxy group is phenoxy.
Examples of alkyl groups and derivatives thereof include, but are not limited to, alkyl groups, substituted alkyl groups such as chloro-substituted alkyl groups, fluoro-substituted alkyl groups, and silicon-substituted alkyl groups; in one embodiment, the alkyl group is a C1 to C20 alkoxy group.
As examples of aryl and its derivatives, including, but not limited to, phenyl, benzyl, naphthyl; substituted aryl, such as fluoro substituted aryl, nitric acid substituted aryl.
As examples of cycloalkyl groups and derivatives thereof, including, but not limited to, cyclohexane, cyclopentane; substituted cycloalkyl groups, such as halo-substituted cycloalkyl groups.
Preferably, R in the invention is selected from one of C1-C20 alkoxy, aryloxy, C1-C20 alkyl and aryl, and R is selected from1One selected from hydrogen atom, C1-C20 alkyl, cycloalkyl, aryl and derivatives thereof.
More preferably, in the chain monovinyl phosphate A, R is selected from one of C1-C20 alkoxy, aryloxy, C1-C20 alkyl and aryl, and R is1One selected from C1-C20 alkyl and aryl; in the chain monovinyl phosphate A, R is selected from one of C1-C10 alkoxy, aryloxy, C1-C10 alkyl and aryl, and R is1One selected from C1-C10 alkyl and aryl.
More preferably, in the chain divinyl phosphate B, R is one selected from C1-C20 alkoxy, aryloxy, C1-C20 alkyl and aryl, and R is1One selected from C1-C20 alkyl and hydrogen atom; in the chain-like divinyl phosphate B, R is selected from one of C1-C20 alkoxy, aryloxy, C1-C10 alkyl and aryl, and R is1One selected from C1-C10 alkyl and hydrogen atom; in the chain-like divinyl phosphate B, R is selected from one of C1-C20 alkoxy, aryloxy, C1-C5 alkyl and aryl, and R is1One selected from C1-C5 alkyl and hydrogen atom; further, in the chain bisvinyl phosphate B of the present invention, R is1One selected from a hydrogen atom and a methyl group.
More preferably, n is 1-10.
In a preferred embodiment, the vinyl phosphate ester of the present invention is a cyclic monovinyl phosphate ester or a cyclic bisvinyl phosphate ester F; further, the cyclic monovinyl phosphate is selected from one of cyclic monovinyl phosphate C, cyclic monovinyl phosphate D and cyclic monovinyl phosphate E;
the structural formula of the cyclic monovinyl phosphate C is shown as a formula 3:
the structural formula of the cyclic monovinyl phosphate D is shown as the formula 4:
the structural formula of the cyclic monovinyl phosphate E is shown as a formula 5:
r2 is selected from one of hydrogen atom, alkyl, aryl and cycloalkyl; r3Is selected from one of hydrogen atom, alkyl, aryl and cycloalkyl.
In a more preferred embodiment, R of the present invention2One selected from hydrogen atom, C1-C20 alkyl, aryl and cycloalkyl; r3One selected from hydrogen atom, C1-C20 alkyl, aryl and cycloalkyl; further, the invention R2One selected from hydrogen atom and C1-C20 alkyl; r3One selected from hydrogen atom and C1-C20 alkyl; further, the invention R2One selected from hydrogen atom and C1-C5 alkyl; r3One selected from hydrogen atom and C1-C5 alkyl; further, the invention R2One selected from hydrogen atom and methyl; r3One selected from hydrogen atom and methyl.
In a further preferred embodiment, the cyclic bis-vinyl phosphate ester F of the present invention has a structural formula as shown in formula 6:
the applicant finds that by adding vinyl phosphate and a diluent monomer together as reaction monomers and carrying out a crosslinking reaction with UV resin, phosphorus atoms can be bonded on a UV main chain, when the flame retardant is used, a compact and stable carbon layer is firstly formed on a phosphate structure on the UV main chain and covers the coating film and the base layer, further degradation of the coating film and the base layer can be reduced, meanwhile, the coating film and the base layer are prevented from being damaged by heat flow, and the prepared UV coating has good flame retardant performance.
In addition, the applicant finds that when vinyl phosphate is added to participate in the reaction, the larger group and the good polarity of the phosphate are beneficial to forming a more compact protective film and improving the hardness of a coating film, but the molecular chain segment is difficult to rotate, and the wettability and the intermolecular force on a base material are reduced, so that the adhesive force is adversely affected. And the applicant found that the amount of the vinyl phosphate is not so large as compared with the UV resin, and when the amount of the phosphate is too large, it is liable to cause a large concentration of the phosphate at the interface, thereby adversely affecting the adsorption.
Applicants have found that when a chain-like vinyl phosphate is used, it has a smaller group of bits than cyclic vinyl phosphates, and thus it is as R and R1Relatively large substituents may be employed, and for cyclic vinyl phosphates, R thereof2And R3The substituent(s) should not be too large in molecular weight otherwise during curing due to the larger volume of the cyclic vinyl phosphate, and R2And R3The excessively long chain curls, and precipitation and the like may occur, which affects the smoothness, adhesion and the like of the coating film; in the case of a chain-type vinyl phosphate, a relatively long chain and a substituent such as a phenyl group can be used to react with the UV resin and to react with the polymer baseThe polymer material generates strong intermolecular force to promote adsorption to the substrate, but the applicant has unexpectedly found that R is a linear bis-vinyl phosphate1Should not be too large, probably because the bisvinylphosphate may act as a cross-linking point if R is1Too large may affect the arrangement of molecules near the cross-linking point, and affect the properties of adhesion and solvent resistance. And the applicant found that when a chain-like bisvinylphosphate B is used, especially a bisvinylphosphate B of a certain chain length is used, the density of the formed cross-linked network is promoted and the density and adhesion are further improved, but when the chain of the bisvinylphosphate B is too long, the distribution and movement of the phosphorus-containing compound are not facilitated, and thus the hardness, adhesion and the like are adversely affected.
Diluting monomer
The diluted monomer is used in the UV curing stage, not only serves as a solvent to dissolve components and adjust viscosity, but also serves as a monomer to participate in the photocuring reaction, and has important influence on the curing speed of a system and the adhesive property of an adhesive. The diluent monomer of the present invention is a diluent monomer well known in the art, and is not particularly limited. In one embodiment, the diluent monomer of the present invention comprises one or more of a monofunctional monomer, a difunctional monomer, and a polyfunctional monomer.
Examples of the monofunctional monomer include, but are not limited to, one or a mixture of styrene, methylstyrene, N-ethylene-2-pyrrolidone, acrylic acid ester, octyl acrylate, isooctyl acrylate, 2-phenoxyethyl acrylate, butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, dodecyl acrylate, hexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyisopropyl acrylate, hydroxybutyl acrylate, isobornyl acrylate, dodecyl acrylate, ethoxyethoxyethyl acrylate, tetrahydrofuran acrylate, and the like;
examples of difunctional monomers include, but are not limited to, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, diethylene glycol diacrylate phthalate, propoxylated neopentyl glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate.
Examples of the polyfunctional monomer include, but are not limited to, one or a mixture of propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, neopentyl glycol diacrylate, triethoxy trimethylolpropane triacrylate, and the like.
In a preferred embodiment, the weight ratio of the vinyl phosphate ester and the diluent monomer according to the present invention is 1: (0.7-4).
Initiator
The initiator is not specifically limited in the present invention, and includes, but is not limited to, phenylbis (2,4, 6-trimethylbenzoyl) -phosphine oxide, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholino) phenyl ] -1-butanone), 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -1-propanone, phenylformates, 1-hydroxycyclohexylphenylmethanone, benzoin dimethyl ether; examples include Darocur 1173, Irgacure 184D, Irgacure TPO, Irgacure 907, Irgacure 651, Irgacure 500, Darocur MBF, Irgacure 754, Irgacure 819, Irgacure 2959, Irgacure 127, Irgacure 784, and Irgacure 369.
In one embodiment, the component B of the present invention further comprises an auxiliary agent.
Auxiliary agent
In one embodiment, the auxiliary agent of the present invention comprises one or more of a matting agent, a leveling agent, a pigment, a filler, a dispersing agent, and a defoaming agent.
Examples of matting agents include, but are not limited to, acrylic matting resins, polyester matting resins, micronized silica; there may be mentioned C803, C805, C807, C809, UK700 from GRACE, USA; in one embodiment, the matting agent of the invention is 5 to 8 wt% of the UV coating.
As examples of the leveling agent, there are included, but not limited to, organically modified polysiloxane acrylic, dimethylpolysiloxane; examples thereof include TEGOGlide450, TEGOGlide482, and Mooney chemical 1073, 1074, available from DEGAHI CHEMICAL CO., LTD, Germany; in one embodiment, the leveling agent accounts for 0.5 to 1.5 wt% of the UV coating.
Examples of pigments include, but are not limited to, inorganic pigments, organic pigments or metallic effect pigments or mixtures thereof, there being listed, transparent red iron oxide, iron yellow, carbon black, permanent violet, phthalocyanine blue, DPP orange, HYDROLAN series aqueous aluminum pastes from ECKART, germany, highly weatherable series pearl powders from MERK, germany; in one embodiment, the pigment of the present invention accounts for 1 to 3 wt% of the UV coating.
Examples of fillers include, but are not limited to, titanium dioxide, barium sulfate, quartz powder, kaolin, mica powder, molybdenum disulfide; in one embodiment, the filler of the present invention accounts for 6 to 15 wt% of the UV coating.
Examples of the dispersant include, but are not limited to, ammonium polyacrylate salts, modified polyacrylic acid solutions, modified polycarboxylic acid salts, or mixtures thereof, and there may be mentioned Hydropalat640A from Shenzhen, Heishuan chemical Co., Ltd, TEGODISpers750W from Germany, and Sokalan PA30CL from Germany, Pastev chemical Co., Ltd; in one embodiment, the dispersant accounts for 0.5 to 1.5 wt% of the UV coating.
As examples of the antifoaming agent, there are included, but not limited to, silicone-polyether copolymer emulsions, polypropylene glycols, polyethylene glycol-hydrophobic solid-silicone mixtures, mineral oil-based or a mixture thereof; there are exemplified TEGO805 of Germany, Kagaku, Inc., Pluriol P2000 of Germany, Pasteur, chemical, Inc., BYK024 of Germany, Bikk chemical (Atai), private, Inc., and Foamster309A of Shenzhen, Hichuan, chemical, Inc.; in one embodiment, the defoaming agent accounts for 0.5 to 1.5 wt% of the UV coating.
The second aspect of the invention provides a preparation method of the flame retardant type UV coating, which comprises the following steps:
and mixing the preparation raw materials of the UV coating to obtain the UV coating.
Examples
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
A1: UV resin
The UV resin is epoxy acrylic resin and is purchased from B-100 of Guangdong Boxing New Material science and technology Co.
A2: UV resin
The UV resin is aliphatic polyurethane acrylic resin and is purchased from B-2051 of Guangdong Boxing new material science and technology limited company.
A3: UV resin
The UV resin is polyester acrylic resin and is purchased from B-509B of Guangdong Boxing new material science and technology Co.
B1: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
b2: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
b3: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
b4: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
b5: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
b6: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
b7: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
b8: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
b9: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
wherein R is2＝Me，R3N-decyl group.
B10: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
wherein R is Ph, R1＝H。
B11: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
wherein R is Ph, R1N-pentadecyl.
B12: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
wherein R is Ph, R1N-decyl, n-6.
B13: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
wherein R is Ph, R1＝Me，n＝30。
B14: vinyl phosphate ester
The structural formula of the vinyl phosphate is shown as follows:
b15: vinyl phosphate ester
The vinyl phosphate is tributyl phosphate.
C1: diluting monomer
The diluent monomer is tripropylene glycol diacrylate.
C2: diluting monomer
The diluent monomer is 1, 6-hexanediol diacrylate.
C3: diluting monomer
The diluent monomer is trimethylolpropane triacrylate.
D: photoinitiator
The photoinitiator is Irgacure 754.
E1: auxiliary agent
The auxiliary agent is a delustering agent and is purchased from UK 700.
E2: auxiliary agent
The auxiliary agent is a flatting agent which is purchased from 1074 of the friction energy chemical industry.
E3: auxiliary agent
The auxiliary agent is a filler, and the filler is titanium dioxide and is purchased from R818 of Jinyun chemical industry Co.
TABLE 1
Examples 1 to 16 provide UV coatings, the raw materials for the preparation of which are shown in table 1 in parts by weight.
Examples 1-16 also provide methods of preparing the UV coatings described above: the method comprises the following steps:
and mixing the preparation raw materials of the UV coating to obtain the UV coating.
Evaluation of Performance
The UV coating provided by the embodiment is coated on a PC-ABS plate and is cured for 80s under the light with the wavelength of 300-400 nm by a UV curing machine, wherein the UV radiation dose is 100mJ/cm2The following experiment was carried out using the obtained coating film as a sample.
1. Adhesion force: the samples provided in the examples were tested for adhesion according to the GB/T5210-85 pull-off method and the results are shown in Table 2.
2. Pencil hardness: the samples provided in the examples were tested for pencil hardness according to GB/T6739-86 and the results are shown in Table 2.
3. Limiting oxygen index: the samples provided in the examples were tested for limiting oxygen index according to GB/T2406-2008, with the results shown in Table 2.
Table 2 characterization test of properties
4. And (3) performance testing: the samples provided in examples 1-8, 10 and 15-16 were tested for their resistance to artificially accelerated aging (250h), water resistance (38 + -2 deg.C, 96h) and oil resistance (121 + -3 deg.C, 24h) according to GB/T1865-97, GB/T1733-93 and GB/T9274-88, respectively, and found to be acceptable in resistance to artificially accelerated aging and oil, and not to blister or discolor during the water resistance test.
As can be seen from the test results in table 2, compared with the additive-type flame retardant, the UV coating provided by the invention, such as the UV coating provided in example 14, has higher flame retardant performance, and also has good adhesion, hardness, and other properties; compared with a vinyl compound containing no phosphorus, the UV coating provided by the embodiment 13 has high flame retardant property while improving the mechanical properties such as adhesive force and the like by adding the phosphorus-containing vinyl phosphate, and the UV coating provided by the invention has good water resistance, oil resistance and aging resistance.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (4)
1. The flame-retardant UV coating is characterized in that a preparation raw material of the UV coating consists of a component A and a component B;
the component A is UV resin;
the component B comprises 7-12 parts by weight of vinyl phosphate, 7-28 parts by weight of diluent monomer and 2-10 parts by weight of photoinitiator;
the weight ratio of the UV resin to the vinyl phosphate is (5-8): 1;
the vinyl phosphate is chain monovinyl phosphate A or chain divinyl phosphate B;
the structural formula of the chain-shaped monovinyl phosphate A is shown as a formula 1:
formula 1;
the structural formula of the chain-shaped divinyl phosphate B is shown as a formula 2:
formula 2;
n is 1 to 20, theIn the chain monovinyl phosphate A, R is selected from one of C1-C10 alkoxy, C1-C10 aryloxy, C1-C10 alkyl and C1-C10 aryl, and R is1One selected from C1-C10 alkyl and C1-C10 aryl, R in the chain-shaped divinyl phosphate B is selected from C1-C20 alkoxy and C1-C5 alkyl, R in the chain-shaped divinyl phosphate B can also be selected from phenoxy, benzyloxy, naphthoxy, phenyl, benzyl and naphthyl, R is selected from phenoxy, benzyloxy, naphthoxy, phenyl, benzyl and naphthyl1One selected from C1-C5 alkyl and hydrogen atom;
the vinyl phosphate is cyclic monovinyl phosphate or cyclic bisvinyl phosphate F;
the cyclic monovinyl phosphate is selected from one of cyclic monovinyl phosphate C, cyclic monovinyl phosphate D and cyclic monovinyl phosphate E;
the structural formula of the cyclic monovinyl phosphate C is shown as a formula 3:
formula 3;
the structural formula of the cyclic monovinyl phosphate D is shown as the formula 4:
formula 4;
the structural formula of the cyclic monovinyl phosphate E is shown as a formula 5:
formula 5;
R2one selected from hydrogen atom and C1-C5 alkyl; r3One selected from hydrogen atom and C1-C5 alkyl;
the structural formula of the cyclic bisvinylphosphate F is shown as the formula 6:
and (6).
2. The flame retardant UV coating according to claim 1, wherein the UV resin is one selected from acrylic resin, modified acrylic resin, polyester resin, and modified polyester resin.
3. The flame retardant UV coating according to any one of claims 1-2, wherein the component B further comprises an auxiliary agent, and the auxiliary agent comprises one or more of a delustering agent, a leveling agent, a pigment, a filler, a dispersing agent and an antifoaming agent.
4. The preparation method of the flame retardant UV coating according to any one of claims 1 to 3, characterized by comprising the following steps:
and mixing the preparation raw materials of the UV coating to obtain the UV coating.
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