CN111978836A

CN111978836A - PVC floor wear-resistant coating

Info

Publication number: CN111978836A
Application number: CN202010949631.3A
Authority: CN
Inventors: 杨爱军; 侯智杰; 徐樊
Original assignee: Fast Solid New Photosensitive Materials Huizhou Co ltd
Current assignee: Huizhou Bishengtang Technology Co ltd
Priority date: 2020-09-10
Filing date: 2020-09-10
Publication date: 2020-11-24

Abstract

The invention provides a PVC floor wear-resistant coating, and relates to the technical field of wear-resistant materials. The material is mainly prepared from the following raw materials in percentage by mass: 15-60% of cation polymerizable compound, 0.5-20% of cation photoinitiator, 0-5% of auxiliary agent and 20-75% of wear-resistant powder. The PVC floor wear-resistant coating disclosed by the invention does not use any volatile organic solvent, can realize high-speed coating by UV (ultraviolet) curing after being coated by a comma scraper, and is suitable for a printed PVC base material. The wear-resistant coating for the PVC floor is high in curing speed, good in adhesion of the cured coating, excellent in wear resistance, good in appearance and odorless. The PVC floor prepared by the hot-pressing compounding process and the PVC base material through the pressing is excellent in wear resistance, good in environmental protection performance and tempering stability and has a good application prospect.

Description

PVC floor wear-resistant coating

Technical Field

The invention relates to the technical field of wear-resistant materials, in particular to a PVC floor wear-resistant coating.

Background

The PVC floor is a novel light floor decoration material which is very popular in the world at present, enters the Chinese market from the beginning of the 80 s, is generally accepted in domestic large and medium cities so far, and is widely used. Such as home, hospital, school, office building, factory, supermarket, market, stadium, etc. The PVC floor is produced by using polyvinyl chloride and its copolymer resin as main material, adding stuffing, plasticizer, stabilizer, coloring agent and other supplementary material and through coating, rolling, extruding or extruding process on sheet or certain length of coiled material base material. The PVC floor is an environment-friendly and completely recyclable material, and has very important significance under the large background that the forest is protected in China and the plastic is used for replacing wood.

At present, the wear-resistant layer of the PVC floor is a polyvinyl chloride film which is prepared by adding a plasticizer and a stabilizer into polyvinyl chloride resin, and processing the polyvinyl chloride resin through processes of stirring, mixing, plasticizing, calendering and the like. Wherein, the plasticizer takes dioctyl phthalate as a main component and epoxidized soybean oil as an auxiliary component to enhance the plasticity of the polyvinyl chloride resin. At present, the PVC has low wear-resistant coefficient, poor skid resistance in the use process, single color and poor decorative performance. In addition, the existing PVC floor can release substances harmful to human bodies, so that the environmental protection is poor. The technical problems of use limitation and the like exist in public places with high public safety requirements, such as airports, hospitals, kindergartens and the like.

Disclosure of Invention

The invention aims to provide a PVC floor wear-resistant coating which is high in wear-resistant strength, impact-resistant, non-deformable and excellent in environmental protection performance.

The technical problem to be solved by the invention is realized by adopting the following technical scheme.

The embodiment of the application provides a PVC floor wear-resistant coating which is mainly prepared from the following raw materials in percentage by mass: 15-60% of cation polymerizable compound, 0.5-20% of cation photoinitiator, 0-5% of auxiliary agent and 20-75% of wear-resistant powder.

Compared with the prior art, the embodiment of the invention has at least the following advantages or beneficial effects:

the wear-resisting intensity of the PVC floor wear-resisting coating that this embodiment provided is high, shock resistance, indeformable and environmental protection can be good, solves the not good technical problem of present PVC floor wearability, effectively improves the coefficient of wear resistance of floor pad pasting, simultaneously, because coefficient of wear resistance increases, this PVC floor wear-resisting coating also can not be restricted to floor coating technical field, still can be applied to other technical field that require high to wear-resisting.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is a structural formula I of the oxazetidine compounds of the present invention;

FIG. 2 is a structural formula II of the oxacyclobutane compounds of the present invention;

FIG. 3 is a structural formula III of the oxacyclobutane compounds of the present invention;

FIG. 4 is a structural formula of an iodonium salt and/or a sulfonium salt of the present invention;

FIG. 5 shows the structural formula I of the cations of the iodonium salt and/or sulfonium salt photoinitiators of the present invention;

FIG. 6 shows the structural formula II of the cation of the iodonium salt and/or sulfonium salt photoinitiator;

FIG. 7 shows the structure III of the cations of the iodonium salt and/or sulfonium salt photoinitiators of the present invention;

FIG. 8 is a structural formula I of an anthracene sensitizer compound of the present invention;

FIG. 9 is a structural formula II of the anthracene sensitizer compound of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to specific examples.

The PVC floor wear-resistant coating is mainly prepared from the following raw materials in percentage by mass: 15-60% of cation polymerizable compound, 0.5-20% of cation photoinitiator, 0-5% of auxiliary agent and 20-75% of wear-resistant powder.

In some embodiments of the invention, the PVC floor wear-resistant coating is prepared from the following raw materials in parts by weight: 29-50% of cationic polymeric compound, 1-10% of cationic photoinitiator, 0-3% of auxiliary agent and 30-70% of wear-resistant powder.

In some embodiments of the present invention, the cationic polymerizable compound in the PVC floor wear coating contains an oxetane compound and an alicyclic epoxy compound.

In some embodiments of the present invention, the mass ratio of the oxetane compound to the alicyclic epoxy compound in the PVC floor wear-resistant coating is 1:1-4, preferably 1:1-1.5, and more preferably 1: 1-1.2.

In some embodiments of the present invention, the oxetane compound in the PVC floor wear-resistant coating is an alkane or alkene of which at least one end capping group is an oxetane group, the alkane or alkene contains a hydroxyl group, and H on the oxetane end is substituted by any one or more of alkyl groups containing 1 to 4 carbon atoms.

In some embodiments of the present invention, the above-mentioned-CH 2-in the alkane or alkene in the PVC floor wear-resistant coating is replaced by one or more of-O-, -COO-, -OCO-, -SO 2-and 1, 4-phenylene, but two O's are not directly connected.

In some embodiments of the present invention, the sum of the mass of the oxetane compound and the alicyclic epoxy compound in the PVC floor wear-resistant coating is 20% by mass or more, preferably 40% by mass or more of the cationically polymerizable compound.

In some embodiments of the present invention, the alicyclic epoxy compound in the PVC floor wear-resistant coating is a multifunctional alicyclic epoxy compound having two or more alicyclic epoxy groups in a molecule, or an alicyclic epoxy compound having one alicyclic epoxy group and one unsaturated double bond group in a molecule.

In some embodiments of the present invention, the alicyclic epoxy compound in the PVC floor wear-resistant coating is an epoxy compound having an epoxycyclohexyl group.

In some embodiments of the present invention, the cationic polymerizable compound in the PVC floor wear-resistant coating further includes one or more of an oxetane compound which does not contain a hydroxyl group and the blocking group is not an oxetane group, an epoxy compound which does not contain an alicyclic epoxy group, and a vinyl ether compound.

In some embodiments of the present invention, the oxetane compound which does not contain a hydroxyl group and whose end capping group is not an oxetane group in the above-mentioned PVC floor wear-resistant coating layer includes 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- [ (phenoxy) methyl ] oxetane, 3-ethyl-3- (chloromethyl) oxetane, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, oxetanyl (meth) ether, and mixtures thereof, Isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, bis [ 1-ethyl (3-oxetanyl) ] methyl ether, 3-bis (chloromethyl) oxetane, 3, 7-bis (3-oxetanyl) -5-oxa-nonane, 1, 2-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ethane, 1, 3-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, and mixtures thereof, Tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, 1, 4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1, 6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, and mixtures thereof, One or more of dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta (3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol tetra (3-ethyl-3-oxetanylmethyl) ether.

In some embodiments of the present invention, the epoxy compound not containing an alicyclic epoxy group in the PVC floor wear coating includes one or more of a hydrogenated epoxy compound, an aromatic epoxy compound, and an aliphatic epoxy compound.

In some embodiments of the present invention, the vinyl ether compounds in the PVC floor wear coating include aryl vinyl ethers, alkyl vinyl ethers, cycloalkyl vinyl ethers, and hydroxyl-containing vinyl ethers.

In some embodiments of the present invention, the cationic photoinitiator in the PVC floor wear coating comprises one or more of iodonium salt, sulfonium salt, and aryl ferrocenium salt.

In some embodiments of the present invention, the auxiliary agents in the PVC floor wear-resistant coating include leveling agents, polymerization inhibitors, thickeners and sensates.

In some embodiments of the present invention, the wear-resistant powder in the PVC floor wear-resistant coating includes one or more of alumina, glass powder, zirconia and ceramic powder.

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

The purpose of this embodiment is to provide a PVC floor wear-resistant coating.

The wear-resistant coating for the PVC floor provided by the embodiment is prepared from the following raw materials shown in Table 1:

TABLE 1

Under the conditions of constant temperature and humidity and radiation light source avoidance, burdening, respectively and uniformly mixing the material A, the material B, the material C and the material D in the table 1 according to a ratio to obtain the uniformly mixed material A, the material B, the material C and the material D, adding the material B into the material A, then adding the material C and the material D into a high-speed stirrer to stir at a constant speed for 1 hour, and filtering impurities to obtain the wear-resistant coating of the PVC floor.

Coating the PVC floor wear-resistant coating on the printed PVC base material by using a comma scraper, irradiating and curing by using energy radiation equipment, and laminating the cured PVC floor wear-resistant coating product with a PVC base material for 30min at 150 ℃ to prepare the PVC floor.

Example 2

The wear-resistant coating for the PVC floor provided by the embodiment is prepared from the following raw materials shown in Table 2:

TABLE 2

Example 3

The wear-resistant coating for the PVC floor provided by the embodiment is prepared from the following raw materials shown in Table 3:

TABLE 3

Example 4

The wear-resistant coating for the PVC floor provided by the embodiment is prepared from the following raw materials shown in Table 4:

TABLE 4

Example 5

The wear-resistant coating for the PVC floor provided by the embodiment is prepared from the following raw materials shown in Table 5:

TABLE 5

Example 6

The wear-resistant coating for the PVC floor provided by the embodiment is prepared from the following raw materials shown in Table 6:

TABLE 6

Example 7

The wear-resistant coating for the PVC floor provided by the embodiment is prepared from the following raw materials shown in Table 7:

TABLE 7

Example 8

The wear-resistant coating for the PVC floor provided by the embodiment is prepared from the following raw materials shown in Table 8:

TABLE 8

Example 9

The wear-resistant coating for the PVC floor provided by the embodiment is prepared from the following raw materials shown in Table 9:

TABLE 9

In embodiments 1 to 9, the radiation light source applied in the preparation process of the PVC floor wear-resistant coating provided by the present invention includes energy radiation sources such as ultraviolet light, visible light, infrared light, electron beam, or laser, and under the radiation of the energy radiation sources, the raw materials in the PVC floor wear-resistant coating undergo a polymerization reaction, thereby achieving rapid drying. As the energy-imparting light source, preferred is a light source having a dominant wavelength in the region of 250-450nm, and examples include various light sources such as an ultrahigh-pressure mercury lamp, a medium-pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, a high-power metal halide lamp, a xenon lamp, a pulse-emission xenon lamp, a deuterium lamp, an LED lamp, an Nd-YAG3 double-wave laser, a He-Cd laser, a nitrogen laser, a Xe-Cl excimer laser, a Xe-F excimer laser, a semiconductor-excited solid-state laser, and the like.

In embodiments 1 to 9, the raw materials of the PVC floor wear-resistant coating provided by the present invention can be selected in the following ranges:

the component A comprises: the component A is a cation polymerizable compound, A comprises A1, A2 and A3, A3 comprises A31, A32 and A33, and specifically:

a1 is a oxetane compound having the meaning commonly understood in the art of organic chemistry, i.e. a compound containing at least one oxetane group. From the viewpoint of properties such as adhesion fastness, curing speed and viscosity of the PVC floor wear-resistant coating, it is preferable that at least one end capping group is an oxetane group and a hydroxyl-containing alkane or alkene, and H atoms on the alkane or alkene can be substituted by other functional groups, for example, H on the end of oxetane can be optionally substituted by an alkyl group, and the alkyl group is any alkyl group with 1-4 carbon atoms; the-CH 2-in the non-end-capping group of the alkane or alkene may each be independently substituted with any one of-O-, -COO-, -OCO-, -SO 2-or 1, 4-phenylene, provided that the two Os are not directly connected. For example, the oxetanyl ring compound may be selected from any one of the compounds shown in FIGS. 1 to 3, preferably any one of 3-ethyl-3-oxetanemethanol (CAS: 3047-32-3), 3-ethyl-3- (phenylmethyloxymethyl) oxirane (CAS: 18933-99-8), 3-ethyl-3- [ (oxomethoxy) methyl ] oxirane (CAS: 15957-34-3) and 3-ethyl-3- [4- [ (3-ethyloxotan-3-yl) methoxy ] butoxymethyl ] oxirane (CAS: 126050-33-7).

A2 represents an alicyclic epoxy compound, and the alicyclic epoxy compound represents a compound having an alicyclic epoxy group. From the viewpoint of further enhancing the curing rate, it is conceivable to use a polyfunctional alicyclic epoxy compound having 2 or more alicyclic epoxy groups in the molecule or an alicyclic epoxy compound having 1 alicyclic epoxy group in the molecule and having an unsaturated double bond group such as a vinyl group, preferably an epoxy compound having an epoxycyclohexyl group, such as 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexylcarboxylate, caprolactone-modified-3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexylcarboxylate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, epoxycyclohexane, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3, 4-epoxycyclohexylmethacrylate, and, 3, 4-epoxycyclohexylmethacrylate, 1, 2-epoxy-4-vinylcyclohexane, 3, 4-epoxycyclohexanecarboxylate, the polymerization product of 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate and caprolactone, 4-methyl-1, 2-epoxycyclohexane, 2-bis (3, 3' -epoxycyclohexyl) propane or 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane. 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate is preferred.

A3, which includes A3 in addition to the two cationically polymerizable compounds mentioned above, A3 being other types of cationically polymerizable compounds such as oxetane compounds (a31, which does not contain a hydroxyl group and the end capping group is not an oxetane group), epoxy compounds (a32 does not contain an alicyclic epoxy group) or vinyl ether compounds (a33) having structures different from those of the two essential components mentioned above. The mass ratio of the cationic polymerizable compound of this type in the total cationic polymerizable compound is preferably not more than 80%, and preferably not more than 60%.

A31, more specifically, this other type of oxetane compound (which does not contain a hydroxyl group and the end-capping group is not an oxetanyl group) may be a monofunctional compound (A311) or a polyfunctional compound (A312).

A311, monofunctional examples include, but are not limited to, the following starting materials: 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- [ (phenoxy) methyl ] oxetane, 3-ethyl-3- (chloromethyl) oxetane, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, 3-ethylhexylmethyloxetanylmethyl) ether, 3-ethylhexylmethyloxetanylmeth-yl (m) ether, 3-ethylhexyloxetanylmeth, Ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, and the like.

A312, examples of multiple functionalities include, but are not limited to, the following starting materials: bis [ 1-ethyl (3-oxetanyl) ] methyl ether, 3-bis (chloromethyl) oxetane, 3, 7-bis (3-oxetanyl) -5-oxa-nonane, 1, 2-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ethane, 1, 3-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, p-xylylene (3-ethyl-3-oxetanylmethyl) ether, p-xylylene, 1, 4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1, 6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetra (3-ethyl-3-oxetanylmethyl) ether, and the like.

Furthermore, the oxetanes disclosed in the chinese patent applications No. 201610548580.7, No. 201610550205.6, No. 201710706339.7 and No. 201710622973.2 can also be used for other types of oxetanes of the present invention (which do not contain a hydroxyl group and the end capping group is not an oxetanyl group).

Specifically, a32, the other type of epoxy compound (not containing an alicyclic epoxy group) may be a hydrogenated epoxy compound (a321), an aromatic epoxy compound (a322) and/or an aliphatic epoxy compound (a 323).

A321, a hydrogenated epoxy compound, preferably a compound having a glycidyl ether group directly or indirectly bonded to a saturated aliphatic cyclic hydrocarbon skeleton, and a polyfunctional glycidyl ether compound is preferable. Such a hydrogenated epoxy compound is preferably a completely or partially hydrogenated product of an aromatic epoxy compound, more preferably a hydrogenated product of an aromatic glycidyl ether compound, and still more preferably a hydrogenated product of an aromatic polyfunctional glycidyl ether compound. Specifically, it can be selected from hydrogenated bisphenol a type epoxy compounds, hydrogenated bisphenol S type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, and the like.

A322, the aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in the molecule. The aromatic epoxy compound may be an epoxy compound having an aromatic ring conjugate system such as a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, a naphthalene ring, or an anthracene ring. Among them, in order to achieve a higher refractive index, a compound having a bisphenol skeleton and/or a fluorene skeleton is preferable, and a compound having a fluorene skeleton is more preferable, whereby the refractive index can be more remarkably increased and the mold release property can be further improved. In addition, a compound in which an epoxy group in the aromatic epoxy compound is a glycidyl group is preferable, and a compound in which the epoxy group is a glycidyl ether group (that is, an aromatic glycidyl ether compound) is more preferable. Further, although it is preferable to use a bromide of an aromatic epoxy compound because a higher refractive index can be achieved, it is preferable to use it as appropriate depending on the application because the Abbe number is slightly increased. Preferred examples include bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, fluorene type epoxy compounds, aromatic epoxy compounds having a bromine substituent, and the like.

The aromatic glycidyl ether compound may be an Epi-bis type glycidyl ether epoxy resin, a high molecular weight Epi-bis type glycidyl ether epoxy resin, a novolak, an aralkyl type glycidyl ether epoxy resin, or the like. The Epi-bis type glycidyl ether type epoxy resin may be a resin obtained by a condensation reaction of bisphenol such as bisphenol a, bisphenol F, bisphenol S, fluorene bisphenol and epihalohydrin. The high molecular weight Epi-bis type glycidyl ether epoxy resin may be a resin obtained by addition reaction of the Epi-bis type glycidyl ether epoxy resin with a bisphenol such as bisphenol a, bisphenol F, bisphenol S, and fluorene bisphenol. Preferred examples include, but are not limited to: bisphenol A type compounds such as 828EL, 1003 and 1007 produced by epoxy resin Co., Ltd., and fluorene type compounds such as ONCOATEX-1020, ONCOATEX-1010, OGSOLEG-210 and OGSOLLPG produced by OSAKAGAS CHEMICALS.

A323, the aliphatic epoxy compound is a compound having an aliphatic epoxy group, such as an aliphatic glycidyl ether type epoxy resin. Preferred examples of the aliphatic glycidyl ether type epoxy resin include, but are not limited to, resins obtained by condensation reaction of a polyhydric compound, which may be selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, glycerol, diglycerol, tetraglycerol, polyglycerols, trimethylolpropane and polymers thereof, pentaerythritol and polymers thereof, mono/polysaccharides (such as glucose, fructose, lactose, maltose, etc.), and the like, with epihalohydrin. Among them, an aliphatic glycidyl ether type epoxy resin having a propylene glycol skeleton, an alkylene skeleton, and an alkylene oxide skeleton in the central skeleton is more preferable.

A33, examples of vinyl ether compounds include but are not limited to: aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and n-octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; hydroxyl-containing vinyl ethers such as 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether and 2-hydroxybutyl vinyl ether; and polyfunctional vinyl ethers such as hydroquinone divinyl ether, 1, 4-butanediol divinyl ether, cyclohexane divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

In addition, as the other type of the cationically polymerizable compound, a compound having different types of cationically polymerizable groups in the molecule may be used. For example, as an example having both an epoxy group (e.g., an alicyclic epoxy group) and a vinyl ether group in the molecule.

In general, the mass ratio of the component A in the PVC floor wear-resistant coating composition is 15-60%, and preferably 30-50%.

And B component: the component B is a cationic photoinitiator, can be selected from one or a combination of more than two of iodonium salt, sulfonium salt and aryl ferrocenium salt, and is preferably an iodonium salt and/or sulfonium salt photoinitiator. A particularly preferred embodiment is illustrated in fig. 4;

wherein R1 and R2 each independently represent hydrogen, a linear or branched alkyl group of C1-C20, a cycloalkylalkyl or alkylcycloalkyl group of C4-C20, and the acyclic-CH 2-of these groups may be optionally substituted by-O-, -S-, or 1, 4-phenylene; preferably, R1 and R2 each independently represent hydrogen, a linear or branched alkyl group of C1-C12, a cycloalkylalkyl or alkylcycloalkyl group of C4-C10, and the acyclic-CH 2-of these groups may be optionally substituted by-O-;

r3 and R4 each independently represent hydrogen, a linear or branched alkyl group from C1 to C20, a cycloalkylalkyl or alkylcycloalkyl group from C4 to C20, a substituted or unsubstituted aryl group from C6 to C20, and the acyclic-CH 2-in these groups may optionally be substituted by-O-, -S-, or a1, 4-phenylene group; preferably, R3 and R4 each independently represent hydrogen, a linear or branched alkyl group of C1-C10, a cycloalkylalkyl or alkylcycloalkyl group of C4-C10, a substituted or unsubstituted aryl group of C6-C12, and the acyclic-CH 2-in these groups may optionally be substituted by-O-, -S-, or 1, 4-phenylene;

r5 represents a substituted or unsubstituted aryl group of C6-C20, a substituted or unsubstituted alkylaryl group of C6-C20, a linear or branched alkyl group of C1-C20, a cycloalkylalkyl or alkylcycloalkyl group of C4-C20, a substituted or unsubstituted phenylthiophenyl group, and the acyclic-CH 2-of these groups may be optionally substituted by carbonyl, -O-, -S-, or 1, 4-phenylene; preferably, R5 represents a substituted or unsubstituted aryl group of C6-C10, a substituted or unsubstituted alkylaryl group of C6-C10, a substituted or unsubstituted phenylthiophenyl group, and the acyclic-CH 2-of these groups may be optionally substituted by carbonyl, -O-, -S-, or 1, 4-phenylene;

r6 and R7 each independently represent an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an aryl group, a heterocycloalkyl group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxyl (poly) alkyleneoxy group, a substitutable amino group, a cyano group, a nitro group, or a halogen atom, and m1 and m2 each represent the number of R6 and R7 and represent an integer of 0 to 4. Preferably, R6 and R7 represent a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkylcarbonyl group having 1 to 10 carbon atoms and a halogen.

X-independently represents M-, ClO4-, CN-, HSO4-, CF3COO-, (BM4) -, (SbM6) -, (AsM6) -, (PM6) -, Al [ OC (CF3)3]4-, sulfonate ion, B (C6M5) 4-or [ (Rf) bPF6-B ] -, wherein M is F or Cl, Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted by fluorine atoms, B represents an integer of 1-5, and B Rf groups are the same or different from each other.

Specifically, the preferable structure of the cationic part of the iodonium salt and sulfonium salt photoinitiator is shown in fig. 5-7. The iodonium salt and sulfonium salt photoinitiator anions can be the following ions: cl-, Br-, PF6-, SbF6-, AsF6-, BF4-, C4F9SO3-, B (C6H5)4-, CF17SO3-, CF3SO3-, Al [ OC (CF3)3]4-, (CF3CF2)2PF4-, (CF3CF2)3PF3-, [ (CF3)2CF2]2PF4-, [ (CF3)2CF2]3PF3-, (CF3)2CF2]2PF4-, (CF3)2CFCF2]3PF 3-.

In addition, commercially available cationic photoinitiators can also be used in the B-component of the present invention, such as products of PAG20001, PAG20002, PAG30201, PAG30101 (manufactured by Changzhou powerful electronic New materials, Inc.), Irgacure250 manufactured by BASF, Germany, and the like. The content of the component B in the PVC floor wear-resistant coating provided by the invention is 0.5-20%, and preferably 1-10%.

Besides the above-mentioned A component and B component, according to the requirements of product application environment, it also includes functional adjuvant C, including but not limited to: the coating comprises a leveling agent, a dispersing agent, a curing agent, a surfactant, a defoaming agent, a storage reinforcing agent and the like, wherein the total content of the auxiliary agent is 0-5%, preferably 1-3% in percentage by mass.

The sensitivity of the wear-resistant coating of the PVC floor is improved, and a sensitizer can be added into the system. Especially when the radiation source is LED, it is preferred to add a sensitizer to the PVC floor abrasion resistant coating composition. The sensitizer may be pyrazoline compound, acridine compound, anthracene compound, coumarin compound, tertiary amine compound, etc. The anthracene-based sensitizer compound is particularly preferably a compound having a structure shown in FIG. 8.

As shown in fig. 8, in the general formula (III), R8 represents C1-C12 alkyl, C1-C12 aryl, C1-C8 alkoxy or aryloxy, C3-C12 cycloalkyl, C4-C12 alkylcycloalkyl or cycloalkylalkyl, wherein one or more of these groups may be substituted by halogen, hydroxy; x1 and Y1 each independently represent hydrogen, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, or an amine group.

In the general formula (IV), R9 represents C1-C12 alkyl, C1-C12 aryl, C1-C8 alkoxy or aryloxy C3-C12 cycloalkyl, C4-C12 alkylcycloalkyl or cycloalkylalkyl, wherein one or more of these groups may be substituted by halogen, hydroxy, as shown in FIG. 8; n1 and n2 each independently represent an integer of 0 to 4, X2 and Y2 may be the same or different and each independently represent hydrogen, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, or an amine group, and when n1 and n2 represent 2 or more, X2 and Y2 may be the same or different from each other.

The anthracene compound may also be one or more of the compounds shown in figure 9. The mass percentage content of the sensitizer is 0-5%, preferably 0-2%.

Besides the ABC three types of components, the composite material also comprises a D component, namely a corresponding filler, which comprises one or more of alumina, glass powder, zirconia and ceramic powder. The particle size of each filler is preferably 200 to 400 meshes.

Test examples

The purpose of this test example is to verify the performance of the PVC floor wear coating provided by the previous examples.

The impact resistance, scratch resistance and wear resistance tests of the PVC floor wear-resistant coating provided by the embodiment are respectively detected by the following methods.

1. Test material

The PVC/PP base material is coated with the PVC floor wear-resistant coating provided by the invention, and the PVC/PP base material is used as a test piece to test various performances of the PVC floor wear-resistant coating on the base material after being cured by UV oil.

2. Testing instrument

Coating machine, UV solidification machine, LED solidification machine, impact tester, slide caliper, steel wool and wearing and tearing appearance etc..

3. Work content

3.1 plate making

3.11 cutting out a PVC film with the width of 220-250mm and the length of 500-800mm, and coating the PVC film on a small-sized coating machine by using special wear-resistant UV oil (according to the operating method of the coating machine) to draw out a wet plate with the thickness of 50-100 mu m (according to the specified plate making thickness).

3.12 the wet plate from step 3.11 is then cured to a dry plate on an LED and UV curing machine as specified by the process. The dried board must be smooth and free from the defects of obvious shrinkage orange peel and the like.

3.2 impact resistance test

3.21 test principle

And (5) impacting the surface of the test piece by using the sphere to determine the impact resistance of the product.

3.22 test instruments and tools

Falling ball impact tester, steel ball (diameter 42.8mm + -0.2 mm, mass 324.0 g + -5.0 g, smooth spherical surface, no concave damage, rust spot, etc.), cushion layer, foamed polyethylene, breadth of 300mm × 300mm, thickness of 2.5mm + -0.2 mm, surface density of 75g/m²。

3.23 test procedure

a. Placing the cushion layer on a horizontal and smooth ground; b. placing the test piece on the cushion layer with the decorative surface upward, and placing a blue copy paper on the decorative surface of the test piece; c. the steel ball is enabled to freely fall from the height of 1.75m to impact the surface of the test piece (the steel ball is prevented from repeatedly jumping on the surface of the test piece), each test piece is only tested once, and the falling point of the steel ball is within the range of 2.5mm from the central point of the test piece.

3.24 results

The diameter of the pit was measured to 0.1mm with a vernier caliper. And (4) qualification judgment: the diameter of the pit is less than or equal to 10 mm. The PVC floor wear-resistant coatings provided by the embodiments 1-9 have the following test results, and therefore, the PVC floor wear-resistant coatings provided by the embodiments all pass the impact resistance test, and the impact resistance is good.

3.3 scratch resistance test

3.31 principle

Surface scratch resistance is the ability of a product to resist scratching by diamond needles or scratching by steel wool under a certain force.

3.32 Instrument and appliance

Scratch resistance, 400 gram weight and steel wool.

3.33 test methods

The method comprises the following steps: wiping off the surface of the test piece, and fixing the side face of the test piece on a scratch test objective table upwards. And adjusting the height of the cross beam to enable the upper edge of the cross beam to be in a horizontal position when the diamond needle contacts the surface of the test piece. And moving the weight to a 4.0N position to start the objective table, and rotating for a circle. And taking down the test piece, and observing the condition that the test piece is scratched. And under natural light, observing the surface decorative pattern of the test piece by naked eyes from any angle to see whether the decorative pattern is scratched or not.

The second method comprises the following steps: wiping off the surface of the test piece, fixing the test piece on a horizontal workbench by the side face upwards, and taking 1cm or about²A weight of 400 g is placed on the steel wool, and the steel wool is driven by fingers to reciprocate 10 times in the horizontal direction. And taking down the test piece, and observing the condition that the test piece is scratched. And under natural light, observing the surface of the test piece by naked eyes from any angle to see whether the surface of the test piece is scratched or not.

After the PVC floor wear-resistant coatings provided by the embodiments 1-9 of the invention are tested by the test methods provided by the first method and the second method, the situation that the surfaces of the test pieces are scratched is not observed.

3.4 surface abrasion resistance test

3.41 principle

The grinding wheel with a pair of adhered abrasive cloth rubs with the rotating test piece to generate a certain number of revolutions when the test piece is worn.

3.42 instruments and materials

An abrasion instrument, a dust collector, P180-granularity abrasive cloth and degreasing abrasive cloth.

3.43 test procedure

a. Cutting the cured dry plate into 100 x 100mm square blocks, drilling a small hole in the center, wiping the square blocks by using a degreasing abrasive cloth, and equally dividing the square blocks into four quadrants; and the test piece was adhered to a special test rotating plate.

b. Special abrasive cloth is pasted on the two abrasive wheels, a dust collector is connected, and two weights with the weight of 500 g are fixed on the support.

c. And fixedly mounting the test rotating plate (with the test surface facing upwards) on an abrasion tester, placing the sanding wheel with weights, starting a dust collector, starting an abrasion tester, and carrying out abrasion test on the test piece under the external force condition of 4.9N +/-0.2N (replacing the abrasive cloth once when the sanding wheel is abraded by 500 turns).

d. Recording that the decorative patterns of the test piece in three quadrants are damaged and the damaged area is not less than 0.6mm²The abrasion revolution is accurate to 100 revolutions.

3.44 test results

After the PVC floor wear-resistant coatings provided by the embodiments 1-9 of the invention are tested by the method, the PVC floor wear-resistant coatings of the embodiments are damaged, and the damaged areas are not less than 0.6mm²The number of abrasion revolutions at that time is shown in table 10, which shows that the abrasion resistant coating of the PVC floor provided by this example has good abrasion resistance.

Watch 10

In summary, the wear-resistant coating for the PVC floor in the embodiment of the invention does not use any volatile organic solvent, can realize high-speed coating by UV curing after being knife-coated with a comma scraper, and is suitable for a printed PVC substrate. The wear-resistant coating for the PVC floor is high in curing speed, good in adhesion of the cured coating, excellent in wear resistance, good in appearance and odorless. The PVC floor prepared by the hot-pressing compounding process and the PVC base material through the pressing is excellent in wear resistance, good in environmental protection performance and tempering stability and has a good application prospect.

The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims

1. The PVC floor wear-resistant coating is characterized by being mainly prepared from the following raw materials in percentage by mass: 15-60% of cation polymerizable compound, 0.5-20% of cation photoinitiator, 0-5% of auxiliary agent and 20-75% of wear-resistant powder.

2. The PVC floor wear-resistant coating as claimed in claim 1, which is prepared from the following raw materials in parts by weight: 29-50% of cationic polymeric compound, 1-10% of cationic photoinitiator, 0-3% of auxiliary agent and 30-70% of wear-resistant powder.

3. The PVC floor wear coating of claim 1, wherein the cationically polymerizable compound comprises an oxetane compound and an alicyclic epoxy compound.

4. The PVC floor wear coating of claim 3, wherein the mass ratio of the alicyclic epoxy compound to the oxetane compound is 1: 1-4.

5. The PVC floor wear coating according to claim 4, wherein the sum of the masses of the oxetane compound and the alicyclic epoxy compound is 20% or more by mass in the cationically polymerizable compound.

6. The PVC floor wear-resistant coating according to claim 3, wherein the alicyclic epoxy compound is a polyfunctional alicyclic epoxy compound having two or more alicyclic epoxy groups in a molecule, or an alicyclic epoxy compound having one alicyclic epoxy group and one unsaturated double bond group in a molecule.

7. The PVC floor wear coating of claim 5, wherein the cationic polymerizable compound further comprises one or more of an oxetane compound which does not contain a hydroxyl group and the end capping group is not an oxetane group, an epoxy compound which does not contain an alicyclic epoxy group, and a vinyl ether compound.

8. The PVC floor wear coating of claim 7, wherein the epoxy compound not containing an alicyclic epoxy group comprises one or more of a hydrogenated epoxy compound, an aromatic epoxy compound and an aliphatic epoxy compound.

9. The PVC floor wear coating of claim 1, wherein the cationic photoinitiator comprises one or more of an iodonium salt, a sulfonium salt, an arylferrocenium salt.

10. The PVC floor wear-resistant coating according to claim 1 or 2, wherein the wear-resistant powder comprises one or more of alumina, glass powder, zirconia and ceramic powder.