CN114456322A - Ultraviolet-curable resin composition - Google Patents

Ultraviolet-curable resin composition Download PDF

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Publication number
CN114456322A
CN114456322A CN202011506957.5A CN202011506957A CN114456322A CN 114456322 A CN114456322 A CN 114456322A CN 202011506957 A CN202011506957 A CN 202011506957A CN 114456322 A CN114456322 A CN 114456322A
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monomer
resin composition
ultraviolet
curable resin
weight
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Inventor
德永幸次
高进贤
林士斌
翁畅健
傅从豪
李翰昇
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Lidye Chemical Co Ltd
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Lidye Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to an ultraviolet-curable resin composition. The composition comprises: 5-40 parts by weight of a photocurable oligomer (A); 10 to 50 parts by weight of a vinyl resin (B); 5 to 40 parts by weight of an unsaturated ethylenic monomer (C); and 0.1 to 15 parts by weight of a photopolymerization initiator (D); wherein the photocurable oligomer (a) + the vinyl resin (B) + the ethylenically unsaturated monomer (C) is 100 parts by weight, and the vinyl resin (B) is formed by polymerizing: aromatic compound monomer or aliphatic monomer (B1), wherein the aromatic compound monomer comprises C8-C12 monovinyl aromatic compound or halogenated derivative thereof; and a dibasic acid monomer (B2), wherein the molar ratio of the aromatic compound monomer or the aliphatic monomer (B1) to the dibasic acid monomer (B2) is 10-20. The ultraviolet-curable resin of the present invention can provide good adhesion to metals.

Description

Ultraviolet-curable resin composition
Technical Field
The invention relates to the field of high polymer resin and paint, in particular to an ultraviolet light hardening resin composition suitable for paint.
Background
The ultraviolet curing technology is a green technology developed from the 1970 s, and has the advantages that the technology can reduce the waste of energy, improve the crosslinking density, shorten the process time, easily control the quality, and reduce the equipment space required for improving the production efficiency and the yield. According to the components and hardening mode of the resin, the ultraviolet curing resin conforms to four principles of the color chemistry of the time-sensitive nature: (1) the requirement of low Volatile Organic Compounds (VOC) can be met without using or using a small amount of solvent; (2) the product of the chemical reaction is non-toxic and environment-friendly; (3) the energy utilization rate is high; (4) the reaction can be carried out at normal temperature and normal pressure. By means of different ultraviolet lamp tube characteristics and matching with various ultraviolet curing resins, the ultraviolet curing technology can be improved into a fast and high-efficiency production process.
The general formulation of the ultraviolet curing resin can be divided into three parts, wherein the first part is Oligomer (Oligomer), and the low viscosity, no odor, high curing speed and low toxicity are required; the second part is a Reactive Monomer (Reactive Monomer) which is required to have photoreactivity, good hardening rate, good solvent power, low volatility and the like; the third part is a photo initiator (photo initiator), which requires the property (1) of being able to attract ultraviolet radiation energy and to induce polymerization; (2) good thermal stability; other additives or a small amount of solvent can be added according to the requirements of the application of the performance. At present, the ultraviolet curing technology is widely applied to various industries such as: home appliances, automobile industry, electronic industry 3C products, and the like.
At present, the ultraviolet curing resin can only be adhered to a specific base material, and most of the ultraviolet curing coating can be adhered to the base material which belongs to organic polymer plastics; there are relatively few products that can meet the requirements of inorganic materials such as metal or ceramic or glass substrates, and there are fewer products that can simultaneously meet the requirements of various general types of substrates (such as engineering plastics, metal substrates, glass, ceramic or composite materials and the like substrates). Thus, although the existing uv curable resins have been generally satisfactory, they are not fully satisfactory, and further improvements are still needed.
Disclosure of Invention
The invention aims to disclose a coating composed of ultraviolet light-curable resin; the ultraviolet coating composition can simultaneously meet the interlayer adhesion of different types of base materials after being irradiated by ultraviolet light, and has the advantages of simultaneously adhering metal base materials, organic high polymer plastic base materials, inorganic glass base materials or the composite material base materials. The composition also has the advantages of good leveling property, recoatability, vapor deposition property and the like of a coating film.
In order to achieve the purpose, the research and development team of the invention obtains the ultraviolet curing coating composition with the advantages of wide application, leveling property, repairability and the like after a great deal of research and reading of literature data and continuous innovative thinking and repeated trial and error of polymer synthesis and formula adjustment.
The present invention provides an ultraviolet-curable resin composition comprising: 5-40 parts by weight of a photocurable oligomer (A); 10 to 50 parts by weight of a vinyl resin (B); 5 to 40 parts by weight of an unsaturated ethylenic monomer (C); and 0.1 to 15 parts by weight of a photopolymerization initiator (D); wherein the photocurable oligomer (a) + the vinyl resin (B) + the ethylenically unsaturated monomer (C) is 100 parts by weight, and the vinyl resin (B) is formed by polymerizing: aromatic compound monomer or aliphatic monomer (B1), wherein the aromatic compound monomer comprises C8-C12 monovinyl aromatic compound or halogenated derivative thereof; and a dibasic acid monomer (B2); wherein the molar ratio of the aromatic compound monomer or aliphatic monomer (B1) to the dibasic acid monomer (B2) is 10-20.
Detailed Description
In order to make the features of the present disclosure comprehensible, embodiments accompanied with other details are described below.
The ultraviolet curable resin composition provided by the present invention will be described in detail below.
In the context of the present disclosure, a term "about" or "approximately" means within 5%, preferably within 3%, more preferably within 1%, or within 2%, or within 1%, or within 0.5% of a given value or range. The amounts given herein are approximate, that is, the meanings of "about", "about" and "substantially" may be implied without specifically stating "about", "about" or "substantially".
In the present specification, a range represented by "one numerical value to another numerical value" is a general expression avoiding that all numerical values in the range are enumerated in the specification. Accordingly, unless otherwise indicated herein or otherwise clearly contradicted by reasonable or ordinary skill in the art, a particular numerical range is defined in this specification as being equivalent to disclosing any value from that numerical range and the lesser numerical range defined by any value from that numerical range (including integers and values immediately following the decimal point) as if such values and the lesser numerical range were written expressly in the specification. For example, when only "1 to 10" is recited, it may be equivalent to disclosing the ranges of "3 to 5" and "2.5 to 6.8", whether or not other numerical values are recited in the specification.
In the present specification, "aromatic groupThe compound "refers to benzene or its derivatives, hydrocarbon compounds having one or more benzene rings in the molecular structure, and examples of the aromatic compounds include, but are not limited to, benzene, toluene, ethylbenzene, and isobutylbenzene. The term "aromatic halogenated compound" means an aromatic compound in which one or more hydrogen atoms are replaced by halogen atoms (fluorine, chlorine, bromine, iodine), and examples of the aromatic halogenated compound include, but are not limited to, chlorostyrene and bromostyrene. "dibasic acid" refers to a hydrocarbon compound having two carboxyl (-COOH) functional groups, and examples thereof include formalin acid and maleic acid, but are not limited thereto. "alkylene" refers to a chain organic functional group containing both carbon and hydrogen atoms, and can be represented by-CnH2nAnd both ends of the chain may be connected to other groups. In some examples, alkylene groups include, but are not limited to, ethylene, propylene, and butylene. "alkenylene" refers to an organofunctional group containing a carbon-carbon double bond, and to which additional groups may be attached at both ends of the chain. In some examples, the alkenylene group may be exemplified by, but not limited to, an ethenylene group, an propenylene group, and a butenylene group.
The embodiment of the invention provides an ultraviolet light hardening resin composition; the UV-curable resin composition can be cured by UV irradiation and then can be adhered to a metal substrate, a plastic substrate, a glass substrate or the composite material substrate, so as to finally achieve the purposes of protecting the substrate and being decorative. The ultraviolet light hardening resin composition for the paint has good substrate adhesion universality and processability, and can be applied to the application of prime coat and top coat in the paint field.
Specifically, the ultraviolet curable resin composition according to the embodiment of the present invention includes:
5-40 parts by weight of a photocurable oligomer (A);
10 to 50 parts by weight of a vinyl resin (B);
5 to 40 parts by weight of an unsaturated ethylenic monomer (C); and
0.1 to 15 parts by weight of a photopolymerization initiator (D);
wherein the photocurable oligomer (a) + the vinyl resin (B) + the ethylenically unsaturated monomer (C) is 100 parts by weight, and the vinyl resin (B) is formed by polymerizing:
aromatic compound monomer or aliphatic monomer (B1), wherein the aromatic compound monomer comprises C8-C12 monovinyl aromatic compound or halogenated derivative thereof; and
diacid monomer (B2)
Wherein the molar ratio of the aromatic compound monomer or aliphatic monomer (B1) to the dibasic acid monomer (B2) is 10-20.
The ultraviolet-curable resin composition of the present invention has a dibasic acid monomer and can provide adhesion to both organic and inorganic materials.
At present, the ultraviolet curing resin can only be adhered to a specific base material, and most of the ultraviolet curing coating can be adhered to the base material which belongs to organic polymer plastics; there are relatively few products that can meet the requirements of inorganic materials such as metal or ceramic or glass substrates, and there are fewer products that can simultaneously meet the requirements of various general types of substrates (such as engineering plastics, metal substrates, glass, ceramic or composite materials and the like substrates). Therefore, the embodiment of the present invention can provide the adhesion of the ultraviolet light curable resin composition to the metal substrate by polymerizing the dibasic acid monomer into the vinyl resin. Further, an organosiloxane may be added as necessary to improve adhesion of the ultraviolet-curable resin composition to a metal substrate and a glass substrate.
In the present invention, the photocurable oligomer (a) + the vinyl resin (B) + the ethylenically unsaturated monomer (C) is defined as 100 parts by weight.
The following will describe each component of the uv curable resin composition in detail:
[ (A) Photocurable oligomer ]
According to some embodiments of the invention, the photocurable oligomer (a) is a compound having two or more ethylenic unsaturations, including, but not limited to: urethane acrylate oligomer, polyacrylic oligomer, polyester oligomer, polyether oligomer, epoxy oligomer, or a combination thereof, preferably urethane acrylate oligomer. The photocuring oligomer can help the coating to generate bridging crosslinking after photocuring so as to achieve the purposes of improving the basic hardness physical property, weather resistance, chemical resistance and the like of the coating.
According to some embodiments of the present invention, the photocurable oligomer (A) has a weight average molecular weight of 1000 to 10,000, preferably 2000 to 8,000.
According to some embodiments of the present invention, the content of the photocurable oligomer (a) is preferably 5 to 40 parts by weight.
According to the research of the inventor, the following steps are shown: in some embodiments, if the content of the photocurable oligomer (a) is more than 40 parts, the crosslinking density is too high, which may cause problems such as poor adhesion or cracking of the coating due to excessive shrinkage of the coating. When the content of the photocurable oligomer (A) is less than 5 parts, the crosslinking density is too low, which tends to cause problems such as insufficient physical properties of the coating layer, poor chemical resistance and poor water resistance.
[ (B) vinyl resin ]
The vinyl resin can be used for controlling the brittleness and the hardness and the viscosity of a coating film and can provide good adhesion to a substrate.
In some embodiments, the weight average molecular weight of the vinyl resin (B) is between 5,000 and 200,000.
According to the research of the inventor, the following steps are shown: in some examples, if the weight average molecular weight of the vinyl resin (B) is less than 5,000, the adhesion effect may be poor because the coating film is brittle and hard. If the weight average molecular weight of the vinyl resin (B) is more than 200,000, the system viscosity is too high, so that the workability is not easy and the coating film properties are adversely affected in practical use.
According to some embodiments of the present invention, the content of the vinyl resin (B) is preferably 10 to 50 parts by weight, and more preferably 20 to 40 parts by weight.
In some embodiments, the vinyl resin (B) comprises a monomer formed by polymerization of: aromatic compound monomer or aliphatic monomer (B1), and dibasic acid monomer (B2).
[ (B1) aromatic monomer or aliphatic monomer ]
In some embodiments, the aromatic monomer, including C8-C12 monovinyl aromatic compound or halogenated derivatives thereof, may be styrene, α -methyl styrene, vinyl toluene, t-butyl styrene, chlorostyrene, but is not limited thereto.
In some embodiments, the aromatic compound monomer preferably has a structure as shown below.
Wherein R1-R5 are each independently C1-C10 alkyl, hydrogen atom or halogen.
Figure BDA0002844944770000051
In some embodiments, the aromatic monomer is more preferably styrene, having the structure shown below.
Figure BDA0002844944770000052
In some embodiments, the aliphatic monomer is an alkyl acrylate or a substituted alkyl acrylate.
In some embodiments, the aliphatic monomer has a structure shown below, wherein R6, R7 are each independently a C1 to C10 alkyl group or a hydrogen atom.
Figure BDA0002844944770000053
In some embodiments, the aliphatic monomer is preferably a C4-C10 alkyl methacrylate monomer or a C3-C10 alkyl acrylate monomer.
In some embodiments, the alkyl methacrylate monomers C4-C10 include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2-methoxyethyl methacrylate, and ethoxymethyl methacrylate.
In some embodiments, the alkyl methacrylate monomer is preferably methyl methacrylate, having the structure shown below.
Figure BDA0002844944770000061
In some embodiments, the alkyl acrylate monomers C3-C10 include, but are not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, 2-methoxyethyl acrylate, and ethoxymethyl acrylate.
In some embodiments, the alkyl acrylate monomer is preferably butyl acrylate, having the structure shown below.
Figure BDA0002844944770000062
In some embodiments, the molar ratio of the aromatic or aliphatic monomer (B1) to the dibasic acid monomer (B2) is 10 to 20.
[ (B2) dibasic acid monomer ]
The diacid monomer can provide the carboxyl group to generate chelation with metal, slightly corrode the surface of the metal and destroy the compact surface of the metal so as to achieve good adhesion to the metal.
In some examples, the diacid monomer (B2) may include, but is not limited to, Maleic Acid (Maleic Acid), formalin Acid (Fumaric Acid), citraconic Acid, mesaconic Acid, Itaconic Acid (Itaconic Acid), 3-vinylphthalic Acid, 4-vinylphthalic Acid, 3,4,5, 6-tetrahydrophthalic Acid, 1,2,3, 6-tetrahydrophthalic Acid, dimethyltetrahydrophthalic Acid, and 1, 4-cyclohexene dicarboxylic Acid.
In some embodiments, the diacid monomer (B2) is preferably of the structure shown below.
Wherein R8 is an alkylene or alkenylene group of C1-C10.
Figure BDA0002844944770000063
In some embodiments, the diacid monomer (B2) has an ethylenic unsaturation.
In some embodiments, the diacid monomer (B2) is more preferably formalin acid or maleic acid.
In some embodiments, the diacid monomer (B2) is particularly preferably formalin acid, having the structure shown below.
Figure BDA0002844944770000071
According to some embodiments of the present invention, the content of the dibasic acid monomer (B2) is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight.
According to the research of the inventor, the following steps are shown: in some embodiments, if the content of the dibasic acid monomer (B2) is more than 20 parts, it may be difficult to actually use as a coating material because the viscosity is too high. If the content of the dibasic acid monomer (B2) is less than 0.1 part, the effect of adhesion to the metal is not good.
[ (C) ethylenically unsaturated monomer ]
The UV curable resin composition can be provided with different hardness by adjusting the amount of the ethylenically unsaturated monomer.
According to some embodiments of the present invention, the content of the ethylenically unsaturated monomer (C) is preferably 5 to 40 parts by weight, more preferably 10 to 35 parts by weight.
In some examples, the ethylenically unsaturated monomer (C) has one or more ethylenically unsaturated bonds, and examples thereof include 1, 6-hexanediol diacrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, butylene glycol di (meth) acrylate, pentaerythritol triacrylate, neopentyl glycol di (meth) acrylate, ditrimethylolpropane tetraacrylate, beta- (acryloyloxy) propionic acid, glycerol trimethylolpropane triacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, polydipentaerythritol hexaacrylate, glycerol di (meth) acrylate, isopentyl diacrylate di (meth) acrylate, ethylene glycol glycidyl ether di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol diacrylate, and the like, Diethylene glycol diglycidyl ether di (meth) acrylate, phthalic diglycidyl ether di (meth) acrylate, hydroxypivalic acid-denatured neopentyl glycol di (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ethylene oxide-denatured di (meth) acrylate isocyanurate, trimethylolpropane trimethacrylate, pentaerythritol tetra (meth) acrylate, diisopentaerythritol tri (meth) acrylate, diisopentaerythritol tetra (meth) acrylate, diisopentaerythritol penta (meth) acrylate, diisopentaerythritol hexa (meth) acrylate, tris (meth) acryloyloxyethoxy trimethylolpropane, glycerol polyglycidyl ether poly (meth) acrylate, The isocyanate is not limited to ethylene oxide-modified tri (meth) acrylate, ethylene oxide-modified dipentyl penta (meth) acrylate, ethylene oxide-modified dipentyl hexa (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tetra (meth) acrylate, and succinic acid-modified pentaerythritol tri (meth) acrylate, but 1, 6-hexanediol diacrylate is preferable.
[ (D) photopolymerization initiator ]
The photopolymerization initiator can cure the ultraviolet-curable resin composition by irradiation with the activation energy of ultraviolet light for a very short time.
According to some embodiments of the present invention, the photopolymerization initiator (D) is preferably contained in an amount of 0.1 to 15 parts by weight, more preferably 1 to 8 parts by weight.
According to the research of the inventor, the following steps are shown: in some embodiments, for example, the content of the photopolymerization initiator (D) is 8 parts or more, which easily causes a reaction after coating. If the content of the photopolymerization initiator (D) is less than 1 part, there is a problem that the coating layer cannot be cured and dried.
In some embodiments, the photopolymerization initiator (D) includes two or more different photopolymerization initiators.
In some examples, the photopolymerization initiator (D) includes, for example, diethoxyacetophenone, 2-hydroxy-methylphenylpropan-1-one, benzyldimethylketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylmethophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like, Benzoin isobutyl ether, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, isopropylthioxanthone, ethyl 4- (N, N-dimethylamino) benzoate, benzophenone, 4-chlorobenzophenone, methyl o-benzoylbenzoate, diphenyliodonium hexafluorophosphate, isooctyl p-N, N-dimethylaminobenzoate, 4-methylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyl-diphenylsulfide, 3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl ] benzenetetramethylammonium bromide, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl ] benzenediamine, (4-benzoylbenzyl) trimethylammonium chloride, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3, 4-dimethyl-9H-thioxanth-9-one methylchloride, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate bis (2, 6-dimethoxybenzoyl ] -2,4, 4-trimethyl-pentylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, but is not necessarily limited thereto, 1-hydroxycyclohexylphenylmethanones are preferred.
[ (E) organosiloxane coupling agents ]
Optionally, an organosiloxane coupling agent may be added, and hydroxyl groups or alkoxy groups of the organosiloxane may be bonded to hydroxyl groups on the surface of the glass by condensation reaction, thereby improving adhesion to the glass.
According to some embodiments of the present invention, the content of the organosiloxane coupling agent (E) is 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight.
In some embodiments, the organosiloxane coupling agent (E) comprises an ethylenic unsaturation.
In some examples, the organosiloxane coupling agent (E) may be exemplified by vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-glycidyloxypropyltrimethoxysilane, N-propyltrimethoxysilane, N-glycidyloxypropyltrimethoxysilane, N-hydroxysilane, and, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and/or 3-mercaptopropyltrimethoxysilane, but the silane is not limited thereto, and 3-methacryloxypropyltrimethoxysilane is preferable.
Hereinafter, the present disclosure will provide several examples and comparative examples to more specifically illustrate the effects of the uv curable resin compositions according to the examples of the present disclosure and the characteristics of the uv curable resin compositions prepared by applying the present disclosure. However, the following examples and comparative examples are illustrative only and should not be construed as limiting the practice of the present disclosure.
[ Synthesis example I ] vinyl Resin A (vinyl Resin A)
After (B1) 51 g of styrene, (B4) 34.3 g of butyl acrylate, 5.7 g of hydroxyethyl methacrylate, (B3) 6 g of methyl methacrylate, (B2) 3 g of formalin acid and 27.4 g of n-butyl acetate were added in succession to a reaction vessel equipped with a stirrer, a temperature controller and a nitrogen gas blowing device: slowly heating to 110 ℃ from room temperature, slowly dripping 2 g of premixed di-tert-butyl peroxide and 27.4 g of n-butyl acetate into a reaction kettle, controlling the titration time to be completed within 3 hours, continuously heating for 8 hours, and then cooling to obtain transparent and viscous vinyl resin; the theoretical solids content is about 65%.
Synthesis example II vinyl Resin B (vinyl Resin B)
In a reaction vessel equipped with a stirrer, a temperature controller, and a nitrogen gas blowing device, (B1) 54 g of styrene, (B4) 31.5 g of butyl acrylate, 5.5 g of hydroxyethyl methacrylate, (B3) 6 g of methyl methacrylate, (B2) 3 g of maleic acid, and 27.4 g of n-butyl acetate were sequentially added and mixed: slowly heating to 110 ℃ from room temperature, slowly dripping 2 g of premixed di-tert-butyl peroxide and 27.3 g of n-butyl acetate into a reaction kettle, controlling the titration time to be completed within 3 hours, and heating for 8 hours and then cooling, thereby obtaining transparent and viscous vinyl resin; the theoretical solids content is about 65%.
Synthesis example III vinyl Resin C (vinyl Resin C)
A reaction vessel equipped with a stirrer, a temperature controller and a nitrogen gas blowing device was charged with (B1) 51 g of styrene, 34.2 g of butyl acrylate (B4), 8.8 g of hydroxyethyl methacrylate, 6 g of methyl methacrylate (B3) and 27.4 g of n-butyl acetate in this order, and after mixing: slowly heating to 110 ℃ from room temperature, slowly dripping 2 g of premixed di-tert-butyl peroxide and 27.4 g of n-butyl acetate into a reaction kettle, controlling the titration time to be completed within 3 hours, and heating for 8 hours and then cooling, thereby obtaining transparent and viscous vinyl resin; the theoretical solids content is about 65%.
[ example one ] ultraviolet light coating composition
Taking 22.9 g of Vinyl resin A in the Vinyl resin (B) in the first example; (A) urethane acryl oligomer UB-630266.9 g (manufacturer: Taiwan Ridgel chemical Co., Ltd.); 4.6 g of a reaction monomer (C) trimethylolpropane propoxy (3) triacrylate (TMP3POTA) (manufacturer: Taiwan department of specialty Chemicals, Ltd., China); 2.3 g of a reactive monomer (C), 1, 6-hexanediol diacrylate (1,6HDDA) (manufacturer: Taiwan national specialty Chemicals Co., Ltd., China); (D) irgacure 1841.4 g photoinitiator (manufacturer: Demerck Basff Co., Ltd.); finally, 31 g of ethyl acetate and 31 g of n-butyl acetate are added and mixed evenly to obtain a coating liquid with the solid content of 30 percent.
Example two UV coating composition
Taking 23.5 g of Vinyl resin B in the Vinyl resin (B) in the first example; (A) urethane acryl oligomer UB-630264.7 g (manufacturer: Taiwan Ridgel chemical Co., Ltd.); 3.5 g of a reaction monomer (C) trimethylolpropane propoxy (3) triacrylate (TMP3POTA) (manufacturer: Taiwan department of specialty Chemicals, Ltd., China); 3.5 g of a reactive monomer (C), 1, 6-hexanediol diacrylate (1,6HDDA) (manufacturer: Taiwan national specialty Chemicals Co., Ltd., China); (D) irgacure 1841.4 g photoinitiator (manufacturer: Demerck Basff Co., Ltd.); finally, 31.7 g of ethyl acetate and 31.7 g of n-butyl acetate are added as solvents and are uniformly mixed to obtain a coating liquid with the solid content of 30%.
EXAMPLE III UV coating composition
Taking 23.7 g of Vinyl resin C in the Vinyl resin (B) in the first example; (A) urethane acryl oligomer UB-630264.7 g (manufacturer: Taiwan Ridgel chemical Co., Ltd.); 3.6 g of a reaction monomer (C) trimethylolpropane propoxy (3) triacrylate (TMP3POTA) (manufacturer: Taiwan department of specialty Chemicals, Ltd., China); 2.4 g of a reactive monomer (C), 1, 6-hexanediol diacrylate (1,6HDDA) (manufacturer: Taiwan national specialty Chemicals Co., Ltd., China); (E) organosiloxane, 3-methacryloxypropyl-trimethoxysilane (KBM-503)0.3 g (manufacturer: Nippon Beacon chemical Co., Ltd.); (D) irgacure 1841.4 g of photoinitiator (manufacturer: Pasteur GmbH, Germany); finally, 32 g of ethyl acetate and 32 g of n-butyl acetate are added and mixed evenly to obtain a coating liquid with the solid content of 30%.
Comparative example one ultraviolet coating composition
Taking 22.9 g of Vinyl resin C in the Vinyl resin (B) in the first example; (A) urethane acryl oligomer UB-630266.9 g (manufacturer: Taiwan Ridgel chemical Co., Ltd.); 4.6 g of a reaction monomer (C) trimethylolpropane propoxy (3) triacrylate (TMP3POTA) (manufacturer: Taiwan Chim Seiko Chemicals GmbH, China); 2.3 g of a reactive monomer (C), 1, 6-hexanediol diacrylate (1,6HDDA) (manufacturer: Taiwan national specialty Chemicals Co., Ltd., China); (D) irgacure 1841.4 g photoinitiator (manufacturer: Demerck Basff Co., Ltd.); finally, adding 31 g of ethyl acetate and 31 g of n-butyl acetate serving as solvents, and uniformly mixing to obtain a coating liquid with the solid content of 30%.
Comparative example two ultraviolet coating composition
Taking 22.9 g of Vinyl resin C in the Vinyl resin (B) in the first example; (A) urethane acrylic oligomer UB-630262.3 g (manufacturer: Taiwan Chihua chemical Co., Ltd.) reaction monomer (C) trimethylolpropane propoxy (3) triacrylate (TMP3POTA)6.9 g (manufacturer: Taiwan Chihua chemical Co., Ltd.); 4.6 g of 1, 6-hexanediol diacrylate (1,6HDDA) as a reactive monomer (C) (manufacturer: Taiwan national specialty Chemicals Co., Ltd., China); (E) organosiloxane, 3-methacryloxypropyl-trimethoxysilane (KBM-503)0.3 g (manufacturer: Nippon Beacon chemical Co., Ltd.); (D) irgacure 1841.4 g of photoinitiator (manufacturer: Pasteur GmbH, Germany); finally, 30.9 g of ethyl acetate and 30.9 g of n-butyl acetate are added and mixed evenly to obtain a coating liquid with the solid content of 30%.
The weight average molecular weights (Mw) of the vinyl resin (B) and the photocurable oligomer (a) in terms of polystyrene were measured by gel chromatography (GPC) under the following conditions.
The device comprises the following steps: ALLANCE e2695 (manufactured by Waters Corporation)
Pipe column: TSK-GEL G5000HXL, TSK-GEL G4000HXL, TSK-GEL G3000HXL, TSK-GEL G2000HXL
Temperature of the pipe column: 40 deg.C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0mL/min
Concentration of solid content in liquid to be detected: 0.4 percent
Injection amount: 100 μ L
A detector: RI (Ri)
Calibration standard substance: TSK POLYSTYRENE STANDARD F-450, F-288, F-128, F-80, F-40, F-10, F-4, F-2, A-5000, A-2500, A-1000, A-500 (manufactured by Tosoh Corp.).
The following ingredients and weight ratios of the examples and comparative examples are shown in table 1.
[ Table 1]
Example one Example two EXAMPLE III Comparative example 1 Comparative example II
Vinyk Resin A 22.9 0.0 23.7 0.0 0.0
Vinyk Resin B 0.0 23.5 0.0 0.0 0.0
Vinyk Resin C 0.0 0.0 0.0 22.9 22.9
UB-63026* 6.9 4.7 4.7 6.9 2.3
TMP3POTA 4.6 3.5 3.6 4.6 6.9
1,6HDDA 2.3 3.5 2.4 2.3 4.6
KBM 503 0.0 0.0 0.3 0.0 0.3
Iragcure 184 1.4 1.4 1.4 1.4 1.4
EAC 31.0 31.7 32.0 31.0 30.9
BAC 31.0 31.7 32.0 31.0 30.9
NV 30％ 30％ 30％ 30％ 30％
In table 1, the compounds represented by the respective components are illustrated as follows:
vinyl Resin A: synthesis of vinyl resin (dibasic acid-containing monomer) obtained in example 1
Vinyl Resin B: synthesis of vinyl resin (diacid-containing monomer) obtained in example 2
Vinyl Resin C: synthesis of vinyl resin obtained in example 3
UB-63026: polyurethane acrylic oligomer (manufacturer: Taiwan Li chemical industry Co., Ltd., China)
TMP3 POTA: trimethylolpropane propoxy (3) triacrylate (manufacturer: Taiwan department of specialty Chemicals, Inc. China)
1,6 HDDA: 1, 6-hexanediol diacrylate (manufacturer: Taiwan national essence chemical Co., Ltd.)
KBM 503: organosiloxane, 3-methacryloxypropyl-trimethoxysilane (manufacturer: Nippon Beacon chemical Co., Ltd.)
Iragcure 184: photoinitiator (manufacturer: Pasteur GmbH, Germany)
EAC: ethyl acetate
BAC: acetic acid n-butyl ester
NV: and the rest part of the dried coating accounts for the mass percentage of the total amount.
[ penetration test ]
The test specifications tested using the Nippon Denshoku NDH-5000 instrument were in accordance with the procedure described in JISK-7105; wherein transmittance is defined as the sum of the light transmitted through the substrate.
[ haze test ]
The test specifications tested using the Nippon Denshoku NDH-5000 instrument were in accordance with the procedure described in JISK-7105; wherein haze is defined as the value of the light diffused through the substrate divided by the transmitted light.
[ hardness test ]
The method used in the present invention is a surface pencil hardness method which is described below in accordance with JIS K-5600: different pencil types (Nippon Mitsubishi red pencil) are used for different pencils, and the types are respectively represented by 6B,5B,4B,3B,2B, B, HB, F, H,2H,3H,4H,5H,6H,7H,8H and 9H, wherein 6B is the softest and 9H is the hardest. The pencil is erected on a unit load of 750gf/cm2On the test trolley, the coating films in different areas are tested for 5 times in a mode that the pencils are pushed forwards; and judging whether the film surface of the test area is damaged by the pencil or not by naked eyes. If the test five areas at least have three areas without scratches, the pencil type is replaced by a softer pencil type and the test is continued until the three areas have no scratches, and the pencil type used at this time is the pencil hardness value (such as pencil hardness 2H or 3H) of the coating film.
[ Table 2]
Example one Example two EXAMPLE III Comparative example 1 Comparative example II
Degree of penetration 92.13 92.22 92.47 92.39 92.37
Haze degree 0.26 0.21 0.23 0.25 0.28
Hardness of 2H H H 2H H
[ test of film adhesion ]
The adherence test refers to the reference specification of the Baige knife test method as ASTM D-3359; the test method is illustrated below:
100 scratches (1x 1 cm) were made on the surface of the pre-test coating film with a special hundred-grid knife2) After the 3M 600 type adhesive tape is attached to the surface of the coating, the adhesive tape is instantly torn off at an angle of more than 90 degrees, and then whether the coating on the surface of the coating is peeled off or not is judged by eyes.
[ evaluation ]
The adhesion of the coating film was judged by the area of the peeled surface of the coating film according to Table 3.
[ Table 3]
Rank of Evaluation criteria
5B The scribed edges are extremely smooth and the square lattice coating does not fall off at all
4B Small coating layers at the crossed parts of the scribed lines fall off, but the area is less than 5 percent
3B Small coating layer falls off at the crossed part of the scribed line, but the area is as small as 5 to 15 percent
2B Small coating layers fall off at the crossed positions of the scribed lines, but the area is as small as 15 to 35 percent
1B Small coating layers fall off at the crossed positions of the scribed lines, but the area is 35 to 65 percent
0B Complete peeling off of the coating
The adhesion between the base material and each of the following examples and comparative examples is shown in Table 4.
[ Table 4]
Example one Example two EXAMPLE III Comparative example 1 Comparative example II
Acrylic plate 5B 5B 5B 5B 5B
Polycarbonate resin 5B 5B 5B 5B 5B
ABS 5B 5B 5B 5B 5B
PET (No treatment) 5B 5B 5B 0B 0B
Nylon 5B 5B 5B 0B 0B
TPU 5B 5B 5B 0B 0B
Carbon fiber 5B 5B 5B 0B 0B
Glass 0B 0B 5B 0B 0B
Tinplate 3B 5B 5B 0B 0B
Galvanized steel sheet 5B 5B 5B 0B 0B
Steel plate 5B 5B 5B 0B 0B
Magnesium-lithium alloy 5B 5B 5B 0B 0B
Aluminium plate 5B 5B 5B 0B 0B
Phosphate treated board 5B 5B 5B 0B 0B
As can be seen from tables 1 and 4, in the first to third embodiments, the uv curable resin is a vinyl resin formed by polymerizing a monomer containing a dibasic acid, wherein the dibasic acid monomer provides a chelating effect between carboxyl groups and metal, and slightly corrodes the metal surface and destroys the metal dense surface, so as to achieve good adhesion to metal.
In contrast, it can be seen from tables 1 and 4 that the uv curable resins of comparative examples one and two do not contain a vinyl resin formed by polymerization of a dibasic acid monomer, and thus have poor adhesion to metals.
As can be seen from tables 1 and 4, in the third embodiment, the uv curable resin includes, in addition to the vinyl resin formed by polymerizing the dibasic acid monomer, the organosiloxane having hydroxyl or alkoxy groups capable of bonding through condensation reaction with hydroxyl groups on the glass surface, thereby providing good adhesion to the glass.
In contrast, it can be seen from tables 1 and 4 that the uv curable resins of examples one and two do not include organosiloxane and thus have poor adhesion to glass.
As can be seen from tables 1 and 4, in the second comparative example, the uv curable resin does not contain a vinyl resin formed by polymerizing a dibasic acid monomer, and since the acid has a catalytic effect on the condensation reaction of the hydroxyl group or alkoxy group of the organosiloxane and the hydroxyl group on the surface of the glass, the uv curable resin does not contain a vinyl resin formed by polymerizing a dibasic acid monomer, and the adhesion to the glass is poor even if the uv curable resin contains the organosiloxane.
As described above, the uv curable resin can provide good adhesion to a metal by using a vinyl resin obtained by polymerizing a monomer containing a dibasic acid. The ultraviolet-curable resin can improve the adhesion to metal and glass by using a vinyl resin obtained by polymerizing a dibasic acid monomer and an organosiloxane.
As can be seen from tables 1 and 2, the uv curable resin of example one includes a higher proportion of the photocurable oligomer than those of examples two and three with respect to the photocurable oligomer and the ethylenically unsaturated monomer, wherein the photocurable oligomer has more than two ethylenically unsaturated bonds, so that the polymerized uv curable resin has a higher bridging density and provides a higher hardness (2H).
In contrast, as can be seen from tables 1 and 2, the uv curable resins of examples two and three include a smaller proportion of the photocurable oligomer having two or more ethylenically unsaturated bonds with respect to the photocurable oligomer and the ethylenically unsaturated monomer, so that the polymerized uv curable resin has a lower crosslinking density and provides a lower hardness (H).
As described above, by adjusting the ratio of the photocurable oligomer to the ethylenically unsaturated monomer, different hardness can be provided, and thus the uv curable resin has adjustable hardness.
The foregoing outlines several embodiments so that those skilled in the art may better understand the aspects of the present embodiments. Those skilled in the art should appreciate that they may readily use the present disclosure as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art should also realize that such equivalent processes and structures do not depart from the spirit and scope of the present invention, and that they may make various changes, substitutions and alterations herein without departing from the spirit and scope of the present invention.

Claims (17)

1. An ultraviolet-curable resin composition comprising:
5-40 parts by weight of a photocurable oligomer (A);
10 to 50 parts by weight of a vinyl resin (B);
5 to 40 parts by weight of an unsaturated ethylenic monomer (C); and
0.1 to 15 parts by weight of a photopolymerization initiator (D);
wherein the photocurable oligomer (a) + the vinyl resin (B) + the ethylenically unsaturated monomer (C) is 100 parts by weight, and the vinyl resin (B) is formed by polymerizing:
an aromatic compound monomer or an aliphatic monomer (B1), wherein the aromatic compound monomer comprises a C8-C12 monovinyl aromatic compound or a halogenated derivative thereof; and
a dibasic acid monomer (B2);
wherein the molar ratio of the aromatic compound monomer or aliphatic monomer (B1) to the dibasic acid monomer (B2) is 10-20.
2. The ultraviolet-curable resin composition according to claim 1, wherein the aromatic monomer or the aliphatic monomer (B1) has a structure represented by formula 1 or a structure represented by formula 2, wherein R1 to R5 are each independently a C1 to C10 alkyl group, a hydrogen atom or a halogen, and R6 and R7 are each independently a C1 to C10 alkyl group or a hydrogen atom
[ chemical formula 1]
Figure FDA0002844944760000011
[ chemical formula 2]
Figure FDA0002844944760000012
3. The ultraviolet-curable resin composition according to claim 2, wherein the aliphatic monomer in the aromatic compound monomer or the aliphatic monomer (B1) is a C4-C10 alkyl methacrylate monomer or a C3-C10 alkyl acrylate monomer.
4. The ultraviolet light-curable resin composition according to claim 1, wherein the dibasic acid monomer (B2) has a structure represented by formula 3, and R8 is an alkylene group or an alkenylene group of from C1 to C10
[ chemical formula 3]
Figure FDA0002844944760000021
5. The ultraviolet-curable resin composition according to claim 4, wherein the dibasic acid monomer (B2) has an ethylenic unsaturation.
6. The ultraviolet light-curing resin composition according to claim 5, wherein the dibasic acid monomer (B2) is formalin acid or maleic acid.
7. The ultraviolet light-curing resin composition according to claim 6, wherein the dibasic acid monomer (B2) has a structure represented by chemical formula 4
[ chemical formula 4]
Figure FDA0002844944760000022
8. The ultraviolet light-curing resin composition according to claim 4, wherein the aromatic monomer or the aliphatic monomer (B1) has a structure represented by chemical formula 5
[ chemical formula 5]
Figure FDA0002844944760000023
9. The ultraviolet light-curable resin composition according to claim 3, wherein the alkyl methacrylate monomer having C4-C10 has a structure represented by formula 6, and the alkyl acrylate monomer having C3-C10 has a structure represented by formula 7
[ chemical formula 6]
Figure FDA0002844944760000031
[ chemical formula 7]
Figure FDA0002844944760000032
10. The ultraviolet-curable resin composition according to claim 1, wherein the vinyl resin (B) has a weight-average molecular weight of 5,000 to 200,000.
11. The ultraviolet-curable resin composition according to claim 1, wherein the photocurable oligomer (A) has a weight-average molecular weight of 1000 to 10,000.
12. The ultraviolet light curable resin composition of claim 11, wherein the photocurable oligomer (a) comprises urethane acrylate oligomer, polyacrylic oligomer, polyester oligomer, polyether oligomer, epoxy oligomer, or combinations thereof.
13. The ultraviolet-curable resin composition according to claim 11, wherein the photocurable oligomer (a) has two or more ethylenically unsaturated bonds.
14. The ultraviolet-curable resin composition according to claim 12, wherein the photocurable oligomer (a) is a urethane acrylic oligomer.
15. The ultraviolet curable resin composition according to claim 1, further comprising 0.1 to 5 parts by weight of an organosiloxane coupling agent (E).
16. The ultraviolet light curing resin composition of claim 15, wherein the organosiloxane coupling agent comprises an ethylenic unsaturation.
17. The ultraviolet-curable resin composition according to claim 1, wherein the photopolymerization initiator (D) comprises two or more different photopolymerization initiators.
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